CN1560092A - Composite catalist of titanium substitued nickle acenaphthene diimine of synthesizing branched polyvinyl and its preparation process - Google Patents

Composite catalist of titanium substitued nickle acenaphthene diimine of synthesizing branched polyvinyl and its preparation process Download PDF

Info

Publication number
CN1560092A
CN1560092A CNA2004100264487A CN200410026448A CN1560092A CN 1560092 A CN1560092 A CN 1560092A CN A2004100264487 A CNA2004100264487 A CN A2004100264487A CN 200410026448 A CN200410026448 A CN 200410026448A CN 1560092 A CN1560092 A CN 1560092A
Authority
CN
China
Prior art keywords
ticl
sio
reaction
compound
mgcl
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
CNA2004100264487A
Other languages
Chinese (zh)
Other versions
CN1246348C (en
Inventor
王海华
胡扬剑
江洪流
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.)
Sun Yat Sen University
National Sun Yat Sen University
Original Assignee
National Sun Yat Sen University
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 National Sun Yat Sen University filed Critical National Sun Yat Sen University
Priority to CN 200410026448 priority Critical patent/CN1246348C/en
Publication of CN1560092A publication Critical patent/CN1560092A/en
Application granted granted Critical
Publication of CN1246348C publication Critical patent/CN1246348C/en
Anticipated expiration legal-status Critical
Expired - Fee Related legal-status Critical Current

Links

Abstract

The invention relates to a Ti-substituted acenaphthene diimine nickel compound catalyste for synthesizing branched polyethylene and its preparing method, supporting Ti compound and substituted acenaphthene diimine nickel complex on a SiO2-MgCl2 compound carrier to act as a main catalyst and using alkyl Al and AlEt2Cl as aid-catalyst. The preparing method adopts dip-reaction method, and the obtained compound catalyst has a spherical particle shape and can make highly branched low-density polyethylene plastics.

