CN110862472A - Olefin polymerization reaction catalyst, preparation method and composite catalyst - Google Patents
Olefin polymerization reaction catalyst, preparation method and composite catalyst Download PDFInfo
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- CN110862472A CN110862472A CN201810985177.XA CN201810985177A CN110862472A CN 110862472 A CN110862472 A CN 110862472A CN 201810985177 A CN201810985177 A CN 201810985177A CN 110862472 A CN110862472 A CN 110862472A
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F110/00—Homopolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
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Abstract
The invention discloses an olefin polymerization reaction catalyst, a preparation method and a composite catalyst. The catalyst comprises: 5-50 wt% of superfine inorganic oxide carrier, based on 100 wt% of the total weight of the catalyst; 1-10 wt% of magnesium; 0.5-5 wt% of titanium; 5-40 wt% of an electron donor compound; 0.1-5 wt% of alternating copolymer macromolecules; the molar ratio of magnesium to titanium is 0.1 to 10. The polymer obtained by the catalyst has higher bulk density and higher melt index. In addition, the catalyst has high activity, and has less breakage and low fine powder content especially in gas phase polymerization.
Description
Technical Field
The invention relates to the technical field of olefin polymerization, in particular to an olefin polymerization reaction catalyst, a preparation method and a composite catalyst.
Background
The catalyst catalyzes ethylene polymerization, and as polymer particles grow, a great deal of polymer particles are crushed, and some seriously crushed products become polymer fine powder.
CN100368440 discloses a spray-dried polymerization catalyst and a polymerization process using the same, the catalyst comprising a spray-dried composition of an inert porous filler and the reaction product of: magnesium halide, solvent, electron donor compound, transition metal compound mixture or reaction product. The filler is substantially spherical and has an average particle size of 1 to 12 um. However, the catalyst activity is not high enough and the amount of oligomers in the polymer is large.
CN1493599 discloses an improved catalyst for ethylene polymerization, which is prepared by adding alkyl silicate in the mother liquor preparation of the active components of the catalyst, so as to improve the activity of the catalyst and reduce the oligomer content in the polymer. The activity of the catalyst is still not high enough.
CN100408603C discloses a catalyst for ethylene polymerization prepared by spray drying process, which has better activity, but still generates more severe crumbling and causes the fine powder content to increase in gas phase polymerization.
Disclosure of Invention
The catalyst has high activity, small crushing degree in gas phase polymerization and low fine powder content.
It is an object of the present invention to provide an olefin polymerization catalyst.
The catalyst comprises:
based on the total weight of the catalyst as 100 percent,
5-50 wt% of superfine inorganic oxide carrier; preferably 10 to 40 wt%, more preferably 15 to 35 wt%;
1-10 wt% of magnesium; preferably 3 to 8 wt%;
0.5-5 wt% of titanium; preferably 1-4 wt%;
5-40 wt% of an electron donor compound; preferably 10 to 35 wt%; more preferably 15 to 30 wt%;
0.1-5 wt% of alternating copolymer macromolecules; preferably 0.3 to 3 wt%;
the molar ratio of magnesium to titanium is 0.1-10, preferably 1-10, and more preferably 2-7;
the particle size of the superfine inorganic oxide carrier is 0.01-10 microns; from 0.02 to 5 microns, more preferably from 0.05 to 1 micron; the inorganic oxide support is preferably silica;
the alternating copolymer macromolecule is an alternating polymerization product of styrene and maleic anhydride; the degree of polymerization is preferably 100-2000;
the electron donor compound is selected from C1-C4Alkyl esters of saturated fatty carboxylic acids, C7-C8Alkyl esters of aromatic carboxylic acids, C2-C6Fatty ethers, C3-C4Cyclic ethersAnd C3-C6At least one saturated aliphatic ketone. More preferably: at least one selected from the group consisting of methyl formate, ethyl formate, isopropyl formate, n-propyl formate, methyl acetate, ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, diethyl ether, propyl ether, hexyl ether, tetrahydrofuran, acetone, and methyl isobutyl ketone.
The second purpose of the invention is to provide a preparation method of the olefin polymerization catalyst.
