CN112759687A - Catalyst component for olefin polymerization, preparation method thereof, catalyst and olefin polymerization method - Google Patents
Catalyst component for olefin polymerization, preparation method thereof, catalyst and olefin polymerization method Download PDFInfo
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- CN112759687A CN112759687A CN201911003662.3A CN201911003662A CN112759687A CN 112759687 A CN112759687 A CN 112759687A CN 201911003662 A CN201911003662 A CN 201911003662A CN 112759687 A CN112759687 A CN 112759687A
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
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Abstract
The invention belongs to the field of catalysts, and discloses a catalyst component for olefin polymerization, a preparation method thereof, a catalyst and an olefin polymerization method, wherein the catalyst component comprises the following components: titanium, magnesium, chlorine and an internal electron donor compound, wherein the internal electron donor compound comprises an internal electron donor compound a shown in a formula (I),
Description
Technical Field
The invention belongs to the field of catalysts, and particularly relates to a catalyst component for olefin polymerization and a preparation method thereof, a catalyst for olefin polymerization, and an olefin polymerization method.
Background
It is known that Ziegler-Natta catalysts for the polymerization of propylene are composed of at least three parts, a magnesium chloride support, an internal electron donor compound and a titanium compound. The electron donor compound can not only improve the activity of the catalyst, but also enhance the stereospecific capacity of the catalyst, and the activity of the catalyst is very low due to the separation of the internal electron donor compound, and the obtained polymer cannot be used due to the low isotactic index. Examples of the internal electron donor compound include aromatic mono-or diesters such as diisobutylphthalate and ethylbenzoate used in patent document US4784983, diol ester compounds used in patent document CN1453298, succinate compounds used in patent document CN1313869, and diether compounds used in patent document EP 361494. In industrial production, each of these internal electron donor compounds has certain disadvantages in practical applications: for example, the catalyst using the aromatic diester compound has low catalytic activity; although the catalyst using the diether compound has high catalytic activity and good hydrogen regulation sensitivity, the obtained polymer has narrow relative molecular mass distribution and the like. Because of the importance of the role of the internal electron donor compound in the catalyst and the disadvantages of the current internal electron donor compounds in practical applications, the improvement of the internal electron donor compound is still a research hotspot in the field.
Therefore, it is of great importance to develop a novel internal electron donor compound for olefin polymerization catalysts that can overcome the above-mentioned drawbacks of the prior art.
Disclosure of Invention
In the research process, the inventor of the invention finds that when the catalyst synthesized by using the compound of the general formula (I) as the internal electron donor compound is used for olefin polymerization, especially propylene polymerization, the catalyst has good hydrogen regulation sensitivity. The present invention has been made based on the above findings.
A first aspect of the present invention provides a catalyst component for the polymerisation of olefins, the catalyst component comprising: titanium, magnesium, chlorine and an internal electron donor compound, wherein the internal electron donor compound comprises an internal electron donor compound a shown in a formula (I),
in the formula (I), 10 < n < 2000, preferably n is 100-.
The second aspect of the present invention provides a method for preparing the above catalyst component, comprising the steps of:
1) preparing a magnesium-containing carrier: obtained by the reaction of a system containing magnesium halide, an alcohol compound and an ethylene oxide compound;
2) and (2) treating the magnesium-containing carrier by adopting a titanium compound, and adding an internal electron donor compound in the treatment process.
A third aspect of the present invention provides a catalyst for olefin polymerization, the catalyst comprising the following components;
A. the catalyst component or the catalyst component prepared by the preparation method;
B. an alkyl aluminum compound;
optionally, C, an external electron donor compound.
A fourth aspect of the present invention provides an olefin polymerization process comprising: one or more olefins are contacted with the above-described catalyst under olefin polymerization conditions.
The compound shown in the general formula (I) is used as an internal electron donor compound, and the synthesized catalyst is used for olefin polymerization, especially when propylene is polymerized, the catalyst has good hydrogen regulation sensitivity.
Additional features and advantages of the invention will be set forth in the detailed description which follows.
Detailed Description
The following describes in detail specific embodiments of the present invention. It should be understood that the detailed description and specific examples, while indicating the present invention, are given by way of illustration and explanation only, not limitation.