Description

The titanium of synthesizing branched polyethylene-replacement acenaphthene diimine nickel composite catalyst and preparation method thereof
Technical field
The present invention relates to titanium-replacement acenaphthene diimine nickel composite catalyst of a kind of synthesizing branched polyethylene and preparation method thereof.
Background technology
Reaction has catalytic activity preferably to traditional Z-N (Z-N) catalyzer to ethene and alpha-olefin copolymer, can make the different degrees of branching in, new LDPE (film grade); But its body can not make polyethylene produce side chain, obtain branched polyethylene, just needs to use expensive alpha-olefin, and this has increased poly cost undoubtedly, simultaneously, also is difficult to obtain the polyethylene of the high degree of branching with this class catalyzer.Last century, 90 diimine ligand compounds for the rear transition metal nickel of finding mid-term, palladium etc. can be from the polyethylene plastomers and the elastomerics of single ethylene oligomerisation, the synthetic various high degrees of branching of in-situ copolymerization at the catalyst system that makes with methylaluminoxane (MAO) or boron compound, this has opened up a frontier for olefinic polymerization, have important application prospects (J.K.Johnson is arranged, C.M.Killian and M.Brookhart, J Am.Chem.Soc, 1995,117:6414).Yet this catalyzer need adopt expensive MAO or boron compound to make promotor, and cost is higher, and the prepared product degree of branching is wayward, and product form is irregular, promotes the use of in industrial production and still has bigger difficulty.
Summary of the invention
The purpose of this invention is to provide a kind of setting out and prepare the composite load catalyzer of branched polyethylene by single ethylene; It has the spheroidal particle form, only needs with general aluminum alkyls (AlR 3) and AlEt 2Cl makes promotor, need not to use expensive MAO or boron compound, can the polymerization of catalysis single ethylene make high degree of branching new LDPE (film grade) plastomer.This catalyst system can directly be used on existing polyethylene production device, need not to carry out scrap build, can solve the existing the problems referred to above of prior art preferably.
Catalyzer of the present invention, its component comprises compound primary catalysts and promotor; Load on MgCl with titanium compound and replacement acenaphthene diimine nickel complex 2, SiO 2On the complex carrier, constitute compound primary catalysts; With aluminum alkyls and AlEt 2Cl is a promotor; Titanium compound is TiCl 4Or TiCl 4With Ti (OR 1) 4, aluminum alkyls is AlR 3, R wherein 1Be propyl group or butyl, R is C 2～C 8Alkyl; Replacing the acenaphthene diimine nickel complex is NiLCl 2, wherein L is selected from L shown in the following structural formula I for replacing acenaphthene diimine compound 1To L 4In arbitrary compound:
Figure A20041002644800051
Wherein:
L 1: R 1=R 2=2-xenyl;
L 2: R 1=R 2=1-naphthyl;
L 3: R 1=2-xenyl, R 2=2, the 6-diisopropyl phenyl;
L 4: R 1=1-naphthyl, R 2=2, the 6-diisopropyl phenyl.
The catalyzer of the invention described above, the component proportioning by weight calculating is: MgCl 2: SiO 2: TiCl 4=1: (2～8): (0.5～3.0), all the other each components are with TiCl 4Mole number calculate its mol ratio and be:
TiCl 4 1.0
Ti(OR 1) 4 0～1.0
NiLCl 2 0.1～3.0
AlR 3 20～200
AlEt 2Cl 20～200
When titanium compound comprises TiCl 4And Ti (OR 1) 4The time, Ti (OR 1) 4With TiCl 4Mol ratio be generally Ti (OR 1) 4: TiCl 4=0.05～1.0: 1.
The used replacement acenaphthene diimine nickel complex of the catalyzer of the invention described above can obtain by the following method: under nitrogen protection; anhydrous chlorides of rase nickel was dissolved in dehydrated alcohol 2～3 hours; after waiting to have dissolved, join the CH of quality replacement acenaphthene diimine compounds (ligand L) such as being dissolved with 2Cl 2In the solution, back flow reaction 12～16 hours is drained and is sloughed solvent, and with anhydrous diethyl ether washing three times, vacuum-drying promptly gets required nickel complex NiLCl 2
The invention described above catalyzer can adopt dipping-reaction method preparation, and concrete steps are as follows:
(1) with microspheroidal SiO 2Place tube furnace, the heating down of logical nitrogen is warming up to 600 ℃, and 4～6 hours postcooling of calcining at constant temperature in the nitrogen protection bottom discharge, in reaction flask, add 10 times of SiO again 2The heptane of volume, nitrogen protection and stirring add and contain AlR down 3Hexane solution, maintain 25～30 ℃ the reaction 30 minutes, vacuumize drying and remove heptane, pre-treatment SiO 2AlR 3: hexane=1: 5～10W/W;
Under (2) 60～65 ℃, with MgCl 2Be dissolved in alcohol, the ether mixing solutions, stir mother liquor; Wherein alcohol is ethanol, and ether is tetrahydrofuran (THF), MgCl 2: alcohol=1: (3～5), MgCl 2: ether=1: (24～40);
(3) N 2Protection down, above-mentioned mother liquor adds and enters pretreated SiO 2In, 60～65 ℃ of stirring reaction 1～2h remove by filter mother liquor, 50～60 ℃ of controlled temperature, and vacuum tightness 30～35kPa drains liquid, gets active SiO 2-MgCl 2Complex carrier;
(4) N 2Protection adds alkane down in (3) products therefrom, be warming up to 60～70 ℃, adds TiCl under agitation condition 4Or TiCl 4And Ti (OR 1) 4Reaction 1～2h; Used alkane is hexane, heptane or octane, and consumption is every gram complex carrier 8～15ml alkane;
(5) in (4) gained mixed solution, add title complex NiLCl 2CH 2Cl 2Solution, 50～70 ℃ of hybrid reaction 0.5～1h drain solvent, and with alkane washing three times, vacuum is drained under 60 ℃ condition again, promptly gets compound primary catalysts; Wherein, NiLCl 2: CH 2Cl 2=1: 10～20W/W; Alkane is hexane or heptane, and consumption is every gram complex carrier 8～15ml; Primary Catalysts and promotor aluminum alkyls and AlEt 2Cl forms the poly composite catalyst of ethylene polymerization for preparing branched, and its mol ratio is: TiCl 4: AlR 3: AlEt 2Cl=1: (20～200): (20～200).
