CN104974280A - 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 for vinyl polymerization or the catalyst component of copolymerization, the preparation method of this catalyst component and its catalyzer.More particularly, relate to and a kind ofly in preparation process, introduce the catalyst component of high reactivity end group, the preparation method of this catalyst component and its catalyzer.
Background technology
The Ziegler-Natta type vinyl polymerization spherical catalyst prepared by magnesium chloride ethanolic vehicle is existing to be studied more widely, and this catalyzer is widely used in ethene (being total to) poly-unit operated with liquid phase or carry out with gas phase.But the use of catalyst component itself is not entirely satisfactory.In fact, due to the hyperergy of ethene, the heat release of polyreaction is very high.Therefore, bear very strong tension force at the starting stage catalyzer of polymerization, this tension force makes catalyzer itself that uncontrolled breaking occur, and this situation is the reason that polymer fine particles is formed.The formation of polymer fine particles directly causes the low bulk density of polymkeric substance and the difficulty of operating process.For addressing these problems, company of Basel has carried out large quantity research.CN1400979A discloses a kind of catalyst component prepared for ethene (being total to) polymkeric substance, this catalyst component can produce the polymkeric substance with high bulk density, the problem that fine powder can be avoided to be formed and there is high reactivity, this catalyst component contains non-cubic selects ingredient of solid catalyst, it contains titanium compound and magnesium dihalide, and it is and alpha-olefin CH
2=CHR
iprepolymerized, wherein R is C1-C8 alkyl, and prepolymerized degree makes for every gram of this ingredient of solid catalyst, and the amount of alpha-olefin prepolymer mostly is 100 grams most, but this method complicated process of preparation.CN101137677A discloses a kind of catalyst component for polymerization of ethylene, described catalyst component comprises Ti, Mg, halogen and as 1 of internal electron donor compound, 2-glycol dimethyl ether, this catalyzer is applicable to (being total to) polymerization technique of ethene, to make (being total to) polymkeric substance with narrow molecular weight distributions (MWD) and high-bulk-density, but it is easily broken that this method does not still solve catalyzer in gas-phase polymerization process, the problem that fine polymer powder is more.
Summary of the invention
The technical problem to be solved in the present invention is to provide a kind of catalyst component for vinyl polymerization and catalyzer thereof, and this catalyzer has the polymerization activity being suitable for ethene gas-phase polymerization technique, and the tap density of resulting polymers is high, and fine powder content is lower.
An object of the present invention is to provide a kind of catalyst component for ethylene polymerization, and this catalyst component comprises the reaction product of following component:
(1) magnesium alcoholate;
(2) titanium compound;
(3) sulfur alcohol compound;
(4) bis-epoxy base class compound;
(5) monocycle oxygen base class compound;
Magnesium alcoholate described in component (1) is general formula is MgCl
2-mR
1the magnesium chloride alcohol adduct of OH, wherein R
1for C
1~ C
4alkyl, m is 1.0 ~ 4.0;
The general formula of the titanium compound described in component (2) is Ti (OR
2)
nx
4-n, R in formula
2for C
1~ C
8alkyl, X is halogen atom, 0≤n≤4;
The general formula of the sulfur alcohol compound described in component (3) is HS (R
3) SH, R in formula
3for C
3~ C
18aryl or aliphatic alkyl;
The general formula of the bis-epoxy base class compound described in component (4) is
r
5for alkyl or aryl that carbonatoms is 4 ~ 18;
The general formula of the monocycle oxygen base class compound described in component (5) is
wherein R
4for carbonatoms is the alkyl of 1 ~ 4, X is halogen atom, 0≤m≤3.
Specifically, the general formula described in component (1) is MgCl
2-mR
1the magnesium chloride alcohol adduct of OH is by C
1~ C
4low-carbon alcohol mix for 2.5:1 ~ 4:1 in molar ratio with magnesium chloride, cool rapidly after heating and melting, obtain the spheroidal particle containing 2.0 ~ 4.0 moles of alcohol per mole magnesium chlorides.This patent adopts the magnesium chloride alcohol adduct of non-dealcoholysis.Preferable range is at 2.5 ~ 3.0 moles of alcohol per mole magnesium chlorides.Above-mentioned magnesium chloride alcohol adduct is disclosed in Chinese patent CN93102795.0, and associated viscera disclosed in it all introduces the present invention as a reference.
Titanium compound general formula described in component (2) is Ti (OR
2)
nx
4-n, R in formula
2for C
1~ C
8alkyl, X is halogen atom, and 0≤n≤4, comprising: TiCl
4, TiBr
4, TiI
4, Ti (OC
2h
5) Cl
3, Ti (OCH
3) Cl
3, Ti (OC
4h
9) Cl
3, Ti (OC
2h
5) Br
3, Ti (OC
2h
5)
2cl
2, Ti (OCH
3)
2cl
2, Ti (OCH
3)
2i
2, Ti (OC
2h
5)
3cl, Ti (OCH
3)
3cl, Ti (OC
2h
5)
3i, Ti (OC
2h
5)
4, Ti (OC
3h
7)
4, Ti (OC
4h
9)
4deng.Preferred TiCl
4, Ti (OC
2h
5) Cl
3, Ti (OCH
3) Cl
3, Ti (OC
4h
9) Cl
3, Ti (OC
4h
9)
4.With TiCl
4for the best.
The general formula of the sulfur alcohol compound described in component (3) is HS (R
3) SH, R in formula
3for C
3~ C
18aryl or aliphatic alkyl.It is characterized in that described sulfur alcohol compound is distant claw type dithiol, be specially 1,6-ethanthiol, 1,8-pungent two mercaptan, Isosorbide-5-Nitrae-succinimide mercaptans, 1,10-the last of the ten Heavenly stems two mercaptan, α, ω-18 carbon mercaptan, Isosorbide-5-Nitrae-p-Xylol mercaptan,
in at least one, preferably 1,8-pungent two mercaptan, 1,10-the last of the ten Heavenly stems two mercaptan, α, ω-18 carbon mercaptan and
these mercaptan compounds both can be used alone, and also can be used in combination.
The bis-epoxy base class compound of component (4) is
in one, wherein preferably
The monocycle oxygen base class compound of component (5) is the one in epoxy chloropropane, butylene oxide ring, wherein preferred epoxy chloropropane.
Of the present invention in the catalyst component of vinyl polymerization, ratio between each reactant is in every mole of magnesium in component (1) magnesium chloride alcohol adduct, component (2) titanium compound is 0.5 ~ 15.0 mole, component (3) sulfur alcohol compound is 0.5 ~ 5.0 mole, component (4) is identical with thiol functionalities sum in component (3) with the epoxy-functional sum in component (5), wherein monocycle oxygen base class compound accounts for the ratio of total epoxy group(ing) compounds is 1% ~ 50%(mole), preferred proportion is 10% ~ 40%(mole).
Present invention also offers a kind of preparation method of the catalyst component for ethylene polymerization, comprise the steps: the magnesium alcoholate described in component (1) to be dispersed in inert solvent, obtain suspension.Dispersion medium comprises: Trimethylmethane, hexane, heptane, hexanaphthene, petroleum naphtha, raffinate oil, the saturated fatty hydro carbons inert solvent such as hydrogenated gasoline, kerosene.Suspension is carried out contact reacts in-20 DEG C ~ 30 DEG C with component (2) titanium compound, component (3) sulfur alcohol compound, component (4) bis-epoxy base class compound and component (5) monocycle oxygen base class compound, and mixture is slowly warming up to 20 ~ 60 DEG C, after the reaction regular hour, removing unreacted reactant and solvent, and adopt inert diluent to wash, and then introduce component (2) titanium compound and react, then through inert diluent washing, namely obtain catalyst component of the present invention.
Another object of the present invention there is provided a kind of spherical catalyst for vinyl polymerization, and it comprises the reaction product of following component:
(1) catalyst component of the invention described above;
(2) promotor is general formula is AlR '
dx
3-dorgano-aluminium compound, in formula R ' for hydrogen or carbonatoms be the alkyl of l ~ 20, X is halogen atom, 0<d≤3.
Promotor is general formula is AlR '
dx
3-dorgano-aluminium compound, in formula, R ' can be the alkyl of l ~ 20 for hydrogen or carbonatoms, particularly alkyl, aralkyl, aryl; X is halogen atom, particularly chlorine and bromine; 0<d≤3.Particular compound is as Al (CH
3)
3, Al (CH
2cH
3)
3, Al (i-Bu)
3, AlH (CH
2cH
3)
2, AlH (i-Bu)
2, AlCl (CH
2cH
3)
2, Al
2cl
3(CH
2cH
3)
3, AlCl (CH
2cH
3)
2, AlCl
2(CH
2cH
3) etc. alkylaluminium cpd.Be preferably Al (CH
2cH
3)
3, Al (i-Bu)
3.Wherein the mol ratio of the aluminium in promotor and the titanium in catalyst component is 5 ~ 500, preferably 20 ~ 200.
Can liquid polymerization be adopted during polymerization, also can adopt vapour phase polymerization.
During liquid polymerization, medium comprises: Trimethylmethane, hexane, heptane, hexanaphthene, petroleum naphtha, raffinate oil, the inert solvent such as aliphatic saturated hydrocarbon or aromatic hydrocarbon such as hydrogenated gasoline, kerosene, benzene,toluene,xylene.
During vapour phase polymerization, adopt withstand voltage reactor, NaCl mixes a bed medium.
In order to regulate the molecular weight of final polymkeric substance, hydrogen is adopted to make molecular weight regulator.
The present inventor finds to add sulfur alcohol compound and epoxy compounds in the preparation process of the catalyst component for ethylene polymerization, gained polyethylene powder not only can be made to have high-bulk-density, and catalyzer almost fragmentation does not occur in the course of the polymerization process, fine polymer powder is few.Do not use aluminum alkyls in this this catalyst component preparation process external, titanium compound consumption is also less, and thus this catalyst component preparation technology is simple, and three waste discharge is few, and cost is low.
Embodiment
Testing method:
1. the relative weight percents of titanium/magnesium elements in catalyst system: adopt spectrophotometry;
2. the relative weight percents of ester in catalyst system: adopt high performance liquid chromatography and liquid nuclear-magnetism hydrogen spectrometry;
3. the mensuration of polymer bulk density: adopt ASTM D1895 plastics apparent density, the test method of bulkfactor and pouring into property measures;
4. the mensuration of polymer particle size distribution: adopt standard sieve to sieve.
Following examples describe the present invention's citing specifically, but the present invention is not limited to these embodiments.
Embodiment 1
In the reactor that high pure nitrogen is fully transposed, add 6.0g ball type carrier MgCl successively
22.6C
2h
5oH, hexanaphthene 150ml, stir borehole cooling to 0 DEG C, drips 12ml TiCl
4, be warming up to 50 DEG C, stirring reaction 1 hour, is then cooled to 30 DEG C, adds 3.6g1 successively, pungent two mercaptan of 8-, epoxy compounds (e) 1.95g and 0.4ml epoxy chloropropane, and maintains reaction 2 hours.Stop stirring, leave standstill, the very fast layering of suspension, extracts supernatant liquid, and throw out hexanaphthene is room temperature washing twice.Add 150ml hexane, this system is cooled to 0 DEG C, slowly drip titanium tetrachloride 4ml, be warming up to 60 DEG C afterwards, react 2 hours.Stop stirring, leave standstill, the very fast layering of suspension, extracts supernatant liquid, and throw out, with after hexanes wash twice, is transferred them in chromatography funnel by hexane, dries up with high pure nitrogen, obtains the solid spherical catalyst component of good fluidity, narrow diameter distribution.Catalyzer composition is in table 1.
(2) vinyl polymerization
Volume is the stainless steel cauldron of 2L, after high pure nitrogen is fully replaced, add 1L hexane and 1.0ml concentration is the triethyl aluminum of 1M, be added with solid catalyst (about containing 0.3 milligram of titanium) prepared by aforesaid method again, be warming up to 75 DEG C, pass into hydrogen and make still internal pressure reach 0.28Mpa, then pass into ethene and make stagnation pressure in still reach 1.03Mpa(gauge pressure), be polymerized 2 hours under 85 DEG C of conditions, polymerization result is in table 2.
(3) gas phase polymerization
Volume is the stainless steel autoclave of 1L, add 500g salt, vacuum pump drainage, nitrogen replacement, be the triethyl aluminum of 1M by hexane by 2.0ml concentration, and introduce reactor by ingredient of solid catalyst (containing 2 milligrams of titaniums) prepared by aforesaid method, be warming up to 75 DEG C, nitrogen purging, evaporates blowout system completely by hexane, is then cooled to 70 DEG C, pass into hydrogen and the ethene of setting pressure ratio simultaneously, still internal pressure is made to reach 1.03Mpa(gauge pressure), be polymerized 2 hours under 70 DEG C of conditions, polymerization result is in table 3.
Embodiment 2
(1) preparation of catalyst component
In the reactor that high pure nitrogen is fully transposed, add 6.0g ball type carrier MgCl successively
22.6C
2h
5oH, hexanaphthene 150ml, stir borehole cooling to-10 DEG C, drip 6ml TiCl
4, be warming up to 50 DEG C, stirring reaction 1 hour, is cooled to 25 DEG C, then adds 4.7g1 successively, 6-ethanthiol, epoxy compounds (e) 2.6g and 0.6ml epoxy chloropropane, and maintains reaction 2 hours.Stop stirring, leave standstill, the very fast layering of suspension, extracts supernatant liquid, and throw out hexanaphthene is room temperature washing twice.Add 150ml hexanaphthene, this system is cooled to 0 DEG C, slowly drip titanium tetrachloride 4ml, be warming up to 60 DEG C afterwards, react 2 hours.Stop stirring, leave standstill, the very fast layering of suspension, extracts supernatant liquid, and throw out, with after hexanes wash twice, is transferred them in chromatography funnel by hexane, dries up with high pure nitrogen, obtains the solid spherical catalyst component of good fluidity, narrow diameter distribution.Catalyzer composition is in table 1.
(2) polyreaction: with embodiment 1, polymerization result is in table 2.
(3) gas phase polymerization: with embodiment 1, polymerization result is in table 3.
Embodiment 3
(1) preparation of catalyst component
In the reactor that high pure nitrogen is fully transposed, add 36.0g ball type carrier MgCl successively
22.6C
2h
5oH, hexanaphthene 750ml, stir borehole cooling to 0 DEG C, drips 60ml TiCl
4, be warming up to 60 DEG C, stirring reaction 1.5 hours, is then cooled to 30 DEG C, adds 36g α successively, ω-18 carbon mercaptan, 21g epoxy compounds (d) and 1.6ml epoxy chloropropane, and maintains reaction 3 hours.Stop stirring, leave standstill, the very fast layering of suspension, extracts supernatant liquid, and throw out hexanaphthene is room temperature washing twice.Add 750ml hexane, this system is cooled to 0 DEG C, slowly drip titanium tetrachloride 24ml, be warming up to 60 DEG C afterwards, react 2 hours.Stop stirring, leave standstill, the very fast layering of suspension, extracts supernatant liquid, and throw out, with after hexanes wash twice, is transferred them in chromatography funnel by hexane, dries up with high pure nitrogen, obtains the solid spherical catalyst component of good fluidity, narrow diameter distribution.Catalyzer composition is in table 1.
(2) polyreaction: with embodiment 1, polymerization result is in table 2.
(3) gas phase polymerization: with embodiment 1, polymerization result is in table 3.
Embodiment 4
(1) preparation of catalyst component
In the reactor that high pure nitrogen is fully transposed, add 6.0g ball type carrier MgCl successively
22.6C
2h
5oH, hexanaphthene 150ml, stir borehole cooling to-5 DEG C, drip 8mlTiCl
4, be warming up to 50 DEG C, stirring reaction 1 hour, is then cooled to 20 DEG C, adds 4.0g1 successively, 10-mercaptan in the last of the ten Heavenly stems two, epoxy compounds (a) 3.0g and 0.6ml epoxy chloropropane, maintains reaction 2 hours.Stop stirring, leave standstill, the very fast layering of suspension, extracts supernatant liquid, and throw out hexanaphthene is room temperature washing twice.Add 150ml hexane, this system is cooled to 0 DEG C, slowly drip titanium tetrachloride 4ml, be warming up to 60 DEG C afterwards, react 2 hours.Stop stirring, leave standstill, the very fast layering of suspension, extracts supernatant liquid, and throw out, with after hexanes wash twice, is transferred them in chromatography funnel by hexane, dries up with high pure nitrogen, obtains the solid spherical catalyst component of good fluidity, narrow diameter distribution.Catalyzer composition is in table 1.
(2) polyreaction: with embodiment 1, polymerization result is in table 2.
(3) gas phase polymerization: with embodiment 1, polymerization result is in table 3.
Embodiment 5
(1) preparation of catalyst component
In the reactor that high pure nitrogen is fully transposed, add 6.0g ball type carrier MgCl successively
22.6C
2h
5oH, hexanaphthene 150ml, stir borehole cooling to 0 DEG C, drips 7ml TiCl
4, be warming up to 50 DEG C, stirring reaction 1 hour, is then cooled to 30 DEG C, add successively 4.0g mercaptan compound (i), epoxy compounds (a) 3.0g and 0.6ml epoxy chloropropane, and maintain reaction 2 hours.Stop stirring, leave standstill, the very fast layering of suspension, extracts supernatant liquid, and throw out hexanaphthene is room temperature washing twice.Add 150ml hexane, this system is cooled to 0 DEG C, slowly drip titanium tetrachloride 4ml, be warming up to 60 DEG C afterwards, react 2 hours.Stop stirring, leave standstill, the very fast layering of suspension, extracts supernatant liquid, and throw out, with after hexanes wash twice, is transferred them in chromatography funnel by hexane, dries up with high pure nitrogen, obtains the solid spherical catalyst component of good fluidity, narrow diameter distribution.Catalyzer composition is in table 1.
(2) polyreaction: with embodiment 1, polymerization result is in table 2.
Embodiment 6
(1) preparation of catalyst component
In the reactor that high pure nitrogen is fully transposed, add 36.0g ball type carrier MgCl successively
22.0C
2h
5oH, hexanaphthene 720ml, stir borehole cooling to 0 DEG C, drips 36ml TiCl
4, be warming up to 50 DEG C, stirring reaction 1 hour, is then cooled to 25 DEG C, add successively 24.0g mercaptan compound (i), epoxy compounds (a) 18.0g and 3.5ml epoxy chloropropane, and maintain reaction 2 hours.Stop stirring, leave standstill, the very fast layering of suspension, extracts supernatant liquid, and throw out hexanaphthene is room temperature washing twice.Add 750ml hexane, this system is cooled to 0 DEG C, slowly drip titanium tetrachloride 24ml, be warming up to 60 DEG C afterwards, react 2 hours.Stop stirring, leave standstill, the very fast layering of suspension, extracts supernatant liquid, and throw out, with after hexanes wash twice, is transferred them in chromatography funnel by hexane, dries up with high pure nitrogen, obtains the solid spherical catalyst component of good fluidity, narrow diameter distribution.Catalyzer composition is in table 1.
(2) polyreaction: with embodiment 1, polymerization result is in table 2.
(3) gas phase polymerization: with embodiment 1, polymerization result is in table 3.
Comparative example 1
(1) preparation of catalyst component
In the reactor that high pure nitrogen is fully transposed, add 6.0g ball type carrier MgCl successively
22.6C
2h
5oH, hexanaphthene 150ml, stir borehole cooling to 0 DEG C, drips 8ml TiCl successively
4, be warming up to 50 DEG C, and maintain reaction 2 hours.Stop stirring, leave standstill, the very fast layering of suspension, extracts supernatant liquid, and throw out hexanaphthene is room temperature washing twice.Add 150ml hexane, this system is cooled to 0 DEG C, slowly drip titanium tetrachloride 4ml, be warming up to 60 DEG C afterwards, react 2 hours.Stop stirring, leave standstill, the very fast layering of suspension, extracts supernatant liquid, and throw out, with after hexanes wash twice, is transferred them in chromatography funnel by hexane, dries up with high pure nitrogen, obtains the solid spherical catalyst component of good fluidity, narrow diameter distribution.Catalyzer composition is in table 1.
(2) polyreaction: with embodiment 1, polymerization result is in table 2.
(3) gas phase polymerization: with embodiment 1, polymerization result is in table 3.
Comparative example 2
(1) preparation of catalyst component
In the reactor that high pure nitrogen is fully transposed, add 6.0g ball type carrier MgCl successively
22.6C
2h
5oH, hexanaphthene 150ml, stir borehole cooling to-10 DEG C, drip 6ml TiCl
4, be warming up to 50 DEG C, stirring reaction 1 hour, is cooled to 25 DEG C, then adds 4.7g1 successively, 6-ethanthiol, epoxy compounds (e) 2.8g, and maintains reaction to 1 hour, and system is solidified, and reacts unsuccessfully, can not obtain the catalyzer that can examine.
Comparative example 3
(1) preparation of catalyst component
In the reactor that high pure nitrogen is fully transposed, add 6.0g ball type carrier MgCl successively
22.6C
2h
5oH, hexanaphthene 150ml, stir borehole cooling to-10 DEG C, drip 6ml TiCl
4, be warming up to 50 DEG C, stirring reaction 1 hour, is cooled to 25 DEG C, then adds 4.7g1 successively, 6-ethanthiol, epoxy chloropropane 1.0ml, and maintains reaction to 2 hours.Stop stirring, leave standstill, the very fast layering of suspension, extracts supernatant liquid, and throw out hexanaphthene is room temperature washing twice.Add 150ml hexane, this system is cooled to 0 DEG C, slowly drip titanium tetrachloride 4ml, be warming up to 60 DEG C afterwards, react 2 hours.Stop stirring, leave standstill, the very fast layering of suspension, extracts supernatant liquid, and throw out, with after hexanes wash twice, is transferred them in chromatography funnel by hexane, dries up with high pure nitrogen, obtains the solid spherical catalyst component of good fluidity, narrow diameter distribution.Catalyzer composition is in table 1.
(2) polyreaction: with embodiment 1, polymerization result is in table 2.
(3) gas phase polymerization: with embodiment 1, polymerization result is in table 3.
Table 1 catalyzer forms
Table 2 polymer performance
As can be seen from the data of table 1, catalyzer of the present invention contrasts with comparative example 1, and titanium content decreases, and after illustrating that electron donor compound is introduced, catalyst Ti content appropriateness being caused to reduce, providing the foundation for controlling the steady activity of catalyzer.
As can be seen from the data of table 2, though polymerization catalyst of the present invention activity slightly reduces, still can meet the requirement of vapour phase polymerization for catalyst activity, and the tap density of polymer powders increases substantially.From powder screening result, the fine powder content (summations of latter three) in the polymer powders in embodiment is lower than the result in comparative example.
Table 3 vapour phase polymerization properties of powder
As can be seen from the data of table 3, under bubble agitation still polymerizing condition, in embodiment, the activity of catalyzer is higher than the catalyzer of comparative example, and major cause is that the catalyst breakage of comparative example is serious, and polymerization activity is affected; And as can be seen from screening result, the fine powder content of the polymkeric substance that embodiment obtains is well below the data of comparative example.
Claims (10)
1., for a catalyst component for ethylene polymerization, this catalyst component comprises the reaction product of following component:
(1) magnesium alcoholate;
(2) titanium compound;
(3) sulfur alcohol compound;
(4) bis-epoxy base class compound;
(5) monocycle oxygen base class compound;
Magnesium alcoholate described in component (1) is general formula is MgCl
2-mR
1the magnesium chloride alcohol adduct of OH, wherein R
1for C
1~ C
4alkyl, m is 1.0 ~ 4.0;
The general formula of the titanium compound described in component (2) is Ti (OR
2)
nx
4-n, R in formula
2for C
1~ C
8alkyl, X is halogen atom, 0≤n≤4;
The general formula of the sulfur alcohol compound described in component (3) is HS (R
3) SH, R in formula
3for C
3~ C
18aryl or aliphatic alkyl;
The general formula of the bis-epoxy base class compound described in component (4) is
r
5for alkyl or aryl that carbonatoms is 4 ~ 18;
The general formula of the monocycle oxygen base class compound described in component (5) is
wherein R
4for carbonatoms is the alkyl of 1 ~ 4, X is halogen atom, 0≤m≤3.
2. a kind of catalyst component for ethylene polymerization according to claim 1, it is characterized in that ratio between each reactant is in every mole of magnesium in component (1) magnesium chloride alcohol adduct, component (2) titanium compound is 0.5 ~ 15.0 mole, component (3) sulfur alcohol compound is 0.5 ~ 5.0 mole, component (4) is identical with thiol functionalities sum in component (3) with the epoxy-functional sum in component (5), and wherein monocycle oxygen base class compound accounts for the ratio of total epoxy group(ing) compounds is 1% ~ 50%(mole).
3. a kind of catalyst component for ethylene polymerization according to claim 1, is characterized in that described sulfur alcohol compound is distant claw type dithiol.
4. a kind of catalyst component for ethylene polymerization according to claim 3, it is characterized in that described sulfur alcohol compound be pungent two mercaptan of 1,8-, 1,10-the last of the ten Heavenly stems two mercaptan, α, ω-18 carbon mercaptan and
in at least one.
5. a kind of catalyst component for ethylene polymerization according to claim 1, is characterized in that the bis-epoxy base class compound of described component (4) comprises
6. a kind of catalyst component for ethylene polymerization according to claim 1, is characterized in that the monocycle oxygen base class compound of described component (5) is the one in epoxy chloropropane, butylene oxide ring.
7., according to the preparation method of the catalyst component for ethylene polymerization one of claim 1-6 Suo Shu, comprise the following steps:
(1) the magnesium chloride alcohol adduct described in component (1) is dispersed in saturated fatty hydro carbons inert solvent, obtains suspension;
(2) suspension is carried out contact reacts in-20 ~ 50 DEG C with component (4) organo-aluminium compound, component (3) sulfur alcohol compound, component (4) bis-epoxy base class compound, component (5) monocycle oxygen base class compound; And mixture is slowly warming up to 20 ~ 60 DEG C, and after the reaction regular hour, removing unreacted reactant and solvent, and adopt inert diluent to wash;
(3) add component (2) titanium compound to react, then adopt inert diluent washing, obtain catalyst component of the present invention.
8., for a catalyzer for ethylene polymerization, it comprises the reaction product of following component:
(1) catalyst component that one of claim 1-6 is described;
(2) general formula is AlR '
dx
3-dorgano-aluminium compound, in formula R ' for hydrogen or carbonatoms be the alkyl of l ~ 20, X is halogen atom, 0<d≤3.
9. the catalyzer for ethylene polymerization according to claim 8, is characterized in that the mol ratio of titanium in aluminium in component (2) and component (1) is 20 ~ 200.
10. catalyzer described in claim 8 closes the application in reaction or copolymerization at ethylene homo.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111072805A (en) * | 2018-10-19 | 2020-04-28 | 中国石油化工股份有限公司 | Catalyst component and catalyst for olefin polymerization, application thereof and olefin polymerization method |
| EP3868794A4 (en) * | 2018-10-19 | 2022-08-17 | China Petroleum & Chemical Corporation | Carrier for alkene polymerization catalyst, and preparation method therefor and application thereof |
| RU2804799C2 (en) * | 2018-10-19 | 2023-10-05 | Чайна Петролеум Энд Кемикл Корпорейшн | Support for catalyst intended for olefin polymerization and method for its production and its application |
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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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| 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 |
| 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 |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN111072805A (en) * | 2018-10-19 | 2020-04-28 | 中国石油化工股份有限公司 | Catalyst component and catalyst for olefin polymerization, application thereof and olefin polymerization method |
| EP3868794A4 (en) * | 2018-10-19 | 2022-08-17 | China Petroleum & Chemical Corporation | Carrier for alkene polymerization catalyst, and preparation method therefor and application thereof |
| RU2804799C2 (en) * | 2018-10-19 | 2023-10-05 | Чайна Петролеум Энд Кемикл Корпорейшн | Support for catalyst intended for olefin polymerization and method for its production and its application |
| TWI832912B (en) * | 2018-10-19 | 2024-02-21 | 大陸商中國石油化工科技開發有限公司 | Carrier for olefin polymerization catalyst and preparation method and application thereof |
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| Publication number | Publication date |
|---|---|
| CN104974280B (en) | 2017-03-22 |
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