CN1258679A - Catalyst for synthesizing polyolefine with wide or double molecular weight distribution and its preparation - Google Patents

Catalyst for synthesizing polyolefine with wide or double molecular weight distribution and its preparation Download PDF

Info

Publication number
CN1258679A
CN1258679A CN 98125667 CN98125667A CN1258679A CN 1258679 A CN1258679 A CN 1258679A CN 98125667 CN98125667 CN 98125667 CN 98125667 A CN98125667 A CN 98125667A CN 1258679 A CN1258679 A CN 1258679A
Authority
CN
China
Prior art keywords
catalyzer
metallocene
preparation
catalyst
methylaluminoxane
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 98125667
Other languages
Chinese (zh)
Other versions
CN1107082C (en
Inventor
常溪燕
尹向春
陈伟
郑刚
景振华
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.)
Sinopec Research Institute of Petroleum Processing
China Petrochemical Corp
Original Assignee
Sinopec Research Institute of Petroleum Processing
China Petrochemical Corp
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 Sinopec Research Institute of Petroleum Processing, China Petrochemical Corp filed Critical Sinopec Research Institute of Petroleum Processing
Priority to CN98125667A priority Critical patent/CN1107082C/en
Publication of CN1258679A publication Critical patent/CN1258679A/en
Application granted granted Critical
Publication of CN1107082C publication Critical patent/CN1107082C/en
Anticipated expiration legal-status Critical
Expired - Fee Related legal-status Critical Current

Links

Images

Abstract

The catalyst consists of one kind of metallocene catalyst carried by inorganic oxide and one kind of transition metal catalyst carried by inorganic oxide and inorganic chloride, and the mole ratio between the transition metal contents in the metallocene catalyst and in the transition metal catalyst is 0.01-50. The preparation process is adding one kind of prepared carried catalyst during the preparation of the other kind of carried catalyst, or is dry mixing in the protective nitrogen.

