CN1169851C - Ethylene polymerizing titanium-nickel-salicy-alimine composite catalyst and its preparing method - Google Patents
Ethylene polymerizing titanium-nickel-salicy-alimine composite catalyst and its preparing method Download PDFInfo
- Publication number
- CN1169851C CN1169851C CNB021343896A CN02134389A CN1169851C CN 1169851 C CN1169851 C CN 1169851C CN B021343896 A CNB021343896 A CN B021343896A CN 02134389 A CN02134389 A CN 02134389A CN 1169851 C CN1169851 C CN 1169851C
- Authority
- CN
- China
- Prior art keywords
- ticl
- alcl
- sio
- add
- nickel
- 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
- 239000003054 catalyst Substances 0.000 title claims abstract description 28
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 title claims abstract description 18
- 239000005977 Ethylene Substances 0.000 title claims abstract description 16
- 239000002131 composite material Substances 0.000 title claims abstract description 10
- 238000000034 method Methods 0.000 title claims abstract description 9
- 230000000379 polymerizing effect Effects 0.000 title claims abstract description 5
- 238000006243 chemical reaction Methods 0.000 claims abstract description 23
- 239000010936 titanium Substances 0.000 claims abstract description 17
- 238000002360 preparation method Methods 0.000 claims abstract description 9
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical group C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 32
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 30
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 23
- 238000003756 stirring Methods 0.000 claims description 16
- 238000006116 polymerization reaction Methods 0.000 claims description 14
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 11
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 8
- 239000000243 solution Substances 0.000 claims description 7
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims description 6
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 6
- 150000002466 imines Chemical class 0.000 claims description 6
- 239000011949 solid catalyst Substances 0.000 claims description 6
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 6
- 229910052782 aluminium Inorganic materials 0.000 claims description 5
- 239000007788 liquid Substances 0.000 claims description 5
- 150000002816 nickel compounds Chemical class 0.000 claims description 5
- 150000003609 titanium compounds Chemical class 0.000 claims description 5
- 238000010792 warming Methods 0.000 claims description 5
- 239000012452 mother liquor Substances 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 3
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 3
- 229920002554 vinyl polymer Polymers 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- 238000013019 agitation Methods 0.000 claims description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- 238000001354 calcination Methods 0.000 claims description 2
- DIOQZVSQGTUSAI-NJFSPNSNSA-N decane Chemical compound CCCCCCCCC[14CH3] DIOQZVSQGTUSAI-NJFSPNSNSA-N 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- 239000011259 mixed solution Substances 0.000 claims description 2
- DIOQZVSQGTUSAI-UHFFFAOYSA-N n-butylhexane Natural products CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 claims description 2
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 claims description 2
- 238000002203 pretreatment Methods 0.000 claims description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- 239000004698 Polyethylene Substances 0.000 abstract description 21
- -1 titanium-nickel-salicylaldehyde-imine Chemical compound 0.000 abstract description 16
- 229920000573 polyethylene Polymers 0.000 abstract description 15
- 230000003197 catalytic effect Effects 0.000 abstract description 8
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 abstract description 8
- 239000002245 particle Substances 0.000 abstract description 7
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 abstract description 2
- 229910052719 titanium Inorganic materials 0.000 abstract description 2
- 239000009566 Mao-to Substances 0.000 abstract 1
- 229910052681 coesite Inorganic materials 0.000 abstract 1
- 229910052906 cristobalite Inorganic materials 0.000 abstract 1
- 238000004519 manufacturing process Methods 0.000 abstract 1
- 229910052759 nickel Inorganic materials 0.000 abstract 1
- BPELEZSCHIEMAE-UHFFFAOYSA-N salicylaldehyde imine Chemical compound OC1=CC=CC=C1C=N BPELEZSCHIEMAE-UHFFFAOYSA-N 0.000 abstract 1
- 239000000377 silicon dioxide Substances 0.000 abstract 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 abstract 1
- 229910052682 stishovite Inorganic materials 0.000 abstract 1
- 229910052905 tridymite Inorganic materials 0.000 abstract 1
- 229960004756 ethanol Drugs 0.000 description 6
- CPOFMOWDMVWCLF-UHFFFAOYSA-N methyl(oxo)alumane Chemical compound C[Al]=O CPOFMOWDMVWCLF-UHFFFAOYSA-N 0.000 description 5
- 150000001639 boron compounds Chemical class 0.000 description 4
- 239000000047 product Substances 0.000 description 3
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 1
- 229960000935 dehydrated alcohol Drugs 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- RAABOESOVLLHRU-UHFFFAOYSA-N diazene Chemical compound N=N RAABOESOVLLHRU-UHFFFAOYSA-N 0.000 description 1
- 229910000071 diazene Inorganic materials 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 229910001629 magnesium chloride Inorganic materials 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 150000003608 titanium Chemical class 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Landscapes
- Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
Abstract
The present invention relates to an ethylene polymerizing titanium-nickel-salicylaldehyde-imine composite catalyst and a preparation method thereof. A titanium compound-nickel compound-the salicylaldehyde-imine is loaded onto a MgCl2-SiO2 composite carrier to form a main catalyst, AlR3-Et2AlCl is used as a cocatalyst, an impregnating reaction method is adopted in the preparation method, and branched polyethylene with the advantages of good particle shape, high bulk density and different density can be prepared without using MAO to catalyze and polymerize single ethylene by an obtained spherical composite catalytic system; the present invention has the advantages of simple preparation method and easy use in production.