The present invention is by titanium compound and NiLCl 2Form composite components and above-mentioned specific dipping reaction method for preparing, make catalyzer only need general aluminum alkyls and Et 2AlCl makes promotor, need not expensive MAO or boron compound, can the highly active catalytic vinyl polymerization, make high degree of branching new LDPE (film grade) plastomer; Owing to adopt MgCl 2, SiO 2Form complex carrier, make to make polyethylene product and have good particle form.Catalyzer of the present invention has above-mentioned excellent comprehensive performance, is beneficial to aborning and promotes the use of, and has significant superiority.
Catalyzer of the present invention is 106.7kPa at pressure, 50～60 ℃ of polymerization temperatures, and slurry polymerization 1.5 hours, to vinyl polymerization, catalytic efficiency is 46～55kgLLDPE/mol (Ti+Ni), making density is 0.925～0.910g/cm 3, the degree of branching is 2.6～14.4 branched polyethylene.
Embodiment
The invention will be further described below by embodiment:
Embodiment one:
1. nickel complex NiL 1Cl 2Preparation: under nitrogen protection, 2 gram anhydrous chlorides of rase nickel were dissolved in the 20ml dehydrated alcohol 2～3 hours, after treating dissolve, join and quality (2 restrain) replacement acenaphthene diimine compounds L such as contain 130 the gram CH 2Cl 2In the solution, back flow reaction 12～16 hours is drained and is sloughed solvent, and with anhydrous diethyl ether washing three times, vacuum-drying promptly gets required replacement acenaphthene diimine nickel complex NiL 1Cl 2
2. Preparation of Catalyst:
2-1. with 5 gram microspheroidal SiO 2Put in the tube furnace, the heating down of logical nitrogen is warming up to 600 ℃, the calcining at constant temperature dehydration, and 6 hours postcooling get 4 gram SiO in the nitrogen protection bottom discharge 2, place reaction flask, add the 40ml heptane, under nitrogen protection and under constantly stirring, add and contain 2.5mol/L AlEt 3Hexane solution 3ml, maintain 25～30 ℃ the reaction 30 minutes, vacuumize drying and remove heptane, pre-treatment SiO 2
2-2. with 1.2 gram MgCl 2Be dissolved in alcohol, the ether mixing solutions, stir mother liquor.Wherein alcohol is ethanol, and ether is tetrahydrofuran (THF), MgCl 2: alcohol=1: 3, MgCl 2: ether=1: (24～40).
2-3. at N 2Protection down, above-mentioned mother liquor adds and enters pretreated SiO 2In, 60～65 ℃ of stirring reaction 2h remove by filter mother liquor, 50～60 ℃ of controlled temperature, and vacuum tightness 30～35kPa drains liquid, promptly gets active SiO 2-MgCl 2Complex carrier.
2-4. at N 2Under the protection, with SiO 2-MgCl 2Complex carrier is added in the reaction flask, adds alkane again, is warming up to 60～70 ℃, adds 1 gram TiCl under agitation condition 4, reaction 1.5h.Used alkane can be hexane, heptane or octane, and consumption is every gram complex carrier 8～15ml alkane.
2-5 adds 1.624g nickel complex NiL in mixed solution 1Cl 2CH 2Cl 2Solution, hybrid reaction 1h drains solvent, uses hexane wash three times, and vacuum is drained under 60 ℃ condition again, promptly gets body of catalyst.Wherein the hexane consumption is every gram complex carrier 8～15ml.Body of catalyst and promotor aluminum alkyls and AlR 2Cl forms ethylene rolymerization catalyst.
3. the ethene slurry polymerization prepares low-density branched polyethylene:
Reaction flask was vacuumized under 100 ℃ dry 1 hour, use N 2Replace three times, at N 2Protection adds 50ml exsiccant toluene and Al/ (Ti+Ni) than the compound aluminum alkyls and the AlR that are 100 down 2Cl (AlR 2Cl: AlR 3=1: 1), under agitation add then and contain 50～10mg Primary Catalysts, after continuation is stirred and catalyzer was uniformly dispersed in 5 minutes, feeding ethylene gas, is under the 106.7kPa at the pressure that keeps ethylene gas, is warming up to 50 ℃, carry out polyreaction, write down the ethene of polyreaction consumption in per 5 minutes, reaction 1.5h, stopped reaction, with acidic alcohol mixing solutions termination reaction thing, use washing with alcohol again, weigh after the drying, calculate catalyst efficiency.
Under above-mentioned polymerizing condition, the density of gained branched polyethylene is 0.902g/cm 3, be the degree of branching (plastomer of number of branches/1000C) that is 14.2.The catalytic efficiency of catalyzer is 51kgLLDPE/mol (Ti+Ni).
Embodiment two:
In embodiment one step 2-4, with 1 gram TiCl 4Change 1 gram TiCl into 4With 0.5 gram Ti (OR 1) 4All the other conditions and operation are with embodiment one, and the catalyzer that makes is polyreaction under embodiment one the same terms.
The density of gained branched polyethylene is 0.901g/cm under above-mentioned polymerizing condition 3, be that the degree of branching is 14.4 plastomeies.The catalytic efficiency of catalyzer is 50kgLLDPE/mol (Ti+Ni).
Embodiment three:
In embodiment one step 1, NiL 1Cl 2Change NiL into 2Cl 2, L 1Change L into 2Among the step 2-5, with 1.624g NiL 1Cl 2Change 1.610gNiL into 2Cl 2, all the other conditions and operation are with embodiment one, and the catalyzer that makes is polyreaction under embodiment one the same terms.
Under above-mentioned polymerizing condition, the density of gained branched polyethylene is 0.910g/cm 3, be that the degree of branching is 11.3 plastomeies.The catalytic efficiency of catalyzer is 53kgLLDPE/mol (Ti+Ni).
Embodiment four:
In embodiment one step 1, NiL 1Cl 2Change NiL into 3Cl 2, L 1Change L into 3Among the step 2-5, with 1.624g NiL 1Cl 2Change 1.577gNiL into 3Cl 2, all the other conditions and operation are with embodiment one, and the catalyzer that makes is polyreaction under embodiment one the same terms.
Under above-mentioned polymerizing condition, the density of gained branched polyethylene is 0.914g/cm 3, be that the degree of branching is 10.3 plastomeies.The catalytic efficiency of catalyzer is 49kgLLDPE/mol (Ti+Ni).
Embodiment five
In embodiment one step 1, NiL 1Cl 2Change NiL into 4Cl 2, L 1Change L into 4Among the step 2-5, with 1.624g nickel complex NiL 1Cl 2Change 1.645gNiL into 4Cl 2, all the other conditions and operation are with embodiment one, and the catalyzer that makes is polyreaction under embodiment one the same terms.
Under above-mentioned polymerizing condition, the density of gained branched polyethylene is 0.917g/cm 3, be that the degree of branching is 9.8 plastomeies.The catalytic efficiency of catalyzer is 54kgLLDPE/mol (Ti+Ni).