Description

A kind of synthetic wide or polyolefinic catalyzer and preparation method that double molecular weight distributes
The present invention is polyolefinic catalyzer and the preparation method who synthesizes wide or bimodal molecular weight distribution in single reaction vessel.More particularly, be the catalyzer and the preparation method of the copolymerized product of the ethylene homo of synthetic wide or bimodal molecular weight distribution or ethene and alpha-olefin.
Comparatively advanced method synthetic wide or the double molecular weight distribution polyethylene is to adopt the catalyzer with a plurality of active centre, as USP5,032,562 disclose a kind of catalyzer with a plurality of active centre, and this catalyzer comprises magnesium compound, zirconium compounds and the TiCl that loads on the porous support with activity hydroxy 4, wherein magnesium compound is alkoxyl magnesium, alkyl magnesium or alkyl magnesium halide, zirconium compounds is the zirconium halide cyclopentadinyl compound.This catalyzer is by flooding the reaction product of described carrier and magnesium compound with titanium compound, and then dipping zirconium cyclopentadinyl compound obtains.This patent is a carrier with activated silicon-dioxide in concrete preparation process, and after handling with dibutyl magnesium, the adding titanium tetrachloride also stirs for some time, adds the methylaluminoxane (methylaluminoxane) and bis cyclopentadienyl zirconium dichloride (Cp that prepare in advance again 2ZrCl 2) toluene solution stir, remove to desolvate then and promptly obtain catalyzer.The add-on of this catalyzer methylaluminoxane in preparation process is too much unsuitable, if the methylaluminoxane that adds is too much, then Zhi Bei catalyzer easily lumps.In addition, in polymerization process, use this Catalyst Production polyethylene product, also need use methylaluminoxane as promotor.
EP436399A 2Also disclose a kind of olefin polymerization catalysis, this catalyzer comprises that [A] is the titanium catalyst of essentially consist with titanium, magnesium and halogen, and [B] contains transistion metal compound and [C] Organoaluminoxy compound of cycloalkyl diene structure part.Titanium catalyst described in this catalyzer [A] is the titanium compound that is carried on the Magnesium Chloride Anhydrous, and [B] is pure metallocene or with silicon dioxide carried metallocene catalyst, [C] is aikyiaiurnirsoxan beta.Above-mentioned three components add reaction system respectively during use, also can be pre-mixed, and feed ethene again and react.After wherein the catalyzer of silicon dioxide carried metallocene need make catalyzer through prepolymerization, be used further to polyreaction to produce polymerization product wide or that double molecular weight distributes.
CN1136286A discloses a kind of catalyst composition that is used for vinyl polymerization and copolymerization, said composition contains a kind of transition metal cyclopentadinyl compound that is activated and a kind of by aluminum alkyls activatory non-metallocene transition metal, wherein used carrier is to use organo-magnesium compound, silicon-dioxide as dibutylmagnesium dipping hydroxyl, make with organic pure agent treated again, the preparation of this carrier has strictness also to control to the usage quantity of organic-magnesium, require its molar content should be roughly suitable with the contained hydroxyl molar weight of silicon-dioxide, otherwise will be harmful to synthetic catalyst.Obviously, the operating process for preparing this catalyzer is strict, and is wayward.
The purpose of this invention is to provide that a kind of raw material is easy to get, can in the single reaction still, synthesize the polyolefinic catalyzer of wide or bimodal molecular weight distribution.
Another object of the present invention provides a kind of above-mentioned Preparation of catalysts method simple and that implement easily for preparing.
Catalyzer of the present invention by (A) a kind of load on the inorganic oxide metallocene catalyst and (B) a kind of transition-metal catalyst that loads on inorganic oxide and the butter form, wherein the mol ratio of contained transition metal is 0.01~50 in (A), (B) two kinds of catalyzer.
Inorganic oxide is silicon-dioxide, aluminum oxide or clay in the described catalyzer, and the also available olefin polymer of this inorganic oxide replaces, and preferred inorganic oxide is silicon-dioxide or aluminum oxide, and most preferred inorganic oxide is a silicon-dioxide.
Butter in the described catalyzer is selected from magnesium chloride.
Metallocene in described (A) catalyzer is to have the metallocene ether inorganic salt adducts that following general formula is formed:
Cp′MQ 2·A·2M′Q
In the formula, Cp ' is selected from the bicyclic pentadiene of bicyclic pentadiene or monoalkyl replacement, and described substituted alkyl can be identical or different, is selected from C 1~C 12Alkyl;
