CN105199022B - For ethylene homo conjunction or catalyst and its application of combined polymerization - Google Patents
For ethylene homo conjunction or catalyst and its application of combined polymerization Download PDFInfo
- Publication number
- CN105199022B CN105199022B CN201410273617.0A CN201410273617A CN105199022B CN 105199022 B CN105199022 B CN 105199022B CN 201410273617 A CN201410273617 A CN 201410273617A CN 105199022 B CN105199022 B CN 105199022B
- Authority
- CN
- China
- Prior art keywords
- compound
- component
- catalyst
- polymerization
- ethylene homo
- 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.)
- Active
Links
Landscapes
- Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
Abstract
The present invention provides the compositions and preparation method of a kind of carried catalyst and the catalyst for vinyl polymerization or combined polymerization, and wherein catalyst is grouped as by tri- groups of A, B, C.Wherein component A is that magnesium halide is dissolved in organic epoxy compound object, organic phosphorus compound, electron donor compound to form homogeneous solution, by TiCl4It is slowly reacted at low temperature with magnesium halide homogeneous solution, photocatalyst crystals is precipitated, then by strict control temperature reaction, and obtain catalytic component A, B component is organo-aluminum compound, the halogenated metallic compound of component C.When catalyst system of the invention is for ethylene homo conjunction or combined polymerization, higher catalytic activity is not only embodied, but also obtained polymer apparent density with higher, the molecular weight distribution of polymer are widened.
Description
Technical field
The present invention relates to the preparation sides of a kind of catalyst for olefinic polymerization especially vinyl polymerization and the catalyst
Method and application.
Background technique
The patent proposition of early stage can make the molecular weight distribution of polyethylene broaden by the way that aluminum halide is added in the course of the polymerization process,
But the shortcomings that this method is that the shape of obtained resin is unsatisfactory；It also has been reported that, can be used to by the way that idohydrocarbon is added
The method for widening molecular weight distribution, but since polymer molecular weight to be widened distribution is needed using excessive idohydrocarbon, so that
It is red on resin band, it is restricted the popularization of this method.
Hanwha Chemical Corp. proposes in patent CN1150955A a kind of prepares the poly- second of wide molecular weight distribution
The method of olefine resin, using tetrahydrofuran, anhydrous MgCl2, TiCl31/3AlCl3, silica powder preparation catalyst, in second
Using the regulator being made of halogenated hydrocarbons and aluminium compound when alkene polymerize, molecular weight of polyethylene distribution can be made to widen, melt flow ratio
(MFR) value improves 20% or so.Halogenated hydrocarbons can be the brominated alkanes or dichloroethanes of 2-4 carbon, and aluminium compound can be two
Dimethyl aluminum hydride, diethylaluminum hydride, diisopropyl aluminum hydride and diisobutyl aluminium hydride.But the regulator makes the poly- of catalyst
Activity is closed to be declined.
CN101939342A proposes that the germanium compound that halogenation is added in the ingredient of solid catalyst of Ti, Mg and halogen can be with
The polymerization activity of catalyst is improved, but this method cannot change the molecular weight distribution of polyethylene.
A kind of method of the vinyl polymerization and combined polymerization of Z/N type catalyst is disclosed in Japan Patent JP49-51378, it should
Catalyst does solvent, alcohol compound and magnesium compound haptoreaction using alkane derivative, since alcohols and alkanes are molten
Agent different polarities are larger, prevent magnesium halide forms homogeneous phase solution from being dissolved completely, it is only to generate a kind of particulate colloidal suspension
Liquid or the magnesium halide slurries of swelling, to generate some disadvantages related with magnesium halide stratiform crystallization property, such as: prepared is poly-
It is lower to close object apparent density, particle shape and distribution are bad etc..
