CN109400775B - Catalyst component for olefin polymerization, preparation method thereof, catalyst for olefin polymerization and olefin polymerization method - Google Patents
Catalyst component for olefin polymerization, preparation method thereof, catalyst for olefin polymerization and olefin polymerization method Download PDFInfo
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- CN109400775B CN109400775B CN201710711475.5A CN201710711475A CN109400775B CN 109400775 B CN109400775 B CN 109400775B CN 201710711475 A CN201710711475 A CN 201710711475A CN 109400775 B CN109400775 B CN 109400775B
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Abstract
The invention relates to the field of olefin polymerization, and discloses a catalyst component for olefin polymerization, a preparation method thereof, a catalyst and an olefin polymerization method, wherein the method comprises the following steps: (1) reacting a magnesium halide of the formula MgXY with a compound of the formula R1Mixing OH alcohol compounds, emulsifying, carrying out contact reaction on the obtained emulsion and an ethylene oxide compound shown in a formula (1), and then carrying out solid-liquid separation; wherein X is halogen, Y is halogen, C1‑C14Alkyl of (C)6‑C14Aryl radical, C1‑C14Alkoxy or C6‑C14An aryloxy group of (a); r1Is C1‑C8Alkyl or C3‑C8Cycloalkyl groups of (a); r2And R3Each independently is hydrogen, C1‑C5Alkyl or haloalkyl of (a); (2) directly mixing a solid phase obtained by solid-liquid separation with an inert solvent without washing, and adjusting the temperature of the obtained mixture to-50 ℃ to 10 ℃; (3) and (3) carrying out contact reaction on the mixture obtained in the step (2), a titanium compound and an optional internal electron donor compound. The prepared catalyst component has high catalytic activity and better hydrogen regulation sensitivity.
Description
Technical Field
The invention relates to the field of olefin polymerization, in particular to a preparation method of a catalyst component for olefin polymerization, a catalyst component for olefin polymerization obtained by the preparation method, a catalyst for olefin polymerization containing the catalyst component for olefin polymerization and an olefin polymerization method.
Background
It is well known that magnesium chloride supported Ziegler-Natta catalysts perform significantly better than other supported catalysts when used in propylene polymerization. Therefore, catalysts for olefin polymerization are mostly prepared by supporting titanium halides on activated magnesium chloride. The spherical magnesium chloride can be used for preparing spherical catalysts, and has good fluidity and wide application. For example, WO99/44009 and US4399054 disclose spherical carriers prepared by high-temperature high-agitation emulsification of magnesium chloride alcoholate systems, followed by quenching to form solids, washing and drying. In addition, CN102040683A proposes a method of obtaining a spherical carrier by reacting a magnesium halide alcoholate with an oxirane to precipitate a solid.
However, to obtain a spherical support for direct use in the preparation of catalysts, the spherical solid obtained by either method needs to be subjected toCan be used for preparing the catalyst after certain processing steps. The use of MgCl is proposed in patent publication CN1047302A (Himont, Simmond)2Reacting with ethanol to obtain MgCl2·(C2H5OH)nThe magnesium chloride alcoholate must be dealcoholized by heating to 180 ℃ in a nitrogen stream to reduce n to less than 1.7 before being used to synthesize the catalyst. This not only increases the dealcoholization equipment and lengthens the flow path, but also increases the nitrogen cost and heat energy consumption. For example, CN102040683A discloses that in the preparation process of a spherical carrier, after a solid is precipitated by reacting an ethylene oxide compound with a magnesium halide alcoholate ethanol solution, the solid-liquid separation is followed by washing with an inert solvent for multiple times, and then vacuum drying is performed to prepare the catalyst. Thus, not only is the process flow increased, but also the solvent and the energy consumption for drying are increased.
Disclosure of Invention
The invention aims to overcome the problem of complex process for preparing the catalyst in the prior art, and provides a catalyst component for olefin polymerization, a preparation method thereof, a catalyst for olefin polymerization and an olefin polymerization method.
In order to achieve the above objects, the present inventors have surprisingly found in a large number of experiments that, in the preparation of a catalyst support, after the catalyst support solid is formed, the separated solid phase inert solvent is mixed by solid-liquid separation, and the temperature of the mixture is merely reduced to a certain temperature, and then the active titanium is supported, so that a spherical catalyst with a good appearance can be prepared. Therefore, the process can be shortened, equipment and energy are saved, the economic benefit is better, and the hydrogen regulation sensitivity of the prepared catalyst is better.