M is a zirconium, and M ' is a lithium;
Q is a halogen, is preferably chlorine;
A is the cycloalkyl ethers that contains a Sauerstoffatom and 2~6 carbon atoms, and preferred cycloalkyl ethers is a tetrahydrofuran (THF).
Preferred metallocene adduct is that expression formula is (BuCp) 2ZrCl 2Two (butyl cyclopentadienyl) zirconium dichloride tetrahydrofuran (THF) lithium chloride of THF2LiCl.
Metallocene adduct of the present invention prepares by the following method: be solvent with the cycloalkyl ethers,-10~30 ℃, preferably-5~10 ℃ make the reaction of Cyclopeutadiene type ligand compound and alkaline reagents generate the part negative ion, at-78~30 ℃, be MQ then with part negative ion and the general formula that generates 4Metallic compound reaction, when metallocene forms, metallocene forms metallocene adduct with inorganic salt and cycloalkyl ethers solvent that reaction discharges, remove and desolvate, preferably remove 50~98% solvent, add alkane resistates is disperseed, filters, is drying to obtain metallocene adduct solid phase prod of the present invention.
Cyclopeutadiene type compounds comprises the cyclopentadiene that cyclopentadiene and monoalkyl replace among the above-mentioned metallocene adduct preparation method, and mono-substituted alkyl is selected from C in the cyclopentadiene 1~C 12Alkyl, preferred C 1~C 8Alkyl, most preferred substituted alkyl is normal-butyl or isobutyl-.The cyclopentadiene compound that replaces of monoalkyl is selected from a kind of in methyl cyclopentadiene, ethyl cyclopentadiene, propyl group cyclopentadiene, butyl cyclopentadiene and the isobutyl-cyclopentadiene or their mixture preferably.The cyclopentadiene that described monoalkyl replaces adopts the known method preparation, as, select for use halogenated alkane and excessive cyclopentadiene under the condition of phase-transfer catalysis, to react acquisition.
Described cycloalkyl ethers solvent is the cycloalkyl ethers that contains a Sauerstoffatom and 2~6 carbon atoms; Preferred cycloalkyl ethers is a tetrahydrofuran (THF).
Described alkaline reagents is the basic metal organic compound, preferred alkyl lithium, lithium aryl, most preferably butyllithium.
Described MQ 4M in the metallic compound is selected from any element of IVB family in the periodic table of elements, preferred zirconium; Q is halogen, most preferably chlorine.
In the adducts preparation process, remove most of solvent after added alkane be selected from C 5~C 12Alkane, preferred boiling range is 60~90 ℃ of sherwood oils.The add-on of alkane is preferably 1~10 times of resistates volume.
In the present invention, the catalyzer of described load metallocene adducts (A) is to be carrier with the activatory inorganic oxide, in the presence of polar solvent, with solution-treated 0.1~3.0 hour formation suspension of this carrier with methylaluminoxane, solution with methylaluminoxane mixes with metallocene adduct with the activation metallocene again, then this mixed solution is added thorough mixing in the above-mentioned suspension, remove and desolvate, promptly obtain carried metallocene catalyst of the present invention.Methylaluminoxane used in the loading process is divided two portions, the methylaluminoxane consumption of handling carrier should be 0.1~0.9 times of used methylaluminoxane total amount, the methylaluminoxane consumption of activation metallocene adduct should be 0.1~0.9 times of methylaluminoxane total amount, the total Al content that methylaluminoxane provided and the mol ratio of metallocene should be controlled to be 10~1000, preferably 50~500, preferred 80~250.
The activating treatment process of described inorganic oxide is: with inorganic oxide, preferred silicon-dioxide is 150~250 ℃ of roastings 0.5~6.0 hour, and then 400~600 ℃ of roastings 1~16 hour.
The used inorganic oxide of load should be anhydrous dried powder, and specific surface area should be 10~300 meters 2/ gram, preferably 100~200 meters 2/ gram, and some activity hydroxies should be contained at least with the supported catalyst active ingredient in its surface.Preferred inorganic oxide is silicon-dioxide, aluminum oxide or clay, and most preferred inorganic oxide is a silicon-dioxide.
The content of transition metal is 0.01~10.0 heavy % in the above-mentioned loaded metallocene adduct catalyst (A), be preferably 0.1~0.9 heavy %, the preferred zirconium of described transition metal, the mol ratio of aluminium and transition metal is 10~1000 in this loaded catalyst, be preferably 50~500, preferred 80~250, most preferably 100~200.
Described carrier-borne transition metal catalysts (B) is the Ziegler-Natta catalyst of loading type, and contained transition metal is a titanium in this catalyzer.The content of titanium in catalyzer is 0.5~3.5 heavy %, preferably 1.0~3.0 heavy %.The carrier of this loaded catalyst is made up of a kind of inorganic oxide and a kind of butter, and the preferred silicon-dioxide of described inorganic oxide also can be aluminum oxide or clay; The preferred Magnesium Chloride Anhydrous of described butter.In the described catalyzer (B), the mol ratio of institute's containing metal is 0.1~10.0 in transition metal and the butter, preferably 0.2~1.0.
