CN103772555A - Ingredients of catalyst for vinyl polymerization and catalyst - Google Patents
Ingredients of catalyst for vinyl polymerization and catalyst Download PDFInfo
- Publication number
- CN103772555A CN103772555A CN201210413209.1A CN201210413209A CN103772555A CN 103772555 A CN103772555 A CN 103772555A CN 201210413209 A CN201210413209 A CN 201210413209A CN 103772555 A CN103772555 A CN 103772555A
- Authority
- CN
- China
- Prior art keywords
- polymerization
- catalyst component
- compound
- sulfonate
- ethylene
- 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.)
- Pending
Links
Landscapes
- Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
Abstract
The invention relates to ingredients of a catalyst for vinyl polymerization. The ingredients comprise the following reaction products: (1) a magnesium compound, (2) an organic alcoholic compound, (3) an organic silicon compound, (4) a sulphonate, and (5) a titanium compound, wherein the structural formula of the sulphonate is X-SO3M; X is alkyl; M is an alkali metal. The catalyst is higher in catalytic activity and hydrogen regulation sensitivity; a polymer obtained by adopting the catalyst is high in bulk density and small in size distribution; the catalyst is suitable for homopolymerization of ethylene or copolymerization between ethylene and other Alpha-alkene.
Description
Technical field
The present invention relates to a kind of catalyst component for vinyl polymerization or copolymerization and preparation method thereof and the catalyzer containing this catalyst component.More particularly, relate to a kind of catalyst component that adds sulfonate in preparation process and preparation method thereof and its catalyzer.
Background technology
As everyone knows, tie up to dominate in poly suitability for industrialized production containing the catalyst body of Ti/Mg mixture, its research focus concentrates on particle form and the size distribution etc. of polymerization activity, hydrogen response, copolymerization performance and the catalyzer of catalyzer.And in the slurry polymerization processes of ethene, except requiring catalyzer should have higher catalytic activity, the hydrogen response of catalyzer is most important.Can say, in the slurry polymerization process of ethene, hydrogen response is directly determining the destiny of a catalyzer, its industry has been applied to direct impact, especially in the time producing the high fusion index trade mark that hydrogen response is had relatively high expectations, the hydrogen response that improves polyethylene catalysts just becomes more urgent.Along with the increase of the various raw materials cost such as ethene, the PP Pipe Compound trade mark that each large petrochemical plant commercial city falls over each other to develop high added value is to increase benefit.And the performance requriementss such as the hydrogen response of these PP Pipe Compound trades mark to catalyzer are higher, harsher, petrochemical industry manufacturer even can be in order to improve the above-mentioned performance sacrificial section catalytic activity of catalyzer.
Hydrogen response, its essence is the size of weighing the macromolecular chain transferance that in olefin polymerization process, hydrogen (or hydrogen atom) is risen.In actual research and production, conventionally in catalyzer, introduce various components and improve the hydrogen response of catalyzer.In the slurry polymerization processes of ethene, except requiring catalyzer should have higher catalytic activity and good size distribution, in order to produce Alathon or the multipolymer with better performance, also require catalyzer to there is good hydrogen response, regulate easily the melting index of final polymkeric substance by hydrogen dividing potential drop in polymerization process, to obtain the polyvinyl resin of the different business trades mark.
In Chinese patent CN1229092A, disclose a kind of catalyst component, it is take magnesium chloride as carrier, and titanium tetrachloride is active ingredient, and the preparation method of catalyzer is as follows: first by MgCl
2be dissolved in solvent system, form homogeneous transparent solution, then precipitation additive phthalic anhydride exist and low temperature under with TiCl
4reaction, separates out solid catalyst by slow intensification.The catalyst component making is during for vinyl polymerization, and the catalytic activity of catalyzer is unsatisfactory, and hydrogen response is more undesirable.Meanwhile, in the time of synthetic this catalyzer, need adopt the organism such as phthalic anhydride as precipitation additive to promote separating out of precipitation, and need to add a large amount of titanium tetrachlorides.Therefore not only the existence of acid anhydrides produces adverse influence to catalyzer, and the use of simultaneously a large amount of titanium tetrachlorides, also can cause a large amount of wastes and pollution.
In Chinese patent CN1958620A, it is take magnesium chloride as carrier, and titanium tetrachloride is active ingredient, and the preparation method of catalyzer is as follows: first by MgCl
2be dissolved in solvent system, form homogeneous transparent solution, then precipitation additive silicon ester compound and TiCl at low temperatures
4reactivity, separates out solid catalyst by slow intensification.The catalyst component making is during for vinyl polymerization, the catalytic activity of catalyzer is higher, although its hydrogen response also has clear improvement compared with the catalyzer in Chinese patent CN1229092A, be still difficult to meet completely the demand of some high fusion index PP Pipe Compound trades mark of industrial production.