Accordingly, in one aspect, the present invention provides a method for preparing a catalyst component for olefin polymerization, wherein the method comprises:
(1) reacting a magnesium halide of the formula MgXY with a compound of the formula R1Mixing OH alcohol compounds, emulsifying, carrying out contact reaction on the obtained emulsion and an ethylene oxide compound shown in a formula (1), and then carrying out solid-liquid separation;
wherein in the general formula MgXY, X is halogen, Y is halogen and C1-C14Alkyl of (C)6-C14Aryl radical, C1-C14Alkoxy or C6-C14An aryloxy group of (a); general formula R1In OH, R1Is C1-C8Alkyl or C3-C8Cycloalkyl groups of (a); in the formula (1), R2And R3Each independently is hydrogen, C1-C5Alkyl or haloalkyl of (a);
(2) mixing the solid phase obtained by solid-liquid separation directly with an inert solvent without washing, and adjusting the temperature of the obtained mixture to-50 ℃ to 10 ℃, preferably-30 ℃ to-10 ℃, and more preferably-30 ℃ to-20 ℃;
(3) and (3) carrying out contact reaction on the mixture obtained in the step (2), a titanium compound and an optional internal electron donor compound.
The second aspect of the present invention provides a catalyst component for olefin polymerization prepared by the preparation method of the present invention.
In a third aspect, the present invention provides a catalyst for olefin polymerization, wherein the catalyst comprises:
(1) the catalyst component for olefin polymerization of the present invention;
(2) an alkyl aluminum compound; and
(3) optionally an external electron donor compound.
In a fourth aspect, the present invention provides an olefin polymerization process, wherein the olefin polymerization process comprises: one or more olefins are contacted with the catalyst component for the polymerization of olefins of the present invention, an aluminum alkyl compound, and optionally an external electron donor compound, under olefin polymerization conditions.
In the preparation method, after the catalyst carrier solid is formed, the solid-liquid separation is carried out, washing is not needed, and the spherical catalyst with good appearance can be prepared by directly mixing the solid phase with the inert solvent and then cooling. Therefore, the process can be shortened, equipment and energy are saved, and the economic benefit is better. Meanwhile, the morphology of the carrier can be improved, the stability of product preparation is improved, and the hydrogen regulation performance of the prepared catalyst is better.
Detailed Description
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
In one aspect, the present invention provides a method for preparing a catalyst component for olefin polymerization, wherein the method comprises:
(1) reacting a magnesium halide of the formula MgXY with a compound of the formula R1Mixing OH alcohol compounds, emulsifying, carrying out contact reaction on the obtained emulsion and an ethylene oxide compound shown in a formula (1), and then carrying out solid-liquid separation;
wherein in the general formula MgXY, X is halogen, Y is halogen and C1-C14Alkyl of (C)6-C14Aryl radical, C1-C14Alkoxy or C6-C14An aryloxy group of (a); general formula R1In OH, R1Is C1-C8Alkyl or C3-C8Cycloalkyl groups of (a); in the formula (1), R2And R3Each independently is hydrogen, C1-C5Alkyl or haloalkyl of (a);
(2) mixing the solid phase obtained by solid-liquid separation directly with an inert solvent without washing, and adjusting the temperature of the obtained mixture to-50 ℃ to 10 ℃, preferably-30 ℃ to-10 ℃, and more preferably-30 ℃ to-20 ℃;
(3) and (3) carrying out contact reaction on the mixture obtained in the step (2), a titanium compound and an optional internal electron donor compound.
In the invention, the solid phase obtained after the solid-liquid separation in the step (1) is a spherical carrier which is not subjected to subsequent washing and drying, and the spherical carrier is directly mixed with an inert solvent and then cooled to prepare the catalyst component with good appearance and catalytic performance.
According to the invention, in step (1), a magnesium halide of the formula MgXY, of the formula R1The condition for mixing the alcohol compound of OH is not particularly limited as long as the condition allows magnesium halide of the formula MgXY to be mixed with the alcohol compound of the formula R1And (3) fully reacting the OH alcohol compound. According to the present invention, preferably, the conditions of the process of mixing the magnesium halide and the alcohol compound include: the temperature is 50-120 ℃; further preferably 60 to 90 ℃; the time is 0.5 to 5 hours, and more preferably 0.5 to 3 hours.
