CN103772554A - Ingredients of catalyst for vinyl polymerization and catalyst - Google Patents
Ingredients of catalyst for vinyl polymerization and catalyst Download PDFInfo
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- CN103772554A CN103772554A CN201210413120.5A CN201210413120A CN103772554A CN 103772554 A CN103772554 A CN 103772554A CN 201210413120 A CN201210413120 A CN 201210413120A CN 103772554 A CN103772554 A CN 103772554A
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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 non-ionic surfactant, and (5) a titanium compound, wherein the structural formula of the organic silicon compound is at least one of R<1>xR<2>ySi(OR<3>)z, wherein R<1> and R<2> are respectively alkyl or halogen of which the carbon numbers are 1 to 10; R<3> is alkyl of which the carbon number is 1 to 10; x, y and z are integral numbers; x is larger than or equal to 0 and smaller than or equal to 2; y is larger than or equal to 0 and smaller than or equal to 2; z is larger than or equal to 0 and smaller than or equal to 4; x+y+z=4; the non-ionic surfactant is at least one of the periodic copolymers of a poly-oxyethylene ether compound, a carbon oxo alcohol ethoxy compound and an epoxy compound. The catalyst is relatively high in catalytic activity and copolymerization performance; a polymer prepared with the catalyst is relatively high in bulk density and relatively small in size distribution; the catalyst is suitable for homopolymerization of ethylene or copolymerization of ethylene and other Alpha-olefin.
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 nonionic class tensio-active agent 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 copolymerization performance of catalyzer is most important.Controlling under the condition of suitable density, the copolymerization performance of catalyzer excellence will reduce the add-on of comonomer greatly, reduces the probability that in polymerization process, polymkeric substance is clamminess, and improves the long-term operation of device.Along with the increase of the various raw materials cost such as depression and ethene of polyolefine overall market, 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 requirement such as the copolymerization performance of these PP Pipe Compound trades mark to catalyzer is higher, harsher, petrochemical industry manufacturer even can be in order to improve the above-mentioned performance sacrificial section catalytic activity of catalyzer.
Copolymerization performance, its essence is the ability of the access of comonomer coordination in ethylene polymerisation process ethylene molecule chain.Desirable copolymerization performance is the molecular chain of comonomer access higher molecular weight, and does not enter low-molecular-weight molecular chain.In actual research and production, conventionally in catalyzer, introduce various components and improve the copolymerization performance of catalyzer.In the slurry polymerization processes of ethene, except requiring catalyzer should have higher catalytic activity, responsive hydrogen tonality and preferably size distribution, quite a few trade mark---especially the copolymerization trade mark of some high added values needs catalyzer to provide excellent copolymerization performance to meet its demand.
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, take the catalytic activity of catalyzer as the over-all properties of representative unsatisfactory.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 over-all properties also has clear improvement compared with the catalyzer in Chinese patent CN1229092A, be still difficult to meet completely the demand of some PP Pipe Compound trades mark that copolymerization performance is had relatively high expectations of industrial production at aspects such as copolymerization performances.
Therefore, be necessary very much to provide a kind of and close 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 copolymerization performance, 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 copolymerization performance, 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) nonionic class tensio-active agent
(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;
Described nonionic class tensio-active agent is selected from least one in the segmented copolymer of Soxylat A 25-7 compounds, carbon oxo process alcohol ethoxylates or epoxy compounds;
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, 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)
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.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.
At least one in the segmented copolymer that nonionic class tensio-active agent of the present invention is Soxylat A 25-7 compounds, carbon oxo process alcohol ethoxylates and epoxy compounds, particular compound and physical data thereof see the following form, wherein Soxylat A 25-7 compounds is the ring-opening reaction thing of fatty alcohol and epoxy compounds, and the segmented copolymer of epoxy compounds is ethylene oxide-propylene oxide block copolymer.Preferably 10 carbon Soxylat A 25-7s (XP70) and ethylene oxide-propylene oxide block copolymer (PE 3100).
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; Tensio-active agent: 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%:0.1～1.0wt%, 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 a 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 nonionic class tensio-active agent, 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 number 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 nonionic class tensio-active agent, 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 nonionic class tensio-active agent add the improvement that also contributes to improve the activity of catalyzer and the particle form of catalyzer, during for vinyl polymerization, show good copolymerization performance at catalyzer.
Embodiment
With embodiment, the present invention is described below, but and unrestricted invention scope.
Testing method:
The density of polymkeric substance: measure according to GB GB/T 1033.2-2010
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 2.0ml 10 carbon Soxylat A 25-7s (XP70), 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 10 carbon Soxylat A 25-7 (XP70) 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 3
(1) catalyzer is synthetic with embodiment 1.10 carbon Soxylat A 25-7 (XP70) consumptions change 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 3.0ml ethylene oxide-propylene oxide block copolymer (PE 3100), 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 ethylene oxide-propylene oxide block copolymer (PE 3100) 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 6
(1) catalyzer is synthetic with embodiment 4.Just ethylene oxide-propylene oxide block copolymer (PE 3100) amount changes 5.0ml into, and tetraethoxy 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.
Comparative example 1
(1) catalyzer is synthetic with embodiment 1, and synthesizing with embodiment 1 of catalyzer, does not add 10 carbon Soxylat A 25-7s (XP70) or ethylene oxide-propylene oxide block copolymer (PE 3100).