According to a first aspect of the present invention, there is provided a catalyst component for the polymerisation of olefins, the catalyst component comprising: titanium, magnesium, chlorine and an internal electron donor compound, wherein the internal electron donor compound comprises an internal electron donor compound a shown in a formula (I),
in the formula (I), 10 < n < 2000, preferably n is 100-.
In the invention, the internal electron donor compound may further comprise an internal electron donor compound b, and the internal electron donor compound b is used in combination with the internal electron donor compound a, and the internal electron donor compound b may be various internal electron donor compounds conventionally used in the preparation of catalysts for olefin polymerization.
Preferably, the internal electron donor compound b is at least one of carboxylic acid ester, alcohol ester, ether, ketone, nitrile, amine and silane, more preferably at least one of mono-or poly-aliphatic carboxylic acid ester, mono-or poly-aromatic carboxylic acid ester, diol ester and binary ether. In the present invention, specific compounds of the mono-or poly-aliphatic carboxylic acid ester, the mono-or poly-aromatic carboxylic acid ester, the glycol ester and the glycol ether may be selected with reference to the prior art, and will not be described in detail herein.
According to a second aspect of the present invention, there is provided a process for preparing the above catalyst component, which comprises the steps of:
1) preparing a magnesium-containing carrier: obtained by the reaction of a system containing magnesium halide, an alcohol compound and an ethylene oxide compound;
2) and (2) treating the magnesium-containing carrier by adopting a titanium compound, and adding an internal electron donor compound in the treatment process.
According to the invention, the magnesium halide may have the general formula MgXY, where X is chlorine or bromine and Y is chlorine, bromine, C1-C14Alkyl of (C)6-C14Aryl of (C)1-C14Alkoxy group of (C)6-C14Aryl or C of6-C14Preferably, 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 groups of (a) include, but are 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, xylyloxy,and (3) trimethylphenoxy.
Preferably, the magnesium halide is selected from at least one of magnesium chloride, magnesium bromide, phenoxymagnesium chloride, isopropoxymagnesium chloride and n-butoxymagnesium chloride; more preferably, the magnesium halide is magnesium dichloride.
In the invention, the general formula of the alcohol compound is ROH, wherein R is C1-C8An alkyl group. Preferably, the alcohol compound is selected from at least one of ethanol, propanol, isopropanol, n-butanol, isobutanol, pentanol, isopentanol, n-hexanol, n-octanol, and 2-ethylhexanol.
According to the invention, the oxirane is represented by formula (II):
in the formula (II), R5And R6The same or different, each is independently selected from hydrogen and C1-C3Alkyl or haloalkyl.
Preferably, the oxirane compound is selected from 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 titanium compound may be various titanium compounds conventionally used in the preparation of catalysts for olefin polymerization. The titanium compound may have the general formula Ti (OR)n)4-mXmWherein R isnIs C1-C14X is F, Cl or Br, and m is an integer from 1 to 4. The titanium compound is preferably at least one of titanium tetrachloride, titanium tetrabromide, titanium tetrafluoride, titanium tributoxide chloride, titanium dibutoxide dichloride, titanium butoxychloride, titanium triethoxide chloride, titanium diethoxide dichloride and titanium ethoxychloride.
According to the present invention, the preparation of the magnesium-containing carrier may be performed using a method conventional in the art. Preferably, the compound is prepared by any one of the following methods:
the method comprises the following steps:
(1) mixing magnesium halide with a general formula of MgXY, a compound with a general formula of ROH, a compound with a general formula of R' OH, a dialkoxyl compound and an inert liquid medium, and heating to obtain a liquid mixture;
(2) emulsifying the liquid mixture obtained in the step (1), and contacting and reacting the emulsified product with an ethylene oxide compound to obtain the magnesium-containing carrier.
In the formula R 'OH, R' is preferably C16-C20Alkyl or aralkyl groups of (a). Specific examples of compounds of formula R' OH may be, but are not limited to: cetyl alcohol and stearyl alcohol.
Specific examples of the dihydrocarbyloxane compound may be, but are not limited to: 2, 2-dimethoxypropane, 2-dimethoxybutane, 2-dimethoxypentane, 3-dimethoxypentane, 2-diethoxypropane and 2, 2-diphenoxypropane.
