CN104974280B - Catalyst component used in ethylene polymerization reaction, catalyst and preparation method thereof - Google Patents
Catalyst component used in ethylene polymerization reaction, catalyst and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a catalyst component used in an ethylene polymerization reaction, a preparation method and a catalyst thereof, wherein the catalyst component includes: (1) a magnesium alcohol adduct; (2) a titanium compound; (3) a mercaptan compound; (4) a double-epoxy group compound and (5) a single-epoxy group compound. The catalyst has a polymerization activity being suitable for a gas-phase polymerization process of ethylene. An obtained polymer is high in stacking density and is low in fine powder content.
Description
Technical field
The present invention relates to a kind of catalytic component for vinyl polymerization or copolymerization, the preparation of the catalytic component
Method and its catalyst.More particularly, it relates to a kind of catalytic component for introducing high activity end group in preparation process, this urges
The preparation method of agent component and its catalyst.
Background technology
The Ziegler-Natta type vinyl polymerizations spheric catalyst prepared by magnesium chloride ethanolic vehicle is existing wide
Research, the catalyst are widely used in the ethylene operated with liquid phase or with gas phase（Altogether）Polyplant.However, catalyst group
The use of itself is divided not to be entirely satisfactory.In fact, due to the high response of ethylene, the heat release of polyreaction is very
It is high.Therefore, the starting stage catalyst in polymerization bears very strong tension force, and it is uncontrolled that the tension force occurs catalyst itself
Rupture, such case is the reason for polymer fine particles are formed.The formation of polymer fine particles directly results in the low of polymer
Bulk density and the difficulty of operating process.For solving these problems, company of Basel has been carried out numerous studies.CN1400979A
A kind of catalytic component prepared for ethylene (co) polymer is disclosed, the catalytic component can be produced with high heap density
Polymer, is avoided that the problem of fine powder formation and has high activity, the catalytic component contains non-cubic selects solid catalyst
Component, which contains titanium compound and magnesium dihalide, and it is and alpha-olefin CH2=CHRIPrepolymerized, wherein R is C1-C8 alkyl, in advance
The degree of polymerization causes the ingredient of solid catalyst for per gram, up to 100 grams of the amount of alpha-olefin prepolymer, but this method
Complicated process of preparation.CN101137677A discloses a kind of catalyst component for polymerization of ethylene, the catalytic component comprising Ti,
Mg, halogen and 1, the 2- dimethoxy-ethanes as internal electron donor compound, the catalyst are applied to the (co) polymerization of ethylene
Technique, to make the (co) polymer with Narrow Molecular Weight Distribution (MWD) and high-bulk-density, but this method is not still solved
Certainly in gas-phase polymerization process, catalyst is broken, the more problem of fine polymer powder.
The content of the invention
The technical problem to be solved in the present invention is to provide a kind of catalytic component and its catalyst for vinyl polymerization, should
Catalyst has the polymerization activity for being suitable to ethene gas-phase polymerization technique, and the bulk density of resulting polymers is high, and fine powder content is relatively low.
An object of the present invention is to provide a kind of catalytic component for ethylene polymerization, the catalytic component bag
Include the product of following component：
（1）Magnesium alcoholate；
（2）Titanium compound；
（3）Sulfur alcohol compound；
（4）Bis-epoxy base class compound；
（5）Monocyclic epoxide class compound；
Component（1）It is MgCl that described magnesium alcoholate is formula2-mR1The chlorination magnesium alcoholate of OH, wherein R1For C1～C4Alkane
Base, m are 1.0～4.0；
Component（2）The formula of described titanium compound is Ti (OR2)nX4-n, R in formula2For C1～C8Alkyl, X is halogen
Atom, 0≤n≤4；
Component（3）The formula of described sulfur alcohol compound is HS (R3) SH, R in formula3For C3～C18Aryl or aliphatic
Alkyl；
Component（4）Described in the formula of bis-epoxy base class compound beR5For carbon atom
Number is 4～18 alkyl or aryl；
Component（5）Described in the formula of monocyclic epoxide class compound beWherein R4For carbon number it is
1～4 alkyl, X is halogen atom, 0≤m≤3.