Therefore, being necessary very much to provide a kind of closes or the catalyzer of copolymerization for ethylene homo, be specially adapted to ethene slurry polymerization processes, its not only catalytic activity higher, there is good hydrogen response, and resulting polymers has narrower size distribution.
Summary of the invention
The technical problem to be solved in the present invention is to provide a kind of catalyst component for polymerization of ethylene and catalyzer thereof, and this solid catalyst has higher catalytic activity, good hydrogen response, and polymkeric substance has narrower size distribution.
A kind of catalyst component for polymerization of ethylene, comprises the reaction product of following component:
(1) magnesium mixture
(2) organic alcohol compound
(3) silicoorganic compound
(4) sulfonate
(5) titanium compound
Wherein said magnesium mixture is that magnesium halide is dissolved in to the product obtaining in the solvent system of organic epoxy compounds and organo phosphorous compounds;
Described organic alcohol compound is that carbonatoms is the alcohol of 1～10 straight chain, side chain or cycloalkyl, the alcohol that contains aryl or the halohydrin that carbonatoms is 6～20; It is R that described silicoorganic compound are selected from general formula
1 xr
2 ysi (OR
3)
zin at least one, wherein R
1and R
2be respectively carbonatoms and be 1～10 alkyl or halogen, R
3for the carbonatoms alkyl that is 1～10, x, y, z is integer, 0≤x≤2,0≤y≤2,0≤z≤4, and x+y+z=4;
The structural formula of described sulfonate is X-SO
3m, wherein X is alkyl or other group, M is basic metal;
It is Ti (OR) that described titanium compound is selected from general formula
ax
bin at least one, wherein R is C
1～C
14aliphatic group or aryl, X is halogen, a is integer, 0≤a≤4, b is integer, 0≤b≤4, a+b=3 or 4.
Detailed description of the present invention:
The preparation of magnesium mixture: be that magnesium halide is dissolved in to the homogeneous solution that the solvent system of organic epoxy compounds and organo phosphorous compounds composition obtains, the solvent system of indication comprises and uses or do not use inert diluent here.
Above-mentioned magnesium halide comprises a kind of or its mixture in the derivative that one of them halogen atom in the complex compound such as water or alcohol, magnesium dihalide molecular formula of magnesium dihalide, magnesium dihalide replaced by-oxyl or halogen-oxyl, and particular compound is magnesium dichloride, dibrominated magnesium, two magnesium iodides, chlorination phenoxy group magnesium, chlorination isopropoxy magnesium, chlorination butoxy magnesium etc.Wherein take magnesium dichloride as best.
Organic epoxy compounds described in solvent system comprises that carbonatoms is the compounds such as the oxide compound, glycidyl ether, inner ether of 2～8 aliphatics alkene, diolefine, halogenated aliphatic alkene or diolefine.Particular compound is as oxyethane, propylene oxide, butylene oxide ring, epoxy chloropropane, methyl glycidyl ether, diglycidylether, tetrahydrofuran (THF) etc.Wherein, be preferably oxyethane, propylene oxide, epoxy chloropropane, tetrahydrofuran (THF), take tetrahydrofuran (THF), epoxy chloropropane as best.
Organo phosphorous compounds described in solvent system comprises hydrocarbyl carbonate or the halogenation hydrocarbyl carbonate of ortho-phosphoric acid or phosphorous acid.Concrete as: ortho-phosphoric acid trimethyl, ortho-phosphoric acid triethyl, ortho-phosphoric acid tri-n-butyl, triphenyl phosphite, trimethyl phosphite, triethyl-phosphite, tributyl phosphate, triphenyl phosphite, phosphorous acid benzene methyl etc.Wherein be preferably ortho-phosphoric acid trimethyl, ortho-phosphoric acid triethyl and ortho-phosphoric acid tri-n-butyl, ortho-phosphoric acid tri-n-butyl is best.
In order to make dissolving more abundant, in this solvent system, optionally add inert diluent, common this inert diluent comprises arene compounds or alkane derivative, and arene compounds comprises benzene,toluene,xylene, monochloro-benzene, dichlorobenzene, trichloro-benzene, monochlorotoluene and derivative thereof; Alkane comprises a kind of in straight-chain paraffin, branched paraffin or the naphthenic hydrocarbon of 3～20 carbon atoms or their mixture, as butane, and pentane, hexane, hexanaphthene, heptane etc., as long as can using of contributing to that magnesium halide dissolves.Above-mentioned inert diluent can be used alone, also use capable of being combined.