In the first method, in the step (1), the mixing of the respective substances is carried out at not less than 60 ℃ so that the magnesium halide represented by the general formula MgXY is sufficiently reacted with the compound represented by the general formula ROH. Preferably, the mixing conditions include: the temperature is 50-120 ℃; more preferably 60-90 ℃, and the mixing time is 0.5-5 h; more preferably 0.5-3 h.
The amount of the magnesium halide of the general formula MgXY, the compound of the general formula ROH, the compound of the general formula R' OH, the dihydrocarbyloxyhydrocarbon compound and the oxirane 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, the compound represented by the general formula ROH is used in an amount of 4 to 30mol, preferably 6 to 20mol, the oxirane compound is used in an amount of 1 to 10mol, preferably 2 to 6mol, the compound represented by the general formula R' OH is used in an amount of 0.001 to 1.5mol, preferably 0.01 to 1mol, and the dihydrocarbyloxane compound is used in an amount of 0.001 to 1.5mol, preferably 0.01 to 1mol, per mole of the magnesium halide represented by the general formula MgXY. The amount of the inert liquid medium may be selected according to the specific amount of MgXY. Generally, the inert liquid medium is used in an amount of 0.8 to 10L, preferably 2 to 8L, per mole of magnesium in MgXY.
In the step (2), the contact reaction conditions include: the temperature is 80-120 deg.C, preferably 80-100 deg.C, and the time is 20-60 min, preferably 20-50 min.
In the magnesium-containing carrier prepared by the first method, preferably, the weight ratio of the titanium element in the titanium compound, the magnesium element in the magnesium-containing carrier and the internal electron donor compound is 1: 5-15: 2-15; more preferably 1: 6-13: 3-12.
The first process can be carried out with reference to patent document CN103788247B, the entire contents of which are incorporated herein by reference.
The second method,
1) Mixing MgXY and ROH, and reacting at the temperature of 110-130 ℃ for 1-3h to obtain MgXY/ROH adduct melt;
2) emulsifying the MgXY/ROH adduct molten body in the presence of inert liquid medium, quenching and shaping the emulsified product, and then drying to obtain the magnesium-containing carrier.
In the first and second methods, the inert liquid medium may be any of various liquid media commonly used in the art that do not chemically interact with the reactants and reaction products, such as: silicone oil and/or hydrocarbon solvent. Specifically, the inert liquid medium may be one or more of 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.
In the second method, the amount of the inert liquid medium can be selected according to the specific amount of MgXY. Generally, the inert liquid medium is used in an amount of 0.2 to 13L, preferably 0.6 to 6.5L, per mole of magnesium in MgXY. The addition of the inert liquid medium can be carried out in step 1) and/or step 2), for example, only in step 2), by mixing the MgXY/ROH adduct melt with the inert liquid medium and emulsifying the resulting mixture to form an emulsion. In both step 1) and step 2), an inert liquid medium is added as a reaction medium in step 1), so that a melt of the MgXY/ROH adduct containing an inert liquid medium is obtained, and then the mixture is mixed with an inert liquid medium and emulsified to form an emulsion. The inert liquid medium in step 1) and step 2) may be the same or different, for example, the inert liquid medium in step 1) may be white oil, and the inert liquid medium in step 2) may be methyl silicone oil. During the mixing in the step 2), the inert liquid medium needs to be preheated to the same temperature as the MgXY/ROH adduct molten mass containing the inert liquid medium. It is also possible to add only in step 1) and to use the inert liquid medium as reaction medium, thus obtaining a melt of the MgXY/ROH adduct containing the inert liquid medium, which is emulsified to form an emulsion.
In the second method, emulsification can be carried out by various methods known to those skilled in the art, for example: emulsification can be achieved by subjecting the MgXY/ROH adduct melt to high shear in the presence of an inert liquid medium. Methods of such high shear are well known to those skilled in the art, for example: emulsification was performed according to the methods of the following patent documents: CN1151183C (i.e., stirring a MgXY/ROH adduct melt in an inert liquid medium at 2000-; CN1267508C discloses that a mixture of a MgXY/ROH adduct melt and an inert liquid medium is dispersed in a super-gravity bed by rotation (the rotation speed can be 100-3000 r/min); CN1463990A discloses that the MgXY/ROH adduct molten mass and the mixture of silicone oil and white oil are output in an emulsifying machine at the speed of 1500-; US6020279 discloses emulsifying a mixture containing a MgXY/ROH adduct melt by spraying.
In the second method, the emulsified product can be rapidly cooled and molded by a method known to those skilled in the art to obtain spherical MgXY mROH. For example: the emulsified product may be quenched to form by transferring the emulsified product into a liquid cooling medium.
The liquid cooling medium may be any of the various liquid media commonly used in the art that do not chemically interact with the magnesium halide adduct. For example, the liquid cooling medium may be an inert hydrocarbon-based solvent. Specific examples of the liquid cooling medium may include, but are not limited to: n-pentane, n-hexane, n-heptane, gasoline, and petroleum ether. The water in the liquid cooling medium may participate in the reaction, or may be subjected to a water removal treatment to control the water content in the liquid cooling medium used within a range that does not affect the test results. Generally, the water content of the liquid cooling medium is controlled to not more than 5ppm (by weight). Methods of controlling or reducing the water content of the liquid cooling medium are well known in the art, for example: the liquid material may be subjected to distillation and/or contact with a water absorbing agent (e.g., molecular sieve), and a stream of high purity inert gas, such as high purity nitrogen, may be continuously passed through the heated liquid material.
The temperature of the liquid cooling medium is such as to enable the emulsified product to be cooled and shaped. In general, the temperature of the liquid cooling medium may be from-50 ℃ to 0 ℃, preferably from-40 ℃ to-20 ℃. There is no particular limitation in the amount of the liquid cooling medium as long as the amount of the liquid cooling medium is sufficient to cool and shape the emulsified product. In particular, the volume ratio of the liquid cooling medium to the emulsified product is 1-15: 1, preferably 2-9: 1.
In the first method and the second method, the preparation of the magnesium-containing carrier also comprises solid-liquid separation, and the solid-phase product is washed and dried. The solid-liquid separation may be any of various conventional methods for separating a solid phase from a liquid phase, such as suction filtration, pressure filtration, or centrifugal separation, and preferably, the solid-liquid separation is a pressure filtration method. 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. The resulting magnesium-containing carrier may be washed by the present invention using an inert hydrocarbon-based solvent (e.g., n-pentane, n-hexane, n-heptane, petroleum ether, and gasoline) well known to those skilled in the art. In the present invention, the drying conditions are not particularly limited, and examples thereof include: the drying temperature can be 20-70 deg.C, the drying time can be 0.5-10 hr, and the drying can be carried out under normal pressure or reduced pressure.
The second method can be carried out with reference to patent document CN1289542C, the entire contents of which are incorporated herein by reference.
According to the invention, it is preferred that the magnesium-containing carrier has an average particle diameter of 1 to 100 μm and a particle size distribution of less than 1.2. More preferably, the magnesium-containing carrier has an average particle diameter of 10 to 70 μm and a particle size distribution of 1.1 or less.
In the present invention, the conditions for the reaction of the magnesium-containing carrier with the titanium compound and the internal electron donor compound are not particularly limited, and preferably, the reaction conditions may include: the reaction temperature is 80-130 ℃ and the reaction time is 0.1-10 hours.
Preferably, the titanium compound and the magnesium-containing carrier are first mixed in contact at a low temperature and then slowly warmed to reach the above reaction temperature. The technical solutions of the present invention can be implemented according to the conventional knowledge in the art after being understood by those skilled in the art, and the present invention is not described herein in detail.
Other parameters which are not defined in the preparation process of the present invention can be routinely selected in accordance with the prior art.
According to a third aspect of the present invention, there is provided a catalyst for olefin polymerization, the catalyst comprising the following components;
A. the catalyst component or the catalyst component prepared by the preparation method;
B. an alkyl aluminum compound;
optionally, C, an external electron donor compound.
According to the present invention, the kind and amount of the catalyst used are not particularly limited, either, for the alkylaluminum compound or the external electron donor compound.
The alkyl aluminum compound may have the general formula AlR8R9R10In the general formula, R8、R9And R10Each may be chlorine and C1-C8And R is one of an alkyl group of8、R9And R10At least one of them being C1-C8Alkyl group of (1).
Preferably, the alkyl aluminum compound is at least one of triethylaluminum, triisobutylaluminum, tri-n-butylaluminum, tri-n-hexylaluminum, tri-n-octylaluminum, diethylaluminum monochloride, diisobutylaluminum monochloride, di-n-butylaluminum monochloride, di-n-hexylaluminum monochloride, ethylaluminum dichloride, isobutylaluminum dichloride, n-butylaluminum dichloride, n-hexylaluminum dichloride and triethylaluminum trichloride.
Preferably, the molar ratio of aluminium in the aluminium alkyl compound to titanium in the catalyst component is in the range 1 to 2000: 1, more preferably 20 to 500: 1.
In the present invention, the "optionally, C, external electron donor compound" means that the external electron donor compound can be present or absent in the catalyst for olefin polymerization of the present invention, and is selected as desired, that is, the catalyst for olefin polymerization of the present invention may or may not contain the external electron donor compound.
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 can be one or more than two of carboxylic acid, anhydride, ester, ketone, ether, alcohol, organic phosphorus compound and organic silicon compound. Preferably, the external electron donor has the general formula R1 xR2 ySi(OR3)zIn the general formula, R1、R2And R3Each is C1-C18Or C containing hetero atoms1-C18A hydrocarbon group of (a); x and y are each an integer of 0 to 2, z is an integer of 1 to 3, and x + y + z is 4. More preferably, of the formula R1 xR2 ySi(OR3)zIn, R1、R2、R3Each independently is C1-C18Substituted or unsubstituted hydrocarbyl of (a); more preferably, a and b are each 1, c is 2, R1、R2Each independently is C3-C10Substituted or unsubstituted hydrocarbyl of, R3Is C1-C10Substituted or unsubstituted hydrocarbyl.
In the present invention, examples of the external electron donor compound may be, but are not limited to: cyclohexylmethyldimethoxysilane, diisopropyldimethoxysilane, di-n-butyldimethoxysilane, diisobutyldimethoxysilane, diphenyldimethoxysilane, methyl-t-butyldimethoxysilane, dicyclopentyldimethoxysilane, 2-ethylpiperidinyl-2-t-butyldimethoxysilane, (1, 1, 1-trifluoro-2-propyl) -2-ethylpiperidinyldimethoxysilane, (1, 1, 1-trifluoro-2-propyl) -methyldimethoxysilane.
According to the invention, the molar ratio of the external electron donor compound to the aluminum in the alkyl aluminum compound is 0.005-0.5: 1, preferably 0.01-0.4: 1.
According to a fourth aspect of the present invention, there is provided an olefin polymerization process comprising: one or more olefins are contacted with the above-described catalyst under olefin polymerization conditions.
The olefin polymerization method of the present invention is not particularly limited with respect to the olefin polymerization conditions and the olefin used. The olefin may be at least one 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 at least one of ethylene, propylene, 1-butene, 2-butene and styrene, more preferably propylene.
The olefin polymerization process of the present invention may be carried out according to conventional methods in the art. For example, the olefin polymerization may be bulk polymerization, gas phase polymerization, or slurry polymerization. The olefin polymerization reaction conditions in the present invention may be conventional in the art, and 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. The medium used for the liquid phase polymerization may be selected from inert solvents such as saturated aliphatic hydrocarbons or aromatic hydrocarbons, such as isobutane, hexane, heptane, cyclohexane, naphtha, raffinate, hydrogenated gasoline, kerosene, benzene, toluene, xylene, etc., and toluene, n-hexane, or cyclohexane is preferable.
In addition, hydrogen is used as a molecular weight regulator in order to regulate the molecular weight of the final polymer.
The polymerization parameters of the olefins not defined in the present invention are all conventional in the art.
The present invention will be further described with reference to the following examples. But is not limited by these examples.
In the following examples and comparative examples, various raw materials used were commercially available without specific description.
1. The average particle diameter and the particle size distribution of the magnesium-containing carrier were measured using a Masters Sizer 2000 particle Sizer (manufactured by Malvern Instruments Ltd.).
2. The apparent morphology of the magnesium-containing carrier was observed by means of an optical microscope commercially available from Nikon under the model Eclipse E200.
3. Determination of the melt index of the polymer (MI): measured according to ASTM D1238-99, load 2.16kg, 190 ℃.
4. 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.
Examples 1 to 10 are for explaining the catalyst component for olefin polymerization and the preparation method thereof and the catalyst and the olefin polymerization method of the present invention.
Example 1
(1) Preparation of catalyst component for olefin polymerization
200mL of white oil, 0.08mol of magnesium chloride, 0.96mol of ethanol, 0.015mol of octadecanol and 0.01mol of 2, 2-dimethoxypropane are added into a 0.6L reaction kettle, stirred and heated to 90 ℃. After reacting for 1 hour, adding 0.48mol of epoxy chloropropane, reacting for half an hour, press-filtering, and washing for 5 times with hexane. Vacuum drying to obtain the magnesium-containing carrier Z1.
The magnesium-containing carrier Z1 had an average particle diameter (D50) of 50 μm and a particle size distribution ((D90-D10)/D50) of 0.9. The particle shape observed by an optical microscope is regular, the surface is smooth, the particles are basically spherical, the particle size distribution is concentrated, and no special-shaped particles exist basically.
In a 300mL glass reaction flask, 100mL of titanium tetrachloride was added, cooled to-20 ℃, 8 grams of magnesium-containing vehicle Z1 was added, and stirred at-20 ℃ for 30 min. Then, the temperature was slowly raised to 110 ℃ and 2g of polyvinylpyrrolidone was added during the temperature raising, and the mixture was maintained at 110 ℃ for 30min, and then the liquid was filtered off. Then, titanium tetrachloride was added and the mixture was washed 2 times and finally 3 times with hexane, and dried to obtain a catalyst component C1 for olefin polymerization.
(2) Propylene polymerization
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. Specific properties are shown in table 1.
Example 2
The amount of hydrogen added in the polymerization of propylene was changed to 6.5L (standard volume), and the procedure was otherwise the same as in example 1. Specific properties are shown in table 1.
Example 3
In the preparation of the catalyst component, 1g of polyvinylpyrrolidone and 0.5mL of diisobutyl phthalate were added instead of the internal electron donor compound to obtain a catalyst component C2, and simultaneously, a catalyst component C2 was added during propylene polymerization, the rest being the same as in example 1. Specific properties are shown in table 1.
Example 4
The amount of hydrogen added in the polymerization of propylene was changed to 6.5L (standard volume), and the procedure was otherwise the same as in example 3. Specific properties are shown in table 1.
Example 5
In the preparation of the catalyst component, 1g of polyvinylpyrrolidone and 1mL of 2, 4-pentanediol dibenzoate are added instead of the internal electron donor compound, the obtained catalyst component is C3, and meanwhile, the catalyst component C3 is added during propylene polymerization, and the rest is the same as that in the example 1. Specific properties are shown in table 1.
Example 6
The amount of hydrogen added in the polymerization of propylene was changed to 6.5L (standard volume), and the procedure was otherwise the same as in example 5. Specific properties are shown in table 1.
Example 7
In the preparation of the catalyst component, 1g of polyvinylpyrrolidone and 0.5mL of 2-isopropyl-2-isoamyl-1, 3-dimethoxypropane are added instead of the internal electron donor compound, the obtained catalyst component is C4, and simultaneously, the catalyst component C4 is added in the polymerization of propylene, and the rest is the same as that in the example 1. Specific properties are shown in table 1.
Example 8
The amount of hydrogen added in the polymerization of propylene was changed to 6.5L (standard volume), and the procedure was otherwise the same as in example 7. Specific properties are shown in table 1.
Example 9
(1) Preparation of catalyst component for olefin polymerization
The magnesium-containing carrier was prepared according to the method disclosed in example 1 in CN1289542C, specifically as follows:
in a 150L reactor with stirring, 10kg of anhydrous magnesium chloride and 12.6kg of ethanol were added to 60L of white oil having a viscosity of 30 cps (20 ℃) and reacted at 125 ℃ for 2 hours. Then transferring the obtained mixed solution of the molten adduct and the white oil into a methyl silicone oil medium preheated to 125 ℃; the viscosity of the methyl silicone oil is 300 centipoises (20 ℃), and the dosage of the methyl silicone oil is 120L; stirring the mixture for 10 to 30 minutes at the rotating speed of 200 revolutions per minute to obtain a mixed solution. Introducing the mixed solution into a hypergravity rotating bed for dispersion, introducing the dispersed mixed solution into a hexane medium which is cooled to minus 35 ℃ in advance under the stirring condition, wherein the using amount of hexane is 1200L, and cooling and solidifying the magnesium chloride/alcohol adduct melt dispersed into small drops to form spherical solid particles. Filtering solid particles from the suspension obtained after quenching, washing the particles by hexane at room temperature, wherein the amount of hexane is 100L/time, washing for 5 times totally, and vacuumizing at 30-50 ℃ to obtain the magnesium-containing carrier Z2.
The magnesium-containing carrier Z2 had an average particle diameter (D50) of 52 μm and a particle size distribution ((D90-D10)/D50) of 1.1. The appearance of the particles is observed by adopting an optical microscope, the particle form of the magnesium-containing carrier Z2 is regular, the surface is smooth, a small amount of special-shaped particles exist, and the particle size distribution is concentrated.
In a 300mL glass reaction flask, 100mL of titanium tetrachloride was added, cooled to-20 ℃, 8 grams of magnesium-containing vehicle Z2 was added, and stirred at-20 ℃ for 30 min. Then, the temperature was slowly raised to 110 ℃ and 1g of polyvinylpyrrolidone and 0.5mL of 2-isopropyl-2-isoamyl-1, 3-dimethoxypropane were added during the temperature raising, and the mixture was maintained at 110 ℃ for 30 minutes, and then the liquid was filtered off. Then, titanium tetrachloride was added and the mixture was washed 2 times and finally 3 times with hexane, and dried to obtain a catalyst component C5 for olefin polymerization.
(3) Propylene polymerization
In a 5L autoclave, purging was conducted with a nitrogen stream, and then 1mmol of a triethylaluminum hexane solution (triethylaluminum concentration: 0.5mmol/mL), 0.05mmol of methylcyclohexyldimethoxysilane, 10mL of anhydrous hexane, 10mg of catalyst C5 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. Specific properties are shown in table 1.
Example 10
The amount of hydrogen added in the polymerization of propylene was changed to 6.5L (standard volume), and the procedure was otherwise the same as in example 9. Specific properties are shown in table 1.
Comparative example 1
In the preparation of the catalyst component, 1.5mL of diisobutyl phthalate is added instead of the internal electron donor compound, the obtained catalyst component is D-C1, and meanwhile, the catalyst component D-C1 is added in the polymerization of propylene, and the rest is the same as that in the example 1. Specific properties are shown in table 1.
Comparative example 2
The amount of hydrogen added at the time of propylene polymerization was changed to 6.5L (standard volume), and the rest was the same as in comparative example 1. Specific properties are shown in table 1.
TABLE 1
As can be seen from the performance results of the examples and the comparative examples, when the catalyst component containing the internal electron donor compound a shown in the formula (I) is used for olefin (especially propylene) polymerization, the hydrogen regulation sensitivity of the catalyst is very good, and the catalyst has a very good industrial application prospect.
Having described embodiments of the present invention, the foregoing description is intended to be exemplary, not exhaustive, and not limited to the embodiments disclosed. Many modifications and variations will be apparent to those of ordinary skill in the art without departing from the scope and spirit of the described embodiments.
Claims (10)
1. A catalyst component for the polymerization of olefins, characterized in that it comprises: titanium, magnesium, chlorine and an internal electron donor compound, wherein the internal electron donor compound comprises an internal electron donor compound a shown in a formula (I),
in the formula (I), 10 < n < 2000, preferably n is 100-.
2. The catalyst component according to claim 1 in which the internal electron donor compound further comprises an internal electron donor compound b, the internal electron donor compound b being at least one of a carboxylic acid ester, an alcohol ester, an ether, a ketone, a nitrile, an amine and a silane, preferably at least one of a mono or poly aliphatic carboxylic acid ester, a mono or poly aromatic carboxylic acid ester, a glycol ester and a di-ether.
3. A process for the preparation of the catalyst component according to claim 1 or 2, characterized in that it comprises the following steps:
1) preparing a magnesium-containing carrier: obtained by the reaction of a system containing magnesium halide, an alcohol compound and an ethylene oxide compound;
2) and (2) treating the magnesium-containing carrier by adopting a titanium compound, and adding an internal electron donor compound in the treatment process.
4. The process according to claim 3, wherein the magnesium halide has the formula MgXY, wherein X is chlorine or bromine, Y is chlorine, bromine or C1-C5Alkyl of (C)1-C5Alkoxy group of (C)6-C10Aryl or C of6-C10An aryloxy group of (a); preferably, the magnesium halide is selected from at least one of magnesium chloride, magnesium bromide, phenoxymagnesium chloride, isopropoxymagnesium chloride and n-butoxymagnesium chloride;
the general formula of the alcohol compound is ROH, wherein R is C1-C8An alkyl group; preferably, the alcohol compound is selected from at least one of ethanol, propanol, isopropanol, n-butanol, isobutanol, pentanol, isopentanol, n-hexanol, n-octanol, and 2-ethylhexanol.
5. The process according to claim 3, wherein the oxirane compound is represented by formula (II):
in the formula (II), R5And R6The same or different, each is independently selected from hydrogen and C1-C3Alkyl or haloalkyl of (a);
preferably, the oxirane compound is selected from at least one of ethylene oxide, propylene oxide, butylene oxide, epichlorohydrin, chlorobutylene oxide, propylene bromide oxide, and butylene bromide oxide.
6. The method according to claim 3, wherein the titanium compound has a general formula of Ti (OR)n)4-mXmWherein R isnIs C1-C14X is F, Cl or Br, m is an integer from 1 to 4; the titanium compound is preferably at least one of titanium tetrachloride, titanium tetrabromide, titanium tetrafluoride, titanium tributoxide chloride, titanium dibutoxide dichloride, titanium butoxychloride, titanium triethoxide chloride, titanium diethoxide dichloride and titanium ethoxychloride.
7. A catalyst for the polymerization of olefins, characterized in that the catalyst comprises the following components;
A. the catalyst component of claim 1 or 2 or the catalyst component produced by the production method of any one of claims 3 to 6;
B. an alkyl aluminum compound;
optionally, C, an external electron donor compound.
8. The catalyst of claim 7, wherein the alkyl aluminum compound is at least one of triethylaluminum, triisobutylaluminum, tri-n-butylaluminum, tri-n-hexylaluminum, tri-n-octylaluminum, diethylaluminum monochloride, diisobutylaluminum monochloride, di-n-butylaluminum monochloride, di-n-hexylaluminum monochloride, ethylaluminum dichloride, monoisobutylaluminum dichloride, mono-n-butylaluminum dichloride, mono-n-hexylaluminum dichloride, and triethylaluminum trichloride;
the molar ratio of aluminium in the aluminium alkyl compound to titanium in the catalyst component is from 1 to 2000: 1, preferably from 20 to 500: 1.
9. The catalyst according to claim 7 or 8, wherein the external electron donor compound is at least one selected from the group consisting of cyclohexylmethyldimethoxysilane, diisopropyldimethoxysilane, di-n-butyldimethoxysilane, diisobutyldimethoxysilane, diphenyldimethoxysilane, methyl-t-butyldimethoxysilane, dicyclopentyldimethoxysilane, 2-ethylpiperidinyl-2-t-butyldimethoxysilane, (1, 1, 1-trifluoro-2-propyl) -2-ethylpiperidinyldimethoxysilane and (1, 1, 1-trifluoro-2-propyl) -methyldimethoxysilane;
the molar ratio of the external electron donor compound to the aluminum in the alkyl aluminum compound is 0.005-0.5: 1, preferably 0.01-0.4: 1.
10. An olefin polymerization process, comprising: contacting one or more olefins with the catalyst of any of claims 7-9 under olefin polymerization conditions;
preferably, the olefin is at least one of ethylene, propylene, 1-butene, 2-butene and styrene, more preferably propylene.
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