(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 copolymerization performance employing is 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, the hexane solution that adds catalyzer (containing the 0.3 milligram of titanium) solid of above-mentioned preparation, is warming up to 70 ℃, passes into the ethene and the 1-butylene gas-phase (co-) polymerisation that prepare according to fixed proportion, the volume ratio of 1-butylene and ethene is 10/100, and passes into modifying polymerization with hydrogen thing molecular weight; When hexene is made comonomer, add 10ml hexene, other is with 1-butylene copolymerization.Concrete investigation the results are shown in Table 3.
Table 1 catalyzer composition
| Numbering | Ti(wt%) | Mg(wt%) | Cl(wt%) | OR(wt%) |
| Example 1 | 7.3 | 16.8 | 59.2 | 7.7 |
| Example 2 | 6.6 | 17.1 | 57.9 | 6.9 |
| Example 3 | 7.0 | 16.3 | 60.1 | 5.9 |
| Example 4 | 7.1 | 16.9 | 59.5 | 7.2 |
| Example 5 | 6.4 | 17.8 | 59.8 | 6.6 |
| Example 6 | 6.5 | 17.3 | 60.1 | 5.7 |
| Contrast 1 | 6.1 | 16.1 | 60.3 | 5.8 |
Table 2 polymer performance
Table 3 copolymerization performance
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, catalyzer 1-butylene and hexene during as comonomer its density have to a certain degree and reduce, show that the copolymerization performance of catalyzer improves.
Claims (11)
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) nonionic class tensio-active agent
(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;
Described nonionic class tensio-active agent is at least one in the segmented copolymer of Soxylat A 25-7 compounds, carbon oxo process alcohol ethoxylates and epoxy compounds;
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, 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 nonionic class tensio-active agent is 1.0～10.0mol, and titanium compound is 1.0～15.0mol.
3. catalyst component for polymerization of ethylene according to claim 1, is characterized in that described nonionic class tensio-active agent is 10 carbon Soxylat A 25-7s or ethylene oxide propylene oxide segmented copolymer.
4. 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.
5. 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.
6. 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.
7. 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.
8. catalyst component for polymerization of ethylene according to claim 1, is characterized in that described titanium compound is TiCl
4.
9. the preparation method of the catalyst component for polymerization of ethylene described in one of claim 1～8, 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 nonionic class tensio-active agent, 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.
10. for the catalyzer of ethylene polymerization, the reaction product that it comprises following component:
(1) the described catalyst component for polymerization of ethylene of one of claim 1～8;
(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 number of 0<n≤3.
11. catalyzer claimed in claim 10 close the application in reaction or copolymerization at ethylene homo.
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Cited By (9)
| 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 |
| CN107880173A (en) * | 2016-09-30 | 2018-04-06 | 中国石油化工股份有限公司 | Catalytic component for olefinic polymerization and preparation method thereof and catalyst |
| CN107880185A (en) * | 2016-09-30 | 2018-04-06 | 中国石油化工股份有限公司 | Catalytic component and its preparation and application for olefinic polymerization |
| CN108341902A (en) * | 2017-01-23 | 2018-07-31 | 中国石油化工股份有限公司 | Catalytic component for vinyl polymerization and preparation method thereof and catalyst for vinyl polymerization |
| CN108341900A (en) * | 2017-01-23 | 2018-07-31 | 中国石油化工股份有限公司 | Catalytic component for vinyl polymerization and preparation method thereof and catalyst for vinyl polymerization |
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| 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 |
| CN115043966A (en) * | 2022-06-17 | 2022-09-13 | 上海化工研究院有限公司 | Main catalyst and catalyst for preparing ultrahigh molecular weight polypropylene, preparation method and application |
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| 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 |
| 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 |
| CN107880173A (en) * | 2016-09-30 | 2018-04-06 | 中国石油化工股份有限公司 | Catalytic component for olefinic polymerization and preparation method thereof and catalyst |
| CN107880185A (en) * | 2016-09-30 | 2018-04-06 | 中国石油化工股份有限公司 | Catalytic component and its preparation and application for olefinic polymerization |
| CN108341900B (en) * | 2017-01-23 | 2021-05-11 | 中国石油化工股份有限公司 | Catalyst component for ethylene polymerization, preparation method thereof and catalyst for ethylene polymerization |
| CN108341900A (en) * | 2017-01-23 | 2018-07-31 | 中国石油化工股份有限公司 | Catalytic component for vinyl polymerization and preparation method thereof and catalyst for vinyl polymerization |
| CN108341902A (en) * | 2017-01-23 | 2018-07-31 | 中国石油化工股份有限公司 | Catalytic component for vinyl polymerization and preparation method thereof and catalyst for vinyl polymerization |
| CN108341902B (en) * | 2017-01-23 | 2021-07-02 | 中国石油化工股份有限公司 | Catalyst component for ethylene polymerization, preparation method thereof and catalyst for ethylene polymerization |
| 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 |
| CN115043966A (en) * | 2022-06-17 | 2022-09-13 | 上海化工研究院有限公司 | Main catalyst and catalyst for preparing ultrahigh molecular weight polypropylene, preparation method and application |
| CN115043966B (en) * | 2022-06-17 | 2023-11-28 | 上海化工研究院有限公司 | Main catalyst and catalyst for preparing ultra-high molecular weight polypropylene, preparation method and application |
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