Organic alcohol compound of the present invention comprises that carbonatoms is that alcohol or the carbonatoms of 1～10 straight chain, side chain or cycloalkyl is 6～20 alcohol that contains aryl or halohydrins.The example of alcohol comprises fatty alcohol: methyl alcohol, ethanol, propyl alcohol, Virahol, butanols, isopropylcarbinol, glycerol, hexanol, 2-methyl amyl alcohol, 2-ethyl butanol, n-Heptyl alcohol, n-Octanol, decyl alcohol etc.; Cycloalkanol, as hexalin, methyl-cyclohexanol etc.; Aromatic alcohol, as phenylcarbinol, methylbenzyl alcohol, ɑ-methylbenzyl alcohol, ɑ, ɑ-dimethylphenylcarbinol etc.Preferred alcohol, butanols, 2-Ethylhexyl Alcohol, glycerol.
The compound general formula of titanium of the present invention is Ti (OR)
ax
b, wherein R is C
1～C
14aliphatic group or aryl, X is halogen, a is integer, 0≤a≤4, b is integer, 0≤b≤4, a+b=3 or 4, particular compound comprises: TiCl
4, TiBr
4, TiCl
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)
2l
2, Ti (OC
2h
5)
3cl, Ti (OCH
3)
3cl, Ti (OC
2h
5)
3l, Ti (OC
2h
5)
4, Ti (OC
3h
7)
4, Ti (OC
4h
9)
4deng.Preferably 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.
General formula without reactive hydrogen silicoorganic compound of the present invention is R
1 xr
2 ysi (OR
3)
z, wherein R
1and R
2be respectively carbonatoms and be 1～10 alkyl or halogen, R
3for the carbonatoms alkyl that is 1～10, x, y, z is integer, 0≤x≤2,0≤y≤2,0≤z≤4, and x+y+z=4, particular compound comprises: tetramethoxy-silicane, tetraethoxysilane, tetrapropoxysilane, four butoxy silanes, four (2-ethyl hexyl oxy) silane, ethyl trimethoxy silane, ethyl triethoxysilane, methyltrimethoxy silane, Union carbide A-162, n-propyl triethoxyl silane, n-propyl Trimethoxy silane, decyl Trimethoxy silane, decyl triethoxyl silane, cyclopentyl-trimethoxy-silane, cyclopentyl triethoxyl silane, 2-methylcyclopentyl Trimethoxy silane, 2,3-dimethylcyclopentyl Trimethoxy silane, cyclohexyl trimethoxy silane, cyclohexyltriethyloxysilane, methyltrimethoxy silane, Union carbide A-162, ethyl triethoxysilane, vinyltrimethoxy silane, vinyltriethoxysilane, tertiary butyl triethoxyl silane, normal-butyl Trimethoxy silane, ne-butyltriethoxysilaneand, isobutyl-Trimethoxy silane, isobutyl triethoxy silane, cyclohexyltriethyloxysilane, cyclohexyl trimethoxy silane, phenyltrimethoxysila,e, phenyl triethoxysilane, one chlorine Trimethoxy silane, one chlorine triethoxyl silane, ethyl three isopropoxy silane, vinyl three butoxy silanes, trimethyl phenoxysilane, methyl three allyloxy silane, vinyl nitrilotriacetic base silane, dimethyldimethoxysil,ne, dimethyldiethoxysilane, diisopropyl dimethoxy silane, di-isopropyl diethoxy silane, tertiary butyl methyl dimethoxysilane, tertiary butyl methyldiethoxysilane, tert-pentyl methyldiethoxysilane, dicyclopentyl dimethoxyl silane, two cyclopentyl diethoxy silanes, methylcyclopentyl diethoxy silane, methylcyclopentyl dimethoxy silane, dimethoxydiphenylsilane, phenylbenzene diethoxy silane, aminomethyl phenyl diethoxy silane, aminomethyl phenyl dimethoxy silane, two o-tolyl dimethoxy silane, two o-tolyl diethoxy silanes, tolyl dimethoxy silane between two, tolyl diethoxy silane between two, biconjugate tolyl dimethoxy silane, biconjugate tolyl diethoxy silane, trimethylammonium methoxy silane, trimethylethoxysilane, three cyclopentyl methoxy silane, three cyclopentyl Ethoxysilanes, wherein one or more such as two cyclopentyl-methyl methoxy silane and cyclopentyl dimethyl methyl TMOS are mixed use.Preferably tetramethoxy-silicane, tetraethoxysilane and four butoxy silanes.In the present invention, silicoorganic compound, except using as precipitation additive, should contain the silicoorganic compound of q.s to improve the over-all properties of catalyzer in the solid titanium catalyst component finally obtaining.