Claims (5)

1. the titanium of a synthesizing branched polyethylene-replacement acenaphthene diimine nickel composite catalyst comprises compound primary catalysts and promotor; It is characterized in that with titanium compound and replace the acenaphthene diimine nickel complex loading on MgCl 2, SiO 2On the complex carrier, constitute compound primary catalysts; With aluminum alkyls and AlEt 2Cl is a promotor; Titanium compound is TiCl 4Or TiCl 4With Ti (OR 1) 4, aluminum alkyls is AlR 3, R wherein 1Be propyl group or butyl, R is C 2～C 8Alkyl; Replacing the acenaphthene diimine nickel complex is NiLCl 2, wherein L is selected from L shown in the following structural formula I for replacing acenaphthene diimine compound 1To L 4In arbitrary compound:
Figure A2004100264480002C1
Wherein:
L 1: R 1=R 2=2-xenyl;
L 2: R 1=R 2=1-naphthyl;
L 3: R 1=2-xenyl, R 2=2, the 6-diisopropyl phenyl;
L 4: R 1=1-naphthyl, R 2=2, the 6-diisopropyl phenyl.
2. according to the described catalyzer of claim 1; it is characterized in that described replacement acenaphthene diimine nickel complex obtains by the following method: under nitrogen protection; anhydrous chlorides of rase nickel was dissolved in dehydrated alcohol 2～3 hours; after waiting to have dissolved, join the CH of quality replacement acenaphthene diimine compounds L such as being dissolved with 2Cl 2In the solution, back flow reaction 12～16 hours is drained and is sloughed solvent, and with the anhydrous diethyl ether washing, vacuum-drying promptly gets required replacement acenaphthene diimine nickel complex NiLCl 2
3. according to claim 1 or 2 described catalyzer, it is characterized in that the each component proportioning is by weight: MgCl 2: SiO 2: TiCl 4=1: (2～8): (0.5～3.0), all the other each components are with TiCl 4Mole number calculate its mol ratio and be:
TiCl 4 1.0
Ti(OR 1) 4 0～1.0
NiLCl 2 0.1～3.0
AlR 3 20～200
AlEt 2Cl 20～200。
4. according to the described catalyzer of claim 3, it is characterized in that Ti (OR wherein 1) 4With TiCl 4Mol ratio be: Ti (OR 1) 4: TiCl 4=0.05～1.0: 1.
5. claim 1,2,3 or 4 described Preparation of catalysts methods is characterized in that adopting the dipping reaction method, and concrete steps are as follows:
(1) with microspheroidal SiO 2Place tube furnace, the heating down of logical nitrogen is warming up to 600 ℃, and 4～6 hours postcooling of calcining at constant temperature in the nitrogen protection bottom discharge, in reaction flask, add 10 times of SiO again 2The heptane of volume, nitrogen protection and stirring add and contain AlR down 3Hexane solution, maintain 25～30 ℃ the reaction 30 minutes, vacuumize drying and remove heptane, pre-treatment SiO 2AlR 3: hexane=1: 5～10W/W;
Under (2) 60～65 ℃, with MgCl 2Be dissolved in alcohol, the ether mixing solutions, stir mother liquor; Wherein alcohol is ethanol, and ether is tetrahydrofuran (THF), MgCl 2: alcohol=1: (3～5), MgCl 2: ether=1: (24～40);
(3) N 2Protection down, above-mentioned mother liquor adds and enters pretreated SiO 2In, 60～65 ℃ of stirring reaction 1～2h remove by filter mother liquor, 50～60 ℃ of controlled temperature, and vacuum tightness 30～35kPa drains liquid, gets active SiO 2-MgCl 2Complex carrier;
(4) N 2Protection adds alkane down in (3) products therefrom, be warming up to 60～70 ℃, adds TiCl under agitation condition 4Or TiCl 4And Ti (OR 1) 4Reaction 1～2h; Used alkane is hexane, heptane or octane, and consumption is every gram complex carrier 8～15ml alkane;
(5) in (4) gained mixed solution, add title complex NiLCl 2CH 2Cl 2Solution, 50～70 ℃ of hybrid reaction 0.5～1h drain solvent, and with alkane washing three times, vacuum is drained under 60 ℃ condition again, promptly gets compound primary catalysts; Wherein, NiLCl 2: CH 2Cl 2=1: 10～20W/W; Alkane is hexane or heptane, and consumption is every gram complex carrier 8～15ml; Primary Catalysts and promotor aluminum alkyls and AlEt 2Cl forms the poly composite catalyst of ethylene polymerization for preparing branched, and its mol ratio is: TiCl 4: AlR 3: AlEt 2Cl=l: (20～200): (20～200).
CN 200410026448 2004-03-12 2004-03-12 Composite catalist of titanium substitued nickle acenaphthene diimine of synthesizing branched polyvinyl and its preparation process Expired - Fee Related CN1246348C (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN 200410026448 CN1246348C (en) 2004-03-12 2004-03-12 Composite catalist of titanium substitued nickle acenaphthene diimine of synthesizing branched polyvinyl and its preparation process

