CN114149518A - Catalyst carrier for olefin polymerization, preparation method and application thereof, catalyst and application thereof - Google Patents
Catalyst carrier for olefin polymerization, preparation method and application thereof, catalyst and application thereof Download PDFInfo
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- CN114149518A CN114149518A CN202010924609.3A CN202010924609A CN114149518A CN 114149518 A CN114149518 A CN 114149518A CN 202010924609 A CN202010924609 A CN 202010924609A CN 114149518 A CN114149518 A CN 114149518A
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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
- C08F110/00—Homopolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F110/04—Monomers containing three or four carbon atoms
- C08F110/06—Propene
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- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
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- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Abstract
The invention relates to the field of olefin polymerization catalysts, and discloses a catalyst carrier for olefin polymerization, a preparation method and application thereof, a catalyst and application thereof, wherein the carrier is at least one compound with a structure shown in a formula (1), and the olefin polymerization catalyst carrier provided by the invention has the advantages of good particle form, smooth surface, narrow particle size distribution and no special-shaped particles; the catalyst prepared by the carrier has good appearance, basically cannot be broken, and has high hydrogen regulation sensitivity when used for olefin polymerization.
Description
Technical Field
The invention relates to the field of olefin polymerization catalysts, in particular to a catalyst carrier for olefin polymerization, a method for preparing the catalyst carrier for olefin polymerization, the catalyst carrier for olefin polymerization prepared by the method, application of the catalyst carrier in preparing a catalyst for olefin polymerization, a catalyst containing the catalyst carrier and application of the catalyst in catalyzing olefin polymerization reaction.
Background
It is well known that magnesium chloride alcoholate supported Ziegler-Natta catalysts perform significantly better than other supported catalysts when used in olefin polymerization, especially propylene polymerization. Therefore, the catalysts currently used for olefin polymerization are mostly prepared by supporting titanium halide on magnesium chloride alcoholate.
To obtain spherical carriers, they can be prepared by spray drying, spray cooling, high pressure extrusion, high speed stirring, emulsifying machine method and supergravity rotating bed method, etc., as disclosed in WO99/44009 and US4399054, etc., where the spherical alcoholate can be formed by emulsifying the magnesium chloride alcoholate system by high speed stirring at high temperature followed by quenching. However, when the catalyst prepared from the above magnesium chloride alcoholate is used for olefin polymerization, the breakage of polymer particles is easily caused during the polymerization, resulting in a large amount of fine polymer powder.
In order to overcome such defects, an electron donor compound is introduced into the preparation of a magnesium chloride alcoholate carrier in advance, for example, CN1397568A and CN1563112A introduce an internal electron donor phthalate compound known in the industry into the synthesis of the magnesium chloride alcoholate carrier, so as to obtain a "magnesium chloride-alcohol-phthalate" spherical carrier, and then the carrier is reacted with titanium tetrachloride to form a catalyst. However, such complex spherical carriers are easily sticky during the preparation process, and it is difficult to form spherical particles having an appropriate particle size.
In order to solve the problem, CN102040683A discloses a method for preparing a carrier by reacting a magnesium halide alcoholate with an oxirane compound, and specifically discloses adding the oxirane compound after melting and dispersing the magnesium halide alcoholate; or the magnesium halide alcoholate is directly added into a reactor containing the ethylene oxide compound after being melted and dispersed. However, the catalyst carrier prepared by the method has the defects of unstable preparation process, easy carrier adhesion and poor carrier forming effect.
Therefore, it is of great interest to develop a new catalyst support for olefin polymerization that overcomes the above-mentioned drawbacks of the prior art.
Disclosure of Invention
The invention aims to overcome the defects of poor forming effect and low strength of a catalyst prepared from a catalyst carrier existing in the prior art.
The inventor of the present invention found that a catalyst carrier having a novel composition can be obtained by adding a halohydrin compound in the preparation process of a catalyst carrier for olefin polymerization, and mixing a specific amount of the halohydrin compound with magnesium halide, an ethylene oxide compound and other components, and the carrier has a good particle form and does not substantially contain irregular particles.
In addition, the inventor also unexpectedly finds that the catalyst carrier prepared by matching the halohydrin compound with a specific dosage with components such as magnesium halide, ethylene oxide compounds and the like has higher strength, the catalyst prepared from the carrier has higher strength, the appearance of the catalyst is good, and the catalyst is basically not broken; and the catalyst has high hydrogen regulation sensitivity when used in olefin polymerization reaction, and based on the findings, the inventor provides the technical scheme of the invention.
The first aspect of the present invention provides a catalyst support for olefin polymerization, which is at least one of compounds having a structure represented by formula (1):
wherein, in the formula (I),
R1is selected from C1-10Alkyl groups of (a);
R2and R3Each independently selected from H, C1-10And C substituted by 1 to 10 halogen atoms1-10A haloalkyl group of (a);
R4selected from C substituted by at least one halogen atom1-10And C substituted by at least one halogen atom6-20A halogenated aromatic group of (a);
x is selected from fluorine, chlorine, bromine and iodine;
m is 0.1-1.9, n is 0.1-1.9, i is 0-1.9, and m + n + i is 2; 0< q < 0.2.
In a second aspect, the present invention provides a process for preparing a catalyst support for olefin polymerization, the process comprising:
(1) heating and emulsifying the first component in sequence optionally in the presence of an inert liquid medium to obtain an intermediate productThe first component contains a compound of the formula R4A halohydrin of formula OH, a magnesium halide of formula MgXY, and a compound of formula R1An alcohol compound represented by OH;
(2) carrying out contact reaction on the intermediate product and a second component, wherein the second component contains an ethylene oxide compound with a structure shown in a formula (II);
wherein, in the formula R1In OH, R1Is selected from C1-10Alkyl groups of (a);
in the formula (II), R2And R3Each independently selected from H, C1-10And C substituted by 1 to 10 halogen atoms1-10A haloalkyl group of (a);
in the formula R4In OH, R4Selected from C substituted by at least one halogen atom1-10And C substituted by at least one halogen atom6-20A halogenated aromatic group of (a);
in the formula MgXY, X is selected from fluorine, chlorine, bromine and iodine; y is selected from fluorine, chlorine, bromine, iodine, C1-6Alkyl of (C)1-6Alkoxy group of (C)6-14Aryl and C6-14An aryloxy group of (a);
wherein the first component and the second component are used in amounts such that the resulting catalyst support has a structure represented by formula (I):
in formula (I), m is 0.1 to 1.9, n is 0.1 to 1.9, I is 0 to 1.9, and m + n + I is 2; 0< q < 0.2;
wherein, in the step (1), the amount of the halohydrin is 0.0001 to 1.5mol and the amount of the alcohol compound is 4 to 30mol with respect to 1mol of the magnesium halide.
A third aspect of the present invention provides a catalyst support prepared by the method as set forth in the second aspect above.
A fourth aspect of the invention provides the use of a catalyst support according to the first or third aspects as hereinbefore described in the preparation of a catalyst for the polymerisation of olefins.
In a fifth aspect, the present invention provides a catalyst comprising the catalyst support of the first or third aspect.
In a sixth aspect the present invention provides the use of a catalyst as described in the fifth aspect hereinbefore to catalyse the polymerisation of olefins.
Compared with the prior art, the invention has at least the following advantages:
(1) the catalyst carrier provided by the invention has the advantages of good particle form, smooth surface, narrow particle size distribution and no special-shaped particles;
(2) the catalyst prepared by the catalyst carrier has high strength, good appearance and basically no breakage;
(3) when the catalyst prepared by the catalyst carrier is used for olefin polymerization, particularly propylene polymerization, the hydrogen regulation sensitivity of the catalyst is higher, and the obtained olefin polymer powder has higher melt flow index, better fluidity, good form and basically no abnormal material.
Additional features and advantages of the invention will be described in detail in the detailed description which follows.
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.
As described above, the first aspect of the present invention provides a catalyst support for olefin polymerization, which is at least one of compounds having a structure represented by formula (1):
wherein, in the formula (I),
R1is selected from C1-10Alkyl groups of (a);
R2and R3Each independently selected from H, C1-10And C substituted by 1 to 10 halogen atoms1-10A haloalkyl group of (a);
R4selected from C substituted by at least one halogen atom1-10And C substituted by at least one halogen atom6-20A halogenated aromatic group of (a);
x is selected from fluorine, chlorine, bromine and iodine;
m is 0.1-1.9, n is 0.1-1.9, i is 0-1.9, and m + n + i is 2; 0< q < 0.2.
In the present invention, m is 0.1 to 1.9, for example, m is 0.1, 1.0, 1.9; n is 0.1 to 1.9, for example n is 0.1, 1.0, 1.9; i is 0 to 1.9, e.g. i is 0, 0.9, 1.0, 1.9; 0< q <0.2, e.g. q is 0.05, 0.1, 0.15.
In the present invention, in the formula (1)
Partially expressed (OC)2H2XR2R3)n。
In the present invention, R1Is selected from C1-10Alkyl of (a), said R1Alkyl groups that are linear, branched, or cyclic include, but are not limited to, methyl, ethyl, n-propyl, isopropyl, cyclopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, cyclobutyl, n-pentyl, isopentyl, neopentyl, cyclopentyl, n-hexyl, isohexyl, cyclohexyl, 1-ethylpropyl, 2-methylbutyl, 3-methylbutyl, 2, 2-dimethylpropyl, and the like.
Herein, with respect to R1The alkyl substituent groups of (a) have similar definitions to those described above, only differing in the number of carbon atoms, and the invention will not be described in detail hereinafter.
In the present invention,R2and R3Each independently selected from H, C1-10And C substituted by 1 to 10 halogen atoms1-10A haloalkyl group of (a).
When said R is2And R3Is selected from C1-10And C substituted by 1 to 10 halogen atoms1-10In the case of haloalkyl groups of (a), the alkyl and haloalkyl groups are straight-chain or branched radicals, e.g. C1-10Alkyl groups of (a) include, but are not limited to, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, neopentyl, n-hexyl, isohexyl, 1-ethylpropyl, 2-methylbutyl, 3-methylbutyl, 2, 2-dimethylpropyl, and the like. Said C substituted by 1 to 10 halogen atoms1-10Haloalkyl of (A) means C1-10The alkyl group of (1) may have a plurality of hydrogen atoms substituted with halogen atoms on the same carbon atom or hydrogen atoms on different carbon atoms; when a plurality of halogen atoms are substituted, the halogen atoms may be the same or different, and the halogen atoms are fluorine atoms, chlorine atoms, bromine atoms or iodine atoms. For example is-CF3、-CH2CF3、-CH2CF2H、-CF2CF3、-CF2CH2CF2H、-CH2CF2CF2H、-CH2CH2CH2Cl、-CH2CH2CH2Br, and the like.
Herein, with respect to R2And R3The alkyl substituent and haloalkyl substituent have similar definitions to those described above, except that the number of carbon atoms is different, and the invention will not be described in detail hereinafter.
In the present invention, R4Selected from C substituted by at least one halogen atom1-10And C substituted by at least one halogen atom6-20The halogenated aromatic group of (1). Said C substituted by at least one halogen atom1-10And C substituted by at least one halogen atom6-20The halogenated aryl group of (A) is C1-10Alkyl of (C)6-20At least one hydrogen atom in the aromatic group of (1) is substituted with a halogen atom. The halogen atom is fluorine atom, chlorine atom, bromine atom or iodine atom. Wherein, the C1-10The haloalkyl group of (a) may be a linear, branched or cyclic group, for example including but not limited to-CF3、-CH2CF3、-CH2CF2H、-CF2CF3、-CF2CH2CF2H、-CH2CF2CF2H、-CH2CH2CH2Cl、-CH2CH2CH2Br, and the like. Said C is6-20The halogenated aryl group of (2) means a halogenated aryl group having 6 to 20 carbon atoms.
Herein, with respect to R4The substituent groups have similar definitions as above, only differing in the number of carbon atoms, and the invention will not be described in detail hereinafter.
Preferably, R1Is selected from C1-8Alkyl group of (1).
More preferably, R is selected to provide a better performing catalyst support1Is selected from C1-6Alkyl group of (1).
To obtain a better performing catalyst support, preferably R2And R3Each independently selected from H, C1-5And C substituted by 1 to 10 halogen atoms1-5A haloalkyl group of (a).
To obtain a better performing catalyst support, preferably R4Selected from C substituted by at least two halogen atoms1-10And C substituted by at least two halogen atoms6-20And the halogen atom is at least one selected from the group consisting of a chlorine atom, a bromine atom and an iodine atom.
In the present invention, the at least two halogen atom substitutions are C1-10Alkyl and C6-20At least two hydrogen atoms in the halogenated aromatic group are replaced by halogen atoms, the hydrogen atoms can be hydrogen atoms on one carbon or hydrogen atoms on different carbons, and the halogen atoms can be the same or different.
Preferably, X is selected from chlorine and bromine.
Preferably, the catalyst support has an average particle diameter of 10 to 100 microns and a particle size distribution of less than 1.2.
More preferably, the catalyst support has an average particle diameter of 20 to 60 microns and a particle size distribution of 0.6 to 0.9.
In the present invention, the average particle diameter is referred to as D50.
In the present invention, the size of the particle size distribution is obtained according to (D90-D10)/D50.
In the present invention, the average particle diameter and the particle size distribution of the catalyst support are measured using a laser particle sizer such as a MasterSizer 2000 laser particle sizer (manufactured by Malvern Instruments Ltd).
As previously mentioned, a second aspect of the present invention provides a method for preparing a catalyst support for olefin polymerization, the method comprising:
(1) sequentially heating and emulsifying a first component containing a compound of formula R optionally in the presence of an inert liquid medium to obtain an intermediate product4A halohydrin of formula OH, a magnesium halide of formula MgXY, and a compound of formula R1An alcohol compound represented by OH;
(2) carrying out contact reaction on the intermediate product and a second component, wherein the second component contains an ethylene oxide compound with a structure shown in a formula (II);
wherein, in the formula R1In OH, R1Is selected from C1-10Alkyl groups of (a);
in the formula (II), R2And R3Each independently selected from H, C1-10And C substituted by 1 to 10 halogen atoms1-10A haloalkyl group of (a);
in the formula R4In OH, R4Selected from C substituted by at least one halogen atom1-10And with at least one halogenAtom-substituted C6-20A halogenated aromatic group of (a);
in the formula MgXY, X is selected from fluorine, chlorine, bromine and iodine; y is selected from fluorine, chlorine, bromine, iodine, C1-6Alkyl of (C)1-6Alkoxy group of (C)6-14Aryl and C6-14An aryloxy group of (a);
wherein the first component and the second component are used in amounts such that the resulting catalyst support has a structure represented by formula (I):
in formula (I), m is 0.1 to 1.9, n is 0.1 to 1.9, I is 0 to 1.9, and m + n + I is 2; 0< q < 0.2;
wherein, in the step (1), the amount of the halohydrin is 0.0001 to 1.5mol and the amount of the alcohol compound is 4 to 30mol with respect to 1mol of the magnesium halide.
In the present invention, it is to be specifically noted that when the halohydrin R is4Provided by OH (R)4O) moiety with said compound of formula (I)
When some of the compounds are the same, the compound having the structure of formula (I) can also be represented by
Where m + n ═ 2, those skilled in the art should not be understood as limiting the invention.
In the second aspect of the present invention, the R group1、R2、R3And R4The definition of the substituent group(s) corresponds to the definition of the first aspect of the present invention, and the present invention is not described in detail herein.
In the present invention, in the formula MgXY, when Y is selected from C1-6Alkyl of (C)1-6In the case of alkoxy groups of (a), the alkyl group and the alkoxy group are linear or branched alkyl and alkoxy groups, C1-6The alkyl group of (A) means an alkyl group having 1 to 6 carbon atoms, including but not limited toIn methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, etc.; said C is1-6The alkoxy group of (b) means an alkoxy group having 1 to 6 carbon atoms, including, but not limited to, methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, sec-butoxy, isobutoxy, tert-butoxy, n-pentoxy, isopentoxy, and the like.
Said C is6-14The aryl group of (a) means an aryl group having 6 to 14 carbon atoms, including but not limited to phenyl, o-tolyl, m-tolyl, p-tolyl, o-ethylphenyl, m-ethylphenyl, p-ethylphenyl, naphthyl, and the like.
Said C is6-14The aryloxy group of (a) means an aryloxy group having 6 to 14 carbon atoms, and includes, for example, but not limited to, phenoxy, naphthoxy, o-methylphenoxy, o-ethylphenoxy, m-methylphenoxy, and the like.
Herein, in the formula MgXY, the substituent groups for Y such as alkyl, alkoxy, aryl and aryloxy have the similar definitions as described above, only differing in the number of carbon atoms, and the present invention will not be described in detail hereinafter.
In order to obtain a better performing catalyst support, according to a preferred embodiment of the invention, in the formula MgXY, X is selected from chlorine and bromine; y is selected from chlorine, bromine and C1-5Alkyl of (C)1-5Alkoxy group of (C)6-10Aryl and C6-10An aryloxy group of (1).
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 magnesium chloride.
According to another preferred embodiment of the invention, in the formula R1In OH, R1Is selected from C1-8Alkyl group of (1).
In order to obtain a better catalyst support, the alcohol compound is preferably selected from at least one of ethanol, propanol, isopropanol, n-butanol, isobutanol, pentanol, isopentanol, n-hexanol, n-octanol, and 2-ethylhexanol.
According to another preferred embodiment of the inventionAccording to an embodiment, in formula (II), R2And R3Each independently selected from H, C1-5And C substituted by 1 to 10 halogen atoms1-5A haloalkyl group of (a).
In order to obtain a better catalyst carrier, the ethylene oxide compound is preferably selected from at least one of ethylene oxide, propylene oxide, butylene oxide, epichlorohydrin, chlorobutylene oxide, propylene bromide oxide and butylene bromide oxide.
According to the invention, the halohydrin may be a monohalohydrin or a polyhalohydrin, preferably a chlorohydrin, a bromohydrin or an iodohydrin, for example 2,2, 2-trichloroethanol, 2, 2-dichloroethanol, 2-chloroethanol, 3-chloro-1-propanol, 6-chloro-1-hexanol, 3-bromo-1-propanol, 5-chloro-1-pentanol, 4-chloro-1-butanol, 2-chlorocyclohexanol, 1, 2-dichloroethanol, 1, 3-dichloropropanol, 1, 4-dichlorobutanol or 2-iodoethanol, etc.
However, in order to be able to obtain a catalyst support with a higher melt flow index, according to a further preferred embodiment of the present invention, in the formula R4In OH, R4Selected from C substituted by at least two halogen atoms1-10And C substituted by at least two halogen atoms6-20And the halogen atom is at least one selected from the group consisting of a chlorine atom, a bromine atom and an iodine atom.
In order to obtain a catalyst support with a higher melt flow index, the halogenated alcohol is preferably at least one selected from the group consisting of 2,2, 2-trichloroethanol, 2, 2-dichloroethanol, 1, 3-dichloropropanol and 1, 4-dichlorobutanol.
Preferably, step (1) is carried out in the presence of a surfactant, the type of which is not particularly limited by the present invention, but in order to be able to obtain a better performing catalyst support, the surfactant is particularly preferably polyvinylpyrrolidone (PVP) and/or span80 (span-80).
According to the invention, the halohydrin compound with a specific dosage is matched with the components such as magnesium halide and ethylene oxide compound, so that the catalyst carrier with a novel composition can be obtained, the particle form of the carrier is good, special-shaped particles are basically absent, and the strength of the prepared catalyst carrier is high. The inventors have found that when the amount of the halohydrin compound is excessively large, the resulting catalyst support is sticky and lumpy, and cannot be subjected to subsequent operations.
According to the present invention, preferably, the oxirane compound is used in an amount of 1 to 10mol with respect to 1mol of the magnesium halide.
More preferably, the halohydrin is used in an amount of 0.03 to 1.1mol with respect to 1mol of the magnesium halide; the usage amount of the alcohol compound is 6-20mol, and the usage amount of the ethylene oxide compound is 2-6 mol.
Preferably, the inert liquid medium is used in an amount of 0.8 to 10L, more preferably 2 to 8L, relative to 1mol of the magnesium halide.
Preferably, the inert liquid medium is a silicone oil and/or an inert liquid hydrocarbon solvent, and more preferably, the inert liquid medium is selected from at least one 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 present invention, it should be noted that the trace amount of water carried in each reactant also participates in the reaction for forming the spherical carrier, and therefore, the spherical carrier obtained by the preparation may contain a trace amount of water from the reaction raw material and the reaction medium, and those skilled in the art should not be construed as limiting the present invention.
Preferably, in step (1), the heating conditions include: the temperature is 80-120 ℃ and the time is 0.5-5 h.
More preferably, in step (1), the heating conditions include: the temperature is 80-100 ℃ and the time is 0.5-3 h.
The present invention is not particularly limited to a specific operation method of the emulsification in the step (1), and a method known to those skilled in the art can be used. For example, emulsification is carried out using low or high shear. Preferably, when low-speed shearing is adopted, the stirring speed of the low-speed shearing is 400-800 rpm. The high-speed shearing method is well known to those skilled in the art, and is carried out by a high-speed stirring method disclosed in CN 1330086A. Furthermore, the emulsification operation can be carried out by referring to the method disclosed in the following patent application, such as CN1580136A, wherein the solution containing the liquid magnesium halide compound is dispersed by rotation in a supergravity bed (the rotation speed is 100-3000 rpm); further, the solution containing the liquid magnesium halide adduct was discharged in an emulsifying machine at a speed of 1500-; also, as disclosed in US6020279A, a solution containing a liquid magnesium halide adduct is emulsified by spraying.
Preferably, in step (2), the conditions of the contact reaction include: the temperature is 80-120 deg.C, and the time is 20-60 min.
More preferably, in step (2), the conditions of the contact reaction include: the temperature is 80-100 deg.C, and the time is 20-50 min.
The method according to the second aspect of the present invention further comprises subjecting the product obtained by the contact reaction to a post-treatment means, such as solid-liquid separation, washing, drying, which is conventional in the art, and the present invention is not particularly limited thereto. The solid-liquid separation can be performed by 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 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. The washing may be carried out by washing the obtained solid phase product by a method known to those skilled in the art, and for example, the obtained solid phase product may be washed by an inert hydrocarbon solvent such as pentane, hexane, heptane, petroleum ether and gasoline. The specific conditions for the drying in the present invention are not particularly limited, and for example, the temperature for the drying may be 20 to 70 ℃, the time for the drying may be 0.5 to 10 hours, and the drying may be performed under normal pressure or reduced pressure.
The catalyst carrier prepared by the method has the advantages of good particle shape, smooth surface, narrow particle size distribution and no special-shaped particles. Particularly, the catalyst carrier obtained by the method has high strength, so that the catalyst prepared from the catalyst carrier has good appearance, is basically not broken, and has high hydrogen regulation sensitivity.
As previously mentioned, a third aspect of the present invention provides a catalyst support prepared by the method as provided in the second aspect.
The inventor finds that the catalyst carrier prepared by the method has good particle shape, smooth surface, narrow particle size distribution, basically no special-shaped particles and high strength.
As mentioned previously, a fourth aspect of the present invention provides the use of a catalyst support according to the first or third aspect described above in the preparation of a catalyst for the polymerisation of olefins.
As mentioned above, the fifth aspect of the present invention provides a catalyst comprising the catalyst carrier of the first or third aspect.
In the present invention, the composition of the catalyst is not particularly limited, and may be a composition of a catalyst for olefin polymerization existing in the art, but in order to obtain a catalyst suitable for olefin polymerization, particularly propylene polymerization, it is preferable that the catalyst contains the carrier, the titanium halide compound, and the electron donor compound. Preferably, the titanium halide compound is selected from at least one of titanium tetrachloride, titanium tetrabromide, titanium tetraiodide, titanium tetra-n-butoxide, titanium tetraethoxide, titanium monochlorotrin-butoxide, titanium dichlorodi-n-butoxide, titanium trichloromono-n-butoxide, titanium monochlorotriethoxide, titanium dichlorodiethoxide, titanium trichloromonoethoxylate and titanium trichloride. Preferably, the electron donor compound is at least one selected from diisobutyl phthalate, glycol carboxylate and phosphate. Meanwhile, the content of each component in the catalyst is not particularly limited, and a person skilled in the art can reasonably adjust and design the catalyst according to actual needs.
The catalyst of the present invention can be prepared by a method of preparing an olefin polymerization catalyst, which is conventional in the art, and a specific procedure is illustrated in the examples hereinafter, and those skilled in the art should not be construed as limiting the present invention.
The inventor finds that the catalyst prepared by the catalyst carrier has good appearance, basically does not break and has high hydrogen regulation sensitivity.
As mentioned above, a sixth aspect of the present invention provides the use of a catalyst as described in the previous fifth aspect for catalysing the polymerisation of olefins.
The present invention is not particularly limited to the specific operation method for the application, and those skilled in the art can operate the method for olefin polymerization existing in the art, and the present invention will not be described in detail herein, and the present invention will hereinafter be described as a specific operation process, and those skilled in the art will not be understood as limiting the present invention.
The inventor finds that when the catalyst prepared by the catalyst carrier is used for olefin polymerization, particularly propylene polymerization, the hydrogen regulation sensitivity of the catalyst is higher, and the obtained olefin polymer powder has higher melt flow index, better fluidity, good shape and basically no abnormal material.
The present invention will be described in detail below by way of examples.
In the following examples, all the raw materials used are commercially available ones unless otherwise specified.
1, 3-dichloropropanol was purchased from carbofuran;
epichlorohydrin was purchased from carbofuran corporation;
2-iodoethanol was purchased from carbofuran;
2,2, 2-trichloroethanol was purchased from carbofuran;
n-octanol was purchased from carbofuran corporation;
propylene oxide was purchased from carbofuran corporation;
diisobutyl phthalate is available from carbofuran corporation;
titanium tetrachloride was purchased from carbofuran;
triethylaluminum was purchased from carbofuran;
methylcyclohexyldimethoxysilane was purchased from carbofuran corporation.
In the following examples, the properties involved were tested as follows:
1. average particle diameter and particle size distribution of catalyst support: the measurement was carried out using a Masters Sizer 2000 particle Sizer manufactured by Malvern Instruments;
2. catalyst support and catalyst morphology: observation was performed by an optical microscope of Nikon corporation, model number Eclipse E200;
3. structure and composition of the catalyst support: carrying out 1H-NMR test on the carrier by adopting an AVANCE 300 nuclear magnetic resonance spectrometer of Bruker company in Switzerland, and testing the carrier by adopting a PY-2020iD type cracker of Fronterelab company, a TraceGC Ultra type chromatograph of Thermo Fisher company and a DSQ II type mass spectrometer;
4. polymer melt flow index: measured according to ISO1133, 230 ℃ under a load of 2.16 kg.
In the following examples, emulsification was performed by stirring at 600rpm during the preparation of the catalyst carrier, unless otherwise specified.
Example 1
(1) Adding 0.08mol of magnesium chloride, 0.96mol of ethanol, 0.042mol of 1, 3-dichloropropanol and 1g of PVP into a 0.6L reaction kettle, heating to 90 ℃ under stirring, heating at constant temperature for 2h, and emulsifying to obtain an intermediate product;
(2) and (3) carrying out contact reaction on the intermediate product and 0.48mol of epichlorohydrin, wherein the contact reaction conditions comprise: the temperature is 90 ℃, the time is 30min, then the filter pressing is carried out, the filter pressing product is washed for 5 times by hexane and dried in vacuum, and the catalyst carrier Z1 is obtained.
Through tests, the structure and the composition of the obtained catalyst carrier Z1 are as follows:
the catalyst support Z1 was tested to have an average particle diameter (D50) of 32 microns and a particle size distribution ((D90-D10)/D50) of 0.8.
The observation shows that the particle shape of the catalyst carrier Z1 is regular, the surface is smooth, the particle size distribution is concentrated, and no special-shaped particles exist basically.
Example 2
(1) Adding 0.08mol of magnesium chloride, 0.96mol of ethanol, 0.084mol of 1, 3-dichloropropanol and 1g of PVP into a 0.6L reaction kettle, heating to 90 ℃ under stirring, heating at constant temperature for 2h, and emulsifying to obtain an intermediate product;
(2) and (3) carrying out contact reaction on the intermediate product and 0.48mol of epichlorohydrin, wherein the contact reaction conditions comprise: the temperature is 90 ℃, the time is 30min, then the filter pressing is carried out, the filter pressing product is washed for 5 times by hexane and dried in vacuum, and the catalyst carrier Z2 is obtained.
Through tests, the structure and the composition of the obtained catalyst carrier Z2 are as follows:
through the test: the catalyst support Z2 had an average particle diameter (D50) of 28 microns and a particle size distribution ((D90-D10)/D50) of 0.8.
The observation shows that the particle shape of the catalyst carrier Z2 is regular, the surface is smooth, the particle size distribution is concentrated, and no special-shaped particles exist basically.
Example 3
(1) Adding 0.08mol of magnesium chloride, 0.96mol of n-octanol, 0.042mol of 2,2, 2-trichloroethanol and 1g of span80 serving as surfactants into a 0.6L reaction kettle, heating to 90 ℃ under stirring, heating at constant temperature for 2 hours, and emulsifying to obtain an intermediate product;
(2) and (3) carrying out contact reaction on the intermediate product and 0.48mol of propylene oxide, wherein the contact reaction conditions comprise: the temperature is 90 ℃, the time is 30min, the filter pressing is carried out after the reaction, the filter pressing product is washed for 5 times by hexane and dried in vacuum, and the catalyst carrier Z3 is obtained.
Through tests, the structure and the composition of the obtained catalyst carrier Z3 are as follows:
the catalyst support Z3 was tested to have an average particle diameter (D50) of 32 microns and a particle size distribution ((D90-D10)/D50) of 0.8.
The catalyst carrier Z3 has the advantages of regular particle shape, smooth surface, basically spherical shape, centralized particle size distribution and basically no special-shaped particles.
Example 4
(1) Adding 300mL of white oil, 0.08mol of magnesium chloride, 0.48mol of ethanol, 0.042mol of 1, 3-dichloropropanol and 1g of PVP into a 0.6L reaction kettle, heating to 100 ℃ under stirring, heating at constant temperature for 1h, and emulsifying to obtain an intermediate product;
(2) and (3) carrying out contact reaction on the intermediate product and 0.16mol of epichlorohydrin, wherein the contact reaction conditions comprise: the temperature is 100 ℃, the time is 20min, the pressure filtration is carried out after the reaction, the product of the pressure filtration is washed for 5 times by hexane, and finally the product is dried in vacuum to obtain the olefin polymerization catalyst carrier Z4.
Through tests, the structure and the composition of the obtained catalyst carrier Z4 are as follows:
the catalyst support Z4 was tested to have an average particle diameter (D50) of 29 microns and a particle size distribution ((D90-D10)/D50) of 0.9.
The catalyst carrier Z4 has the advantages of regular particle shape, smooth surface, basically spherical shape, centralized particle size distribution and basically no special-shaped particles.
Example 5
(1) Adding 0.08mol of magnesium chloride, 0.48mol of ethanol, 0.0026mol of 2-iodoethanol and 1g of PVP into a 0.6L reaction kettle, heating to 100 ℃ under stirring, heating at constant temperature for 1h, and emulsifying to obtain an intermediate product;
(2) and (3) carrying out contact reaction on the intermediate product and 0.16mol of epichlorohydrin, wherein the contact reaction conditions comprise: the temperature is 100 ℃, the time is 20min, the pressure filtration is carried out after the reaction, the product of the pressure filtration is washed for 5 times by hexane, and finally the product is dried in vacuum to obtain the olefin polymerization catalyst carrier Z5.
Through tests, the structure and the composition of the obtained catalyst carrier Z5 are as follows:
the catalyst support Z5 was tested to have an average particle diameter (D50) of 27 microns and a particle size distribution ((D90-D10)/D50) of 0.9.
The catalyst carrier Z5 has the advantages of regular particle shape, smooth surface, basically spherical shape, centralized particle size distribution and basically no special-shaped particles.
Comparative example 1
(1) Adding 0.08mol of magnesium chloride, 0.96mol of ethanol and 1g of PVP into a 0.6L reaction kettle, heating to 90 ℃ under stirring, heating at constant temperature for 2h, and emulsifying to obtain an intermediate product;
(2) and adding 0.48mol of the intermediate product into epichlorohydrin, reacting at the temperature of 90 ℃ for 30min, performing pressure filtration after reaction, washing the pressure filtration product with hexane for 5 times, and performing vacuum drying to obtain the catalyst carrier DZ 1.
Through tests, the structure and the composition of the obtained catalyst carrier DZ1 are as follows:
the catalyst support DZ1 was tested to have an average particle diameter (D50) of 60 microns and a particle size distribution ((D90-D10)/D50) of 1.3.
It was observed that there were irregularly shaped particles in the catalyst support DZ 1.
The following test examples and comparative test examples are provided to illustrate the preparation of olefin polymerization catalysts and olefin polymers using the above catalyst supports.
Test examples 1-1
(1) Preparation of olefin polymerization catalyst
100mL of titanium tetrachloride was charged into a 300mL glass reaction flask, the reaction flask was cooled to-20 ℃ and 40g of the catalyst support Z1 obtained in example 1 was added and stirred at-20 ℃ for 30min, and then the temperature was gradually increased to 110 ℃ and 1.5mL of diisobutyl phthalate was added thereto during the temperature increase, and the mixture was maintained at 110 ℃ for 30min, and then the liquid was filtered off. Then washed with titanium tetrachloride 2 times, then washed with hexane 3 times, and dried to obtain an olefin polymerization catalyst C1.
(2) Propylene polymerization
In a 5L stainless steel autoclave, under a nitrogen atmosphere, 1mmol of a triethylaluminum hexane solution (triethylaluminum concentration: 0.5mmol/mL), 0.05mmol of methylcyclohexyldimethoxysilane, 10mL of anhydrous hexane, 10mg of the olefin polymerization catalyst C1 obtained in step (1), 1.5L (standard volume) of hydrogen and 2.5L of a liquid propylene monomer were charged. Heating to 70 ℃, reacting for 1h, then cooling, releasing pressure, discharging and drying to obtain the polypropylene powder.
The catalyst C1 has no breakage, good appearance and high catalyst strength; the melt flow index of the obtained propylene powder is 12.3g/10min, the particle shape of the polypropylene powder is good, and special-shaped materials are basically not existed.
Test examples 1 to 2
Polypropylene was prepared in a similar manner to test example 1-1, except that: in the step (2), the volumes of hydrogen used were different,
specifically, the method comprises the following steps: 1.5L (standard volume) of hydrogen was replaced with 6.5L (standard volume) of hydrogen to obtain polypropylene powder.
The melt flow index of the polypropylene powder is 46.1g/10min, the polypropylene powder has good particle shape, and special-shaped materials are basically absent.
Test example 2-1
Polypropylene was prepared in a similar manner to test example 1-1, except that: in the step (1), the kind of the catalyst carrier used is different,
specifically, the method comprises the following steps: replacing the catalyst support Z1 with the same weight of the catalyst support Z2 prepared in example 2 to obtain an olefin polymerization catalyst C2;
then, a polypropylene powder was prepared by following the procedure (2) of test example 1-1 using olefin polymerization catalyst C2.
The obtained catalyst C2 is basically not broken, has good appearance and high catalyst strength; the melt flow index of the obtained polypropylene powder is 13.6g/10min, the particle shape of the polypropylene powder is good, and special-shaped materials are basically not existed.
Test examples 2 to 2
Polypropylene was prepared in a similar manner to test example 2-1, except that: in the step (2), the volumes of hydrogen used were different,
specifically, the method comprises the following steps: 1.5L (standard volume) of hydrogen was replaced with 6.5L (standard volume) of hydrogen to obtain polypropylene powder.
The melt flow index of the polypropylene powder is 48.6g/10min, the particle shape of the polypropylene powder is good, and special-shaped materials are basically absent.
Test example 3-1
Polypropylene was prepared in a similar manner to test example 1-1, except that: in the step (1), the kind of the catalyst carrier used is different,
specifically, the method comprises the following steps: replacing the catalyst support Z1 with the same weight of the catalyst support Z3 prepared in example 3 to obtain an olefin polymerization catalyst C3;
then, a polypropylene powder was prepared by following the procedure (2) of test example 1-1 using olefin polymerization catalyst C3.
The obtained catalyst C3 is basically not broken, has good appearance and high catalyst strength; the melt flow index of the obtained polypropylene powder is 11.7g/10min, the particle shape of the polypropylene powder is good, and special-shaped materials are basically not existed.
Test examples 3 and 2
Polypropylene was prepared in a similar manner to test example 3-1, except that: in the step (2), the volumes of hydrogen used were different,
specifically, the method comprises the following steps: 1.5L (standard volume) of hydrogen was replaced with 6.5L (standard volume) of hydrogen to obtain polypropylene powder.
The melt flow index of the polypropylene powder is 43.8g/10min, the polypropylene powder has good particle shape, and special-shaped materials are not basically existed.
Test example 4-1
Polypropylene was prepared in a similar manner to test example 1-1, except that: in the step (1), the kind of the catalyst carrier used is different,
specifically, the method comprises the following steps: replacing the catalyst support Z1 with the same weight of the catalyst support Z4 prepared in example 4 to obtain an olefin polymerization catalyst C4;
then, a polypropylene powder was prepared by following the procedure (2) of test example 1-1 using olefin polymerization catalyst C4.
The catalyst C4 is not broken basically, has good appearance and high catalyst strength; the melt flow index of the obtained polypropylene powder is 10.8g/10min, the polypropylene powder has good particle shape, and special-shaped materials are basically absent.
Test example 4-2
Polypropylene was prepared in a similar manner to test example 4-1, except that: in the step (2), the volumes of hydrogen used were different,
specifically, the method comprises the following steps: 1.5L (standard volume) of hydrogen was replaced with 6.5L (standard volume) of hydrogen to obtain polypropylene powder.
The melt flow index of the polypropylene powder is 44.1g/10min, the polypropylene powder has good particle shape, and special-shaped materials are basically absent.
Test example 5-1
Polypropylene was prepared in a similar manner to test example 1-1, except that: in the step (1), the kind of the catalyst carrier used is different,
specifically, the method comprises the following steps: replacing the catalyst support Z1 with the same weight of the catalyst support Z5 prepared in example 5 to obtain an olefin polymerization catalyst C5;
then, a polypropylene powder was prepared by following the procedure (2) of test example 1-1 using olefin polymerization catalyst C5.
The catalyst C5 has less breakage, better appearance and higher catalyst strength; the melt flow index of the obtained polypropylene powder is 10.2g/10min, the polypropylene powder has good particle shape, and special-shaped materials are basically absent.
Test example 5-2
Polypropylene was prepared in a similar manner to test example 5-1, except that: in the step (2), the volumes of hydrogen used were different,
specifically, the method comprises the following steps: 1.5L (standard volume) of hydrogen was replaced with 6.5L (standard volume) of hydrogen to obtain polypropylene powder.
The melt flow index of the polypropylene powder is 42.5g/10min, the polypropylene powder has good particle shape, and special-shaped materials are basically absent.
Comparative test example 1-1
Polypropylene was prepared in a similar manner to test example 1-1, except that: in the step (1), the kind of the catalyst carrier used is different,
specifically, the method comprises the following steps: replacing the catalyst carrier Z1 with the same weight of the catalyst carrier DZ1 prepared in comparative example 1 to obtain an olefin polymerization catalyst DC 1;
then, a polypropylene powder was prepared by following the procedure (2) of test example 1-1 using olefin polymerization catalyst DC 1.
Non-spherical particles exist in the catalyst DC1, and the surface is rough; the melt flow index of the obtained polypropylene powder is 7.0g/10min, and the polypropylene powder has more special-shaped materials and poor fluidity.
Comparative test examples 1 to 2
Polypropylene was prepared in a similar manner to comparative test example 1-1, except that: in the step (2), the volumes of hydrogen used were different,
specifically, the method comprises the following steps: 1.5L (standard volume) of hydrogen was replaced with 6.5L (standard volume) of hydrogen to obtain polypropylene powder.
The melt flow index of the polypropylene powder is 37.0g/10min, and the polypropylene powder has more special-shaped materials and poor fluidity.
From the above results, it can be seen that the olefin polymerization catalyst support prepared by the method of the present invention has good particle morphology, smooth surface, substantially spherical shape, and substantially no presence of irregular particles.
In addition, the catalyst carrier obtained by the method has high strength, and the catalyst prepared by the carrier has good appearance and is basically not broken; when the prepared catalyst is used for olefin polymerization, such as propylene polymerization, the obtained olefin polymer powder has the advantages of higher melt flow index, higher hydrogen regulation sensitivity, better fluidity, good form and no abnormal material basically.
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 (15)
1. A catalyst support for olefin polymerization, characterized in that the support is at least one of compounds having a structure represented by formula (1):
wherein, in the formula (I),
R1is selected from C1-10Alkyl groups of (a);
R2and R3Each independently selected from H, C1-10And C substituted by 1 to 10 halogen atoms1-10A haloalkyl group of (a);
R4selected from C substituted by at least one halogen atom1-10And C substituted by at least one halogen atom6-20A halogenated aromatic group of (a);
x is selected from fluorine, chlorine, bromine and iodine;
m is 0.1-1.9, n is 0.1-1.9, i is 0-1.9, and m + n + i is 2; 0< q < 0.2.
2. The catalyst carrier according to claim 1, wherein, in formula (I),
R1is selected from C1-8Alkyl groups of (a); preferably, R1Is selected from C1-6Alkyl groups of (a);
preferably, R2And R3Each independently selected from H, C1-5And C substituted by 1 to 10 halogen atoms1-5A haloalkyl group of (a);
preferably, R4Selected from C substituted by at least two halogen atoms1-10And C substituted by at least two halogen atoms6-20A halogenated aromatic group of (a);
preferably, X is selected from chlorine and bromine.
3. The catalyst carrier according to claim 1 or 2, wherein the catalyst carrier has an average particle diameter of 10-100 microns and a particle size distribution of less than 1.2;
preferably, the catalyst support has an average particle diameter of 20 to 60 microns and a particle size distribution of 0.6 to 0.9.
4. A method of preparing a catalyst support for olefin polymerization, the method comprising:
(1) sequentially heating and emulsifying a first component containing a compound of formula R optionally in the presence of an inert liquid medium to obtain an intermediate product4A halohydrin of formula OH, a magnesium halide of formula MgXY, and a compound of formula R1An alcohol compound represented by OH;
(2) carrying out contact reaction on the intermediate product and a second component, wherein the second component contains an ethylene oxide compound with a structure shown in a formula (II);
wherein, in the formula R1In OH, R1Is selected from C1-10Alkyl groups of (a);
in the formula (II), R2And R3Each independently selected from H, C1-10And C substituted by 1 to 10 halogen atoms1-10A haloalkyl group of (a);
in the formula R4In OH, R4Selected from C substituted by at least one halogen atom1-10And C substituted by at least one halogen atom6-20A halogenated aromatic group of (a);
in the formula MgXY, X is selected from fluorine, chlorine, bromine and iodine; y is selected from fluorine, chlorine, bromine, iodine, C1-6Alkyl of (C)1-6Alkoxy group of (C)6-14Aryl and C6-14An aryloxy group of (a);
wherein the first component and the second component are used in amounts such that the resulting catalyst support has a structure represented by formula (I):
in formula (I), m is 0.1 to 1.9, n is 0.1 to 1.9, I is 0 to 1.9, and m + n + I is 2; 0< q < 0.2;
wherein, in the step (1), the amount of the halohydrin is 0.0001 to 1.5mol and the amount of the alcohol compound is 4 to 30mol with respect to 1mol of the magnesium halide.
5. A process according to claim 4, wherein, in the formula MgXY, X is selected from chlorine and bromine; y is selected from chlorine, bromine and C1-5Alkyl of (C)1-5Alkoxy group of (C)6-10Aryl and C6-10An 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.
6. A process according to claim 4 or 5, wherein in formula R1In OH, R1Is selected from C1-8Alkyl groups of (a);
preferably, the alcohol compound is selected from at least one of ethanol, n-propanol, isopropanol, n-butanol, isobutanol, pentanol, isopentanol, n-hexanol, n-octanol, and 2-ethylhexanol.
7. The method according to any one of claims 4 to 6, wherein, in formula (II), R2And R3Each independently selected from H, C1-5And C substituted by 1 to 10 halogen atoms1-5A haloalkyl group 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.
8. The process according to any one of claims 4 to 7, wherein in formula R4In OH, R4Selected from C substituted by at least two halogen atoms1-10And C substituted by at least two halogen atoms6-20A halogenated aromatic group of (a);
preferably, the halogenated alcohol is at least one selected from 2,2, 2-trichloroethanol, 2, 2-dichloroethanol, 1, 3-dichloropropanol and 1, 4-dichlorobutanol.
9. The method according to any one of claims 4 to 8, wherein the halohydrin is used in an amount of 0.03 to 1.1mol with respect to 1mol of the magnesium halide; the usage amount of the alcohol compound is 6-20mol, and the usage amount of the ethylene oxide compound is 2-6 mol;
preferably, the inert liquid medium is selected from at least one 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.
10. The method according to any one of claims 4 to 9, wherein in step (1), the heating conditions comprise: the temperature is 80-120 ℃, and the time is 0.5-5 h;
preferably, in step (1), the heating conditions include: the temperature is 80-100 ℃ and the time is 0.5-3 h.
11. The method according to any one of claims 4 to 10, wherein in step (2), the conditions of the contact reaction comprise: the temperature is 50-120 deg.C, and the time is 20-60 min;
preferably, in step (2), the conditions of the contact reaction include: the temperature is 60-100 deg.C, and the time is 20-50 min.
12. A catalyst support prepared by the process of any one of claims 4 to 11.
13. Use of a catalyst support according to any one of claims 1 to 3 and 12 in the preparation of a catalyst for the polymerisation of olefins.
14. A catalyst comprising a catalyst support according to any one of claims 1 to 3 and 12.
15. Use of the catalyst of claim 14 for catalyzing the polymerization of olefins.
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