The preferred magnesium chloride of described butter, the preferred silicon-dioxide of inorganic oxide, the weight ratio of inorganic oxide and butter is 1.0~20.0: 1, preferably 1.0~10.0: 1
In the present invention, the preparation method of carrier-borne transition metal catalysts (B) is: add at least a polar solvent in the exsiccant butter, preferably add a kind of alcoholic solvent simultaneously, 10~70 ℃ are fully stirred, and butter is dissolved fully, add transistion metal compound, and under this temperature, reacted 0.5~6.0 hour, add inorganic oxide reaction 0.5~3.0 hour again, remove and desolvate, promptly obtain the catalyzer of good fluidity.
Used polar solvent is a kind of C in the preparation process of described catalyzer (B) 2~C 20Cycloalkyl ethers, preferred cycloalkyl ethers is a tetrahydrofuran (THF); Its consumption is 1~80 times of butter weight, and described alcoholic solvent is C 2~C 20Monohydroxy-alcohol, preferred C 2~C 7Monohydroxy-alcohol, most preferred alcoholic solvent is ethanol, n-hexyl alcohol, 1-butanols, Pentyl alcohol; The mol ratio of added alcohol and transition metal is 60~250: 1, preferred 60~150: 1, and the catalyzer that adds behind the alcohol can make the form of polymkeric substance that very big change is arranged.
The halogenide of the preferred titanium of described transistion metal compound or the complex compound of halogenated titanium are as TiCl 4, TiCl 3Or TiCl 4(THF) 2, TiCl most preferably 4Or TiCl 4(THF) 2
Preparation of catalysts method of the present invention comprises is doing the catalyzer that blending is closed or the adding another kind prepares in advance in the process of a kind of loaded catalyst of preparation with described (A), (B) two kinds of loaded catalysts under the nitrogen protection.
Do blending among the described preparation method and close the amount of two kinds of used loaded catalysts should to make the mol ratio of transition metal in metallocene in (A) catalyzer and (B) catalyzer be 0.01~50.0, be preferably 0.1~6.0, preferably 0.2~2.0.
Catalyzer of the present invention also can add the another kind of catalyzer for preparing in advance in the process of a kind of loaded catalyst of preparation, wherein method is in preparation carried metallocene catalyst process preferably, earlier with silicon-dioxide and (B) catalyst mix of preparing in advance, again to wherein adding nonpolar solvent and methylaluminoxane, reacted at normal temperatures 0.5~2.0 hour, the mixed solution that adds metallocene adduct and methylaluminoxane, reacted 0.1~5.0 hour, preferably after 0.5~2.0 hour, removing desolvates promptly gets catalyzer of the present invention.
Catalyzer of the present invention is applicable to ethylene homo or ethene and the C for preparing wide or bimodal molecular weight distribution 3~C 8The copolymerized product of alpha-olefin, the described preferred 1-butylene of alpha-olefin, 1-hexene, the 4-methyl-1-pentene that is used for copolymerization.Should use aluminum alkyls to be promotor during polymerization, so that (B) activation of the transition metal component in the catalyzer, the alkyl in the aluminum alkyls is selected from any one in straight chained alkyl, cycloalkyl and the aralkyl.Preferred aluminum alkyls is trimethyl aluminium, triethyl aluminum, triisobutyl aluminium or their mixture.The amount of used aluminum alkyls is counted Al/Ti mol ratio 10~1000: 1 with Al during polymerization, and preferred 15~500: 1, most preferably 20~200: 1.
Mixed catalyst of the present invention is applicable to gas phase or slurry reaction process, and suitable reaction conditions is 30~115 ℃, and pressure is 0.1~6.0MPa, and the solvent that slurry polymerization is selected for use is C 5~C 12Alkane, preferred solvent is a hexane.
The present invention adopts the metallocene catalyst (A) of loading type and carrier-borne transition metal catalysts (B) preparation is synthetic wide or the polyolefin catalyst of bimodal molecular weight distribution, and used (B) catalyzer selects for use inorganic oxide and butter to make carrier, simplified the Preparation of catalysts step, and made the catalyzer of preparation have good mobility.The polyolefin products that makes with this catalyzer has two fusing points and wide molecular weight distribution, its molecular weight distribution (M w/ M n) reach 2.0~70.0.
Describe the present invention in detail below by embodiment, but the present invention is not limited to this.
Example 1
This examples preparation expression formula is (BuCp) 2ZrCl 2The metallocene adduct of two (butyl cyclopentadienyl) zirconium dichloride-tetrahydrofuran (THF)-lithium chlorides of THF2LiCl.
(a) preparation of butyl cyclopentadienyl lithium