The method comprises the following steps:
adding an electron donor compound, magnesium halide, titanium halide, an alternating copolymer and a superfine inorganic oxide carrier into a preparation kettle, heating for dissolution reaction, wherein the reaction temperature is 60-80 ℃, the pressure in the reaction kettle is not higher than 0.2MPa, and the reaction time is not lower than 2 hours; after magnesium halide is completely dissolved, cooling the slurry to 30-55 ℃, and carrying out spray drying to obtain the catalyst;
the total amount of the raw materials is 100 percent:
the magnesium halide is preferably: at least one selected from the group consisting of magnesium dichloride, magnesium dibromide, and magnesium diiodide;
the titanium halide is preferably: at least one selected from the group consisting of titanium tribromide, titanium tetrabromide, titanium trichloride and titanium tetrachloride;
the content of the superfine inorganic oxide carrier in the slurry is 3-10 wt%; preferably 4 wt% to 8 wt%; the content of the magnesium halide is 3-10 wt%, preferably 3-7 wt%; the titanium halide content is 1 to 5 wt%, preferably 1 to 3 wt%; the electron donor compound content is 70-90 wt%, preferably 75-88 wt%; the alternating copolymer has a macromolecular content of 0.02 to 3 wt.%, preferably 0.05 to 1 wt.%.
The spray drying conditions were: the inlet temperature is 80-240 ℃; preferably 120-180 ℃; the outlet temperature is 60 to 130 ℃ and preferably 90 to 120 ℃.
The invention also aims to provide a composite catalyst.
The composite catalyst comprises:
(A) an olefin polymerization catalyst according to any one of claims 1 to 4;
(B) the general formula is A1RnX3-n(ii) an organoaluminum compound of (a),
r is hydrogen or alkyl with 1-20 carbon atoms; x is a halogen, and X is a halogen,
0＜n≤3；
the molar ratio of aluminum contained in component (B) to titanium contained in component (A) is 5:1 to 500:1, preferably 10:1 to 200: 1.
The organoaluminum compound is preferably: one or a combination of triethyl aluminum, triisobutyl aluminum, tri-n-hexyl aluminum, tri-n-octyl aluminum or diethyl aluminum monochloride.
The invention can adopt the following technical scheme:
a catalyst for the polymerization of olefins. The catalyst comprises:
1) a superfine inorganic oxide carrier, wherein the carrier is a superfine inorganic oxide carrier,
2) magnesium alloy
3) Titanium (IV)
4) A reaction product of an electron donor compound,
5) an alternating copolymer macromolecule.
According to the catalyst component of the invention, the reaction product of the magnesium, the titanium, the alternating copolymer macromolecule and the electron donor compound is loaded on the ultrafine inorganic oxide carrier.
According to a preferred embodiment of the catalyst component of the present invention, the titanium content in the catalyst component is between 0.5 and 5% by mass, preferably between 1 and 4%.
According to a preferred embodiment of the catalyst component of the present invention, the molar ratio of titanium to magnesium is between 0.1 and 10, preferably between 1 and 10, more preferably between 2 and 7.
According to a preferred embodiment of the catalyst component of the present invention, the ultrafine inorganic oxide support is present in the catalyst component in an amount of 5 to 50 wt.%, preferably 10 to 40 wt.%, more preferably 15 to 35 wt.%, and the alternating copolymer macromolecule is present in the catalyst component in an amount of 0.1 to 5 wt.%, preferably 0.3 to 3 wt.%.
The ultrafine inorganic oxide support is generally selected from oxides of silicon and/or aluminum. The particle size is generally in the range of 0.01 to 10 microns, preferably less than 5 microns, more preferably 0.02 to 2 microns, most preferably 0.05 to 1 micron. Silica supports of 0.05 to 1 micron are most preferred. The catalyst produced by the fine silica gel has good particle shape and high strength, and is not easy to crush.
According to a preferred embodiment of the catalyst component of the present invention, the alternating copolymer macromolecule is an alternating polymerization product of styrene and maleic anhydride having a suitable degree of polymerization, suitably in the range of 100-2000.