The structural formula of sulfonate of the present invention is X-SO
3m, wherein X is alkyl, M is sodium Metal 99.5 or potassium, particular compound is sulfo-succinic acid ethylhexyl sodium, aerosol-OT, alkyl polyoxyethylene ether monomester succinate disodium sulfonate, succsinic acid monooctyl ester sodium sulfonate, n-propylbenzene sodium sulfonate, Sodium dodecylbenzene sulfonate, octadecyl benzene sulfonic acid sodium salt, 2-ethylhexyl benzene sulfonic acid sodium salt, 2-butyl octyl benzene sulfonic acid sodium salt, 1-amyl group heptyl benzene sodium sulfonate, diisooctyl amber sodium sulfonate, dimethyl semi-annular jade pendant sodium succinate, two different certain herbaceous plants with big flowers methyl semi-annular jade pendant sodium succinates.Preferably diisooctyl amber sodium sulfonate and two different certain herbaceous plants with big flowers methyl semi-annular jade pendant sodium succinates.
In catalyst component for polymerization of ethylene of the present invention, the ratio between each reactant is in every mole of magnesium halide, organic epoxy compounds: 0.5～5.0mol, preferably 0.3～4.0mol; Organo phosphorous compounds: 0.1～4.0mol, preferably 1.0～4.0mol; Organic alcohol compound: 0.1～10.0mol, preferably, 0.5～2.0mol; Sulfonate: 1.0～10.0ml, preferably 1.0～5.0ml; Silicoorganic compound: 0.05～1.0 mole, preferably 0.1～0.5mol; Titanium compound: 1.0～15.0 moles, preferably 2.0～5.0mol; .
In the catalyst component obtaining in the present invention, Ti:4.0～8.0wt%, Mg:15.0～20.0wt%, Cl:60.0～70.0wt%, Si:0.2～1.2wt%, OR:4.0～8.5wt%, Al:0～0.6wt%.
The present invention also provides a kind of preparation method of catalyst component for polymerization of ethylene, comprise the steps: that (1) is dissolved in magnesium halide in the solvent system containing organic epoxy compounds and organo phosphorous compounds, in preferred solvent system, add inert diluent, form homogeneous solution, preferably 50～90 ℃ of solvent temperatures; Forming in the process of solution or solution adds alkylol cpd after forming, then add or do not add organo-aluminium compound, the reaction regular hour.(2) at lower temperature, in preferably-40 ℃-20 ℃, above-mentioned solution and titanium compound are carried out to contact reacts, add subsequently without reactive hydrogen silicoorganic compound and tensio-active agent sulfonate, and mixture is slowly warming up to 50～120 ℃, particle is separated out and formed to solids gradually, after the reaction regular hour, remove unreacted reactant and solvent, and adopt inert diluent washing, obtain catalyst component of the present invention.
The present invention also provides a kind of catalyzer for the equal polyreaction of ethene or the copolymerization of ethene and other alpha-olefin, and alpha-olefin wherein comprises propylene, butene-1,4-methylpentene-1, hexene-1, octene-1, vinylbenzene, vinyl toluene etc.; It is AlR with (2) general formula that this catalyzer comprises (1) above-mentioned catalyst component of the present invention
nx
3-nthe reaction product of organo-aluminium compound, in formula, R can be hydrogen, carbonatoms be l～20 alkyl, particularly alkyl, aralkyl, aryl; X is halogen, particularly chlorine and bromine; N is the integer of 0<n≤3.Particular compound is as aluminum alkyl halides such as trimethyl aluminium, triethyl aluminum, triisobutyl aluminium, trioctylaluminum, a hydrogen diethyl aluminum, a hydrogen diisobutyl aluminum, aluminium diethyl monochloride, a chloro-di-isobutyl aluminum, sesquialter ethyl aluminum chloride, ethyl aluminum dichlorides, wherein preferably triethyl aluminum, triisobutyl aluminium.Wherein aluminium is 5～500 with the mol ratio of the middle titanium of component (1) in component (2), preferably 20～200.
When polymerization, can adopt liquid polymerization, also can adopt vapour phase polymerization.
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.
In order to regulate the molecular weight of final polymkeric substance, adopt hydrogen to make molecular weight regulator.
Due to the acting in conjunction without reactive hydrogen silicoorganic compound and tensio-active agent sulfonate, therefore time prepared by catalyst component, separate out easily granules of catalyst, improve tap density, do not need to impel separating out of precipitation with a large amount of titanium tetrachlorides, therefore the add-on of titanium tetrachloride greatly reduces.Simultaneously silicoorganic compound and tensio-active agent sulfonate add the improvement that also contributes to improve the activity of catalyzer and the particle form of catalyzer.In the time that catalyzer is used for vinyl polymerization, show good hydrogen response.