Under the ice-water bath cooling, in 4.2 milliliters of tetrahydrofuran (THF)s (THF) solution of 6.03 gram (0.05 mole) butyl cyclopentadiene, slowly drip the hexane solution of 2.5 mol of 20 milliliters of (0.05 mole) butyllithiums, dropwise the back and continue to stir 1 hour, obtain the white opacity solution of butyl cyclopentadienyl lithium.
(b) preparation of metallocene adduct
Under-78 ℃, in the butyl cyclopentadienyl lithium solution of above-mentioned acquisition, slowly add 5.76 gram (0.025 mole) ZrCl 4, dropwise the back stirred overnight at room temperature, get yellow turbid solution.Remove 90% solvent, resistates disperses after-filtration, drying with 4.2 milliliters of sherwood oils, gets yellow powder powder solid adduct gram.It is 16.66 heavy % that inductance coupled plasma atomic emission spectrum is measured in this adducts zirconium content.
Example 2
The metallocene adduct catalyzer of this examples preparation loading type.
Get 955 grades of SiO of Davison 21.0 gram was calcined 2 hours for 200 ℃, calcined 4 hours for 600 ℃, to slough SiO 2The part of hydroxyl on surface is carried out activation treatment.SiO in above-mentioned activated processing 2(wherein contain methylaluminoxane 10 heavy %, density is 0.9 gram per centimeter to the toluene solution of 6 milliliters of methylaluminoxane of middle adding 3), 20 ℃ were reacted 1 hour, and adducts 0.1 gram that again example 1 is made adds wherein with the mixed solution of the toluene solution of 5 milliliters of methylaluminoxane, 45 ℃ were reacted 2 hours, drain solvent under the decompression, obtain free-pouring yellow powder shape catalyst A 1.85 grams, wherein contain zirconium 0.83 heavy %.
Example 3
This examples preparation carrier-borne transition metal catalysts.
Get dry anhydrous MgCl 20.5 gram (production of Jinzhou aluminium manufacturer) is put into reaction flask, adds 10 milliliters of tetrahydrofuran (THF)s, 6 milliliters of ethanol were 65 ℃ of reactions 3 hours.30 milliliters of tetrahydrofuran (THF)s are splashed into be dissolved with 10 milliliters of TiCl 4Toluene in generate TiCl 4(THF) 2, filter then, drain filter cake, get solid matter 0.52 gram and put into reaction flask reaction 4 hours, add the SiO that carries out activation treatment by example 2 described methods 22.0 nitrogen purging is used in gram reaction 2 hours, removes and desolvates, and obtains free-pouring white powder catalyst B 3.05 grams.Wherein titaniferous 1.40 weighs %.
Example 4
This example is with doing the legal preparation of blending catalyzer of the present invention, and with this catalyst to synthesize ethene.
Get the catalyzer of 0.1 gram example 2 preparation and the catalyzer of 0.05 gram example, 3 preparations, do blending in the glove box of nitrogen and close evenly being filled with, make mixed catalyst C.
Under 50 ℃, in 1 liter of stainless steel autoclave, add 30 milliliters of hexenes and 15 milliliters of triethyl aluminums, suspension with 0.15 gram catalyzer C and 250 milliliters of hexanes is pressed in the still again, feed ethene, and to keep its pressure be 1.0MPa, 70 ℃ of following polymerizations 1 hour, collects the polyethylene products that obtain 82 grams, it is 113 ℃ and 128 ℃ that the differential scanning method records its fusing point, and gel chromatography records M w=1.17 * 10 6, M n=6.32 * 10 4, M w/ M n=18.49, gel permeation chromatography shown in Figure 1 (GPC) shows that this polymkeric substance has bimodal molecular weight distribution.
Example 5
This example adds the carrier-borne transition metal catalysts prepare in advance and prepares catalyzer of the present invention in the process of preparation carried metallocene catalyst, and with this catalyst to synthesize ethene.
Get 955 grades of SiO of Davison 20.5 gram was calcined 2 hours for 200 ℃, calcined 4 hours for 600 ℃, to slough SiO 2The part of hydroxyl on surface is carried out activation treatment.Will be through the SiO of activation treatment 2With 0.7 catalyst mix that makes of gram example 3, add 20 milliliters of hexanes, drip 8 milliliters of methylaluminoxane again, normal temperature reacted 1 hour down, add metallocene adduct and 12 milliliters of solution that the methylaluminoxane toluene solution is made into that 0.176 gram example 1 makes, 55 ℃ were reacted 1 hour, under reduced pressure drained solvent, obtained free-pouring catalyzer D 2.72 grams.
At 50 ℃, in 1 liter of stainless steel autoclave, add 20 milliliters of hexenes and 22 milliliters of triethyl aluminums, suspension with 0.3 gram catalyzer D and 250 milliliters of hexanes is pressed in the still again, feed ethene, and to keep its pressure be 1.0MPa, 70 ℃ of following polymerizations 1 hour, collects the polyethylene that obtain 42 grams, it is 120 ℃ and 133 ℃ that the differential scanning method records its fusing point, M wBe 1.88 * 10 6, M nBe 2.73 * 10 4, M w/ M nBe 68.81.Fig. 2 is the GPC spectrogram of this polymkeric substance, and as shown in Figure 2, the polymkeric substance that is made by catalyzer D has wide or bimodal molecular weight distribution.