According to a preferred embodiment of the catalyst component of the present invention, the electron donor compound is an ester, ether or ketone, preferably C1-C4Alkyl esters of saturated fatty carboxylic acids, C7-C8Alkyl esters of aromatic carboxylic acids, C2-C6Fatty ethers, C3-C4Cyclic ethers and C3-C6At least one saturated aliphatic ketone.
According to some embodiments, the electron donor compound is selected from at least one of methyl formate, ethyl formate, isopropyl formate, n-propyl formate, methyl acetate, ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, diethyl ether, propyl ether, hexyl ether, tetrahydrofuran, acetone and methyl isobutyl ketone. Preferred are methyl formate, ethyl acetate, butyl acetate, diethyl ether, hexyl ether, tetrahydrofuran, acetone, methyl isobutyl ketone and the like, and tetrahydrofuran is most preferred. These electron donors may be used alone or in combination.
According to a preferred embodiment of the catalyst component of the invention, the preparation process of the catalyst component comprises:
step S1, mother liquor preparation: reacting an electron donor compound, magnesium halide, titanium halide and alternating copolymer macromolecules to prepare mother liquor;
step S3, carrier blending: blending the mother liquor prepared in the step S1 with an ultrafine inorganic oxide carrier to obtain a slurry liquid material;
step S3, spray forming: spray-drying the slurry liquid obtained in step S2 to obtain the catalyst component.
According to a preferred embodiment of the catalyst component of the present invention, said magnesium halide is selected from at least one of magnesium dichloride, magnesium dibromide and magnesium diiodide.
According to a preferred embodiment of the catalyst component of the present invention, the titanium halide is titanium bromide or titanium chloride, preferably at least one of titanium tribromide, titanium tetrabromide, titanium trichloride and titanium tetrachloride, more preferably titanium trichloride and/or titanium tetrachloride.
Preferably, the spray drying is carried out at an inlet temperature of 80-240 ℃ and an outlet temperature of 60-130 ℃.
Accordingly, the present invention also provides a process for the preparation of the catalyst component comprising:
step S1, mother liquor preparation: reacting an electron donor compound, magnesium halide, titanium halide and alternating copolymer macromolecules to prepare mother liquor;
step S2, carrier blending: mixing the mother liquor prepared in the step S1 with an ultrafine inorganic oxide carrier to obtain a slurry liquid material;
step S3, spray forming: spray-drying the slurry obtained in step S2 to obtain the catalyst component.
According to a preferred embodiment of the production method of the present invention, the spraying conditions in the step S3 are: the inlet temperature is 80-240 ℃, preferably 120-180 ℃; the outlet temperature is 60 to 130 ℃ and preferably 90 to 120 ℃.
In the above preparation method, the ultrafine inorganic oxide support should be dry, i.e., free from adsorbed water, at the time of use. A sufficient amount of the carrier should be mixed with the mother liquor to form a slurry suitable for spray drying, i.e. the carrier content in the slurry is from 5% to 50% by weight, preferably from 10% to 30% by weight.
In order to make the solid catalyst component obtained after spray-drying suitable for the production of ethylene polymers, it is necessary to reduce the titanium atom in the catalyst component to a state capable of efficiently polymerizing ethylene with an organoaluminum compound which is an activator component. Generally, the solid catalyst component obtained in step S3 is reacted with an activator component in a hydrocarbon solvent to obtain a catalyst; the catalyst component obtained in step S3 may also be reacted with an activator component during polymerization to initiate olefin polymerization.
The present invention also provides a catalyst for olefin polymerization comprising the reaction product of:
(A) the catalyst component of the present invention;
(B) the general formula is A1RnX3-nWherein R is hydrogen or a hydrocarbon group having 1 to 20 carbon atoms, X is halogen, preferably chlorine, bromine or iodine, and n is 0 < n.ltoreq.3.
According to a specific embodiment, in the general formula A1R'nX3-nIn the formula, n is more than 1 and less than or equal to 3. In certain embodiments, the formula is A1RnX3-nThe organic aluminum compound is selected from one of triethyl aluminum, triisobutyl aluminum, tri-n-hexyl aluminum, tri-n-octyl aluminum or diethyl aluminum chloride or a mixture thereof. Preferably, in the catalyst, the molar ratio of aluminum contained in component (B) to titanium contained in component (a) is from 5:1 to 500:1, preferably from 10:1 to 200: 1.