Description
Technical field
The present invention relates to titanium-nickel-salicy-alimine composite catalyst of a kind of branched polyethylene for preparing the various density that particle form is good, bulk density is high by single ethylene and preparation method thereof.
Background technology
For a long time, the chemist tries hard to research and develop and a kind ofly can be used for the single ethylene polymerization to prepare particle form good, the branched polyethylene new catalyst of the various density that bulk density is high.Recently, reported in literature adopts rear transition metal Ni, the diimine ligand compound of Pd etc. and methylaluminoxane (MAO) or boron compound are formed catalyzer can prepare various branched polyethylenes from single ethylene, cause extensive attention (K.Johnson, C.M.Killian and M.Brookhart, J Am Chem Soc, 1995,117:6414).This Preparation of Catalyst is complicated, need adopt expensive MAO or boron compound to make promotor again, and the product form that makes is irregular, bulk density is low, is unfavorable for promoting the use of aborning.
Summary of the invention
The invention provides a kind of titanium-nickel-salicy-alimine composite catalyst for preparing the high branched polyethylene of the good bulk density of particle form by the single ethylene polymerization; It has the spheroidal particle form, honest and clean aluminum alkyls of a call for bids and Et
2AlCl makes promotor, need not to use expensive MAO or boron compound, can the polymerization of catalysis single ethylene makes the branched polyethylene of various density; It is good to make the polymerisate particle form, the bulk density height.Method for preparing catalyst is easy, is easy to use aborning; Thereby solve the existing problem of prior art.
Catalyzer of the present invention, its component comprises Primary Catalysts and promotor; With titanium compound, nickel compound and salicylic alidehyde imine load on MgCl2, SiO
2On the complex carrier, constitute Primary Catalysts, with aluminum alkyls-Et
2AlCl 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; Nickel compound is NiX
2, wherein X is Cl or Br; Salicylic alidehyde imine (S) is (S shown in the following structural formula I
1To S
3) in arbitrary compound.
Salicylic alidehyde imine
S wherein
1: R
1=R
2=H;
S
2∶R
1＝CH
3；R
2＝H
S
3∶R
1＝H；R
2＝CH
3
The invention described above catalyzer each component proportioning is generally: calculate MgCl by weight
2: SiO
2: TiCl
4=1: (2～15): (0.5～3.0), all the other each components are with TiCl
4Mole number calculate, its mol ratio is:
TiCl
4 1
Ti(OR
1)
4 0～1.0
NiX
2 0.1～5
S 0.1～3
AlR
3 20～200
Et
2AlCl 15～150
The invention described above catalyzer can adopt dipping-reaction method preparation, and concrete steps are as follows:
(1) with NiX
2Be dissolved in 95% ethanol, wherein the ethanol consumption is 1g NiX
2Add 15～20ml, add SiO
2, 35～36 ℃ of stirring reactions 1～2 hour, 60～85 ℃ drain after, under logical N2,600 ℃ of calcining microspheroidal SiO
24～6 hours;
(2) with anhydrous MgCl
2Be dissolved in the pure and mild ether mixed solution at 60～75 ℃, or add Ti (OR again
1)
4, stirring reaction 2～3 hours gets the homogeneous phase mother liquor; Wherein alcohol is ethanol, and ether is THF (tetrahydrofuran (THF)), and consumption is calculated in molar ratio as MgCl
2: alcohol=1: (1～5), MgCl
2: THF=1: (24～40);
(3) at N
2Under the protection, with (2) the mother liquid obtained pre-treatment SiO that adds
2, add the THF solution (its weight concentration is 8～20%) of S part again, 60～70 ℃ of following stirring reactions 2 hours, liquid was drained in heating;
(4) in (3) products therefrom, add alkane and TiCl
4, be warming up to 60～75 ℃ of stirring reactions 1～2 hour, filter, with alkane washing 2～3 times, obtain solid catalyst; Alkane can be used hexane, heptane, octane or decane, and consumption is every gram SiO
25～12ml;
(5) in solid catalyst, add hexane and Et
2AlCl under agitation, is warming up to 40～70 ℃ of reactions 0.5～1.5 hour, filters; Drain solvent in 60～80 ℃ of following vacuum, get Primary Catalysts; Wherein the hexane consumption is every gram solid catalyst 5～12ml, Et
2AlCl is with respect to TiCl
4The consumption mol ratio be TiCl
4: Et
2AlCl=1: (0.1～5); Primary Catalysts and AlR
3-Et
2The AlCl promotor is formed the vinyl polymerization composite catalyst, and its mol ratio is TiCl
4: AlR
3: Et
2AlCl=1: (20～200): (10～150).