CN1229092A proposes a kind of preparation of catalyst and the catalyst for ethylene homo conjunction or combined polymerization
Method, wherein catalyst be organic epoxy compound object is dissolved in by magnesium halide, organic phosphorus compound adds the electron bodily form
It at homogeneous solution, then acts on and obtains at least one precipitation additive and the halide of transition metals Ti or derivatives thereof, gather
When conjunction in conjunction with organo-aluminum compound.The catalyst preparation process is simple, shows very high activity for vinyl polymerization, simultaneously
The particle shape of resulting polymers is preferable, and apparent density is higher, and low-molecular material content is less.But the caltalyst ties up to system
Catalyst solid precipitate in order to obtain during standby, joined precipitation additive is organic acid anhydride, organic acid, ether, one in ketone
Kind, precipitation additive makes the activity of catalyst decrease, and more demanding to operating condition.
For deficiency existing for above-mentioned catalyst system, the present inventor draws in catalyst system by numerous studies discovery
Enter halogenated metallic compound, can make catalyst ethylene polymerization resulting polymers molecular weight distribution widen, polymer it is apparent
Density improves, while showing higher catalyst activity.
Summary of the invention
The object of the present invention is to provide a kind of catalyst system for vinyl polymerization, introduced in the catalyst system
Catalyst activity can be improved in halogenated metallic compound, and the molecular weight distribution of vinyl polymerization resulting polymers is widened, polymer
Apparent density improves.
A kind of catalyst system for olefinic polymerization of the present invention, including following components:
(A) ingredient of solid catalyst of titaniferous is that organic epoxy compound object, organic phosphorus chemical combination are dissolved in by magnesium halide
Object add electron donor formed homogeneous solution, be slowly added in above-mentioned homogeneous solution transition metals Ti halide or its spread out
Biology carries out carrying titanium process, is washed with inert diluent, obtains the ingredient of solid catalyst of titaniferous；(B) organo-aluminum compound；
(C) halogenated metallic compound.
The halogenated metallic compound be selected from germanium tetrachloride, germanium tetrabromide, four antimony chlorides, telluric chloride, telluric bromide,
Tin tetrachloride, tin tetrabromide, diethyl germanous chloride, dimethyl germanous chloride, diethyl tellurium chloride, dimethyl dichloride
Tellurium, tetraethoxy germanium and tetraethoxy tellurium.
The molar ratio of the halogenated metallic compound and titanium is 200~0.01, and the dosage of component B is with mole of aluminium and titanium
Than being calculated as 100~0.001；The molar ratio of the halogenated metallic compound and titanium is preferred with 30~0.5, the dosage of component B with
The molar ratio computing of aluminium and titanium preferably 10~0.01, is preferred with 1~0.1.
Magnesium halide described in component (A) includes the complex compounds such as magnesium dihalide, the water of magnesium dihalide or alcohol, magnesium dihalide point
The derivative that one of halogen atom is replaced by oxyl or halocarbon oxygroup in minor, above-mentioned magnesium dihalide are specially dichloride
Magnesium, magnesium dibromide, magnesium diiodide.It wherein, is best with magnesium dichloride.
The magnesium halide granularity used is to stir preferably lower easy dissolution, and solution temperature is -10 DEG C~150 DEG C, with 20 DEG C
~130 DEG C preferably.Can add when dissolution or inert diluent is not added such as: benzene,toluene,xylene, 1,2- dichloroethanes, chlorobenzene with
And other hydro carbons or halogenated hydrocarbon compound.Wherein, benzene,toluene,xylene is preferable, and toluene, dimethylbenzene are best.
Organic epoxy compound object described in component (A) includes aliphatic olefin of the carbon atom number 2~8, alkadienes halogen
The compounds such as the oxide of fat subsitutes race alkene or alkadienes, glycidol ether, inner ether.Particular compound is such as: ethylene oxide, ring
Ethylene Oxide, epoxy butane, epoxychloropropane, methyl glycidyl ether, diglycidyl ether, tetrahydrofuran etc..Wherein, preferably
Be ethylene oxide, propylene oxide, epoxychloropropane, tetrahydrofuran, be best with tetrahydrofuran, epoxychloropropane.