Such as isopentane, hexane, heptane, toluene, xylene, naphtha, mineral oil, and the like.
The catalyst of the present invention can be used for the homopolymerization and copolymerization of olefin.
The catalyst of the present invention is suitable for homopolymerization of ethylene or copolymerization of ethylene and other olefin, and the α -olefin is selected from propylene, butene, pentene, hexene, octene and 4-methylpentene-1.
Compared with the prior art, the invention has the following obvious advantages:
the catalyst for olefin polymerization or copolymerization of the invention adopts superfine inorganic oxide as a carrier, electron donor compound solvent is used for dissolving magnesium halide, and a certain proportion of alternating copolymer macromolecules and titanium compound are added, so that the catalyst with high activity is generated by a spray forming mode, and the obtained polymer has higher bulk density and higher melt index. In addition, the catalyst has high activity, and has less breakage and low fine powder content especially in gas phase polymerization.
Detailed Description
The present invention will be further described with reference to the following examples.
The test method comprises the following steps:
1. activity: expressed as the weight of resin obtained per gram of catalyst;
2. polymer Melt Index (MI): model 6932 melt index apparatus, CEAST, Italy;
3. polymer apparent density (BD): reference is made to ASTM D1895-69.
4. The contents of titanium, magnesium and silicon were analyzed by 7500cx ICP-MS element analyzer of Aglient, USA.
5. THF content, determined by gas chromatography, Rayleigh form P-300.
6. The copolymer content, determined by liquid nuclear magnetism, was AVANCE model 300 from Bruker, Switzerland.
The following examples are given for the purpose of illustrating the invention and are not to be construed as limiting the invention.
The raw materials used in the examples are all commercial products;
example 1
(1) Preparation of the catalyst
To 2.5m31300L of tetrahydrofuran and 13L of TiCl are added in sequence into the reaction kettle454 kg of anhydrous MgCl21.0 kg of an alternating styrene-maleic anhydride copolymer (Mn 20000) was heated to 67 ℃ with stirring and reacted at this temperature for 6 hours at constant temperature. Cooling to 35 deg.C, adding 80 kg of silica gel (Cabot Corporation TS-610, particle size 0.05-0.5 μm), keeping at 65 deg.C, stirring for 3 hr, cooling to 50 deg.C, and spray drying the slurry with centrifugal spray dryer under the following spray conditions: the inlet temperature was 150 ℃ and the outlet temperature was 100 ℃ to give 220 kg of the solid catalyst component, the titanium content of which was 2.17 Wt%.
(2) Ethylene slurry polymerization
Adding 1L of hexane into a 2L polymerization kettle which is blown off by nitrogen, simultaneously adding 1 mL of 1mmol of triethyl aluminum and 0.02 g of catalyst, wherein the molar ratio of aluminum to titanium is 150, heating to 75 ℃, adding 0.18Mpa of hydrogen, adding 0.75Mpa of ethylene after hydrogenation, heating to 85 ℃, reacting for 2 hours, cooling and discharging. The contents of the catalyst elements are shown in Table 1, and the polymerization results are shown in Table 2.
(3) Gas phase polymerization of ethylene
Taking 1 kg of catalyst component, adding the catalyst component into a catalyst feeding preparation kettle, preparing the catalyst component and 10L of hexane into suspension, and feeding the suspension into a peristaltic pump
Gas-phase fluidized bed, aluminum-titanium ratio is 50, reaction temperature is 85 ℃, hydrogen-ethyl ratio is 0.19, and continuous polymerization is carried out for one week. The polymerization results are shown in Table 2.
Example 2
(1) The catalyst was prepared as in example 1. Except that the styrene maleic anhydride alternating copolymer had a number average molecular weight Mn of 80000, still used in an amount of 1.0 kg, and the titanium content of the resulting solid catalyst component was 2.29 Wt%.
(2) Ethylene slurry polymerization example 1, the catalyst element contents are shown in table 1, and the polymerization results are shown in table 2.