According to the present invention, the amount of the magnesium halide of the formula MgXY, the compound of the formula ROH, and the ethylene oxide compound to be used may be appropriately selected depending on the composition of the catalyst support for olefin polymerization to be expected. In the present invention, it is preferable. With respect to 1mol of magnesium halide of the formula MgXY, said formula being R1The dosage of OH alcohol compounds is 4-30mol, and the dosage of ethylene oxide compounds is 1-10 mol.
More preferably, in the present invention, the compound of the formula R is used in an amount of 1mol per mole of magnesium halide of the formula MgXY1The dosage of OH alcohol compounds is 6-20mol, and the dosage of ethylene oxide compounds is 2-6 mol.
According to the invention, in the magnesium halide of formula MgXY, X is chlorine or bromine and Y is chlorine, bromine, C1-C5Alkyl of (C)1-C5Alkoxy group of (C)6-C10Aryl or C of6-C10An aryloxy group of (1). In the present invention, said C1-C5Alkyl groups of (a) include, but are not limited to, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl; said C is1-C5Alkoxy group ofIncluding but not limited to methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, tert-butoxy, n-pentoxy, isopentoxy; said C is6-C10Aryl groups of (a) include, but are not limited to, phenyl, methylphenyl, ethylphenyl, dimethylphenyl, trimethylphenyl; said C is6-C10The aryloxy group of (a) includes, but is not limited to, phenoxy, methylphenoxy, ethylphenoxy, dimethylphenoxy, trimethylphenoxy.
In the present invention, more preferably, the magnesium halide having the formula MgXY is at least one of magnesium chloride, magnesium bromide, phenoxymagnesium chloride, isopropoxymagnesium chloride and n-butoxymagnesium chloride.
According to the invention, R is in the general formula1In the alcohol compounds of OH, R1Preferably C1-C8Alkyl groups of (a); more preferably, the general formula is R1The alcohol compound of OH is at least one of ethanol, propanol, isopropanol, n-butanol, isobutanol, pentanol, isopentanol, n-hexanol, n-octanol and 2-ethylhexanol.
In the present invention, preferably, in the oxirane compound represented by formula (1), R is2And R3The same or different, each independently can be hydrogen or C1-C3Alkyl or haloalkyl of (a); further preferably, the ethylene oxide compound is at least one of ethylene oxide, propylene oxide, butylene oxide, epichlorohydrin, chlorobutylene oxide, propylene bromide oxide and butylene bromide oxide.
In the present invention, the solid-liquid separation in step (1) may be performed by any conventional method capable of separating a solid phase from a liquid phase, such as suction filtration, pressure filtration or centrifugal separation, and preferably, the solid-liquid separation is performed by pressure filtration. In the present invention, the conditions for the pressure filtration are not particularly limited, and it is considered that the separation of the solid phase and the liquid phase is sufficiently achieved as much as possible.
According to the present invention, the amount of the inert solvent used in the step (2) is not particularly limited as long as the solid phase obtained by the solid-liquid separation can be dissolved. Preferably, the amount of the inert solvent used in step (2) is 300-3000mL with respect to 1mol of the magnesium halide.
In the present invention, the inert solvent may be various liquids commonly used in the art that do not chemically interact with the reactants and the reaction products. Preferably, the inert solvent is a silicone oil and/or an inert liquid hydrocarbon solvent. Further preferably, the inert solvent is C4-C10One or more of alkane, kerosene, paraffin oil, vaseline oil, white oil, methyl silicone oil, ethyl silicone oil, methyl ethyl silicone oil, phenyl silicone oil and methyl phenyl silicone oil; more preferably, the inert solvent is C4-C10Alkanes and/or white oils.
According to the present invention, preferably, the mixing of the magnesium halide and the alcohol compound is carried out in an inert liquid medium solvent. The amount of the inert liquid medium may be selected according to the amount of magnesium halide of the general formula MgXY. In general, the inert liquid medium may be used in an amount of 0.8 to 10L, preferably 2 to 8L, based on 1mol of magnesium halide of the formula MgXY. The inert liquid medium may be selected from the same inert solvents as in step (2), and will not be described in detail herein.
In the present invention, in the step (3), the weight ratio of the titanium compound in terms of titanium element, the solid phase in terms of magnesium element, and the internal electron donor compound is preferably 1: 5-15: 2-15; more preferably 1: 6-13: 3-12.