The present invention adopts titanium compound, nickel compound and salicylic alidehyde imine component, and above-mentioned specific dipping reaction method for preparing makes load type main catalyst, a general AlR of need
3-Et
2AlCl makes catalyzer, need not MAO or boron compound; The branched polyethylene that can the polymerization of catalysis single ethylene makes the various density that particle form is good, bulk density is high.Method for preparing catalyst of the present invention is easy, has above-mentioned excellent comprehensive performance, is easy to use aborning, has significant superiority.
Catalyzer of the present invention is 106.7kPa at pressure, and 30～70 ℃, ethene slurry polymerization 1.5 hours, catalytic efficiency are 2.0～4.8kg PE/g (Ti+Ni), and making density is 0.938-0.910g PE/cm
3, the degree of branching 2.0～18 (branched polyethylene of number of branches/1000C).The polymerisate bulk density is 0.35～0.40, is 0.25～0.30 will significantly improve than adopt the Z-N Titanium series catalyst to make the polymerisate bulk density with condition.
Embodiment
The invention will be further described below by embodiment
Example one
1. Preparation of Catalyst
1-1 is with 1.0g NiCl
2Be dissolved in 20ml 95% ethanol, add 3.0g SiO
2, 35～40 ℃ of stirring reactions 1 hour are drained solvent under 60～80 ℃, pressed powder, logical N
2Down, the heat temperature raising dehydration is warming up to 6 hours postcooling of 600 ℃ of constant temperature, at N
2The protection bottom discharge places reaction flask.
1-2 is with anhydrous MgCl
20.3g place another reaction flask, add in 12ml THF and the 0.55ml dehydrated alcohol, be heated to 60～75 ℃ of stirring reactions 2 hours to dissolving fully and make mother liquor.
1-3 is at N
2Protection makes pretreated SiO with 1-1 down
2Add 1-2 and make in the mother liquor, stirring is added down again and is contained 1.0g S
18ml THF solution, 65～70 ℃ of stirring reactions 2 hours, and under 65～80 ℃, drain solvent.
1-4 adds hexane 20ml in the 1-3 product, stir to add 0.25ml TiCl down
4, 65～70 ℃ of stirring reactions 2 hours filter, and drain after adding the 15ml hexane wash, repeat this washing operation 1 time.
1-5 adds hexane 20ml, Et
2AlCl 0.7ml 60～65 ℃ of stirring reactions 0.5 hour, is heated to 60～80 ℃ and drains liquid, solid main catalyst, Primary Catalysts and AlR
3-Et
2The complex catalyst system that the AlCl promotor is formed is used for following polymerization process, makes the branched polyethylene of the various density of high bulk density from single ethylene.
2. vinyl polymerization prepares high bulk density branched polyethylene
Through 120 ℃ of vacuum-dryings, N
2Replace 3 times reaction flask, add 200ml hexane or heptane and Al/Ti mol ratio and be 3: 1 Et
2AlCl adds the catalyzer that contains 0.5～1.5mg titanium again, takes out N
2The logical ethene in back maintains 106.7kPa, stirs polymerase 10s after .5 hour at 30～40 ℃, adds the Al/Ti mol ratio and be 80: 1 Al (i-Bu)
3, continued polymerizations 1 hour at 50 ℃, stopped reaction, the reaction product calculating catalytic efficiency of weighing.
Under above-mentioned polymerizing condition, obtain the degree of branching 4.0, density is 0.930, the branched polyethylene of bulk density 0.36, catalytic efficiency are 3.2kgPE/g (Ti+Ni).
Embodiment two
In embodiment one 1-3 step, add and contain 1.0g S
18ml THF solution change into adopting and contain 1.5g S
212ml THF solution, its condition and the operation make catalyzer with embodiment one, press polyreaction under embodiment one the same terms.
