CN104250322A - Catalyst component for ethene polymerization and catalyst - Google Patents
Catalyst component for ethene polymerization and catalyst Download PDFInfo
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- CN104250322A CN104250322A CN201310269111.8A CN201310269111A CN104250322A CN 104250322 A CN104250322 A CN 104250322A CN 201310269111 A CN201310269111 A CN 201310269111A CN 104250322 A CN104250322 A CN 104250322A
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Abstract
The invention relates to a catalyst component for ethene polymerization and a catalyst, and use of the catalyst. The catalyst component comprises a superfine inorganic oxide carrier, the carrier is loaded with a reaction product of a magnesium halide, a halogenated alcohol, at least a titanium halide and at least an electron donor compound, and the catalyst component is obtained by the reaction including the following steps: (1) mother liquor preparation, to be more specific, reacting the magnesium halide, the titanium halide and the halogenated alcohol with the general formula of XnROH in the electron donor compound to prepare mother liquor; (2) carrier mixing, to be more specific, mixing the mother liquor prepared by the step (1) with the superfine inorganic oxide carrier to obtain slurry; and (3) spray forming, to be more specific, performing spray drying on the slurry obtained by the step (2) to obtain the solid catalyst component. The prepared catalyst has high activity when the catalyst is used for ethylene homopolymerization or copolymerization of ethene and other alpha olefins, and the obtained polymers are low in hexane extract, and low in oligomer content.
Description
Technical field
The present invention relates to a kind of catalyst component for ethylene polymerization and catalyzer thereof, and the purposes of this catalyzer.
Background technology
In the polyreaction of ethene or the copolymerization of ethene and alpha-olefin, the performance impact of catalyzer the performance of polymkeric substance.Can produce some oligopolymer while catalyst vinyl polymerization, oligopolymer makes the force-bearing situation between polyethylene molecule change, and affects use properties and the processing characteristics of product, and it has impact to the yield strength of product, elongation and rigidity etc.How many general hexane extract of oligopolymer number weigh, therefore, hexane extract number be also the important indicator weighing catalyst performance.
CN100368440 discloses a kind of spray-dired polymerizing catalyst and adopts the polymerization process of this polymerizing catalyst, and this catalyzer comprises the spray-dried compositions of inertia protruded packing and following substance reaction product: the mixture of magnesium halide, solvent, electron donor compound, transistion metal compound or reaction product.Filler is spherical substantially and mean particle size is 1 μm ~ 12 μm.But the activity of this catalyzer is not high enough, the oligopolymer in polymkeric substance is many.
CN1493599 discloses a kind of catalyzer for vinyl polymerization of improvement, by adding alkyl silicic acids fat in the mother liquor preparation of catalyst activity component, to improve catalyst activity, and reduces the oligomer in polymkeric substance.But the activity of this catalyzer is not high enough.
For above the deficiencies in the prior art, the invention provides a kind of catalyst component for ethylene polymerization and catalyzer thereof, this catalyzer is not only active high, and the oligomer of resulting polymers is low.
Summary of the invention
The technical problem to be solved in the present invention there is provided a kind of catalyst component for ethylene polymerization and catalyzer thereof, and this catalyst activity is high, and the hexane extract of resulting polymers is low, and the oligomer of resulting polymers is low.
A kind of catalyst component for ethylene polymerization, it comprises a kind of ultra-fine inorganic oxide carrier, the reaction product of a kind of magnesium halide of load, halohydrin, at least one halogenated titanium and at least one electron donor compound on this carrier, it is by comprising being obtained by reacting of following steps:
(1) mother liquor preparation: be X by magnesium halide, halogenated titanium and general formula in electron donor compound
nthe halohydrin of ROH carries out reaction and prepares mother liquor, wherein R to be carbonatoms be 1 ~ 10 straight chain, the alkyl of side chain, cycloalkyl or carbonatoms be the aryl of 6 ~ 20, X is halogen, and n is the integer of 1 ~ 3, and described electron donor compound is selected from ether, ester or ketone;
(2) carrier blending: the mother liquor of preparation in step (1) and ultra-fine inorganic oxide carrier are carried out blending and obtains slurry, wherein the particle diameter of ultra-fine inorganic oxide carrier is 0.01 ~ 10 micron;
(3) spray shaping: the slurry obtained in step (2) is carried out spraying dry, obtains ingredient of solid catalyst, wherein spray condition is inlet temperature 80 ~ 240 DEG C, temperature out 60 ~ 130 DEG C.
The general formula of described halohydrin is X
nthe straight chain of ROH, R to be carbonatoms be 1-10, the alkyl of side chain, cycloalkyl or carbonatoms are the aryl of 6 ~ 20; X is halogen, and n is the integer of 1 ~ 3.Particular compound is selected from trichloro-ethyl alcohol, 2,2-dichlroroethanol, ethylene chlorhydrin, trimethylene chlorohydrin, the chloro-1-hexanol of 6-, the bromo-1-propyl alcohol of 3-, the chloro-1-amylalcohol of 5-, the chloro-n-butyl alcohol of 4-, 6-amino-1-hexanol, at least one in 2-chloro cyclohexanol.Preferred trichloro-ethyl alcohol.
Described electron donor compound is selected from ether, ester or ketone, concrete as C
1~ C
4the alkyl ester of aliphatic saturated monocarboxylic acid, C
7~ C
8aromatic carboxylic acid alkyl ester, C
2~ C
6aliphatic ether, C
3~ C
4cyclic ethers, C
3~ C
6a kind of in saturated fatty ketone or their mixture, preferable formic acid methyl esters, ethyl acetate, butylacetate, ether, hexyl ether, tetrahydrofuran (THF), acetone and methyl iso-butyl ketone (MIBK) etc., most preferably tetrahydrofuran (THF).These electron donors can be used alone, also can be used in combination.
Described halogenated titanium is titanium chloride or titanium bromide, preferred TiCl
3or TiCl
4.
Described magnesium halide is magnesium dichloride, dibrominated magnesium or diiodinating magnesium, preferred magnesium dichloride.
Described ultra-fine inorganic oxide carrier generally selects the oxide compound of silicon and/or aluminium, and its particle diameter is generally 0.01 ~ 10 micron, and preferable particle size is less than 5 microns, more preferably 0.1 ~ 2 micron, the most preferably silica supports of 0.1 ~ 1 micron.The catalyzer particle shape that so thin silica gel generates is good, and intensity is high, not easily broken pure.
The mol ratio of described halogenated titanium and halohydrin is 1:0.5 ~ 20; Preferred 1:1 ~ 10.
The ratio of described halogenated titanium and magnesium dihalide is: 0.1 < magnesium/titanium < 10; The mol ratio general control of titanium and electron donor compound, at 1 mole to 600 moles, is preferably 20 moles to 200 moles.
The above-mentioned catalyst component for ethylene polymerization can adopt following methods to prepare:
(1) mother liquor preparation: be X by magnesium halide, halogenated titanium and general formula in electron donor compound
nthe halohydrin of ROH carries out reaction and prepares mother liquor, wherein R to be carbonatoms be 1 ~ 10 straight chain, the alkyl of side chain, cycloalkyl or carbonatoms be the aryl of 6 ~ 20, X is halogen, and n is the integer of 1 ~ 3, and described electron donor compound is selected from ether, ester or ketone;
(2) carrier blending: the mother liquor of preparation in step (1) and ultra-fine inorganic oxide carrier are carried out blending and obtains slurry;
Described ultra-fine inorganic oxide carrier generally selects the oxide compound of silicon and/or aluminium, and its particle diameter is generally 0.01 ~ 10 micron, and preferable particle size is less than 5 microns, more selects 0.1 ~ 2 micron, most preferably the silica supports of 0.1 ~ 1 micron.This carrier should be dry in use, the water namely do not adsorbed.Should by the carrier of sufficient amount and female liquid-phase mixing, formed and be suitable for carrying out spray-dired slurry, namely in slurry, the content of this carrier is 5wt% ~ 50wt%, preferred 10wt% ~ 30wt%.
(3) spray shaping: the slurry obtained in step (2) is carried out spraying dry, obtains ingredient of solid catalyst.Spray condition: inlet temperature 80-240 DEG C, temperature out 60-130 DEG C.Preferred inlet temperatures 120-180 DEG C, temperature out 90-110 DEG C.
In order to the ingredient of solid catalyst obtained after making spraying dry is applicable to produce ethene polymers, activator component organo-aluminium compound must be adopted the titanium atom in described catalyst component to be reduced into the state that ethene can be made effectively to be polymerized.Usually, in varsol, the ingredient of solid catalyst obtain step (3) and activator component are reacted, and obtain catalyzer; The ingredient of solid catalyst that also can step (3) be obtained in the course of the polymerization process and activator component are reacted, thus cause olefinic polyreaction.
Described activator component is general formula AlR '
nx
3-norgano-aluminium compound, in formula R ' for hydrogen or carbonatoms be the alkyl of 1 ~ 20, X is halogen, and n is the number of 1 < n≤3, concrete as a kind of in triethyl aluminum, triisobutyl aluminium, tri-n-hexyl aluminum, tri-n-octylaluminium or aluminium diethyl monochloride or their mixture.Wherein in activator component, in aluminium and titaniferous active ingredient, the mol ratio of titanium is 5 ~ 500, preferably 10 ~ 200.
Described varsol is as iso-pentane, hexane, heptane, toluene, dimethylbenzene, petroleum naphtha and mineral wet goods.
The catalyzer that the present invention relates to is applicable to the copolymerization of all polymerization or ethene and other alpha-olefins of various ethene, and alpha-olefin wherein selects the one in propylene, butylene, amylene, hexene, octene, 4-methylpentene-1.Its polymerization technique adopts vapor phase process, slurry process and solution method, is more suitable for gas fluidised bed polymerisation.
Compared with the prior art the present invention, has following obviously advantage:
Catalyzer for vinyl polymerization or copolymerization of the present invention, it adopts ultra-fine inorganic oxide compound to do carrier, with electron donor compound solvent, magnesium halide is dissolved, and add a certain proportion of halohydrin, highly active catalyzer is created by the mode of spray shaping, the hexane extract of resulting polymers is low, and the oligomer in the polymkeric substance of this catalyst preparing is low.
Embodiment
Testing method:
1, active: to represent by the weight of every gram of catalyzer gained resin
2, the percentage composition of hexane extract is with being in the hexane polymkeric substance of boiling temperature after 4 hours, weighs after polymkeric substance being evaporated hexane, and calculates minimizing weight, obtains the percentage composition of hexane extract.
Embodiment given below is in order to the present invention is described, instead of limits the invention.
Embodiment 1
(1) preparation of catalyzer
Blow through nitrogen in the 250ml there-necked flask of row to one and successively add 1.5 grams of TiCl
4, 4.4 grams of anhydrous MgCl
2, 6.1 grams of ethapon and 100ml tetrahydrofuran (THF)s, be warming up to 65 DEG C under stirring, at this temperature isothermal reaction 3 hours.Be cooled to 35 DEG C.
Blow through nitrogen in the 250ml there-necked flask of row to one and add 6 grams of silica gel (Cabot Corporation TS-610, particle diameter is 0.02 ~ 0.1 micron), mother liquor after cooling is added, keep temperature 35 DEG C, stir after 1 hour, the mother liquor spray-dryer after silica gel blending is carried out spraying dry, spray condition: inlet temperature 180 DEG C, temperature out 110 DEG C, obtains ingredient of solid catalyst, and wherein titanium content is 2.2Wt%.
(2) ethene slurry polymerization
Add 1 liter of hexane by the 2 liters of polymeric kettles blowing row through nitrogen, add triethyl aluminum and 0.03 gram of catalyzer of 1 milliliter of 1mmol simultaneously, be warming up to 75 DEG C and add hydrogen 0.18Mpa, ethene 0.75Mpa is added after hydrogenation, be warmed up to 85 DEG C, react after 2 hours, cooling discharge.Polymerization result is in table 1.
Embodiment 2
(1) preparation of catalyzer is with embodiment 1.Just the amount of ethapon is 12.2 grams, and the titanium content of gained ingredient of solid catalyst is 2.2Wt%.
(2) ethene slurry polymerization is with embodiment 1.Polymerization result is in table 1.
Embodiment 3
(1) preparation of catalyzer is with embodiment 1.Just the amount of ethapon is 15.3 grams, and the titanium content of gained ingredient of solid catalyst is 2.3Wt%.
(2) ethene slurry polymerization is with embodiment 1.Polymerization result is in table 1.
Comparative example 1
(1) preparation of catalyzer
Blow through nitrogen in the 250ml there-necked flask of row to one and successively add 1.5 grams of TiCl
4, 4.0 grams of anhydrous MgCl
2with 100ml tetrahydrofuran (THF), under stirring, be warming up to 65 DEG C, at this temperature isothermal reaction 3 hours.Be cooled to 35 DEG C.
Blow through nitrogen in the 250ml there-necked flask of row to one and add 6 grams of silica gel (Cabot Corporation TS-610, particle diameter is 0.02 ~ 0.1 micron), mother liquor after cooling is added, keep temperature 35 DEG C, stir after 1 hour, the mother liquor spray-dryer after silica gel blending is carried out spraying dry, spray condition: inlet temperature 195 DEG C, temperature out 110 DEG C, obtains ingredient of solid catalyst, and wherein titanium content is 2.4Wt%.
(2) ethene slurry polymerization is with embodiment 1.Polymerization result is in table 1.
Table 1
As can be seen from the aggregated data of table 1, under same polymerizing condition, catalyst activity of the present invention is higher, and the hexane extract of resulting polymers is low, and oligomer is low.
Claims (13)
1. the catalyst component for ethylene polymerization, it comprises a kind of ultra-fine inorganic oxide carrier, the reaction product of a kind of magnesium halide of load, halohydrin, at least one halogenated titanium and at least one electron donor compound on this carrier, it is by comprising being obtained by reacting of following steps:
(1) mother liquor preparation: be X by magnesium halide, halogenated titanium and general formula in electron donor compound
nthe halohydrin of ROH carries out reaction and prepares mother liquor, wherein R to be carbonatoms be 1 ~ 10 straight chain, the alkyl of side chain, cycloalkyl or carbonatoms be the aryl of 6 ~ 20, X is halogen, and n is the integer of 1 ~ 3, and described electron donor compound is selected from ether, ester or ketone;
(2) carrier blending: the mother liquor of preparation in step (1) and ultra-fine inorganic oxide carrier are carried out blending and obtains slurry, wherein the particle diameter of ultra-fine inorganic oxide carrier is 0.01 ~ 10 micron;
(3) spray shaping: the slurry obtained in step (2) is carried out spraying dry, obtains ingredient of solid catalyst, wherein spray condition is inlet temperature 80 ~ 240 DEG C, temperature out 60 ~ 130 DEG C.
2. the catalyst component for ethylene polymerization according to claim 1, it is characterized in that the mol ratio of halogenated titanium and halohydrin described in step (1) is 1:0.5 ~ 20, the mol ratio of described halogenated titanium and magnesium halide is 0.1 < magnesium/titanium < 10, the mol ratio of titanium and electron donor compound is 1 ~ 600, and in the slurry described in step (2), the weight ratio of ultra-fine inorganic oxide carrier is 5wt% ~ 50wt%.
3. the catalyst component for ethylene polymerization according to claim 2, it is characterized in that the mol ratio of described halogenated titanium and halohydrin is 1:1 ~ 10, the mol ratio of titanium and electron donor compound is 20 ~ 200, and in the slurry described in step (2), the weight ratio of ultra-fine inorganic oxide carrier is 10wt% ~ 30wt%.
4., according to the catalyst component for ethylene polymerization one of claim 1-3 Suo Shu, it is characterized in that described ultra-fine inorganic oxide carrier to be particle diameter be the silicon-dioxide of 0.1 ~ 1 micron.
5. the catalyst component for ethylene polymerization according to claim 1, is characterized in that described halohydrin is 2,2,2-ethapon, 2,2-dichlroroethanol, ethylene chlorhydrin, trimethylene chlorohydrin, the chloro-1-hexanol of 6-, the bromo-1-propyl alcohol of 3-, the chloro-1-amylalcohol of 5-, the chloro-n-butyl alcohol of 4-, 6-amino-1-hexanol, at least one in 2-chloro cyclohexanol.
6. the catalyst component for ethylene polymerization according to claim 1, is characterized in that described halohydrin is trichloro-ethyl alcohol.
7. the catalyst component for ethylene polymerization according to claim 1, is characterized in that described halogenated titanium is selected from titanous chloride or titanium tetrachloride.
8. the catalyst component for ethylene polymerization according to claim 1, is characterized in that described electron donor compound is selected from C
1~ C
4the alkyl ester of aliphatic saturated monocarboxylic acid, C
7~ C
8aromatic carboxylic acid alkyl ester, C
2~ C
6aliphatic ether, C
3~ C
4cyclic ethers, C
3~ C
6a kind of in saturated fatty ketone or their mixture.
9. the catalyst component for ethylene polymerization according to claim 1, is characterized in that described electron donor compound is selected from methyl-formiate, ethyl acetate, butylacetate, ether, hexyl ether, tetrahydrofuran (THF), acetone and methyl iso-butyl ketone (MIBK).
10. the catalyst component for ethylene polymerization according to claim 1, is characterized in that described electron donor compound is selected from tetrahydrofuran (THF).
11. catalyst components for ethylene polymerization according to claim 1, is characterized in that described magnesium halide is magnesium dichloride, dibrominated magnesium or diiodinating magnesium.
12. 1 kinds of catalyzer for ethylene polymerization, it comprises the reaction product of following component:
(1) catalyst component for ethylene polymerization that one of claim 1-11 is described;
(2) general formula is AlR '
nx
3-norgano-aluminium compound, in formula R ' for hydrogen or carbonatoms be the alkyl of 1 ~ 20, X is halogen, the organo-aluminium compound of 1 < n≤3.
13. application of catalyzer in vinyl polymerization or copolymerization for ethylene polymerization according to claim 12.
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| CN110431125A (en) * | 2017-03-14 | 2019-11-08 | 沙特阿拉伯石油公司 | The method of ethylene oligomerization reaction generation alpha-olefin |
| CN110862473A (en) * | 2018-08-28 | 2020-03-06 | 中国石油化工股份有限公司 | Catalyst for olefin polymerization reaction, preparation method and composite catalyst |
| WO2020083386A1 (en) * | 2018-10-26 | 2020-04-30 | 中国石油化工股份有限公司 | Polyolefin catalyst component containing mesoporous material, preparation method therefor and use thereof |
| CN112625153A (en) * | 2019-10-09 | 2021-04-09 | 中国石油化工股份有限公司 | Catalyst component for olefin polymerization, preparation method, catalyst and application thereof |
| CN112812205A (en) * | 2019-11-18 | 2021-05-18 | 中国石油化工股份有限公司 | Catalyst component for olefin polymerization reaction, catalyst thereof, preparation method and application thereof |
| RU2786576C2 (en) * | 2018-10-26 | 2022-12-22 | Чайна Петролеум Энд Кемикал Корпорейшн | Polyolefin catalyst component containing mesoporous material, its production method, and its use |
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