In the present invention, the internal electron donor compound may be various internal electron donor compounds conventionally used in the process of preparing a catalyst for olefin polymerization, and preferably, the internal electron donor compound is at least one of carboxylate, alcohol ester, ether, ketone, nitrile, amine and silane; more preferably, the internal electron donor compound is at least one of mono-or poly-aliphatic carboxylic acid ester, mono-or poly-aromatic carboxylic acid ester, glycol ester and glycol ether. In the present invention, the selection of the specific kinds of the mono-or poly-aliphatic carboxylic acid ester, mono-or poly-aromatic carboxylic acid ester, glycol ester and glycol ether can be selected with reference to the prior art, and the present invention will not be described in detail herein.
According to the inventionThe titanium compound may be various titanium-containing compounds conventionally used in the preparation of catalysts for olefin polymerization. The titanium compound is preferably of the formula Ti (OR)n)4-mXmWherein R isnIs C1-C14X is F, Cl or Br, m is an integer from 1 to 4; more preferably, the titanium compound is at least one of titanium tetrachloride, titanium tetrabromide, titanium tetrafluoride, titanium tributoxide chloride, titanium dibutoxide dichloride, titanium butoxytrichloride, titanium triethoxy chloride, titanium diethoxide dichloride and titanium ethoxytrichloride.
In the present invention, the rate of cooling is not particularly limited, and a reasonable rate of cooling may be determined according to the configuration of the apparatus.
In the present invention, the conditions of the contact reaction in step (3) preferably include: the reaction temperature is 80-130 ℃ and the reaction time is 0.5-10 hours.
In the invention, in the step (3), the titanium compound and the mixture obtained in the step (2) are preferably mixed, and then the temperature is slowly increased to reach the reaction temperature, and the internal electron donor compound is preferably added in the process of temperature increase.
The second aspect of the present invention provides a catalyst component for olefin polymerization prepared by the preparation method of the present invention.
In a third aspect, the present invention provides a catalyst for olefin polymerization, wherein the catalyst comprises:
(1) the catalyst component for olefin polymerization of the present invention;
(2) an alkyl aluminum compound; and
(3) optionally an external electron donor compound.
In the present invention, the catalyst component for olefin polymerization has been described in detail in the foregoing, and will not be described in detail herein.
In the invention, the catalyst for olefin polymerization contains the catalyst component for olefin polymerization, so that when the catalyst for olefin polymerization is used as a catalyst for olefin polymerization reaction, the melt flow rate of a polymer obtained by polymerization is greatly improved, and the catalyst has higher hydrogen regulation sensitivity.
In the present invention, it is preferable that, in the catalyst for olefin polymerization, the molar ratio of the alkylaluminum compound in terms of aluminum element to the catalyst component for olefin polymerization in terms of titanium element is from 1 to 2000: 1, preferably 20 to 500: 1; the molar ratio of the external electron donor compound to the alkyl aluminum compound is 0.005-0.5: 1, preferably 0.01 to 0.4: 1.
in the present invention, the alkyl aluminum compound may be various alkyl aluminum compounds commonly used in the art. For example, the alkyl aluminum compound may be one or more of triethylaluminum, triisobutylaluminum, tri-n-butylaluminum, tri-n-hexylaluminum, diethylaluminum monochloride, diisobutylaluminum monochloride, di-n-butylaluminum monochloride, di-n-hexylaluminum monochloride, ethylaluminum dichloride, isobutylaluminum dichloride, n-butylaluminum dichloride, and n-hexylaluminum dichloride.
In the present invention, the external electron donor compound may be various external electron donor compounds commonly used in the art, for example, the external electron donor compound may be one or more of carboxylic acid, acid anhydride, ester, ketone, ether, alcohol, organic phosphorus compound, and organic silicon compound; preferably, the external electron donor is of the formula R4 aR5 bSi(OR6)cWherein a and b are each independently an integer of 0, 1 or 2, c is an integer of 1 to 3, and the sum of a + b + c is 4, R4、R5、R6Each independently is C1-C18Substituted or unsubstituted hydrocarbyl of (a); more preferably, a and b are each 1, c is 2, R4、R5Each independently is C3-C10Substituted or unsubstituted hydrocarbyl of, R6Is C1-C10Substituted or unsubstituted hydrocarbyl. Specifically, examples of the organosilicon compound may be, but are not limited to: cyclohexylmethyldimethoxysilane, diisopropyldimethoxysilane, di-n-butyldimethoxysilane, diisobutyldimethoxysilane, diphenyldimethoxysilane, methyl-t-butyldimethoxysilane, dicyclopentyldimethoxysilaneAt least one of dimethoxysilane, 2-ethylpiperidinyl-2-t-butyldimethoxysilane, (1,1, 1-trifluoro-2-propyl) -2-ethylpiperidinyldimethoxysilane and (1,1, 1-trifluoro-2-propyl) -methyldimethoxysilane.