Under these conditions, from the single ethylene polymerization, having obtained the degree of branching is 13.1, and density is 0.915, and bulk density is 0.38 branched polyethylene, and catalytic efficiency is 3.3kg PE/g (Ti+Ni).
Embodiment three
In embodiment one 1-3 step, add and contain 1.0g S
18ml THF solution change into adopting and contain 2.0g S
312ml THF solution, all the other conditions and the operation make catalyzer with embodiment one, press polyreaction under embodiment one the same terms.
Under these conditions, from the single ethylene polymerization, having obtained the degree of branching is 6.0, and density is 0.925, and bulk density is 0.37 branched polyethylene, and catalytic efficiency is 2.6kg PE/g (Ti+Ni).
Embodiment four
At embodiment one, in the 1-2 step with anhydrous MgCl
20.3g in the dissolution process, add 0.2ml Ti (OBu) again
4, all the other conditions and operation make catalyzer with embodiment one, press polyreaction under embodiment one the same terms.
Under these conditions, from the single ethylene polymerization, having obtained the degree of branching is 5.0, and density is 0.926, and bulk density is 0.36 branched polyethylene, and catalytic efficiency is 2.8kg PE/g (Ti+Ni).
Embodiment five
In embodiment one step with 1.0g NiCl
2Be dissolved in and change NiBr in 20ml 95% ethanol into 1.5g
2Be dissolved in the 25ml ethanol, all the other conditions and operation make catalyzer with embodiment one, press polyreaction under embodiment one the same terms.
Under these conditions, from the single ethylene polymerization, having obtained the degree of branching is 4.7, and density is 0.928, and bulk density is 0.37 branched polyethylene, and catalytic efficiency is 3.5kg PE/g (Ti+Ni).
Claims (3)
1. ethylene polymerizing titanium-nickel-salicy-alimine composite catalyst, its component comprises Primary Catalysts and promotor; It is characterized in that loading on MgCl with titanium compound, nickel compound and salicylic alidehyde imine
2, SiO
2On the complex carrier, constitute Primary Catalysts; With aluminum alkyls-Et
2AlCl 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; Nickel compound is NiX
2, wherein X is Cl or Br; Salicylic alidehyde imine S is S shown in the following structural formula I
1To S
3In arbitrary compound:
S wherein
1: R
1=R
2=H;
S
2：R
1＝CH
3；R
2＝H
S
3：R
1＝H；R
2＝CH
3
2. according to the described catalyzer of claim 1, it is characterized in that proportioning by weight calculating is in the each component: MgCl
2: SiO
2: TiCl
4=1: (2～15): (0.5～3.0), all the other each components are with TiCl
4Mole number calculate, its mol ratio is:
TiCl
4 1
Ti(OR
1)
4 0～1.0
NiX
2 0.1～5
S 0.1～3
AlR
3 20～200
Et
2AlCl 15～150。
3. claim 1 or 2 described Preparation of catalysts methods is characterized in that adopting dipping-reaction method, and concrete steps are as follows:
(1) with NiX
2Be dissolved in 95% ethanol, wherein the ethanol consumption is 1g NiX
2Add 15～20ml, add SiO
2, 35～36 ℃ of stirring reactions 1～2 hour, 60～85 ℃ drain after, under logical N2,600 ℃ of calcining microspheroidal SiO
24～6 hours;
(2) with anhydrous MgCl
2Be dissolved in the pure and mild ether mixed solution at 60～75 ℃, or add Ti (OR again
1)
4, stirring reaction 2～3 hours gets the homogeneous phase mother liquor; Wherein alcohol is ethanol, and ether is tetrahydrofuran (THF), and consumption is calculated in molar ratio as MgCl
2: alcohol=1: (1～5), MgCl
2: tetrahydrofuran (THF)=1: (24～40);
(3) at N
2Under the protection, with (2) the mother liquid obtained pre-treatment SiO that adds
2, adding the tetrahydrofuran solution of S part again, its weight concentration is 8～20%, 60～70 ℃ of following stirring reactions 2 hours, liquid was drained in heating;
(4) in (3) products therefrom, add alkane and TiCl
4, be warming up to 60～75 ℃ of stirring reactions 1～2 hour, filter, with alkane washing 2～3 times, obtain solid catalyst; Alkane can be used hexane, heptane, octane or decane, and consumption is every gram SiO
25～12ml;
(5) in solid catalyst, add hexane and Et
2AlCl under agitation, is warming up to 40～70 ℃ of reactions 0.5～1.5 hour, filters; Drain solvent in 60～80 ℃ of following vacuum, get Primary Catalysts; Wherein the hexane consumption is every gram solid catalyst 5～12ml, Et
2AlCl is with respect to TiCl
4The consumption mol ratio be TiCl
4: Et
2AlCl=1: (0.1～5); Primary Catalysts and AlR
3-Et
2The AlCl promotor is formed the vinyl polymerization composite catalyst, and its mol ratio is TiCl