Embodiment
With embodiment, the present invention is described below, but and unrestricted invention scope.
Testing method:
Melting index (MI): measure according to ASTM D1238-99
Embodiment 1
(1) preparation of catalyst component
In the reactor of fully replacing through high pure nitrogen, add successively 6.0g magnesium dichloride, toluene 90ml, epoxy chloropropane 5.0ml, tributyl phosphate 9.0ml, ethanol 6.0ml, under stirring, be warming up to 70 ℃, after solid dissolves the solution that forms homogeneous completely, under 70 ℃ of conditions, react 1 hour.Then this system is cooled to-10 ℃, slowly drips 60ml titanium tetrachloride, then add 4.0ml tetraethoxy and 1.0ml diisooctyl amber sodium sulfonate, react 1 hour.Slowly be warming up to 80 ℃, react 2 hours.Stop stirring, leave standstill, the very fast layering of suspension, extracts the upper strata stillness of night, twice of toluene wash, hexane washing four times, and high pure nitrogen dries up, and obtains the ingredient of solid catalyst of good fluidity, narrow diameter distribution.The composition of catalyst component is in table 1.
(2) vinyl polymerization
Volume is the stainless steel cauldron of 2L, after high pure nitrogen is fully replaced, add hexane 1L, the triethyl aluminum 1.0ml of concentration 1M, adds the ingredient of solid catalyst (containing 0.3 milligram of titanium) of above-mentioned preparation, is warming up to 80 ℃, passing into hydrogen makes still internal pressure reach 0.28Mpa, passing into ethene makes stagnation pressure in still reach 0.73Mpa(gauge pressure again), polymerization 2 hours under 80 ℃ of conditions, polymerization result is in table 2.
Embodiment 2
(1) catalyzer is synthetic with embodiment 1.Tetraethoxy consumption changes 3.0ml into, and diisooctyl amber sodium sulfonate (OT75) consumption changes 2.0ml into.
(2) vinyl polymerization is with embodiment 1.The composition of catalyst component and polymerization result are in table 1 and table 2.
Embodiment 3
(1) catalyzer is synthetic with embodiment 1.Diisooctyl amber sodium sulfonate (OT75) consumption changes 4.0ml into.
(2) vinyl polymerization is with embodiment 1.The composition of catalyst component and polymerization result are in table 1 and table 2.
Embodiment 4
(1) preparation of catalyst component: in the reactor of fully replacing through high pure nitrogen, add successively 6.0g magnesium dichloride, toluene 70ml, epoxy chloropropane 6.0ml, tributyl phosphate 7ml, ethanol 5.0ml, under stirring, be warming up to 70 ℃, after solid dissolves the solution that forms homogeneous completely, under 70 ℃ of conditions, react 1 hour.Then this system is cooled to-10 ℃, slowly drips 60ml titanium tetrachloride, then add 4.0ml tetraethoxy and the different certain herbaceous plants with big flowers methyl of 2.0ml bis-semi-annular jade pendant sodium succinate, react 1 hour, be slowly warming up to 80 ℃, react 2 hours.Stop stirring, leave standstill, the very fast layering of suspension, extracts the upper strata stillness of night, twice of toluene wash, hexane washing four times, and high pure nitrogen dries up, and obtains the ingredient of solid catalyst of good fluidity, narrow diameter distribution.The composition of catalyst component is in table 1.
(2) vinyl polymerization is with embodiment 1.The composition of catalyst component and polymerization result are in table 1 and table 2.
Embodiment 5
(1) catalyzer is synthetic with embodiment 4.Just two different certain herbaceous plants with big flowers methyl semi-annular jade pendant sodium succinate consumptions change 3.0ml into.
(2) vinyl polymerization is with embodiment 1.The composition of catalyst component and polymerization result are in table 1 and table 2.
Embodiment 6
(1) catalyzer is synthetic with embodiment 4.Just two different certain herbaceous plants with big flowers methyl semi-annular jade pendant sodium succinate consumptions change 5.0ml into, and tetraethoxy consumption changes 3.0ml into.
(2) vinyl polymerization is with embodiment 1.The composition of catalyst component and polymerization result are in table 1 and table 2.
Comparative example 1
(1) catalyzer is synthetic with embodiment 1, does not add diisooctyl amber sodium sulfonate (OT75) or two different certain herbaceous plants with big flowers methyl semi-annular jade pendant sodium succinates.
(2) vinyl polymerization condition is with embodiment 1.The composition of catalyst component and polymerization result are in table 1 and table 2.
The catalyzer of investigating hydrogen response employing is the catalyzer of embodiment 1, embodiment 4 and comparative example 1.The stainless steel cauldron that is 2L at volume, after high pure nitrogen is fully replaced, add hexane 1L, the triethyl aluminum 1.0ml of concentration 1M, adds the hexane solution of catalyzer (containing the 0.3 milligram of titanium) component of above-mentioned preparation, is warming up to 70 ℃, pass into ethene and hydrogen, and change the mol ratio of hydrogen and ethene, and polymerization 2 hours under 80 ℃ of conditions, polymerization stagnation pressure is 0.73MPa.Wherein, the mol ratio of hydrogen and ethene is respectively: 0.28/0.45; 0.38/0.35; 0.48/0.25; 0.58/0.15; 0.68/0.05.Concrete investigation the results are shown in Table 3.
Table 1 catalyzer composition
| Numbering | Ti(wt%) | Mg(wt%) | Cl(wt%) | OR(wt%) |
| Example 1 | 7.2 | 17.1 | 58.3 | 7.4 |
| Example 2 | 6.5 | 16.5 | 57.6 | 6.7 |
| Example 3 | 6.7 | 16.8 | 60.4 | 5.8 |
| Example 4 | 7.5 | 16.7 | 59.3 | 6.9 |
| Example 5 | 6.7 | 17.3 | 59.7 | 6.2 |
| Example 6 | 6.5 | 17.5 | 60.1 | 5.6 |
| Contrast 1 | 6.6 | 16.6 | 60.2 | 5.7 |
Table 2 polymer performance
Table 3 hydrogen response
Can find out from the aggregated data of table 2, under same polymerizing condition, catalyst activity of the present invention is higher, and tap density is higher, the centralized particle diameter of polymkeric substance.
Can find out from the data of table 3, the hydrogen response of catalyzer of the present invention improves to some extent.
Claims (14)
1. a catalyst component for polymerization of ethylene, comprises the reaction product of following component:
(1) magnesium mixture
(2) organic alcohol compound
(3) silicoorganic compound
(4) sulfonate
(5) titanium compound
Wherein said magnesium mixture is that magnesium halide is dissolved in to the product obtaining in the solvent system of organic epoxy compounds and organo phosphorous compounds;
Described organic alcohol compound is that carbonatoms is the alcohol of 1～10 straight chain, side chain or cycloalkyl, the alcohol that contains aryl or the halohydrin that carbonatoms is 6～20;
It is R that described silicoorganic compound are selected from general formula
1 xr
2 ysi (OR
3)
zin at least one, wherein R
1and R
2be respectively carbonatoms and be 1～10 alkyl or halogen, R
3for the carbonatoms alkyl that is 1～10, x, y, z is integer, 0≤x≤2,0≤y≤2,0≤z≤4, and x+y+z=4;
The structural formula of described sulfonate is X-SO
3m, wherein X is alkyl, M is basic metal;
It is Ti (OR) that described titanium compound is selected from general formula
ax
bin at least one, wherein R is C
1～C
14aliphatic group or aryl, X is halogen, a is integer, 0≤a≤4, b is integer, 0≤b≤4, a+b=3 or 4.
2. catalyst component for polymerization of ethylene according to claim 1, is characterized in that M is sodium Metal 99.5.
3. catalyst component for polymerization of ethylene according to claim 1, it is characterized in that in every mole of magnesium halide in magnesium mixture, organic epoxy compounds is 0.5～5.0mol, organo phosphorous compounds is 0.1～4.0mol, organic alcohol compound is 0.1～10.0mol, silicoorganic compound are 0.05～1.0mol, and sulfonate is 1.0～10.0mol, and titanium compound is 1.0～15.0mol.
4. catalyst component for polymerization of ethylene according to claim 1, is characterized in that described sulfonate is fatty sulfonate or alkylbenzene sulfonate.
5. catalyst component for polymerization of ethylene according to claim 1, is characterized in that described sulfonate is alkyl sodium sulfonate or sodium alkyl benzene sulfonate.
6. catalyst component for polymerization of ethylene according to claim 1, is characterized in that described sulfonate is diisooctyl amber sodium sulfonate or two different certain herbaceous plants with big flowers methyl semi-annular jade pendant sodium succinates.
7. catalyst component for polymerization of ethylene according to claim 1, is characterized in that described silicoorganic compound are at least one in tetramethoxy-silicane, tetraethoxysilane and four butoxy silanes.
8. catalyst component for polymerization of ethylene according to claim 1, is characterized in that described organic epoxy compounds comprises that carbonatoms is at least one in oxide compound, glycidyl ether and the inner ether of 2～8 aliphatics alkene, diolefine or halogenated aliphatic alkene or diolefine.