In a fourth aspect, the present invention provides an olefin polymerization process, wherein the olefin polymerization process comprises: one or more olefins are contacted with the catalyst component for the polymerization of olefins of the present invention, an aluminum alkyl compound, and optionally an external electron donor compound, under olefin polymerization conditions.
In the present invention, the conditions for olefin polymerization and the olefin to be used are not particularly limited. The olefin may be, for example, one or more of ethylene, propylene, 1-butene, 2-methyl-1-butene, 3-methyl-1-butene, 2-methyl-2-butene, 1-pentene, 2-pentene, 1-hexene and styrene, preferably one or more of ethylene, propylene, 1-butene, 2-butene and styrene.
In the present invention, the olefin polymerization may be carried out according to a conventional method in the art. For example, the olefin polymerization may be bulk polymerization, gas phase polymerization, or slurry polymerization. The olefin polymerization conditions may be conventional in the art, for example, the polymerization temperature may be from 0 to 150 ℃, preferably from 60 to 90 ℃; the polymerization pressure may be atmospheric pressure or elevated pressure.
More preferably, the process for the polymerization of olefins according to the present invention comprises: at least one olefin is contacted with the catalyst component for olefin polymerization, an alkyl aluminum compound and an optional external electron donor compound under olefin polymerization conditions to carry out olefin polymerization reaction.
The present invention will be described in detail below by way of examples.
The following examples relate to performance tests as follows:
1. the apparent morphology of the catalyst component for olefin polymerization was observed by means of an optical microscope, commercially available from Nikon under the model Eclipse E200;
2. polymer melt flow rate: measured according to ASTM D1238-99;
3. polymer isotactic index: the determination is carried out by adopting a heptane extraction method (boiling extraction for 6 hours by heptane), namely, a 2g dried polymer sample is taken and placed in an extractor to be extracted for 6 hours by boiling heptane, then, the residue is dried to constant weight, and the ratio of the weight (g) of the obtained polymer to 2 is the isotactic index.
Preparation example 1
Adding 0.08mol of magnesium chloride and 0.96mol of ethanol into a 0.6L reaction kettle, heating to 80 ℃ under stirring, and reacting for 2 hours at constant temperature. Adding 0.48mol (38mL) of epichlorohydrin, reacting for half an hour, then performing pressure filtration, directly mixing a pressure filtration product with 200mL of hexane, cooling to-30 ℃, adding 150mL (1.35mol) of titanium tetrachloride, stirring at-30 ℃ for 30min, then slowly heating to 110 ℃, adding 1.5mL of diisobutyl phthalate in the heating process, maintaining at 110 ℃ for 30min, and then filtering out the liquid. The obtained solid was washed 2 times with titanium tetrachloride and 3 times with hexane, and dried to obtain catalyst component C1 for olefin polymerization.
The catalyst component C1 for olefin polymerization was observed with an optical microscope without substantially breaking.
Preparation example 2
Adding 0.08mol of magnesium chloride and 1.6mol of ethanol into a 0.6L reaction kettle, heating to 90 ℃ under stirring, and reacting for 3 hours at constant temperature. Adding 0.32mol of epoxy chloropropane, reacting for half an hour, then performing pressure filtration, directly mixing a pressure filtration product with 100mL of hexane, cooling to-20 ℃, adding 145mL of titanium tetrachloride, stirring at-20 ℃ for 30min, then slowly heating to 120 ℃, adding 1.3mL of diisobutyl phthalate in the heating process, maintaining at 120 ℃ for 40min, and then filtering out liquid. The obtained solid was washed 2 times with titanium tetrachloride and 3 times with hexane, and dried to obtain catalyst component C2 for olefin polymerization.
The catalyst component C2 for olefin polymerization was observed with an optical microscope without substantially breaking.
Preparation example 3
Adding 0.08mol of magnesium chloride and 0.48mol of ethanol into a 0.6L reaction kettle, heating to 60 ℃ under stirring, and reacting for 1 hour at constant temperature. Adding 0.16mol (38mL) of epichlorohydrin, reacting for half an hour, then performing pressure filtration, directly mixing a pressure filtration product with 40mL of hexane, cooling to-30 ℃, adding 124mL of titanium tetrachloride, stirring at-30 ℃ for 30min, then slowly heating to 90 ℃, adding 1.05mL of diisobutyl phthalate in the heating process, maintaining at 90 ℃ for 60min, and then filtering out the liquid. The obtained solid was washed 2 times with titanium tetrachloride and 3 times with hexane, and dried to obtain catalyst component C2 for olefin polymerization.
The catalyst component C2 for olefin polymerization was observed with an optical microscope without substantially breaking.
Preparation example 4
Adding 0.08mol of magnesium chloride and 0.96mol of ethanol into a 0.6L reaction kettle, heating to 80 ℃ under stirring, and reacting for 2 hours at constant temperature. Adding 0.48mol (38mL) of epichlorohydrin, reacting for half an hour, then performing pressure filtration, directly mixing a pressure filtration product with 24mL of hexane, cooling to-30 ℃, adding 150mL (1.35mol) of titanium tetrachloride, stirring at-30 ℃ for 30min, then slowly heating to 110 ℃, adding 1.5mL of diisobutyl phthalate in the heating process, maintaining at 110 ℃ for 30min, and then filtering out the liquid. The obtained solid was washed 2 times with titanium tetrachloride and 3 times with hexane, and dried to obtain catalyst component C4 for olefin polymerization.
The catalyst component C4 for olefin polymerization was observed with an optical microscope without substantially breaking.
Preparation example 5
A catalyst component for olefin polymerization was prepared according to the method of preparation example 1, except that paraffin oil was used in place of hexane.
To obtain a catalyst component C5 for olefin polymerization.
The catalyst component C5 for olefin polymerization was observed with an optical microscope without substantially breaking.
Preparation example 6
In a 0.6L reaction kettle, 0.08mol of magnesium chloride, 0.96mol of ethanol and 0.5g of polyvinylpyrrolidone are added, and the temperature is raised to 80 ℃ under stirring. After 2 hours of isothermal reaction. Adding 0.48mol (38mL) of epoxy chloropropane, reacting for half an hour, then performing pressure filtration, mixing a pressure filtration product with 200mL of hexane, cooling to-30 ℃, adding 150mL of titanium tetrachloride, and stirring for 30min at-30 ℃. Then, the temperature was slowly increased to 110 ℃ and 1.5mL of diisobutyl phthalate was added during the temperature increase, and the solution was filtered off after maintaining at 110 ℃ for 30 min. The obtained solid was washed 2 times with titanium tetrachloride and finally 3 times with hexane, and dried to obtain olefin polymerization catalyst C6.
The catalyst component C6 for olefin polymerization was observed with an optical microscope without substantially breaking.
Comparative preparation example 1
0.08mol of magnesium chloride and 0.96mol of ethanol are added into a 0.6L reaction kettle, and the temperature is raised to 80 ℃ under stirring. After 2 hours of isothermal reaction. Adding 0.48mol (38ml) of epichlorohydrin, reacting for half an hour, then performing pressure filtration, washing a pressure filtration product with hexane for 5 times, and performing vacuum drying to obtain a catalyst carrier D-Z1 for olefin polymerization;
in a 300mL glass reaction flask, 150mL of titanium tetrachloride was added, cooled to-30 ℃, to which D-Z1 was added and stirred at-30 ℃ for 30 min. Then, the temperature was slowly raised to 110 ℃ and 1.5mL of diisobutyl phthalate was added during the temperature raising, and the temperature was maintained at 110 ℃ for 30min, after which the liquid was filtered off. The obtained solid was washed 2 times with titanium tetrachloride and 3 times with hexane, and dried to obtain catalyst components D-C1 for olefin polymerization.
The catalyst component D-C1 for olefin polymerization was observed with an optical microscope to be broken more.
Example 1
In a 5L autoclave, purging was conducted with a nitrogen stream, and then 1mmol of a hexane solution of triethylaluminum (concentration of triethylaluminum is 0.5mmol/mL), 0.05mmol of methylcyclohexyldimethoxysilane, 10mL of anhydrous hexane, and 10mg of catalyst component C1 for olefin polymerization, 1.5L (standard volume) of hydrogen, and 2.5L of liquid propylene were introduced into the nitrogen stream. Heating to 70 ℃, reacting for 1 hour at the temperature, cooling, releasing pressure, discharging and drying to obtain the polypropylene powder.
The catalyst activity and the isotactic index and melt flow rate of the resulting polypropylene powder are shown in Table 1.
Examples 2 to 6
Polypropylene powder was prepared by the method of example 1, except that C2, C3, C4, C5 and C6 were used in place of C1, respectively, as the catalyst components for olefin polymerization. The catalyst activity and the isotactic index and melt flow rate index of the resulting polypropylene powder are shown in Table 1.
Example 7
Polypropylene powder was prepared according to the method of example 1, except that 6.5L of hydrogen was used. The catalyst activity and the isotactic index and melt flow rate of the resulting polypropylene powder are shown in Table 1.
Comparative example 1
Polypropylene powder was prepared by the method of example 1, except that the catalyst component D-C1 for olefin polymerization was used in place of C1. The catalyst activity and the isotactic index and melt flow rate of the resulting polypropylene powder are shown in Table 1.
Comparative example 2
Polypropylene powder was prepared according to the method of comparative example 1, except that 6.5L of hydrogen was used. The catalyst activity and the isotactic index and melt flow rate of the resulting polypropylene powder are shown in Table 1.
TABLE 1
As can be seen from the results of the above preparation examples, the catalyst component for olefin polymerization prepared by the preparation method of the present invention has the advantages of no substantial breakage of the prepared catalyst component and good morphology; as can be seen from the results in Table 1, the catalyst component prepared by the preparation method of the invention is used for olefin polymerization, shows better catalytic activity and hydrogen regulation sensitivity, and the obtained polyolefin powder also has better isotactic index and higher melt flow rate index; as can be seen from a comparison of examples 1 and 6, the effect is better in the presence or absence of the surfactant.
The preferred embodiments of the present invention have been described above in detail, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, many simple modifications can be made to the technical solution of the invention, including combinations of various technical features in any other suitable way, and these simple modifications and combinations should also be regarded as the disclosure of the invention, and all fall within the scope of the invention.
Claims (20)
1. A process for the preparation of a catalyst component for the polymerization of olefins, characterized in that it comprises:
(1) reacting a magnesium halide of the formula MgXY with a compound of the formula R1Mixing OH alcohol compounds, emulsifying, carrying out contact reaction on the obtained emulsion and an ethylene oxide compound shown in a formula (1), and then carrying out solid-liquid separation;
wherein in the general formula MgXY, X is halogen, Y is halogen and C1-C14Alkyl of (C)6-C14Aryl radical, C1-C14Alkoxy or C6-C14An aryloxy group of (a); general formula R1In OH, R1Is C1-C8Alkyl or C3-C8Cycloalkyl groups of (a); in the formula (1), R2And R3Each independently is hydrogen, C1-C5Alkyl or haloalkyl of (a);
(2) directly mixing a solid phase obtained by solid-liquid separation with an inert solvent without washing, and adjusting the temperature of the obtained mixture to-50 ℃ to 10 ℃;
(3) and (3) carrying out contact reaction on the mixture obtained in the step (2), a titanium compound and an optional internal electron donor compound.
2. The production process according to claim 1, wherein in the step (2), the solid phase obtained by the solid-liquid separation is mixed with an inert solvent without washing, and the temperature of the resulting mixture is adjusted to-30 ℃ to-10 ℃.
3. The production process according to claim 2, wherein in the step (2), the solid phase obtained by the solid-liquid separation is mixed with an inert solvent without washing, and the temperature of the resulting mixture is adjusted to-30 ℃ to-20 ℃.
4. The production process according to any one of claims 1 to 3, wherein in the step (1), the mixing of the magnesium halide and the alcohol compound is carried out in an inert liquid medium solvent.
5. The production method according to any one of claims 1 to 3, wherein the conditions of the process of mixing the magnesium halide and the alcohol compound in the step (1) include: the temperature is 50-120 ℃ and the time is 0.5-5 h.
6. The preparation method according to claim 5, wherein the conditions of the process of mixing the magnesium halide and the alcohol compound in step (1) include: the temperature is 60-90 ℃ and the time is 0.5-3 h.
7. The preparation method according to claim 4, wherein the conditions of the process of mixing the magnesium halide and the alcohol compound in step (1) include: the temperature is 50-120 ℃ and the time is 0.5-5 h.
8. The preparation method according to claim 7, wherein the conditions of the process of mixing the magnesium halide and the alcohol compound in step (1) include: the temperature is 60-90 ℃ and the time is 0.5-3 h.
9. The production method according to any one of claims 1 to 3, wherein, in the step (1), the general formula R is R with respect to 1mol of the magnesium halide of the general formula MgXY1The dosage of OH alcohol compounds is 4-30mol, and the dosage of ethylene oxide compounds is 1-10 mol.
10. The production method according to claim 9, wherein, in the step (1), the general formula of R is R with respect to 1mol of the magnesium halide of the general formula of MgXY1The dosage of OH alcohol compounds is 6-20mol, and the dosage of ethylene oxide compounds is 2-6 mol.
11. The production process according to claim 4, wherein, in the step (1), the general formula R is R with respect to 1mol of the magnesium halide of the general formula MgXY1The dosage of OH alcohol compounds is 4-30mol, and the dosage of ethylene oxide compounds is 1-10 mol.
12. The production method according to claim 11, wherein, in the step (1), the general formula of R is R with respect to 1mol of the magnesium halide of the general formula of MgXY1The dosage of OH alcohol compounds is 6-20mol, and the dosage of ethylene oxide compounds is 2-6 mol.
13. The production method according to any one of claims 1 to 3, wherein the amount of the inert solvent used in step (2) is 300-3000ml relative to 1mol of the magnesium halide.
14. The production method according to claim 4, wherein the amount of the inert solvent used in step (2) is 300-3000ml relative to 1mol of the magnesium halide.
15. The production method according to any one of claims 1 to 3, wherein in the step (2), the inert solvent is a silicone oil and/or an inert liquid hydrocarbon solvent.
16. The production method according to claim 4, wherein, in the step (2), the inert solvent is a silicone oil and/or an inert liquid hydrocarbon solvent.
17. The method of claim 15, wherein the inert solvent is C4-C10Paraffin, kerosene, paraffin oil, vaseline oil,One or more of white oil, methyl silicone oil, ethyl silicone oil, methyl ethyl silicone oil, phenyl silicone oil and methyl phenyl silicone oil.
18. The method of claim 17, wherein the inert solvent is C4-C10Alkanes and/or white oils.
19. The method according to claim 16, wherein the inert solvent is C4-C10And one or more of alkane, kerosene, paraffin oil, vaseline oil, white oil, methyl silicone oil, ethyl silicone oil, methyl ethyl silicone oil, phenyl silicone oil and methyl phenyl silicone oil.
20. The method of claim 19, wherein the inert solvent is C4-C10Alkanes and/or white oils.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0018738A1 (en) * | 1979-04-10 | 1980-11-12 | Mitsui Petrochemical Industries, Ltd. | Solid titanium catalyst component and use thereof in the production of olefin polymers or copolymers |
| JPH10212315A (en) * | 1997-01-25 | 1998-08-11 | Samsung General Chem Co Ltd | Olefin polymerization and copolymerization method |
| CN103059174A (en) * | 2011-10-18 | 2013-04-24 | 中国石油化工股份有限公司 | Catalyst component for olefin polymerization and catalyst thereof |
| CN105440176A (en) * | 2014-08-15 | 2016-03-30 | 中国石油化工股份有限公司 | Olefin polymerization catalyst carrier and preparation method and application thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0018738A1 (en) * | 1979-04-10 | 1980-11-12 | Mitsui Petrochemical Industries, Ltd. | Solid titanium catalyst component and use thereof in the production of olefin polymers or copolymers |
| JPH10212315A (en) * | 1997-01-25 | 1998-08-11 | Samsung General Chem Co Ltd | Olefin polymerization and copolymerization method |
| CN103059174A (en) * | 2011-10-18 | 2013-04-24 | 中国石油化工股份有限公司 | Catalyst component for olefin polymerization and catalyst thereof |
| CN105440176A (en) * | 2014-08-15 | 2016-03-30 | 中国石油化工股份有限公司 | Olefin polymerization catalyst carrier and preparation method and application thereof |
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