Claims (12)

1, a kind of synthetic wide or polyolefinic catalyzer that double molecular weight distributes, it is characterized in that this catalyzer by (A) a kind of load on the inorganic oxide metallocene catalyst and (B) a kind of transition-metal catalyst that loads on inorganic oxide and the butter form, wherein the mol ratio of contained transition metal is 0.01~50 in (A), (B) two kinds of catalyzer.
2,, it is characterized in that described inorganic oxide is a silicon-dioxide according to the described catalyzer of claim 1.
3,, it is characterized in that described butter is a magnesium chloride according to the described catalyzer of claim 1.
4,, it is characterized in that the metallocene described in (A) is to have the metallocene ether inorganic salt adducts that following general formula is formed according to the described catalyzer of claim 1:
Cp′MQ 2·A·2M′Q
In the formula, Cp ' is selected from the bicyclic pentadiene of bicyclic pentadiene or monoalkyl replacement, and described substituted alkyl can be identical or different, is selected from C 1~C 12Alkyl;
M is a zirconium;
Q is a halogen;
A is the cycloalkyl ethers that contains a Sauerstoffatom and 2~6 carbon atoms;
M ' is a lithium.
5,, it is characterized in that described metallocene adduct is that expression formula is (BuCp) according to the described catalyzer of claim 4 2ZrCl 2Two (butyl cyclopentadienyl) zirconium dichloride tetrahydrofuran (THF) lithium chloride of THF2LiCl.
6,, it is characterized in that the transition metal described in (B) is a titanium according to the described catalyzer of claim 1.
7, according to the described any catalyzer of claim 1~5, it is characterized in that described inorganic oxide re-uses after the activation treatment in advance, its activation treatment condition is 150~250 ℃ of roastings 0.5~6.0 hour, 400~600 ℃ of roastings 1.0~16.0 hours.
8, according to the described any catalyzer of claim 1~5, it is characterized in that also containing in (A) methylaluminoxane, its content is that to make the mol ratio of contained aluminium of methylaluminoxane and metallocene be 10~1000.
9, the described Preparation of catalysts method of a kind of claim 1 comprises described (A), (B) two kinds of loaded catalysts are being done the catalyzer that blending is closed or the adding another kind prepares in advance in the process of a kind of loaded catalyst of preparation under the nitrogen protection.
10, in accordance with the method for claim 9, it is characterized in that described (A) Preparation of catalysts method comprises: in the presence of polar solvent, the mixture of methylaluminoxane and metallocene adduct is joined thorough mixing in the inorganic oxide of activatory in advance that methylaluminoxane is handled, the used methylaluminoxane of processing metallocene adduct is 0.1~0.99 times of used methylaluminoxane total amount, and total methylaluminoxane consumption is that the mol ratio of aluminium and metallocene is 10~1000.
11, in accordance with the method for claim 9, it is characterized in that described (B) Preparation of catalysts method comprises: in the exsiccant butter, add at least a polar solvent, add a kind of alcoholic solvent again, 10~70 ℃ of abundant stirrings are dissolved butter fully, add transistion metal compound reaction 0.5~6.0 hour, add butter reaction 0.5~3.0 hour again, collect solid matter and dry.
12, in accordance with the method for claim 9, be included in and add ready made (B) catalyzer in the process of preparation (A) catalyzer.
CN98125667A 1998-12-25 1998-12-25 Catalyst for synthesizing polyolefine with wide or double molecular weight distribution and its preparation Expired - Fee Related CN1107082C (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN98125667A CN1107082C (en) 1998-12-25 1998-12-25 Catalyst for synthesizing polyolefine with wide or double molecular weight distribution and its preparation

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN98125667A CN1107082C (en) 1998-12-25 1998-12-25 Catalyst for synthesizing polyolefine with wide or double molecular weight distribution and its preparation

Publications (2)

Publication Number Publication Date
CN1258679A true CN1258679A (en) 2000-07-05
CN1107082C CN1107082C (en) 2003-04-30

Family

ID=5229270

Family Applications (1)

Application Number Title Priority Date Filing Date
CN98125667A Expired - Fee Related CN1107082C (en) 1998-12-25 1998-12-25 Catalyst for synthesizing polyolefine with wide or double molecular weight distribution and its preparation

Country Status (1)

Country Link
CN (1) CN1107082C (en)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN100343290C (en) * 2002-10-18 2007-10-17 中国石油化工股份有限公司 Metallocene catalyst for production of polyolefine with broad peak or double peaks molecular weight distribution in monoreactor and its preparation
CN101817892B (en) * 2009-02-27 2011-11-30 中国石油化工股份有限公司 Method for preparing magnesium chloride loaded metallocene catalyst
CN102108104B (en) * 2009-12-23 2012-11-14 中国石油天然气股份有限公司 Polyolefin catalyst with wide or bimodal molecular weight distribution and preparation method thereof

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5032562A (en) * 1989-12-27 1991-07-16 Mobil Oil Corporation Catalyst composition and process for polymerizing polymers having multimodal molecular weight distribution
US5145818A (en) * 1989-12-29 1992-09-08 Mitsui Petrochemical Industries, Ltd. Olefin polymerization catalyst and process for the polymerization of olefins
JPH10505622A (en) * 1994-09-08 1998-06-02 モービル・オイル・コーポレーション Catalytic control of wide / 2 mode MWD resin in a single reactor

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN100343290C (en) * 2002-10-18 2007-10-17 中国石油化工股份有限公司 Metallocene catalyst for production of polyolefine with broad peak or double peaks molecular weight distribution in monoreactor and its preparation
CN101817892B (en) * 2009-02-27 2011-11-30 中国石油化工股份有限公司 Method for preparing magnesium chloride loaded metallocene catalyst
CN102108104B (en) * 2009-12-23 2012-11-14 中国石油天然气股份有限公司 Polyolefin catalyst with wide or bimodal molecular weight distribution and preparation method thereof

Also Published As

Publication number Publication date
CN1107082C (en) 2003-04-30

Similar Documents

Publication Publication Date Title
CN1209386C (en) Catalyst
US5525678A (en) Process for controlling the MWD of a broad/bimodal resin produced in a single reactor
KR100262245B1 (en) Supported olefin polymerization catalyst, its preparation and use
AU701536B2 (en) Catalyst for biomodal molecular weight distribution ethylene polymers and copolymers
CN1033859C (en) Metallocene catalysts with lewis acids and aluminum alkyls
KR100300486B1 (en) A solid precursor of a catalyst system for olefin polymerization, a process for producing the same, a catalyst system containing a former precursor and a polymerization method of an olefin in the presence of this catalyst system
AU698111B2 (en) Catalytic control of the MWD of a broad/bimodal resin in a single reactor
AU654867B2 (en) Process for the preparation of ethylene (co)polymers
EP0514594A1 (en) Catalyst composition and process for preparing polymers having multimodal molecular weight distribution
US20040198588A1 (en) Bimetallic catalysts with higher activity
CN1013581B (en) Solid catalyst for polymerizing olefin
BG63015B1 (en) Multistage process for polymerization (copolymerization) of olefins
CN1069033A (en) Many active sites olefin polymerization catalysis and preparation thereof
CN1123795A (en) Compositions useful for olefin polymerization and processes therefor and therewith
AU2001275496A1 (en) A catalyst system and its use in a polymerization process
CN1107082C (en) Catalyst for synthesizing polyolefine with wide or double molecular weight distribution and its preparation
CN1091451C (en) Catalyst for synthesis of polyolefine with wide or two-peak molecular weight distribution and its preparation
CN102108104B (en) Polyolefin catalyst with wide or bimodal molecular weight distribution and preparation method thereof
US5880055A (en) Catalyst for polymerization of ethylene
CN1060179C (en) Preparation of metallocene carrier catalyst
CN86103356A (en) The preparation method who is used for a kind of transition metal composition of catalytic systems for polymerization of olefins
CN100549038C (en) A kind of preparation method of polyethylene catalysts of loaded by semi-metallocene
CN1345887A (en) Semi-metallocene supported polyvinyl catalyst and preparation method thereof
JPH05105718A (en) Catalyst composition and process for polymerization of polymer having polymodal molecular weight distribution
JPH072922A (en) Organometallic-modified polyolefin catalyst for improving molecular characteristics

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: 20030430

Termination date: 20101225