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN 200410026448 CN1246348C (en) 2004-03-12 2004-03-12 Composite catalist of titanium substitued nickle acenaphthene diimine of synthesizing branched polyvinyl and its preparation process

Publications (2)

Publication Number Publication Date
CN1560092A true CN1560092A (en) 2005-01-05
CN1246348C CN1246348C (en) 2006-03-22

Family

ID=34441219

Family Applications (1)

Application Number Title Priority Date Filing Date
CN 200410026448 Expired - Fee Related CN1246348C (en) 2004-03-12 2004-03-12 Composite catalist of titanium substitued nickle acenaphthene diimine of synthesizing branched polyvinyl and its preparation process

Country Status (1)

Country Link
CN (1) CN1246348C (en)

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101531724A (en) * 2009-04-17 2009-09-16 南昌航空大学 Polynuclear nickel(II) acenaphthenequinonediimine catalyst for synthesizing branched polyethylene and preparation method thereof
CN102050840A (en) * 2010-12-04 2011-05-11 西北师范大学 Naphthalene nucleus containing alpha-diketiminato nickel (II) composition as well as preparation method and application thereof
CN102504058A (en) * 2011-11-10 2012-06-20 上海化工研究院 Composite catalyst for producing wide molecular weight distribution polyethylene, preparation method and application thereof
JP2014520078A (en) * 2011-05-16 2014-08-21 上海 インスティテュート オブ オーガニック ケミストリー、チャイニーズ アカデミー オブ サイエンシーズ Catalyst system for the production of highly branched alkanes from olefins.
CN108530563A (en) * 2017-03-03 2018-09-14 天津工业大学 A kind of application of the loaded article of alpha-diimine and its metal complex in olefin polymerization

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101531724A (en) * 2009-04-17 2009-09-16 南昌航空大学 Polynuclear nickel(II) acenaphthenequinonediimine catalyst for synthesizing branched polyethylene and preparation method thereof
CN102050840A (en) * 2010-12-04 2011-05-11 西北师范大学 Naphthalene nucleus containing alpha-diketiminato nickel (II) composition as well as preparation method and application thereof
CN102050840B (en) * 2010-12-04 2013-06-05 西北师范大学 Naphthalene nucleus containing alpha-diketiminato nickel (II) composition as well as preparation method and application thereof
JP2014520078A (en) * 2011-05-16 2014-08-21 上海 インスティテュート オブ オーガニック ケミストリー、チャイニーズ アカデミー オブ サイエンシーズ Catalyst system for the production of highly branched alkanes from olefins.
US9315755B2 (en) 2011-05-16 2016-04-19 Shanghai Institute Of Organic Chemistry, Chinese Academy Of Sciences Catalytic system for preparation of high branched alkane from olefins
US10294440B2 (en) 2011-05-16 2019-05-21 Shanghai Chemrun Co., Ltd. Catalytic system for preparation of high branched alkane from olefins
CN102504058A (en) * 2011-11-10 2012-06-20 上海化工研究院 Composite catalyst for producing wide molecular weight distribution polyethylene, preparation method and application thereof
CN102504058B (en) * 2011-11-10 2014-04-02 上海化工研究院 Composite catalyst for producing wide molecular weight distribution polyethylene, preparation method and application thereof
CN108530563A (en) * 2017-03-03 2018-09-14 天津工业大学 A kind of application of the loaded article of alpha-diimine and its metal complex in olefin polymerization

Also Published As

Publication number Publication date
CN1246348C (en) 2006-03-22

Similar Documents

Publication Publication Date Title
CN1962702B (en) Carry type non-metallocene calalyst for polymerization of olefine, its preparation method and uses
CN101580561B (en) Supported polyolefin catalyst, preparation and application
CN1246348C (en) Composite catalist of titanium substitued nickle acenaphthene diimine of synthesizing branched polyvinyl and its preparation process
WO2011050566A1 (en) Supported non-metallocene catalyst, preparation method and uses thereof
CN1273502C (en) Multinuclear acenaphthene diimine nickle catalyst for synthesis of branched polyethylene
CN101531724A (en) Polynuclear nickel(II) acenaphthenequinonediimine catalyst for synthesizing branched polyethylene and preparation method thereof
CN1172969C (en) Titanium-nickel acetylacetonate composite catalyst for preparing branched polyethylene and its preparation method
CN102358761A (en) Olefin polymerization catalyst and preparation method thereof
CN100554288C (en) The method of organically-modified LDHs loaded acenaphthenequinonednickel nickel catalyst in-situ preparation of polyethylene-LDHs nano composite material
CN114316100B (en) Boron trifluoride modified silica gel, preparation method and application thereof, supported catalyst, preparation method and application thereof
CN1169851C (en) Ethylene polymerizing titanium-nickel-salicy-alimine composite catalyst and its preparing method
CN1637023A (en) Mononuclear and multinuclear polyvinyl acenaphthenyl diimido nickel catalyst and its prepn process
CN1966536A (en) Spherical carrier loaded late transition metal catalyst and its preparing process
CN101029096A (en) Neutral non-bridged combined metal chromium catalyst and its use
CN1216082C (en) Ti-Ni match as composite catalyst and its application in preparing branch polyethylene from ethylene
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
CN1263778C (en) 4-vinylpyridine homopolymerized and ethylene copolymerized acenaphthenyl diimido nickel catalyst and the prepn process
CN1282673C (en) Catalyst for ethylene polymerization or copolymerization and its prepn and application
CN112745423A (en) Preparation method of olefin-unsaturated carboxylic acid copolymer, olefin-unsaturated carboxylic acid copolymer and application thereof
CN1163532C (en) Ethylene copolymerized titanium-nickel compound catalyst and preparation process thereof
CN1163524C (en) Composite Ti-Ni catalyst for oligomerization and copolymerization of ethylene and its preparing process
CN114890987B (en) Thiophenol-thiophene ligand and preparation method thereof, olefin polymerization catalyst and preparation method and application thereof
CN1163531C (en) Ethylene copoly merized titanium-cobalt compound composite catalyst and its preparing method
CN1152063C (en) Solid catalyst for polymerization of olefin and its preparing process

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: 20060322