9. catalyst component for polymerization of ethylene according to claim 1, is characterized in that described organo phosphorous compounds is hydrocarbyl carbonate or the halo hydrocarbyl carbonate of ortho-phosphoric acid or phosphorous acid.
10. catalyst component for polymerization of ethylene according to claim 1, is characterized in that described organic alcohol compound is ethanol, butanols, 2-Ethylhexyl Alcohol, glycerol.
11. catalyst component for polymerization of ethylene according to claim 1, is characterized in that described titanium compound is TiCl
4.
The preparation method of the catalyst component for polymerization of ethylene described in one of 12. claims 1～11, comprise the steps: magnesium halide to be dissolved in the solvent system containing organic epoxy compounds and organo phosphorous compounds and to form homogeneous transparent solution, solvent temperature is 50～90 ℃, forming in the process of solution or solution adds organic alcohol compound after forming, the reaction regular hour, obtain reaction soln; In-40 ℃～20 ℃, above-mentioned solution and titanium compound are carried out to contact reacts, add subsequently silicoorganic compound and sulfonate, and mixture is slowly warming up to 50～120 ℃, particle is separated out and formed to solids gradually, after the reaction regular hour, removes unreacted reactant and solvent, and adopt inert diluent washing, obtain catalyst component of the present invention.
13. 1 kinds of catalyzer for ethylene polymerization, the reaction product that it comprises following component:
(1) the described catalyst component for polymerization of ethylene of one of claim 1～11;
(2) general formula is AlR
nx
3-norgano-aluminium compound, in formula, R is the alkyl that hydrogen or carbonatoms are l～20, X is halogen, the integer of 0<n≤3.
Catalyzer described in 14. claims 13 closes the application in reaction or copolymerization at ethylene homo.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210413209.1A CN103772555A (en) | 2012-10-25 | 2012-10-25 | Ingredients of catalyst for vinyl polymerization and catalyst |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210413209.1A CN103772555A (en) | 2012-10-25 | 2012-10-25 | Ingredients of catalyst for vinyl polymerization and catalyst |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN103772555A true CN103772555A (en) | 2014-05-07 |
Family
ID=50565364
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201210413209.1A Pending CN103772555A (en) | 2012-10-25 | 2012-10-25 | Ingredients of catalyst for vinyl polymerization and catalyst |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103772555A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105622801A (en) * | 2014-11-06 | 2016-06-01 | 中国石油化工股份有限公司 | Catalyst component for ethylene polymerization, catalyst for ethylene polymerization, and preparation method of catalyst component |
| WO2022078492A1 (en) * | 2020-10-15 | 2022-04-21 | 中国石油化工股份有限公司 | Magnesium-based solid and catalyst component having multimodal pore distribution, and preparation methods therefor |
| CN114426609A (en) * | 2020-10-15 | 2022-05-03 | 中国石油化工股份有限公司 | Solid catalyst component for olefin polymerization and catalyst system |
| CN114426602A (en) * | 2020-10-15 | 2022-05-03 | 中国石油化工股份有限公司 | Preparation method of solid catalyst component for olefin polymerization |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5192729A (en) * | 1990-10-10 | 1993-03-09 | Korea Advanced Institute Of Science And Technology | Highly active ziegler-natta catalyst for polymerizing HDPE and LLDPE and method for preparation thereof |
| CN101104656A (en) * | 2006-07-13 | 2008-01-16 | 中国石油化工股份有限公司 | Catalyst component used for olefin polymerization reaction and its catalyst |
| CN101274967A (en) * | 2007-03-28 | 2008-10-01 | 中国石油化工股份有限公司 | Catalyst for ethylene polymerization and components thereof |
| CN101628950A (en) * | 2009-08-07 | 2010-01-20 | 中国石油天然气股份有限公司 | Polypropylene catalyst containing sulfonyl compound and preparation method and application thereof |
| CN101633705A (en) * | 2008-07-24 | 2010-01-27 | 中国石油化工股份有限公司 | Catalyst component used for ethylene polymerization reaction and catalyst thereof |
| CN101864013A (en) * | 2010-06-24 | 2010-10-20 | 东北石油大学 | Catalyst for gas-phase polymerization or copolymerization of ethylene and preparation method thereof |
-
2012
- 2012-10-25 CN CN201210413209.1A patent/CN103772555A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5192729A (en) * | 1990-10-10 | 1993-03-09 | Korea Advanced Institute Of Science And Technology | Highly active ziegler-natta catalyst for polymerizing HDPE and LLDPE and method for preparation thereof |