Specifically, component（1）Described in formula be MgCl2-mR1The chlorination magnesium alcoholate of OH is by C1～C4It is low
Carbon alcohol is 2.5 with magnesium chloride in molar ratio:1～4:1 is mixed, and is rapidly cooled down after heating melting, obtain containing 2.0～
The spheroidal particle of 4.0 moles of alcohol per mole magnesium chlorides.Chlorination magnesium alcoholate of this patent using non-dealcoholysis.Preferred scope 2.5～
3.0 moles of alcohol per mole magnesium chlorides.Above-mentioned chlorination magnesium alcoholate is disclosed in Chinese patent CN93102795.0, disclosed in which
Related content is all incorporated herein by reference.
Component（2）Described in titanium compound formula be Ti (OR2)nX4-n, R in formula2For C1～C8Alkyl, X is that halogen is former
Son, 0≤n≤4, including：TiCl4、TiBr4、TiI4、Ti(OC2H5)Cl3、Ti(OCH3)Cl3、Ti(OC4H9)Cl3、Ti(OC2H5)
Br3、Ti(OC2H5)2Cl2、Ti(OCH3)2Cl2、Ti(OCH3)2I2、Ti(OC2H5)3Cl、Ti(OCH3)3Cl、Ti(OC2H5)3I、Ti
(OC2H5)4、Ti(OC3H7)4、Ti(OC4H9)4Deng.It is preferred that TiCl4、Ti(OC2H5)Cl3、Ti(OCH3)Cl3、Ti(OC4H9)Cl3、Ti
(OC4H9)4.With TiCl4For optimal.
Component（3）Described in sulfur alcohol compound formula be HS (R3) SH, R in formula3For C3～C18Aryl or fat
Race's alkyl.It is characterized in that described sulfur alcohol compound is distant claw type dithiol, specially 1,6- ethanthiols, 1,8- pungent two
Mercaptan, 1,4- succinimide mercaptans, two mercaptan of the 1,10- last of the ten Heavenly stems, α, ω -18 carbon mercaptan, 1,4- xylol mercaptan, In at least one, preferably 1,8- pungent two
Mercaptan, two mercaptan of the 1,10- last of the ten Heavenly stems, α, ω -18 carbon mercaptan andThis
A little mercaptan compounds both can be used alone, it is also possible to be used in combination.
Component（4）Bis-epoxy base class compound be In one kind, wherein preferably
Component（5）Monocyclic epoxide class compound be epoxychloropropane, the one kind in epoxy butane, wherein preferred epoxy chlorine
Propane.
In catalytic component for vinyl polymerization of the present invention, the ratio between each reactant is with component（1）Chlorine
Change every mole of magnesium meter in magnesium alcoholate, component（2）Titanium compound is 0.5～15.0 mole, component（3）Sulfur alcohol compound is
0.5～5.0 mole, component（4）And component（5）In epoxy-functional sum and component（3）Middle thiol functionalities sum is identical,
It is 1%～50% that wherein monocyclic epoxide class compound accounts for the ratio of total epoxy base class compound（Mole）, it is preferably in a proportion of 10%～
40%（Mole）.
Present invention also offers a kind of preparation method of the catalytic component for ethylene polymerization, including following steps
Suddenly：By component（1）Described magnesium alcoholate is dispersed in atent solvent, obtains suspension.Disperse medium includes：Iso-butane, oneself
Alkane, heptane, hexamethylene, Petroleum, raffinate oil, the saturated fat hydro carbons atent solvent such as hydrogasoline, kerosene.By suspension in-
20 DEG C～30 DEG C and component（2）Titanium compound, component（3）Sulfur alcohol compound, component（4）Bis-epoxy base class compound and component
（5）Monocyclic epoxide class compound carries out haptoreaction, and mixture is to slowly warm up to 20～60 DEG C, reacts the regular hour
Afterwards, unreacted reactant and solvent is removed, and is washed using inert diluent, be then re-introduced into component（2）Titanium compound is reacted,
Then Jing inert diluents washing, that is, obtain the catalytic component of the present invention.
A kind of spheric catalyst for vinyl polymerization is another object of the present invention is to provide, which includes following components
Product：
（1）The catalytic component of the invention described above；
（2）It is AlR ' that promoter is formuladX3-dOrgano-aluminum compound, in formula R ' be hydrogen or carbon number be l～20
Alkyl, X is halogen atom, 0<d≤3.
It is AlR ' that promoter is formuladX3-dOrgano-aluminum compound, in formula R ' can be hydrogen or carbon number be l～
20 alkyl, particularly alkyl, aralkyl, aryl；X is halogen atom, particularly chlorine and bromine；0<d≤3.Particular compound is such as：
Al(CH3)3、Al(CH2CH3)3、Al(i-Bu)3、AlH(CH2CH3)2、AlH(i-Bu)2、AlCl(CH2CH3)2、Al2Cl3
(CH2CH3)3、AlCl(CH2CH3)2、AlCl2(CH2CH3) etc. alkyl aluminum compound.Preferably Al (CH2CH3)3、Al(i-Bu)3。
The mol ratio of the titanium in aluminum and catalytic component wherein in promoter is 5～500, preferably 20～200.
Liquid phase polymerization can be adopted during polymerization, it would however also be possible to employ gas-phase polymerization.
During liquid phase polymerization, medium includes：Iso-butane, hexane, heptane, hexamethylene, Petroleum, raffinate oil, hydrogasoline, coal
The atent solvent such as the aliphatic saturated hydrocarbons such as oil, benzene,toluene,xylene or aromatic hydrocarbon.
During gas-phase polymerization, using pressure reactor, NaCl mixes a bed medium.
In order to adjust the molecular weight of final polymer, molecular weight regulator is made using hydrogen.
The inventors discovered that adding thio-alcohol chemical combination in the preparation process for the catalytic component of ethylene polymerization
Thing and epoxy compounds, can not only make gained polyethylene powder have high-bulk-density, and catalyst in polymerization process
In almost do not crush, fine polymer powder is few.In addition alkyl aluminum, titanium are not used in the catalytic component preparation process
Compound amount is also less, thus the catalytic component preparation process is simple, and three waste discharge is few, low cost.
Specific embodiment
Method of testing：
1. in catalyst system titanium/magnesium elements relative weight percents：Using spectrophotography；
2. in catalyst system ester relative weight percents：Using high performance liquid chromatography and liquid nuclear-magnetism hydrogen spectrometry；
3. the measure of polymer bulk density：Using ASTM D1895 plastics apparent densities, bulkfactor and pouring into property
Test method be measured；
4. the measure that polymer particle size is distributed：Sieved using standard screen.
Following examples are citing descriptions more detailed to the present invention, but the invention is not limited in these embodiments.
Embodiment 1
In the reactor being sufficiently displaced from through high pure nitrogen, 6.0g ball type carrier MgCl are sequentially added2·
2.6C2H5OH, hexamethylene 150ml, are cooled to 0 DEG C, Deca 12ml TiCl under stirring4, 50 DEG C are warming up to, stirring reaction 1 hour,
Then 30 DEG C are cooled to, 3.6g1, pungent two mercaptan of 8-, epoxide is sequentially added（e）1.95g and 0.4ml epoxychloropropane,
And maintain reaction 2 hours.Stop stirring, stand, suspension is layered quickly, extracts the supernatant, and precipitate hexamethylene exists
Room temperature washing is twice.150ml hexanes are added, the system is cooled to into 0 DEG C, titanium tetrachloride 4ml is slowly added dropwise, 60 are warming up to afterwards
DEG C, react 2 hours.Stop stirring, stand, suspension is layered quickly, extracts the supernatant, and precipitate washs twice with hexane
Afterwards, transferred them in chromatography funnel by hexane, dried up with high pure nitrogen, obtain the solid of good fluidity, narrow diameter distribution
Spherical catalyst components.Catalyst composition is shown in Table 1.
(2) vinyl polymerization
Stainless steel cauldron of the volume for 2L, Jing after high pure nitrogen is sufficiently displaced from, adds 1L hexanes and 1.0ml concentration to be 1M
Triethyl aluminum, add by said method prepare solid catalyst（Containing about 0.3 milligram of titanium）, 75 DEG C are warming up to, are passed through
Hydrogen makes pressure in kettle reach 0.28Mpa, then being passed through ethylene makes stagnation pressure in kettle reach 1.03Mpa（Gauge pressure）, under the conditions of 85 DEG C
Polymerization 2 hours, polymerization result is shown in Table 2.
（3）Gas phase polymerization
Rustless steel autoclave of the volume for 1L, addition 500g Sal, vacuum pump drainage, nitrogen displacement will by hexane
Triethyl aluminum of the 2.0ml concentration for 1M, and the ingredient of solid catalyst prepared by said method（Containing 2 milligrams of titaniums）Introduce anti-
Kettle is answered, 75 DEG C are warming up to, hexane evaporating completely is blown out system, is then cooled to 70 DEG C by nitrogen purging, while being passed through setting pressure
The hydrogen and ethylene of power ratio, makes pressure in kettle reach 1.03Mpa（Gauge pressure）, it is polymerized 2 hours under the conditions of 70 DEG C, polymerization result is shown in
Table 3.
Embodiment 2
（1）The preparation of catalytic component
In the reactor being sufficiently displaced from through high pure nitrogen, 6.0g ball type carrier MgCl are sequentially added2·
2.6C2H5OH, hexamethylene 150ml, are cooled to -10 DEG C under stirring, Deca 6ml TiCl4, 50 DEG C are warming up to, stirring reaction 1 is little
When, 25 DEG C are cooled to, 4.7g1,6- ethanthiols, epoxide is then sequentially added（e）2.6g and 0.6ml epoxy chloropropionates
Alkane, and maintain reaction 2 hours.Stop stirring, stand, suspension is layered quickly, extracts the supernatant, precipitate hexamethylene
In room temperature washing twice.150ml hexamethylene is added, the system is cooled to into 0 DEG C, titanium tetrachloride 4ml is slowly added dropwise, is heated up afterwards
To 60 DEG C, react 2 hours.Stop stirring, stand, suspension is layered quickly, extracts the supernatant, and precipitate washs two with hexane
After, transferred them in chromatography funnel by hexane, dried up with high pure nitrogen, obtained good fluidity, narrow diameter distribution and consolidate
Body spherical catalyst components.Catalyst composition is shown in Table 1.
（2）Polyreaction：With embodiment 1, polymerization result is shown in Table 2.
（3）Gas phase polymerization：With embodiment 1, polymerization result is shown in Table 3.
Embodiment 3
（1）The preparation of catalytic component
In the reactor being sufficiently displaced from through high pure nitrogen, 36.0g ball type carrier MgCl are sequentially added2·
2.6C2H5OH, hexamethylene 750ml, are cooled to 0 DEG C, Deca 60ml TiCl under stirring4, 60 DEG C are warming up to, stirring reaction 1.5 is little
When, 30 DEG C are then cooled to, 36g α, ω -18 carbon mercaptan, 21g epoxides is sequentially added（d）With 1.6ml epoxychloropropane,
And maintain reaction 3 hours.Stop stirring, stand, suspension is layered quickly, extracts the supernatant, and precipitate hexamethylene exists
Room temperature washing is twice.750ml hexanes are added, the system is cooled to into 0 DEG C, titanium tetrachloride 24ml is slowly added dropwise, is warming up to afterwards
60 DEG C, react 2 hours.Stop stirring, stand, suspension is layered quickly, extracts the supernatant, and precipitate washs twice with hexane
Afterwards, transferred them in chromatography funnel by hexane, dried up with high pure nitrogen, obtain the solid of good fluidity, narrow diameter distribution
Spherical catalyst components.Catalyst composition is shown in Table 1.
（2）Polyreaction：With embodiment 1, polymerization result is shown in Table 2.
（3）Gas phase polymerization：With embodiment 1, polymerization result is shown in Table 3.
Embodiment 4
（1）The preparation of catalytic component
In the reactor being sufficiently displaced from through high pure nitrogen, 6.0g ball type carrier MgCl are sequentially added2·
2.6C2H5OH, hexamethylene 150ml, are cooled to -5 DEG C, Deca 8mlTiCl under stirring4, 50 DEG C are warming up to, stirring reaction 1 hour,
Then 20 DEG C are cooled to, 4.0g1, two mercaptan of the 10- last of the ten Heavenly stems, epoxide is sequentially added（a）3.0g and 0.6ml epoxychloropropane,
Maintain reaction 2 hours.Stop stirring, stand, suspension is layered quickly, extracts the supernatant, and precipitate hexamethylene is in room temperature
Wash twice.150ml hexanes are added, the system are cooled to into 0 DEG C, titanium tetrachloride 4ml is slowly added dropwise, 60 DEG C are warming up to afterwards,
Reaction 2 hours.Stop stirring, stand, suspension is layered quickly, extracts the supernatant, and precipitate hexane is washed after twice, lead to
Cross hexane to transfer them in chromatography funnel, dried up with high pure nitrogen, obtain good fluidity, the solid spherical of narrow diameter distribution is urged
Agent component.Catalyst composition is shown in Table 1.
（2）Polyreaction：With embodiment 1, polymerization result is shown in Table 2.
（3）Gas phase polymerization：With embodiment 1, polymerization result is shown in Table 3.
Embodiment 5
（1）The preparation of catalytic component
In the reactor being sufficiently displaced from through high pure nitrogen, 6.0g ball type carrier MgCl are sequentially added2·
2.6C2H5OH, hexamethylene 150ml, are cooled to 0 DEG C, Deca 7ml TiCl under stirring4, 50 DEG C are warming up to, stirring reaction 1 hour,
Then 30 DEG C are cooled to, 4.0g mercaptan compounds are sequentially added（i）, epoxide（a）3.0g and 0.6ml epoxychloropropane,
And maintain reaction 2 hours.Stop stirring, stand, suspension is layered quickly, extracts the supernatant, and precipitate hexamethylene exists
Room temperature washing is twice.150ml hexanes are added, the system is cooled to into 0 DEG C, titanium tetrachloride 4ml is slowly added dropwise, 60 are warming up to afterwards
DEG C, react 2 hours.Stop stirring, stand, suspension is layered quickly, extracts the supernatant, and precipitate washs twice with hexane
Afterwards, transferred them in chromatography funnel by hexane, dried up with high pure nitrogen, obtain the solid of good fluidity, narrow diameter distribution
Spherical catalyst components.Catalyst composition is shown in Table 1.
（2）Polyreaction：With embodiment 1, polymerization result is shown in Table 2.
Embodiment 6
（1）The preparation of catalytic component
In the reactor being sufficiently displaced from through high pure nitrogen, 36.0g ball type carrier MgCl are sequentially added2·
2.0C2H5OH, hexamethylene 720ml, are cooled to 0 DEG C, Deca 36ml TiCl under stirring4, 50 DEG C are warming up to, stirring reaction 1 hour,
Then 25 DEG C are cooled to, 24.0g mercaptan compounds are sequentially added（i）, epoxide（a）18.0g and 3.5ml epoxy chloropropionates
Alkane, and maintain reaction 2 hours.Stop stirring, stand, suspension is layered quickly, extracts the supernatant, precipitate hexamethylene
In room temperature washing twice.750ml hexanes are added, the system is cooled to into 0 DEG C, titanium tetrachloride 24ml is slowly added dropwise, is heated up afterwards
To 60 DEG C, react 2 hours.Stop stirring, stand, suspension is layered quickly, extracts the supernatant, and precipitate washs two with hexane
After, transferred them in chromatography funnel by hexane, dried up with high pure nitrogen, obtained good fluidity, narrow diameter distribution and consolidate
Body spherical catalyst components.Catalyst composition is shown in Table 1.
（2）Polyreaction：With embodiment 1, polymerization result is shown in Table 2.
（3）Gas phase polymerization：With embodiment 1, polymerization result is shown in Table 3.
Comparative example 1
（1）The preparation of catalytic component
In the reactor being sufficiently displaced from through high pure nitrogen, 6.0g ball type carrier MgCl are sequentially added2·
2.6C2H5OH, hexamethylene 150ml, are cooled to 0 DEG C, successively Deca 8ml TiCl under stirring4, 50 DEG C are warming up to, and remain anti-
Answer 2 hours.Stop stirring, stand, suspension is layered quickly, extracts the supernatant, and precipitate hexamethylene is in room temperature washing two
It is secondary.150ml hexanes are added, the system is cooled to into 0 DEG C, titanium tetrachloride 4ml is slowly added dropwise, 60 DEG C are warming up to afterwards, reaction 2 is little
When.Stop stirring, stand, suspension is layered quickly, extracts the supernatant, and precipitate hexane is washed after twice, by hexane
Transfer them in chromatography funnel, dried up with high pure nitrogen, obtain the solid spherical catalyst group of good fluidity, narrow diameter distribution
Point.Catalyst composition is shown in Table 1.
（2）Polyreaction：With embodiment 1, polymerization result is shown in Table 2.
（3）Gas phase polymerization：With embodiment 1, polymerization result is shown in Table 3.
Comparative example 2
（1）The preparation of catalytic component
In the reactor being sufficiently displaced from through high pure nitrogen, 6.0g ball type carrier MgCl are sequentially added2·
2.6C2H5OH, hexamethylene 150ml, are cooled to -10 DEG C under stirring, Deca 6ml TiCl4, 50 DEG C are warming up to, stirring reaction 1 is little
When, 25 DEG C are cooled to, 4.7g1,6- ethanthiols, epoxide is then sequentially added（e）2.8g, and maintain to react to 1
Hour, system solidification, reaction failure, it is impossible to obtain the catalyst that can be examined.
Comparative example 3
（1）The preparation of catalytic component
In the reactor being sufficiently displaced from through high pure nitrogen, 6.0g ball type carrier MgCl are sequentially added2·
2.6C2H5OH, hexamethylene 150ml, are cooled to -10 DEG C under stirring, Deca 6ml TiCl4, 50 DEG C are warming up to, stirring reaction 1 is little
When, 25 DEG C are cooled to, 4.7g1,6- ethanthiols, epoxychloropropane 1.0ml are then sequentially added, and is maintained reaction little to 2
When.Stop stirring, stand, suspension is layered quickly, extract the supernatant, precipitate hexamethylene in room temperature washing twice.Plus
Enter 150ml hexanes, the system is cooled to into 0 DEG C, be slowly added dropwise titanium tetrachloride 4ml, be warming up to 60 DEG C afterwards, react 2 hours.Stop
Only stir, stand, suspension is layered quickly, extracts the supernatant, and precipitate hexane is washed after twice, by hexane by its turn
Move in chromatography funnel, dried up with high pure nitrogen, obtain the solid spherical catalytic component of good fluidity, narrow diameter distribution.Urge
Agent composition is shown in Table 1.
（2）Polyreaction：With embodiment 1, polymerization result is shown in Table 2.
（3）Gas phase polymerization：With embodiment 1, polymerization result is shown in Table 3.
1 catalyst of table is constituted
2 polymer performance of table
From the data of table 1 can be seen that the present invention catalyst compare with comparative example 1, Ti content decreases, illustrate to
After electron compound is introduced, catalyst Ti content can be caused moderately to reduce, be that the steady activity of control catalyst provides the foundation.
Though the polymerization catalyst activity that the present invention is can be seen that from the data of table 2 is slightly reduced, can still meet gas phase
Polymerization is for the requirement of catalyst activity, and the bulk density of polymer powders is increased substantially.It is from terms of powder screening result, real
Apply the fine powder content in the polymer powders in example（The summation of three afterwards）Less than the result in comparative example.
3 gas-phase polymerization properties of powder of table
Can be seen that under bubble agitation kettle polymerizing condition from the data of table 3, in embodiment, the activity of catalyst is higher than
The catalyst of comparative example, main cause are that the catalyst breakage of comparative example is serious, and polymerization activity is affected；And from screening result
As can be seen that data of the fine powder content of polymer that obtains of embodiment well below comparative example.
Claims (10)
1. a kind of catalytic component for ethylene polymerization, the catalytic component include the product of following component：
(1) magnesium alcoholate；
(2) titanium compound；
(3) sulfur alcohol compound；
(4) bis-epoxy base class compound；
(5) monocyclic epoxide class compound；
It is MgCl that magnesium alcoholate described in component (1) is formula2-mR1The chlorination magnesium alcoholate of OH, wherein R1For C1～C4Alkyl, m
For 1.0～4.0；
The formula of the titanium compound described in component (2) is Ti (OR2)nX4-n, R in formula2For C1～C8Alkyl, X is halogen atom, 0
≤n≤4；
The formula of the sulfur alcohol compound described in component (3) is HS (R3) SH, R in formula3For C3～C18Aryl or aliphatic hydrocarbon
Base；
Bis-epoxy base class compound described in component (4) selected from formula isCompound orR5For the alkyl that carbon number is 4～18；
The formula of the monocyclic epoxide class compound described in component (5) isWherein R4It is 1～4 for carbon number
Alkyl, X is halogen atom, 0≤m≤3.
2. a kind of catalytic component for ethylene polymerization according to claim 1, it is characterised in that each reactant
Between ratio in terms of every mole of magnesium in component (1) chlorination magnesium alcoholate, component (2) titanium compound be 0.5～15.0 mole,
Component (3) sulfur alcohol compound is 0.5～5.0 mole, the epoxy-functional sum and component (3) in component (4) and component (5)
Middle thiol functionalities sum is identical, and it is 1%～50% that wherein monocyclic epoxide class compound accounts for the ratio of total epoxy base class compound
(mole).
3. a kind of catalytic component for ethylene polymerization according to claim 1, it is characterised in that described sulfur
Alcohol compound is distant claw type dithiol.
4. a kind of catalytic component for ethylene polymerization according to claim 3, it is characterised in that described sulfur
Alcohol compound be pungent two mercaptan of 1,8-, two mercaptan of the 1,10- last of the ten Heavenly stems, α, ω -18 carbon mercaptan andIn
At least one.
5. a kind of catalytic component for ethylene polymerization according to claim 1, it is characterised in that the component
(4) bis-epoxy base class compound includes
6. a kind of catalytic component for ethylene polymerization according to claim 1, it is characterised in that the component
(5) monocyclic epoxide class compound is epoxychloropropane, the one kind in epoxy butane.
7. the preparation method of the catalytic component for ethylene polymerization according to one of claim 1-6, including with
Lower step：
(1) the chlorination magnesium alcoholate described in component (1) is dispersed in saturated fat hydro carbons atent solvent, obtains suspension；
(2) by suspension in -20～50 DEG C and component (2) titanium compound, component (3) sulfur alcohol compound, component (4) bis-epoxy
Base class compound, the monocyclic epoxide class compound of component (5) carry out haptoreaction；And mixture is to slowly warm up to into 20～60 DEG C,
After the reaction regular hour, unreacted reactant and solvent is removed, and is washed using inert diluent；
(3) add component (2) titanium compound to be reacted, then washed using inert diluent, obtain the catalyst of the present invention
Component.
8. a kind of catalyst for ethylene polymerization, which includes the product of following components：
(1) catalytic component described in one of claim 16；
(2) formula is AlR 'dX3-dOrgano-aluminum compound, in formula R ' be hydrogen or carbon number for l～20 alkyl, X is halogen
Atom, 0<d≤3.
9. the catalyst for ethylene polymerization according to claim 8, it is characterised in that the aluminum in component (2) with
In component (1), the mol ratio of titanium is 20～200.
10. catalyst described in claim 8 closes the application in reaction or copolymerization in ethylene homo.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101139407A (en) * | 2006-09-07 | 2008-03-12 | 北京金鼎科化工科技有限公司 | Catalyst active component for ethylene polymerization or copolymerization and catalyst precursor comprising the active component and preparation method thereof |
| CN102807634A (en) * | 2011-06-03 | 2012-12-05 | 中国石油化工股份有限公司 | Catalyst component for vinyl polymerization reaction and catalyst of catalyst component |
| CN103087224A (en) * | 2011-10-28 | 2013-05-08 | 中国石油化工股份有限公司 | Catalyst ingredient used for ethylene polymerization, and preparation method thereof |
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| JPS56152808A (en) * | 1980-04-23 | 1981-11-26 | Denki Kagaku Kogyo Kk | Catalyst component for olefin polymerization |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101139407A (en) * | 2006-09-07 | 2008-03-12 | 北京金鼎科化工科技有限公司 | Catalyst active component for ethylene polymerization or copolymerization and catalyst precursor comprising the active component and preparation method thereof |
| CN102807634A (en) * | 2011-06-03 | 2012-12-05 | 中国石油化工股份有限公司 | Catalyst component for vinyl polymerization reaction and catalyst of catalyst component |
| CN103087224A (en) * | 2011-10-28 | 2013-05-08 | 中国石油化工股份有限公司 | Catalyst ingredient used for ethylene polymerization, and preparation method thereof |
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