Organic phosphorus compound described in component (A) includes the hydrocarbyl carbonate or halogenation hydrocarbyl carbonate of orthophosphoric acid or phosphorous acid.Tool
Body is such as: orthophosphoric acid trimethyl, orthophosphoric acid triethyl, orthophosphoric acid tributyl, triphenyl phosphite, Trimethyl phosphite, phosphorous acid
Triethyl, tributyl phosphite, triphenyl phosphite, phosphorous acid benzene methyl etc..Wherein, preferably orthophosphoric acid trimethyl, just
Triethyl phosphate and orthophosphoric acid tributyl, orthophosphoric acid tributyl are best.
Electron donor described in component (A) can be selected from C1~C20Alcohol or isomery alcohol, such as: methanol, ethyl alcohol, third
Alcohol, isopropanol, butanol, isobutanol, 2-Ethylhexyl Alcohol, n-octyl alcohol, lauryl alcohol, glycerine, amylalcohol, decyl alcohol, dodecanol, 18
Alkanol, Bian alcohol, benzyl carbinol, with C1~C8Straight chain alcohol be best.
Alkyl metal cpd can be also added in magnesium halide described in component (A) during dissolution forms homogeneous solution
Such as zinc alkyl and/or alkyl aluminum.
Organo-silicon compound can also be added in component (A), the general formula of organo-silicon compound is R1 XR2 YSi(OR3)z, wherein
R1And R2Respectively alkyl or halogen, R3For alkyl, 0≤x≤2,0≤y≤2 and 0≤z≤4, and x+y+z=4.Particular compound
It include: tetramethoxy-silicane, tetraethoxysilane, tetrapropoxysilane, four butoxy silicon, silicon tetrachloride etc..
In terms of every mole of magnesium halide, organic epoxy compound object 0.01~10 rubs molar ratio in component (A) between each component
You, preferably 0.02~4 mole；0.01~10 mole of organic phosphorus compound, preferably 0.02~4 mole；Electron donor 0.005
~15 moles, preferably 0.05~10 mole；0~2 mole of alkyl metal cpd, preferably 0~0.5 mole；Transition metal
The halide of titanium or 0.2~20 mole of derivative；Organo-silicon compound are 0.05~1 mole.Titaniferous amount is in component (A)
1wt%~8wt%.
The preparation method of component A: magnesium halide is dissolved in organic epoxy compound object and organic phosphorus compound under stiring
Electron donor is added, homogeneous transparent solution is formed, adds or be not added alkyl metal cpd, at a temperature of -35~60 DEG C, most
It is -30~10 DEG C good, the halide of transition metals Ti or derivative are instilled into magnesium halide homogeneous solution, can be added at -30~110 DEG C
Enter organo-silicon compound, be filtered, washed, obtains component A solids.
Component (B) organo-aluminum compound is alkyl aluminum compound.Wherein the molar ratio computing of aluminium and titanium be 100~
0.001, preferably 10~0.01, preferably 1~0.1.
The halogenated metallic compound is added after the completion of carrying titanium process, and adding manner has following several, and (1) is halogenated
Metallic compound is added in component A；(2) organo-aluminum compound is reacted to obtain mixture in advance with halogenated metallic compound,
Preparation method is, will halogenated metallic compound diluted by a certain percentage under the conditions of -10~60 DEG C, be slowly dropped to organo-aluminium
In compound, rate of addition is 0.1~0.5ml/min, and said mixture is added in polymerization；(3) successively in polymerization reaction
Tri- component of A, B, C is added.
Catalyst A, B of the present invention, component C may be directly applied to polymerization system, and condensate is applied to after can also being first complexed in advance
System.
Catalyst of the invention can be used for the homopolymerization of ethylene, it can also be used to which the combined polymerization of ethylene and alpha-olefin, copolymerization are single
Propylene, butylene, amylene, hexene, octene, 4- methyl 1- amylene can be used in body.
Polymerization process the following steps are included: (1) component A preparation: magnesium halide is dissolved in organic epoxidation under stiring
It closes and adds electron donor in object and organic phosphorus compound, form homogeneous transparent solution, add or be not added alkyl metal cpd,
At a temperature of -35~60 DEG C, best -30~10 DEG C, it is uniformly molten that the halide of transition metals Ti or derivative are instilled into magnesium halide
Liquid can be filtered, washed in -30~110 DEG C of addition organo-silicon compound, obtain component A solids；(2) in reaction unit
In, component B organo-aluminum compound, the halogenated metallic compound of component C are mixed with component A, carry out vinyl polymerization.
Halogenated metallic compound can also be added in the preparation process of component A, then mix again with organo-aluminum compound,
Carry out vinyl polymerization.
Component B organo-aluminum compound and the halogenated metallic compound of component C in step (2) can also be reacted in advance and be mixed
Object is closed, is then mixed again with component A, vinyl polymerization is carried out.
Liquid phase polymerization can be used when polymerization, gas-phase polymerization can also be used.When carrying out liquid phase polymerization, can be used propane,
Hexane, heptane, hexamethylene, iso-butane, isopentane, naphtha, raffinate oil, hydrogasoline, kerosene, benzene,toluene,xylene etc. it is full
Make reaction medium with atent solvents such as aliphatic hydrocarbon or aromatic hydrocarbon, prepolymerization can be first carried out before polymerization.Polymerization methods can use
Intermittent, semi continuous or continous way.Polymerization temperature is room temperature~150 DEG C, preferably 50 DEG C~100 DEG C.In order to adjust polymerization
The molecular weight of object makees molecular weight regulator using hydrogen.
Due to the component A in catalyst system and organo-aluminum compound and halogenated metallic compound collective effect, the present invention
When the catalyst system is for ethylene homo conjunction or combined polymerization, higher catalytic activity is not only embodied, but also acquired
The molecular weight distribution of polyethylene widen, the apparent density of polymer improves.
Specific embodiment
Following embodiment is to describe to more detailed citing of the invention, but the invention is not limited to these embodiments.
Embodiment 1
Catalyst (A) component preparation: through high-purity N2In the reactor being sufficiently displaced from, the anhydrous MgCl of 4.0g is sequentially added2、
50mL toluene, 2.0mL epoxychloropropane, 3.0mL tributyl phosphate are warming up to 50 DEG C, and maintain 15 minutes under stirring, add
6.0mL ethyl alcohol, the reaction was continued 15 minutes, which is cooled to -5~0 DEG C, then 30mL titanium tetrachloride is added dropwise to above-mentioned chlorination
In magnesium homogeneous solution, 5ml tetraethoxy-silicane is added, solution is warming up to 80 DEG C, removes mother liquor.4 times are washed with hexane, vacuum
It is dry, obtain ingredient of solid catalyst.
Vinyl polymerization: the stainless steel kettle that volume is 2 liters is through H2After being sufficiently displaced from, hexane 1000mL, metering are added wherein
Containing the above-mentioned prepared ingredient of solid catalyst of 0.5mmolTi, triethyl aluminum 1.0mmol, germanium tetrachloride, which is added, to be made it and urges
Agent Ti molar ratio is 3.6, is warming up to 70 DEG C plus hydrogen 0.26MPa, then being passed through ethylene keeps kettle interior up to 0.73MPa (gauge pressure), 85
At DEG C, it polymerize 2 hours.