| CN101104656A (en) * | 2006-07-13 | 2008-01-16 | 中国石油化工股份有限公司 | Catalyst component used for olefin polymerization reaction and its catalyst |
| CN101274967A (en) * | 2007-03-28 | 2008-10-01 | 中国石油化工股份有限公司 | Catalyst for ethylene polymerization and components thereof |
| CN101633705A (en) * | 2008-07-24 | 2010-01-27 | 中国石油化工股份有限公司 | Catalyst component used for ethylene polymerization reaction and catalyst thereof |
| CN101628950A (en) * | 2009-08-07 | 2010-01-20 | 中国石油天然气股份有限公司 | Polypropylene catalyst containing sulfonyl compound and preparation method and application thereof |
| CN101864013A (en) * | 2010-06-24 | 2010-10-20 | 东北石油大学 | Catalyst for gas-phase polymerization or copolymerization of ethylene and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| 何铁林等: "《世界水处理剂商品手册》", 31 October 2004 * |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105622801A (en) * | 2014-11-06 | 2016-06-01 | 中国石油化工股份有限公司 | Catalyst component for ethylene polymerization, catalyst for ethylene polymerization, and preparation method of catalyst component |
| CN105622801B (en) * | 2014-11-06 | 2018-08-17 | 中国石油化工股份有限公司 | A kind of catalytic component for vinyl polymerization, catalyst and preparation method thereof |
| WO2022078492A1 (en) * | 2020-10-15 | 2022-04-21 | 中国石油化工股份有限公司 | Magnesium-based solid and catalyst component having multimodal pore distribution, and preparation methods therefor |
| CN114426609A (en) * | 2020-10-15 | 2022-05-03 | 中国石油化工股份有限公司 | Solid catalyst component for olefin polymerization and catalyst system |
| CN114426602A (en) * | 2020-10-15 | 2022-05-03 | 中国石油化工股份有限公司 | Preparation method of solid catalyst component for olefin polymerization |
| CN114426609B (en) * | 2020-10-15 | 2023-05-12 | 中国石油化工股份有限公司 | Solid catalyst component and catalyst system for olefin polymerization |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN100513433C (en) | Catalyst components in use for polymerizing ethylene, and catalyst | |
| CN103772554A (en) | Ingredients of catalyst for vinyl polymerization and catalyst | |
| CN101633704B (en) | Catalyst component used for ethylene polymerization reaction and catalyst thereof | |
| CN101274967B (en) | Catalyst for ethylene polymerization and components thereof | |
| CN102295717B (en) | Catalyst compound used for vinyl polymerization reaction and catalyst thereof | |
| CN101838353A (en) | Catalyst component for vinyl polymerization and catalyst thereof | |
| CN104080824A (en) | Internal electron donor for olefin polymerization catalysts, method of making and using the same | |
| CN103772555A (en) | Ingredients of catalyst for vinyl polymerization and catalyst | |
| CN102875707A (en) | Preparation method of catalyst component for ethylene polymerization or copolymerization and catalyst thereof | |
| CN102993343B (en) | Catalyst component for ethylene polymerization, and catalyst thereof | |
| CN102295715B (en) | Catalyst component used for vinyl polymerization reaction and catalyst thereof | |
| CN101633705B (en) | Catalyst component used for ethylene polymerization reaction and catalyst thereof | |
| CN100532406C (en) | Catalyst components in use for polymerizing ethylene, and catalyst | |
| CN102040686B (en) | Catalyst component and catalyst for vinyl polymerization | |
| CN103130931B (en) | Spherical ethylene polymerization solid titanium catalyst, preparation and application thereof | |
| CN102040685B (en) | Catalyst component for ethylene polymerization and catalyst | |
| CN105622801A (en) | Catalyst component for ethylene polymerization, catalyst for ethylene polymerization, and preparation method of catalyst component | |
| CN102286119A (en) | Catalyst component and catalyst for polymerization of ethylene | |
| CN102453172A (en) | Method for homopolymerizing or copolymerizing ethylene | |
| CN102993344B (en) | A kind of catalyst component for vinyl polymerization and catalyzer | |
| CN101838352B (en) | Catalyst component for vinyl polymerization or copolymerization and catalyst thereof | |
| CN102344515B (en) | Catalyst component for ethylene polymerization and catalyst thereof | |
| CN102286120A (en) | Catalyst component and catalyst for polymerization of ethylene | |
| CN104231140B (en) | A kind of ethene-alpha-olefin catalyst for copolymerization and preparation thereof and application | |
| CN102875709B (en) | Preparation method of catalyst component for ethylene polymerization reaction and catalyst thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20140507 |