Example 3
(1) Preparation of the catalyst
A250 ml four-necked flask purged with nitrogen was charged first with 0.7 g TiCl33.5 g of anhydrous MgCl2130m of 1 tetrahydrofuran, the temperature was raised to 66 ℃ with stirring, and the reaction was carried out at this temperature for 3 hours at constant temperature. The temperature was reduced to 35 ℃, 1.0 g of styrene maleic anhydride alternating copolymer (number average molecular weight Mn 75000) was added and stirring was continued for 1 hour.
6 g of silica gel (Cabot Corporation TS-610, particle size 0.05 to 0.5 μm) was added to a 250m1 four-necked flask purged with nitrogen, and the mother liquor after cooling was added thereto, and stirred at 35 ℃ for 1 hour. The slurry was spray-dried using a spray dryer under the following spray conditions: the inlet temperature was 140 ℃ and the outlet temperature was 102 ℃ to obtain a solid catalyst component in which the titanium content was 1.07 Wt%.
(2) Ethylene slurry polymerization example 1, the catalyst element contents are shown in table 1, and the polymerization results are shown in table 2.
Example 4
(1) Preparation of the catalyst
To 2.5m31300L of tetrahydrofuran and 15 kg of TiCl are added in sequence into the reaction kettle354 kg of anhydrous MgCl21.0 kg of an alternating styrene-maleic anhydride copolymer (Mn 60000) was heated to 67 ℃ with stirring and reacted at this temperature for 6 hours at a constant temperature. Cooling to 35 deg.C, adding 80 kg of silica gel (Cabot Corporation TS-610, particle size 0.05-0.5 μm), keeping at 65 deg.C, stirring for 3 hr, cooling to 50 deg.C, and spray drying the slurry with centrifugal spray dryer under the following spray conditions: the inlet temperature was 140 ℃ and the outlet temperature was 94 ℃ to give 220 kg of the solid catalyst component, the titanium content of which was 2.27 Wt%.
(2) Ethylene slurry polymerization example 1, the catalyst element contents are shown in table 1, and the polymerization results are shown in table 2.
(3) The results of the gas phase polymerization of ethylene, as in example 1, are shown in Table 3.
Example 5
(1) Preparation of the catalyst
Into a 250ml four-necked flask purged with nitrogen, 3.65 g of TiCl were added46.0 g of anhydrous MgCl21.0 g of alternating styrene-maleic anhydride copolymer (Mn 120000) and 120m of 1 tetrahydrofuran were heated to 65 ℃ with stirring and reacted at this temperature for 4 hours. The temperature is reduced to 35 ℃.
6 g of silica gel (Cabot Corporation TS-610, particle size 0.05 to 0.5 μm) was added to a 250m1 four-necked flask purged with nitrogen, the mother liquor after cooling was added, the temperature was maintained at 35 ℃ and stirred for 1 hour, and the slurry was spray-dried using a spray dryer under spray conditions: the inlet temperature was 150 ℃ and the outlet temperature was 110 ℃ to obtain a solid catalyst component in which the titanium content was 4.02 Wt%.
(2) Ethylene slurry polymerization example 1, the catalyst element contents are shown in table 1, and the polymerization results are shown in table 2.
Comparative example 1
(1) Preparation of the catalyst
1.5 g TiCl were added first and second to a 250m1 four-necked flask purged with nitrogen44.0 g of anhydrous MgCl2And 100m of 1 tetrahydrofuran, and the temperature was raised to 65 ℃ with stirring, and the reaction was carried out at this temperature for 3 hours at constant temperature. The temperature is reduced to 35 ℃.
Adding 6 g of silica gel (Cabot Corporation TS-610, particle size 0.02-0.1 micron) into a 250ml three-neck flask which is blown off by nitrogen, adding the mother liquor after cooling, keeping the temperature at 35 ℃, stirring for 1 hour, and then carrying out spray drying on the mother liquor after mixing the silica gel by a spray dryer, wherein the spray conditions are as follows: the inlet temperature was 155 ℃ and the outlet temperature was 110 ℃ to obtain a solid catalyst component in which the titanium content was 2.2 Wt%.
(2) Ethylene slurry polymerization example 1, the catalyst element contents are shown in table 1, and the polymerization results are shown in table 2.
Comparative example 2
(1) Preparation of the catalyst
To 2.5m31300L of tetrahydrofuran and 13L of TiCl are added in sequence into the reaction kettle454 kg of anhydrous MgCl2The temperature was raised to 67 ℃ with stirring, and the reaction was carried out at this temperature for 6 hours at constant temperature. Cooling to 35 deg.C, adding 80 kg of silica gel (Cabot corporation TS-610, particle size 0.05-0.5 μm), keeping at 65 deg.C, stirring for 3 hr, cooling to 50 deg.C, and spray drying the slurry with centrifugal spray dryer under the following spray conditions: the inlet temperature was 150 ℃ and the outlet temperature was 100 ℃ to give 220 kg of the solid catalyst component, the titanium content of which was 2.20 Wt%.
(2) Ethylene slurry polymerization example 1, the catalyst element contents are shown in table 1, and the polymerization results are shown in table 2.
TABLE 1 catalyst component content
| Numbering | Ti％ | Mg％ | Carrier% | THF％ | Copolymer% |
| Example 1 | 2.17 | 6.1 | 28.5 | 26.1 | 0.5 |
| Example 2 | 2.29 | 6.2 | 29.0 | 25.8 | 0.5 |
| Example 3 | 1.07 | 3.8 | 28.7 | 16.3 | 0.3 |
| Example 4 | 2.27 | 6.2 | 33.9 | 26.2 | 0.5 |
| Example 5 | 4.02 | 7.3 | 15.8 | 29.9 | 2.5 |
| Comparative example 1 | 2.20 | 6.2 | 18.6 | 28.5 | 0 |
| Comparative example 2 | 2.20 | 6.2 | 18.7 | 28.9 | 0 |
TABLE 2 Polymer Properties
As can be seen from the data in Table 2, the catalyst obtained according to the invention has a higher polymerization activity and a higher bulk density of the polymer powder. From the results of the powder screening, the powder of the examples was still lower in the ratio of the three items after screening than in the comparative example. The difference is not yet sufficiently significant. In the gas phase polymerization, however, the results showed very large differences, as shown in Table 3.
TABLE 3 gas-phase polymerization powder Properties
As can be seen from the data in Table 3, the catalyst activity under pilot gas fluidized bed polymerization conditions was close to that of the pilot slurry runs, but the polymerization conditions were very different and not suitable for direct comparison. Under the same conditions, the catalysts of the examples have higher activity than the catalysts of the comparative examples, mainly because the catalysts of the comparative examples are seriously crushed and the polymerization activity is affected, and the specific reasons are discussed in special papers and are not described in detail in the patent. The screening results show that the embodiment has great difference from the comparative example, and the embodiment effectively overcomes the crushing problem under the gas-phase polymerization condition.
Claims (9)
1. An olefin polymerization catalyst, characterized in that said catalyst comprises:
based on the total weight of the catalyst as 100 percent,
the molar ratio of magnesium to titanium is 0.1-10;
the particle size of the superfine inorganic oxide carrier is 0.01-10 microns;
the alternating copolymer macromolecule is an alternating polymerization product of styrene and maleic anhydride;
the electron donor compound is selected from C1-C4Alkyl esters of saturated fatty carboxylic acids, C7-C8Alkyl esters of aromatic carboxylic acids, C2-C6Fatty ethers, C3-C4Cyclic ethers and C3-C6At least one saturated aliphatic ketone.
2. An olefin polymerization catalyst as claimed in claim 1 wherein:
based on the total weight of the catalyst as 100 percent,
the particle size of the superfine inorganic oxide carrier is 0.02-5 microns;
the polymerization degree of the alternating polymerization product of styrene and maleic anhydride is 100-2000;
the molar ratio of magnesium to titanium is 1-10.
3. The olefin polymerization catalyst of claim 2, wherein:
based on the total weight of the catalyst as 100 percent,
the particle size of the superfine inorganic oxide carrier is 0.05-1 micron; the inorganic oxide is silicon dioxide;
the molar ratio of magnesium to titanium is 2-7.
4. The olefin polymerization catalyst of claim 1, wherein:
the electron donor compound is at least one selected from the group consisting of methyl formate, ethyl formate, isopropyl formate, n-propyl formate, methyl acetate, ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, diethyl ether, propyl ether, hexyl ether, tetrahydrofuran, acetone, and methyl isobutyl ketone.
5. A process for preparing a catalyst for olefin polymerization according to any one of claims 1 to 4, which comprises:
adding an electron donor compound, magnesium halide, titanium halide, an alternating copolymer and a superfine inorganic oxide carrier into a preparation kettle, heating for dissolution reaction, wherein the reaction temperature is 60-80 ℃, the pressure in the reaction kettle is not higher than 0.2MPa, and the reaction time is not lower than 2 hours; after magnesium halide is completely dissolved, cooling the slurry to 30-55 ℃, and carrying out spray drying to obtain the catalyst;
the total amount of the raw materials is 100 percent:
the magnesium halide is selected from at least one of magnesium dichloride, magnesium dibromide and magnesium diiodide;
the titanium halide is selected from at least one of titanium tribromide, titanium tetrabromide, titanium trichloride and titanium tetrachloride.
6. The process for preparing a catalyst for olefin polymerization according to claim 5, wherein:
the content of the superfine inorganic oxide carrier in the slurry is 3-10 wt%;
the spray drying conditions were: the inlet temperature is 80-240 ℃; the outlet temperature is 60-130 ℃.
7. The process for preparing a catalyst for olefin polymerization according to claim 6, wherein:
the spray drying conditions were: the inlet temperature is 120-180 ℃; the outlet temperature is 90-120 ℃.
8. A composite catalyst of an olefin polymerization catalyst according to any one of claims 1 to 4, wherein the composite catalyst comprises:
(A) an olefin polymerization catalyst according to any one of claims 1 to 4;
(B) the general formula is A1RnX3-n(ii) an organoaluminum compound of (a),
r is hydrogen or alkyl with 1-20 carbon atoms; x is a halogen, and X is a halogen,
0＜n≤3；
the molar ratio of aluminum contained in component (B) to titanium contained in component (A) is 5:1 to 500: 1.
9. The composite catalyst of claim 8, wherein:
the organic aluminum compound is selected from one or a combination of triethyl aluminum, triisobutyl aluminum, tri-n-hexyl aluminum, tri-n-octyl aluminum or diethyl aluminum monochloride;
the molar ratio of aluminum contained in component (B) to titanium contained in component (A) is 10:1 to 200: 1.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113527554A (en) * | 2020-04-21 | 2021-10-22 | 中国石油化工股份有限公司 | Catalyst component, preparation method thereof, catalyst and application thereof |
| CN114426605A (en) * | 2020-10-09 | 2022-05-03 | 中国石油化工股份有限公司 | Catalyst component for olefin polymerization and preparation method and application thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102050896A (en) * | 2009-10-27 | 2011-05-11 | 中国石油化工股份有限公司 | Catalyst for ethylene polymerization and preparation method thereof |
| CN102050894A (en) * | 2009-10-30 | 2011-05-11 | 中国石油化工股份有限公司 | Catalyst used for vinyl polymerization |
| CN102432710A (en) * | 2010-09-29 | 2012-05-02 | 中国石油化工股份有限公司 | Preparation method of ethylene polymerization catalyst carrier, catalyst components and catalyst |
| CN104974283A (en) * | 2014-04-11 | 2015-10-14 | 中国石油化工股份有限公司 | Catalyst component used in ethylene polymerization reaction, catalyst and preparation method thereof |
-
2018
- 2018-08-28 CN CN201810985177.XA patent/CN110862472A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102050896A (en) * | 2009-10-27 | 2011-05-11 | 中国石油化工股份有限公司 | Catalyst for ethylene polymerization and preparation method thereof |
| CN102050894A (en) * | 2009-10-30 | 2011-05-11 | 中国石油化工股份有限公司 | Catalyst used for vinyl polymerization |
| CN102432710A (en) * | 2010-09-29 | 2012-05-02 | 中国石油化工股份有限公司 | Preparation method of ethylene polymerization catalyst carrier, catalyst components and catalyst |
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| CN113527554A (en) * | 2020-04-21 | 2021-10-22 | 中国石油化工股份有限公司 | Catalyst component, preparation method thereof, catalyst and application thereof |
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