4: AlR
3: Et
2AlCl=1: (20～200): (15～150).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB021343896A CN1169851C (en) | 2002-07-18 | 2002-07-18 | Ethylene polymerizing titanium-nickel-salicy-alimine composite catalyst and its preparing method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB021343896A CN1169851C (en) | 2002-07-18 | 2002-07-18 | Ethylene polymerizing titanium-nickel-salicy-alimine composite catalyst and its preparing method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1392164A CN1392164A (en) | 2003-01-22 |
| CN1169851C true CN1169851C (en) | 2004-10-06 |
Family
ID=4747722
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB021343896A Expired - Fee Related CN1169851C (en) | 2002-07-18 | 2002-07-18 | Ethylene polymerizing titanium-nickel-salicy-alimine composite catalyst and its preparing method |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1169851C (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102850391B (en) * | 2011-07-01 | 2015-12-09 | 中国石油化工股份有限公司 | The method of salicylic aldehyde pyridine imine titanous chloride title complex and its preparation method and application and ethylene polymerization |
| CN103804550B (en) * | 2012-11-09 | 2016-02-24 | 中国石油化工股份有限公司 | A kind of method of a kind of catalyst precursor and preparation method thereof and catalyzer and application and vinyl polymerization |
-
2002
- 2002-07-18 CN CNB021343896A patent/CN1169851C/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| CN1392164A (en) | 2003-01-22 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN1138597C (en) | Nickel diimine catalysts with methylalumoxane as cocatalyst, method of polymerization of olefins therewith and polymers produced | |
| CN1172969C (en) | Titanium-nickel acetylacetonate composite catalyst for preparing branched polyethylene and its preparation method | |
| CN105622795A (en) | Metallocene catalyst composition and preparation method thereof | |
| CN103145891A (en) | Olefin polymerization catalyst, preparation and application thereof | |
| CN102358761B (en) | Olefin polymerization catalyst and preparation method thereof | |
| CN1169851C (en) | Ethylene polymerizing titanium-nickel-salicy-alimine composite catalyst and its preparing method | |
| 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 | |
| CN1246348C (en) | Composite catalist of titanium substitued nickle acenaphthene diimine of synthesizing branched polyvinyl and its preparation process | |
| CN1176957C (en) | Titanium-cobalt acetylacetonate composite catalyst for preparing branched polyethylene and its preparation method | |
| CN1273502C (en) | Multinuclear acenaphthene diimine nickle catalyst for synthesis of branched polyethylene | |
| CN1263778C (en) | 4-vinylpyridine homopolymerized and ethylene copolymerized acenaphthenyl diimido nickel catalyst and the prepn process | |
| CN1966536A (en) | Spherical carrier loaded late transition metal catalyst and its preparing process | |
| CN1216082C (en) | Ti-Ni match as composite catalyst and its application in preparing branch polyethylene from ethylene | |
| CN1163524C (en) | Composite Ti-Ni catalyst for oligomerization and copolymerization of ethylene and its preparing process | |
| CN1129614C (en) | Carried post-transition metal catalyst and its prepn. and application | |
| CN1197883C (en) | Polor monomer homopolymerization and copolymerization titanium-substituted beta-dione-cobalt acetylacetonate composite catalyst and its preparing method | |
| CN1197884C (en) | Polar monomer homopolymerizatino and copolymerization titanium-cobalt acetylacetonate composite catalyst and its preparing method | |
| CN1163531C (en) | Ethylene copoly merized titanium-cobalt compound composite catalyst and its preparing method | |
| CN1163532C (en) | Ethylene copolymerized titanium-nickel compound catalyst and preparation process thereof | |
| CN1637023A (en) | Mononuclear and multinuclear polyvinyl acenaphthenyl diimido nickel catalyst and its prepn process | |
| CN113461850B (en) | Trans-1, 4-poly (4, 8-2-methyl-1, 3, 7-nonane triene) and preparation method thereof | |
| CN100376604C (en) | Olefin polymerization catalyst and its uses | |
| CN102030843A (en) | Non-metallocene catalyst system for olefin polymerization and preparation and application thereof | |
| 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 | ||
| 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 |