Embodiment 2
For catalyst (A) component with embodiment 1, only germanium tetrachloride will be added in polymerization is changed to it with catalyst Ti molar ratio
9
Embodiment 3
For catalyst (A) component with embodiment 1, only germanium tetrachloride will be added in polymerization is changed to it with catalyst Ti molar ratio
18
Embodiment 4
Catalyst (A) component will be added germanium tetrachloride and be changed to it with catalyst Ti molar ratio with embodiment 1 in polymerization
27
Embodiment 5
Catalyst (A) component will be added germanium tetrachloride and be changed to it with catalyst Ti molar ratio with embodiment 1 in polymerization
36
Embodiment 6
Catalyst (A) component will be added germanium tetrachloride and make itself and Ti moles of catalyst with embodiment 1 in polymerization
Embodiment 7
Catalyst (A) component preparation: through high-purity N2In the reactor being sufficiently displaced from, the anhydrous MgCl of 4.0g is sequentially added2、
50mL toluene, 2.0mL epoxychloropropane, 3.0mL tributyl phosphate are warming up to 50 DEG C, and maintain 15 minutes under stirring, add
6.0mL ethyl alcohol, the reaction was continued 15 minutes, which is cooled to -5~0 DEG C, then 30mL titanium tetrachloride is added dropwise to above-mentioned magnesium chloride
In homogeneous solution, 5ml germanium tetrachloride is added, solution is warming up to 80 DEG C, removes mother liquor.It is washed 4 times with hexane, vacuum is dry
It is dry, obtain solid catalyst.Comparative example
Catalyst is synthesized with embodiment 1 (A) component
Vinyl polymerization: the stainless steel kettle that volume is 2 liters is through H2After being sufficiently displaced from, hexane 1000mL, metering are added wherein
Containing the above-mentioned prepared ingredient of solid catalyst of 0.5mmolTi, triethyl aluminum 1.0mmol.It is warming up to 70 DEG C plus hydrogen 0.26MPa
(gauge pressure), then being passed through ethylene keeps kettle interior up to 0.73MPa (gauge pressure), at 85 DEG C, polymerize 2 hours.
Experimental result is shown in Table 1
1 polymerization result of table
It can be seen that catalyst system of the invention from the data of table 1 to close for ethylene homo or when combined polymerization, not only body
Reveal higher catalytic activity, and the molecular weight distribution of obtained polyethylene is widened, the apparent density of polymer improves.
Claims (17)
1. for the catalyst of ethylene homo conjunction or combined polymerization, including following components: the ingredient of solid catalyst of (A) titaniferous,
Be organic epoxy compound object is dissolved in by magnesium halide, organic phosphorus compound add electron donor formed homogeneous solution, upper
It states halide for being slowly added to transition metals Ti in homogeneous solution or derivatives thereof to carry out carrying titanium process, be washed with inert diluent
It washs, obtains the ingredient of solid catalyst of titaniferous；(B) organo-aluminum compound；(C) halogenated metallic compound；
The halogenated metallic compound be selected from germanium tetrachloride, germanium tetrabromide, diethyl germanous chloride, dimethyl germanous chloride or
Tetraethoxy germanium；The molar ratio of the halogenated metallic compound and titanium is 18~27；It is including general formula in the component (A)
R1 XR2 YSi(OR3)zOrgano-silicon compound, wherein R1And R2Respectively alkyl or halogen, R3For alkyl, 0≤x≤2,0≤y≤2
With 0≤z≤4, and x+y+z=4；
Wherein, the adding manner of halogenated metallic compound is one of following two mode:
Mode one: organo-aluminum compound is reacted to obtain mixture in advance with halogenated metallic compound, in polymerization by the mixing
Object is added in component A；
Mode two: by organo-aluminum compound and halogenated metallic compound respectively with component A haptoreaction.
2. the catalyst according to claim 1 for ethylene homo conjunction or combined polymerization, which is characterized in that the use of component B
Amount is with the molar ratio computing of aluminium and titanium for 100~0.001.
3. the catalyst according to claim 1 for ethylene homo conjunction or combined polymerization, which is characterized in that the use of component B
Amount is with the molar ratio computing of aluminium and titanium for 1~0.1.
4. the catalyst according to claim 1 for ethylene homo conjunction or combined polymerization, it is characterised in that the step of mode one
Suddenly include: by halogenated metallic compound diluted by a certain percentage under the conditions of -10~60 DEG C, be slowly dropped to organo-aluminium chemical combination
In object, rate of addition is 0.1~0.5ml/min, is added the mixture in component A.
5. the catalyst according to claim 1 for ethylene homo conjunction or combined polymerization, it is characterised in that described is organic
Silicon compound is at least one of tetramethoxy-silicane, tetraethoxysilane, tetrapropoxysilane and four butoxy silicon.
6. the catalyst according to claim 1 for ethylene homo conjunction or combined polymerization, it is characterised in that the halogenation
Magnesium be in magnesium dihalide, the water of magnesium dihalide or alcohol complex and magnesium dihalide molecular formula one of halogen atom by oxyl or
At least one of the derivative that halocarbon oxygroup is replaced.
7. the catalyst according to claim 1 for ethylene homo conjunction or combined polymerization, it is characterised in that described is organic
Epoxide be carbon atom number 2~8 aliphatic olefin, alkadienes halogenated aliphatic alkene or alkadienes oxide,
At least one of glycidol ether and interior ether compound.
8. the catalyst according to claim 1 for ethylene homo conjunction or combined polymerization, it is characterised in that described is organic
Phosphorus compound is the hydrocarbyl carbonate or halogenation hydrocarbyl carbonate of orthophosphoric acid or phosphorous acid.
9. the catalyst according to claim 1 for ethylene homo conjunction or combined polymerization, it is characterised in that the component
It (A) further include alkyl metal cpd in.
10. the catalyst according to claim 1 for ethylene homo conjunction or combined polymerization, it is characterised in that with every mole of halogen
Change magnesium meter, 0.01~10 mole of organic epoxy compound object；0.01~10 mole of organic phosphorus compound；Electron donor 0.005~15
Mole；The halide of transition metals Ti or 0.2~20 mole of derivative.
11. the catalyst according to claim 10 for ethylene homo conjunction or combined polymerization, it is characterised in that with every mole
Magnesium halide meter, 0.02~4 mole of organic epoxy compound object.
12. the catalyst according to claim 10 for ethylene homo conjunction or combined polymerization, it is characterised in that with every mole
Magnesium halide meter, 0.02~4 mole of organic phosphorus compound.
13. the catalyst according to claim 10 for ethylene homo conjunction or combined polymerization, it is characterised in that with every mole
Magnesium halide meter, 0.05~10 mole of electron donor.
14. the application described in claim 1 for the catalyst of ethylene homo conjunction or combined polymerization in polymerization, including following step
It is rapid: (1) preparation of component A: magnesium halide to be dissolved in organic epoxy compound object and organic phosphorus compound add under stiring
Electron donor forms homogeneous transparent solution, and at a temperature of -35~60 DEG C, the halide of transition metals Ti or derivative are instilled
Magnesium halide homogeneous solution is filtered, washed in -30~110 DEG C of addition organo-silicon compound, obtains component A solids；(2) anti-
It answers in device, component B organo-aluminum compound, the halogenated metallic compound of component C are mixed with component A, carry out vinyl polymerization.
15. the application according to claim 14 for the catalyst of ethylene homo conjunction or combined polymerization in polymerization, special
Sign is to react organo-aluminum compound in advance with halogenated metallic compound to obtain mixture, then mixes with component A, carries out ethylene
Polymerization.
16. the application according to claim 14 for the catalyst of ethylene homo conjunction or combined polymerization in polymerization, special
Sign is at a temperature of -30~10 DEG C, and the halide of transition metals Ti or derivative are instilled magnesium halide homogeneous solution.
17. the application according to claim 14 for the catalyst of ethylene homo conjunction or combined polymerization in polymerization, special
Sign is in the preparation process of component A, after forming homogeneous transparent solution, in the halide or derivative for instilling transition metals Ti
Before, add or be not added alkyl metal cpd.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410273617.0A CN105199022B (en) | 2014-06-18 | 2014-06-18 | For ethylene homo conjunction or catalyst and its application of combined polymerization |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410273617.0A CN105199022B (en) | 2014-06-18 | 2014-06-18 | For ethylene homo conjunction or catalyst and its application of combined polymerization |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105199022A CN105199022A (en) | 2015-12-30 |
| CN105199022B true CN105199022B (en) | 2019-06-28 |
Family
ID=54947004
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410273617.0A Active CN105199022B (en) | 2014-06-18 | 2014-06-18 | For ethylene homo conjunction or catalyst and its application of combined polymerization |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105199022B (en) |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101939342A (en) * | 2008-02-07 | 2011-01-05 | 巴塞尔聚烯烃意大利有限责任公司 | Catalyst for the polymerization of olefins |
| CN102295716A (en) * | 2010-06-25 | 2011-12-28 | 中国石油化工股份有限公司 | Catalyst used for vinyl polymerization and preparation method as well as application thereof |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1101826C (en) * | 1995-11-23 | 2003-02-19 | 韩华综合化学株式会社 | Process for preparing ethylene polymer |
| CN100363389C (en) * | 2004-09-23 | 2008-01-23 | 中国石油化工股份有限公司 | Catalyst used for ethylene polymerization or copolymerization and its preparation method |
| CN102532357B (en) * | 2010-12-10 | 2013-08-14 | 中国石油化工股份有限公司 | Catalyst applied to vinyl polymerization and preparation method and application thereof |
-
2014
- 2014-06-18 CN CN201410273617.0A patent/CN105199022B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101939342A (en) * | 2008-02-07 | 2011-01-05 | 巴塞尔聚烯烃意大利有限责任公司 | Catalyst for the polymerization of olefins |
| CN102295716A (en) * | 2010-06-25 | 2011-12-28 | 中国石油化工股份有限公司 | Catalyst used for vinyl polymerization and preparation method as well as application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN105199022A (en) | 2015-12-30 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101173014B (en) | Catalyst for polymerization of ethylene or combined polymerization, producing method and application of the same | |
| CN101942050B (en) | Catalyst component for ethylene polymerization in slurry process and preparation method thereof | |
| CN106478845A (en) | For the catalytic component of olefinic polymerization, catalyst and preparation method thereof | |
| CN103772543B (en) | A kind of catalyst for ethylene polymerization and preparation method thereof | |
| CN105111336A (en) | Electron donor of ethylene polymerization catalyst, ball-like catalyst and preparation method | |
| CN103772542B (en) | A kind of catalyst component for ethene slurry polymerization and catalyzer thereof | |
| CN103130931B (en) | A kind of Ball shape ethylene polymerization solid titanium catalytic and Synthesis and applications thereof | |
| CN103772553B (en) | A kind of catalyst for vinyl polymerization and preparation method thereof | |
| CN102295716B (en) | Catalyst used for vinyl polymerization and preparation method as well as application thereof | |
| CN104710549B (en) | A kind of emulsion process prepares Ball shape ethylene polymerization solid titanium catalytic and its application | |
| CN105330770B (en) | A kind of catalyst and its application for ethylene slurry polymerization | |
| CN105482002A (en) | Catalyst component for polymerization of ethylene, catalyst and preparation method of catalyst component | |
| CN105199022B (en) | For ethylene homo conjunction or catalyst and its application of combined polymerization | |
| CN105085734B (en) | A kind of preparation method of catalytic component for olefinic polymerization | |
| JPS58183708A (en) | Solid catalytic component for polymerizing alpha-olefin | |
| CN102977232B (en) | A kind of catalyst system for vinyl polymerization | |
| CN100586953C (en) | Catalyst system including organic siloxane compounds | |
| CN102977233B (en) | Catalyst system for ethylene polymerization | |
| CN106008759B (en) | A kind of electron donor of Ziegler Natta catalyst and its application in ethylene polymerization | |
| CN101565476B (en) | Catalyst for ethylene polymerization or copolymerization through slurry method and preparation method and application thereof | |
| CN105085735B (en) | A kind of preparation method of catalytic component for olefinic polymerization | |
| CN105175587A (en) | Catalyst used for ethylene polymerization, and application thereof | |
| CN108084305A (en) | Solid titanium catalyst component for vinyl polymerization and preparation method thereof and ethane polymerization solid titanium catalyst | |
| CN105085742B (en) | A kind of preparation method of catalytic component for olefinic polymerization | |
| CN102977235B (en) | Catalyst component for ethylene polymerization and catalyst |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |