CN108484805A - A kind of Highh activity polyethylene Ziegler-Natta catalyst and its preparation method and application - Google Patents
A kind of Highh activity polyethylene Ziegler-Natta catalyst and its preparation method and application Download PDFInfo
- Publication number
- CN108484805A CN108484805A CN201810240619.8A CN201810240619A CN108484805A CN 108484805 A CN108484805 A CN 108484805A CN 201810240619 A CN201810240619 A CN 201810240619A CN 108484805 A CN108484805 A CN 108484805A
- Authority
- CN
- China
- Prior art keywords
- natta catalyst
- highh
- alkaline
- ziegler
- activity
- 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
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F110/00—Homopolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F110/02—Ethene
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
Abstract
The present invention relates to a kind of Highh activity polyethylene Ziegler Natta catalyst and its preparation method and application.Alkaline-earth halide or alkaline-earth metal alkoxy compound, halogenated alkyl compound, transition metal halide are mixed under certain condition, the Ziegler Natta catalyst for ethylene polymerization is made in reaction.The invention further relates to the preparation methods of the polyethylene under the catalyst action, i.e., polymerize ethylene under an increased pressure and generate polyethylene.The present invention is by using polyhydroxy-alcohol as precipitating reagent, using the method for recrystallization activation, making the load factor of transition metal obtain significant raising alkaline-earth halide or alkaline-earth metal alkoxy compound, to obtain the higher polyethylene catalysts of activity.The result shows that.Transition metal load factor has reached 13~18wt% in catalyst, and catalytic activity has reached 40000~67000gPE/g cath.
Description
Technical field
The invention belongs to the olefin polymerization catalysis fields in petrochemical industry, more particularly to a kind of polyethylene of high activity
The preparation method of Ziegler-Natta catalyst.
Background technology
Polyethylene is the polymer made of vinyl monomer polymerization, odorless, nontoxic, feel ceraceous, is had good resistance to low
Temperature, corrosion resistance do not dissolve in common solvent under room temperature, and water imbibition is small, and electrical insulating property is excellent.It is widest organic high to belong to purposes
The maximum kind of yield in one of molecule synthesis material and plastic product.Polyethylene is in light industry, organic synthesis work
Industry, agricultural, machinery manufacturing industry, textile industry, the numerous areas such as pharmaceutical sector have a wide range of applications.Sub-polyethylene is high-density polyethylene
Alkene, low density polyethylene (LDPE) and linear low density polyethylene.The performance of polyethylene depends on its polymerization methods.In middle pressure
That progress Ziegler-Natta is polymerized under (15-30 atmospheric pressure) catalytic condition is high density polyethylene (HDPE) (HDPE).It is this
Under the conditions of the polyethylene molecule that polymerize be linear, and strand is very long, and molecular weight is up to hundreds of thousands.
Ziegler-Natta catalyst is a kind of organo-metallic catalyst.Usually it is made of titanium tetrachloride triethyl aluminium,
Nineteen fifty-three is invented by K.Ziegler and G.Ziegler-Natta, is suitable for catalyzed alkene type of polymerization.Later people will be all
The catalyst that the metal alkyl compound of the A of I A~III races is formed with the B group 4 transition metal halide of IVB~VII in phase table is referred to as
Ziegler-Natta catalyst.Wherein transition metal halide is known as major catalyst, and metal alkyl compound is then referred to as to help to urge
Agent.In practical applications, other components are added toward contact, these components are the electron substances with lone pair electrons, so
Also known as Donor compound.
106467587 A of patent CN provide a kind of improved Ziegler-Natta for ethene gas-phase polymerization technique and urge
Agent.By the way that the nano inorganic oxide being modified by surface is added in the preparation process of catalyst activity component suspension,
Keep catalyst kinetic controllable, polyethylene product particle shape and size distribution also make moderate progress, but its catalytic activity still have compared with
Big room for promotion (6500~14000gPE/g-cath).106928381 A of patent CN disclose a kind of spray drying
Method polyethylene catalysts, obtained catalyst wherein active component Ti content are obtained with alkoxyl magnesium and titaniferous metallocene
No more than 4wt%.Therefore develop it is a kind of efficiently, the polyethylene catalysts that have excellent performance have far-reaching significance.
Invention content
In order to overcome the shortcoming of existing technologies, the present invention provides a kind of method is simple, transition metal load factor is high,
Catalytic activity is good, less energy consumption, the synthetic method of the excellent polyethylene Ziegler-Natta catalyst of properties of product, that is, selects and close
Suitable transition metal salt, alkyl aluminium halide, the alkaline-earth halide with higher load ability or alkaline-earth metal alkoxylate
Close object carrier, in the reaction unit being sufficiently displaced from by high pure nitrogen, certain mixing speed and at a temperature of height is obtained by the reaction
Activated polyethylene Ziegler-Natta catalyst.
The present invention is achieved through the following technical solutions：A kind of Highh activity polyethylene Ziegler-Natta catalyst, system
Preparation Method includes the following steps：In the reactor being sufficiently displaced from through high pure nitrogen, with alkaline-earth halide or alkaline-earth metal
Alkoxide compound is carrier, and carrier is activated；By the carrier of activation, halogenated alkyl compound, transition metal halide
After mixing under certain condition, 50~85 DEG C, 0.5~10h is reacted, Ziegler-Natta catalyst is obtained.
Preferably, the alkaline-earth halide is BeCl2、MgCl2、CaCl2、SrCl2And BaCl2One or two
Above mixing.It is furthermore preferred that the alkaline-earth halide is magnesium chloride.
Preferably, the alkaline-earth metal alkoxy compound is magnesium methoxide and/or magnesium ethylate.It is furthermore preferred that institute
The alkaline-earth metal alkoxy compound stated is magnesium ethylate.
Preferably, the halogenated alkyl compound be trimethyl aluminium, triethyl aluminum, three n-butylaluminums, triisobutyl aluminium,
One kind of tri-n-hexyl aluminum, tri-n-octylaluminium, methylaluminoxane, aluminium diethyl monochloride, ethyl aluminum dichloride and dichloro aluminium isobutyl
Or two or more mixing.It is furthermore preferred that the halogenated alkyl compound is triethyl aluminum, aluminium diethyl monochloride or two chloroethenes
Base aluminium.
Preferably, the transition metal halide is TiCl4、TiCl3、ZrCl4And HfCl4One or more
Mixing.It is furthermore preferred that the transition metal halide is TiCl4Or TiCl3。
A kind of above-mentioned Highh activity polyethylene Ziegler-Natta catalyst, it is described to activate carrier, specifically
For：By carrier alkaline-earth halide or alkaline-earth metal alkoxy compound, at 50~85 DEG C, under stirring, it is dissolved in electron
In body compound, alcohol is then added, the reaction was continued 2~3h, product removes extra electron donor chemical combination with organic solvent washing
Object, vacuum drying, obtains the carrier of activation.
Preferably, the electron donor compound be tetrahydrofuran, butyl titanate, dimethyl suflfate, dithyl sulfate,
N-butyl phthalate, diisobutyl phthalate, tributyl phosphate, ethyl acetate, ethyl orthosilicate, four different sulphur cyanogen
Esters of silicon acis, methyltrimethoxysilane, ethyl triethoxysilane, n-propyl triethoxysilane, butyl trimethoxy silane,
One or more kinds of mixing of phenyl triethoxysilane and benzyl triethoxysilane.It is furthermore preferred that described gives electricity
Donor compound is tetrahydrofuran, butyl titanate, four different sulphur cyanogen esters of silicon acis or methyltrimethoxysilane.
Preferably, the alcohol is methanol, ethyl alcohol, 1,4-butanediol and 2, one kind of 2- diisopropyls -1,3-PD
Or two or more mixing.It is furthermore preferred that the addition of alcohol is, and in molar ratio, hydroxyl:Alkaline-earth halide or alkaline-earth metal
Alkoxide compound=2:1.
Above-mentioned Highh activity polyethylene Ziegler-Natta catalyst answering in catalyzed ethylene polymerization is reacted at polyethylene
With method is as follows：The pressure polymerization reaction unit being sufficiently displaced from by high pure nitrogen is fully blown into row with hydrogen, is then added de-
The hexane of water and above-mentioned Highh activity polyethylene Ziegler-Natta catalyst, are heated to 75 DEG C by reaction unit, are passed through hydrogen
It is 0.3~0.5MPa to pressure, then being passed through ethylene makes pressure in reaction unit reach 1.3~1.5MPa, is warming up to 80 DEG C, reaction
2h is cooled to room temperature, and filters out hexane, and product is dried in vacuo at 60 DEG C, obtains polyethylene.
The chemical general formula of Highh activity polyethylene Ziegler-Natta catalyst prepared by the present invention is AX2·aNR·bB[c
(OBuO)·d(OEt)]·eCX4, A is the one or more of alkaline-earth metal Be, Mg, Ca, Sr, Ba etc.；B is in B, Al, Ga
It is one or more of；C is one or more of Ti, Zr, Hf transition metal；X is the one or more of halogen F, Cl, Br, I etc.；
NR represents Donor compound, including tetrahydrofuran, butyl titanate, dimethyl suflfate, dithyl sulfate, phthalic acid two are just
Butyl ester, diisobutyl phthalate, tbp, ethyl acetate, ethyl orthosilicate, four different sulphur cyanogen esters of silicon acis, methyl three
Methoxy silane, ethyl triethoxysilane, n-propyl triethoxysilane, butyl trimethoxy silane, phenyl triethoxy
The one or more of silane, benzyl triethoxysilane etc.；Bu represents butyl；Et represents ethyl.A is 0.3~0.9；B is 0.1
~0.3；C is 0.3~0.8；D is 0.1~1.0；E is 0.1~0.6；Element is by its halide, alcohols or esters in chemical formula
The forms such as object, alkoxide compound, halogenated alkyl compound are closed to provide.
The beneficial effects of the invention are as follows：Compared with the prior art, the advantages of the present invention are as follows improve alkaline-earth metal halogenation
The mode of loading of object carrier and transition metal halide is lived using polyhydroxy alcohol compound as precipitating reagent using recrystallization
The method of change makes the load factor of transition metal obtain significant raising, to obtain the higher polyethylene catalysts of activity.Knot
Fruit shows.Transition metal load factor has reached 13~18wt% in catalyst, and catalytic activity has reached 40000~67000gPE/
g-cat·h.Meanwhile the catalyst prod granularity and specific surface area are also easier to control, stability is good, long lifespan, more domestic
Polyethylene catalysts in similar technique process units are had excellent performance.
Description of the drawings
Fig. 1 is the scanning electron microscope diagram of catalyst prepared by embodiment 1.
Fig. 2 is the scanning electron microscope diagram of catalyst prepared by embodiment 2.
Fig. 3 is the scanning electron microscope diagram of catalyst prepared by embodiment 3.
Fig. 4 is the scanning electron microscope diagram of catalyst prepared by embodiment 4.
Fig. 5 is the X-ray energy spectrogram of catalyst prepared by embodiment 1.
Fig. 6 is the X-ray energy spectrogram of catalyst prepared by embodiment 2.
Fig. 7 is the X-ray energy spectrogram of catalyst prepared by embodiment 3.
Fig. 8 is the X-ray energy spectrogram of catalyst prepared by embodiment 4.
Specific implementation mode
It is further illustrated the present invention below by specific example of implementing, these are implemented example and are only used for having in more detail
Body ground purposes of discussion, rather than the limitation present invention in any form.It will be apparent to those skilled in the art that hereinafter, it is such as not special
Different to illustrate, raw material and operating method selected by the present invention are well known in the art.
A kind of 1 Highh activity polyethylene Ziegler-Natta catalyst of embodiment
Preparation method is as follows：
In the reactor being sufficiently displaced from through high pure nitrogen, anhydrous magnesium chloride 2g and tetrahydrofuran 60mL is added, 50~
At 85 DEG C, with 100~500rpm magnetic agitation speeds, stirring is to being completely dissolved.According to hydroxyl and anhydrous magnesium chloride 2:1 mole
1,4-butanediol is added in ratio, after reacting 2.5h, normal heptane is added and repeatedly washs to remove extra tetrahydrofuran, then vacuum
It is dry, obtain the magnesium chloride support of activation.
In the magnesium chloride support of activation, normal heptane 50mL and triethyl aluminum 20ml is added, at 50~85 DEG C, with 100
~500rpm magnetic agitation speeds stir, and after reacting 2.5h, normal heptane is added, and repeatedly washing is to remove extra triethyl aluminum, so
After be dried in vacuo, obtain intermediate product, mobility is excellent.
In intermediate product, normal heptane 50mL and titanium tetrachloride 3ml is added, at 50~85 DEG C, with 100~500rpm magnetic
Power stir speed (S.S.) stirs, and after reacting 2.5h, normal heptane is added, and repeatedly washing is to remove extra titanium tetrachloride, then at 60 DEG C
It is dried in vacuo, obtains Highh activity polyethylene Ziegler-Natta catalyst 1.
A kind of 2 Highh activity polyethylene Ziegler-Natta catalyst of embodiment
Preparation method is as follows：
In the reactor being sufficiently displaced from through high pure nitrogen, anhydrous magnesium chloride 2g and tetrahydrofuran 60mL is added, 50~
At 85 DEG C, with 100~500rpm magnetic agitation speeds, stirring is to being completely dissolved.According to hydroxyl and anhydrous magnesium chloride 2:1 mole
Ethyl alcohol is added in ratio, reduces system temperature to 0 DEG C, after reacting 2.5h in ice-water bath, the multiple washing of normal heptane is added to remove
Extra tetrahydrofuran, is then dried in vacuo, and obtains the magnesium chloride support of activation.
In the magnesium chloride support of activation, normal heptane 50mL and triethyl aluminum 20ml is added, at 50~85 DEG C, with 100
~500rpm magnetic agitation speeds stir, and after reacting 2.5h, normal heptane is added, and repeatedly washing is to remove extra triethyl aluminum, so
After be dried in vacuo, obtain intermediate product, mobility is excellent.
In intermediate product, normal heptane 50mL and titanium tetrachloride 3ml is added, at 50~90 DEG C, with 100~500rpm magnetic
Power stir speed (S.S.) stirs, and after reacting 2.5h, normal heptane is added, and repeatedly washing is to remove extra titanium tetrachloride, then at 60 DEG C
It is dried in vacuo, obtains Highh activity polyethylene Ziegler-Natta catalyst 2.
A kind of preparation method of 3 Highh activity polyethylene Ziegler-Natta catalyst of embodiment
Preparation method is as follows：
In the reactor being sufficiently displaced from through high pure nitrogen, anhydrous magnesium chloride 2g and tetrahydrofuran 60mL is added, 50~
At 85 DEG C, with 100~500rpm magnetic agitation speeds, stirring is to being completely dissolved.According to hydroxyl and anhydrous magnesium chloride 2:1 mole
2,2- diisopropyls -1,3-PD is added in ratio, after reacting 2.5h, forms uniform transparent magnesium alcoholate solution, is added
Repeatedly then washing is dried in vacuo to remove extra tetrahydrofuran, obtains the magnesium chloride support of activation normal heptane.
In the magnesium chloride support of activation, it is added normal heptane 55mL and triethyl aluminum 25ml, magnetic agitation at 50~85 DEG C,
After reacting 3h, normal heptane is added, and repeatedly then washing is dried in vacuo to remove extra triethyl aluminum, obtains intermediate product, flows
Dynamic property is excellent.
In intermediate product, it is added normal heptane 55mL and titanium tetrachloride 4ml, magnetic agitation at 50~85 DEG C reacts 2.5h
Afterwards, normal heptane is added, and repeatedly washing is dried in vacuo at 60 DEG C to remove extra titanium tetrachloride, obtains the poly- second of high activity
Alkene Ziegler-Natta catalyst 3.
A kind of 4 Highh activity polyethylene Ziegler-Natta catalyst of embodiment
Preparation method is as follows：
In the reactor being sufficiently displaced from through high pure nitrogen, magnesium ethylate 2g and tetrahydrofuran 60mL is added, 50~85
At DEG C, with 100~500rpm magnetic agitation speeds, stirring is to being completely dissolved.According to hydroxyl and magnesium ethylate 2:1 molar ratio
1,4-butanediol is added, after reacting 3h, normal heptane is added, and repeatedly then washing is dried in vacuo with removing extra tetrahydrofuran,
The magnesium ethylate carrier that must be activated.
In the magnesium ethylate carrier of activation, normal heptane 100mL is added, at 50~85 DEG C, with 100~500rpm magnetic force
Stir speed (S.S.) is stirred to being completely dissolved, and is then cooled to -20~20 DEG C of holding 2h, titanium tetrachloride 10ml is added, reacts 1~2h.
50~85 DEG C are warming up to, butyl titanate 10mL is added and (usually chooses 1 with titanium tetrachloride molar ratio:1) 1~2h, is reacted, is added just
Heptane repeatedly washs.It is added triethyl aluminum 40ml, at 50~85 DEG C after reaction 3h, normal heptane is added, and repeatedly washing is extra to remove
Triethyl aluminum, then carried out at 60 DEG C, obtain Highh activity polyethylene Ziegler-Natta catalyst 4.
Fig. 1-Fig. 4 is the SEM figures of catalyst prepared by embodiment 1-4.By Fig. 1-Fig. 4 as it can be seen that four embodiment sample grains
Diameter is all between 5~20 μm, and four embodiment degrees of cross linking are all bigger, and crystalline structure is more chaotic, this shows to add tetrachloro
After change titanium so that carrier can be activated fully.Wherein embodiment 1 and 4 sample adhesion degree of embodiment is bigger, illustrates polyhydroxy
The addition of alcohol increases the viscosity of sample, further increases support-activated degree, to improve the load factor of Ti.
Fig. 5-Fig. 8 is the EDS figures of catalyst prepared by embodiment 1-4.By Fig. 5-Fig. 8 as it can be seen that four embodiment samples
Ti contents are relatively high, this illustrates that alcohol closes treated carrier and is easier to load titanium tetrachloride, wherein the Ti load factors of embodiment 1
It is that twice of embodiment 2 this concludes the description of the load that polyhydroxy-alcohol is more advantageous to Ti.
A kind of polyethylene under Ziegler-Natta catalyst effect of embodiment 5
Method is as follows：
The ethylene slurry pressure polymerization reaction unit being sufficiently displaced from by high pure nitrogen is fully blown into row with hydrogen, 1L is added
By the hexane being fully dehydrated, 15~40mg of catalyst prepared in above-described embodiment 1~4 is added immediately, by reaction unit
75 DEG C are heated to, it is 0.3MPa to be passed through hydrogen to pressure, then being passed through ethylene makes reaction unit internal pressure reach 1.5MPa, heating
To 80 DEG C or so, 2h is reacted.Then it is down to room temperature, filters out hexane, product is dried in vacuo at 60 DEG C, polymerisation
Evaluation result such as table 1.
Table 1 prepares polyethylene small testing device evaluation result under Ziegler-Natta catalyst effect
By table 1 as it can be seen that the catalyst Ti load factors formed as carrier by 1.4- butanediols and magnesium chloride in example 1 most
Height, catalytic activity highest.
The foregoing description of the disclosed embodiments enables professional and technical personnel in the field to realize or using the present invention.It is right
A variety of modifications of these embodiments will be apparent to those skilled in the art, as defined herein general
Principle can be realized in other embodiments without departing from the spirit or scope of the present invention.Therefore, the present invention will not
It can be intended to be limited to the embodiments shown herein, and be to fit to consistent most with principle novel features disclosed herein
Wide range.
Claims (10)
1. a kind of Highh activity polyethylene Ziegler-Natta catalyst, which is characterized in that preparation method includes the following steps：With
Alkaline-earth halide or alkaline-earth metal alkoxy compound are carrier, and carrier is activated；By the carrier of activation, alkyl halide
After based compound, transition metal halide mix under certain condition, 50~85 DEG C, 0.5~10h is reacted, Ziegler- is obtained
Natta catalyst.
2. a kind of Highh activity polyethylene Ziegler-Natta catalyst according to claim 1, which is characterized in that described
Alkaline-earth halide be BeCl2、MgCl2、CaCl2、SrCl2And BaCl2One or more kinds of mixing.
3. a kind of Highh activity polyethylene Ziegler-Natta catalyst according to claim 1, which is characterized in that described
Alkaline-earth metal alkoxy compound be magnesium methoxide and/or magnesium ethylate.
4. a kind of Highh activity polyethylene Ziegler-Natta catalyst according to claim 1, which is characterized in that described
Halogenated alkyl compound be trimethyl aluminium, triethyl aluminum, three n-butylaluminums, triisobutyl aluminium, tri-n-hexyl aluminum, three n-octyls
One or more kinds of mixing of aluminium, methylaluminoxane, aluminium diethyl monochloride, ethyl aluminum dichloride and dichloro aluminium isobutyl.
5. a kind of Highh activity polyethylene Ziegler-Natta catalyst according to claim 1, which is characterized in that described
Transition metal halide be TiCl4、TiCl3、ZrCl4And HfCl4One or more kinds of mixing.
6. a kind of Highh activity polyethylene Ziegler-Natta catalyst according to claim 1, which is characterized in that described
Carrier is activated, specially：By carrier alkaline-earth halide or alkaline-earth metal alkoxy compound, 50~85
DEG C, under stirring, it is dissolved in electron donor compound, alcohol is then added, the reaction was continued 2~3h, product organic solvent washing
Extra electron donor compound is removed, is dried in vacuo, obtains the carrier of activation.
7. a kind of Highh activity polyethylene Ziegler-Natta catalyst according to claim 6, which is characterized in that described
Electron donor compound be tetrahydrofuran, butyl titanate, dimethyl suflfate, dithyl sulfate, n-butyl phthalate,
Diisobutyl phthalate, tributyl phosphate, ethyl acetate, ethyl orthosilicate, four different sulphur cyanogen esters of silicon acis, methyl trimethoxy oxygroup
Silane, ethyl triethoxysilane, n-propyl triethoxysilane, butyl trimethoxy silane, phenyl triethoxysilane and
One or more kinds of mixing of benzyl triethoxysilane.
8. a kind of Highh activity polyethylene Ziegler-Natta catalyst according to claim 6, which is characterized in that described
Alcohol be methanol, ethyl alcohol, 1,4- butanediols and 2,2- diisopropyl -1,3- propylene glycol one or more kinds of mixing.
9. a kind of Highh activity polyethylene Ziegler-Natta catalyst according to claim 6, which is characterized in that alcohol
Addition is, in molar ratio, hydroxyl:Alkaline-earth halide or alkaline-earth metal alkoxy compound=2:1.
10. Highh activity polyethylene Ziegler-Natta catalyst described in claim 1 is anti-at polyethylene in catalyzed ethylene polymerization
Application in answering, which is characterized in that method is as follows：The pressure polymerization reaction unit hydrogen that will be sufficiently displaced from by high pure nitrogen
Row is fully blown, the hexane of dehydration and Highh activity polyethylene Ziegler-Natta catalyst described in claim 1 is then added,
Reaction unit is heated to 75 DEG C, it is 0.3~0.5MPa to be passed through hydrogen to pressure, then being passed through ethylene makes pressure in reaction unit reach
To 1.3~1.5MPa, 80 DEG C are warming up to, 2h is reacted, is cooled to room temperature, filters out hexane, product is dried in vacuo at 60 DEG C, is obtained poly-
Ethylene.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810240619.8A CN108484805B (en) | 2018-03-22 | 2018-03-22 | High-activity polyethylene Ziegler-Natta catalyst and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810240619.8A CN108484805B (en) | 2018-03-22 | 2018-03-22 | High-activity polyethylene Ziegler-Natta catalyst and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN108484805A true CN108484805A (en) | 2018-09-04 |
| CN108484805B CN108484805B (en) | 2021-02-09 |
Family
ID=63319248
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810240619.8A Active CN108484805B (en) | 2018-03-22 | 2018-03-22 | High-activity polyethylene Ziegler-Natta catalyst and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108484805B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113087824A (en) * | 2021-03-19 | 2021-07-09 | 上海簇睿低碳能源技术有限公司 | Improved Ziegler-Natta catalyst and preparation method and application thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102775528A (en) * | 2012-08-30 | 2012-11-14 | 中国科学院长春应用化学研究所 | Preparation method of Ziegler-Natta catalyst and preparation method of polyethylene |
| CN103665206A (en) * | 2013-12-10 | 2014-03-26 | 上海化工研究院 | Preparation method of multi-active-centre catalyst for olefin polymerization |
| US20150274857A1 (en) * | 2012-09-24 | 2015-10-01 | Indian Oil Corporation Limited | Distance measuring method and distance measuring element |
-
2018
- 2018-03-22 CN CN201810240619.8A patent/CN108484805B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102775528A (en) * | 2012-08-30 | 2012-11-14 | 中国科学院长春应用化学研究所 | Preparation method of Ziegler-Natta catalyst and preparation method of polyethylene |
| US20150274857A1 (en) * | 2012-09-24 | 2015-10-01 | Indian Oil Corporation Limited | Distance measuring method and distance measuring element |
| CN103665206A (en) * | 2013-12-10 | 2014-03-26 | 上海化工研究院 | Preparation method of multi-active-centre catalyst for olefin polymerization |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113087824A (en) * | 2021-03-19 | 2021-07-09 | 上海簇睿低碳能源技术有限公司 | Improved Ziegler-Natta catalyst and preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN108484805B (en) | 2021-02-09 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105440185B (en) | A kind of loaded catalyst and preparation method thereof and its method for being used for propylene polymerization | |
| CN1726080A (en) | Magnesium dichloride-based adducts and catalyst components obtained therefrom | |
| CN1038593C (en) | Method for preparing solid catalyst component for ethylene (co) polymerization | |
| CN106471018A (en) | Raw catalyst for the polymerization of alkene | |
| Cho et al. | Characteristics of ethylene polymerization over Ziegler–Natta/metallocene catalysts: Comparison between hybrid and mixed catalysts | |
| JP2011511135A (en) | Polyethylene materials prepared using mixed Ziegler-Natta catalyst systems | |
| CN103351443A (en) | Supported olefin polymerization catalyst, preparation method and application thereof | |
| WO2007036135A1 (en) | Catalyst active component, preparation method thereof and catalyst comprising said active component | |
| EP3138856B1 (en) | Method for preparation of a catalyst component used for olefin polymerization | |
| CN109790251A (en) | The method for being used to prepare the major catalyst for olefinic polymerization | |
| CN105482004A (en) | Composite catalyst for preparation of broad peak / bimodal distribution high density polyethylene | |
| CN108059689A (en) | Olefin polymerization procatalyst compositions and preparation method thereof, olefin Polymerization catalyst compositions | |
| JP2014114435A (en) | Method for manufacturing a propylene polymer | |
| CN107446070A (en) | A kind of carrier for olefin polymerization catalysis, preparation method and applications | |
| CN108484805A (en) | A kind of Highh activity polyethylene Ziegler-Natta catalyst and its preparation method and application | |
| CN104974283A (en) | Catalyst component used in ethylene polymerization reaction, catalyst and preparation method thereof | |
| CN100400554C (en) | Catalyst components for propylene polymerization and catalyst thereof | |
| CN104031183A (en) | A catalyst component used for olefin polymerization, and a preparing method and applications thereof | |
| TWI294886B (en) | ||
| CN104672356B (en) | Catalyst component for olefin, the preparation method of this component and catalyst | |
| CN105985462B (en) | Clay alteration silica gel complex carrier and preparation method thereof | |
| CN1177873C (en) | Catalyst component for ethylene polymerization or copolymerization, and catalyst and use thereof | |
| CN105859927B (en) | Vinyl polymerization Ziegler-Natta catalyst electron donor, catalytic component, catalyst | |
| CN102286121B (en) | Catalyst component of ethylene polymerization and catalyst | |
| CN106543307B (en) | The preparation method and catalyst for olefines polymerizing of catalyst for olefines polymerizing and its application |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |