CN112759682B - Catalyst composition, catalyst and preparation method thereof, composite catalyst and olefin polymerization method - Google Patents
Catalyst composition, catalyst and preparation method thereof, composite catalyst and olefin polymerization method Download PDFInfo
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- CN112759682B CN112759682B CN201911060404.9A CN201911060404A CN112759682B CN 112759682 B CN112759682 B CN 112759682B CN 201911060404 A CN201911060404 A CN 201911060404A CN 112759682 B CN112759682 B CN 112759682B
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Abstract
The invention relates to the field of catalysts, and in particular relates to a catalyst composition, a catalyst and a preparation method thereof, a composite catalyst and an olefin polymerization method. The catalyst composition comprises a magnesium compound, an organic acid anhydride compound, an acetate compound, a diphenylanthracene derivative and a titanium-containing compound, wherein the diphenylanthracene derivative is a compound shown in a formula (I). The composite catalyst has higher catalytic activity when used for catalyzing olefin polymerization.
Description
Technical Field
The invention relates to the field of catalysts, in particular to a catalyst composition, a method for preparing a catalyst from the catalyst composition, the catalyst prepared by the method, a composite catalyst containing the catalyst, and an olefin polymerization method using the composite catalyst.
Background
Spherical catalysts for ethylene polymerization of the Ziegler-Natta type, prepared using a magnesium chloride ethanol support, have been commercialized for many years, limited by insufficient activity of the catalyst, and such catalysts are mainly used in gas phase polymerization processes. If the activity of the catalyst can be improved to be applied to a slurry polymerization process, spherical polyethylene granules which have similar shapes with better fluidity and bulk density and do not need to be granulated can be obtained.
In the prior art, some electron donors are introduced into a spherical catalyst to improve the ethylene polymerization activity, for example, CN1861645A introduces chlorosilane and a reaction product thereof into the catalyst as electron donors, so that the activity of the catalyst is improved; for example, CN102807638A introduces a long carbon chain/short carbon chain monoester compound as an electron donor into the catalyst, thereby improving the catalytic activity of the catalyst. Therefore, the electron donor is a key component for improving the activity of the catalyst.
Therefore, under the current situation that the catalyst has been intensively studied, the goal of breaking through the technical barrier of improving the activity of the catalyst is expected to be achieved by finding a new electron donor.
Disclosure of Invention
The present invention aims to further improve the activity of a Ziegler-Natta type polyolefin catalyst, and provides a catalyst composition, a method for preparing a catalyst from the catalyst composition, a catalyst prepared by the method, a composite catalyst containing the catalyst, and an olefin polymerization method using the composite catalyst. The composite catalyst has higher catalytic activity when used for catalyzing olefin polymerization.
The inventors of the present invention have found in their research that when a diphenylanthracene derivative is introduced as an electron donor into a Ziegler-Natta type polyolefin catalyst, the catalytic activity of the resulting catalyst is unexpectedly significantly improved.
The first aspect of the present invention provides a catalyst composition, wherein the catalyst composition comprises a reaction product of a magnesium alkoxide, a titanium-containing compound, an electron donor a, and optionally a first organoaluminum compound, wherein the electron donor a is selected from compounds represented by general formula (I):
m in the formula (I) 1 、M 2 、M 3 、M 4 The same or different, are respectively and independently selected from hydrogen, hydroxyl, amino, aldehyde group, carboxyl, acyl, halogen atom and general formula-R 1 A hydrocarbon group represented by the formula-OR 2 Alkoxy of the formula (I), wherein R 1 And R 2 Are each independently selected from C 1 -C 10 The substituted or unsubstituted hydrocarbon group of (2), wherein the substituent group is selected from the group consisting of a hydroxyl group, an amino group, an aldehyde group, a carboxyl group, an acyl group, a halogen atom, an alkoxy group and a heteroatom-containing group.
In a second aspect the present invention provides a process for the preparation of a catalyst, wherein the process comprises the steps of:
(1) First mixing a magnesium alcoholate with a first component group selected from one of the following options in a first inert solvent at a temperature of-20 ℃ to obtain a first mixture:
option one, an electron donor a, an optional first organoaluminum compound, and an optional electron donor b,
option two, a first organoaluminum compound and optionally an electron donor b, and
option three, at least a portion of the titanium-containing compound;
(2) Carrying out a first contact reaction on the first mixture at the temperature of 50-85 ℃, and carrying out first solid-liquid separation on the reacted materials;
(3) Second mixing the solid obtained in step (2) with a second component group in a second inert solvent at a temperature of-20 ℃ to obtain a second mixture, wherein the second component group is the component except the magnesium alcoholate and the first component group in the catalyst composition of the first aspect of the invention;
(4) And carrying out a second contact reaction on the second mixture at the temperature of 50-85 ℃.
In a third aspect, the present invention provides a catalyst prepared by the method of the second aspect of the present invention.
In a fourth aspect, the present invention provides a composite catalyst comprising the following components:
component one, the catalyst of the third aspect of the present invention;
component two, a second organoaluminum compound having the general formula AlR " d X”’ 3 -d, wherein R' is selected from hydrogen and C l -C 20 X' is a halogen atom, and d satisfies 0 < d.ltoreq.3.
In a fifth aspect, the present invention provides an olefin polymerization process, wherein the olefin polymerization process comprises: in the presence of the composite catalyst according to the fourth aspect of the present invention, homopolymerization or copolymerization of olefins is carried out.
When the catalyst and the composite catalyst prepared by the catalyst composition are used for olefin reaction, the catalytic activity can reach 2.7 multiplied by 10 4 gPE/gcat is higher than that, and in a preferred embodiment, can reach 3.0X 10 4 gPE/gcat is higher than that, and in a further preferred embodiment, may be 3.5X 10 4 More than gPE/gcat.
Other specific features and advantages of the invention will be described in the following detailed description.
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.
The first aspect of the present invention provides a catalyst composition, wherein the catalyst composition comprises a magnesium alcoholate, a titanium-containing compound, an electron donor a and optionally a first organoaluminum compound, wherein the electron donor a is selected from compounds represented by general formula (I):
m in the formula (I) 1 、M 2 、M 3 、M 4 The same or different, are respectively and independently selected from hydrogen, hydroxyl, amino, aldehyde group, carboxyl, acyl, halogen atom and general formula-R 1 A hydrocarbon group represented by the formula-OR 2 Alkoxy of the formula (I), wherein R 1 And R 2 Are each independently selected from C 1 -C 10 The substituted or unsubstituted hydrocarbon group of (1), the substituent group in the substituted hydrocarbon group being selected from the group consisting of a hydroxyl group, an amino group, an aldehyde group, a carboxyl group, an acyl group, a halogen atom, an alkoxy group and a hetero atom-containing group.
The catalyst composition according to the invention, in said formula (I), M 1 、M 2 、M 3 、M 4 May be the same or different, and may be selected independently. When selected from the above range, a catalyst/composite catalyst having a higher catalytic activity can be obtained. In order to further increase the catalytic activity, according to a more preferred embodiment of the invention, said M 1 、M 2 、M 3 、M 4 Each independently selected from hydroxyl, amino, aldehyde, halogen atom, general formula-R 1 To representAnd a hydrocarbyl group of the formula-OR 2 Alkoxy groups are shown.
Still more preferably, in said electron a, M 1 、M 2 、M 3 And M 4 Form a specific combination, M 1 、M 2 、M 3 And M 4 The combination of (A) is selected from the following combinations A to P:
combination A: m 1 ＝M 2 ＝M 3 ＝M 4 ＝OCH 3 ；
Combination B: m 1 ＝M 2 ＝M 3 ＝M 4 ＝OCH 2 CH 3 ；
And (3) combination C: m 1 ＝M 2 ＝M 3 ＝M 4 ＝OCH 2 CH 2 CH 3 ；
And (3) combination D: m 1 ＝M 2 ＝OCH 3 ，M 3 ＝M 4 ＝OCH 2 CH 3 ；
Combination E: m 1 ＝M 3 ＝OCH 3 ，M 2 ＝M 4 ＝OCH 2 CH 3 ；
And (3) combination F: m 1 ＝M 2 ＝M 3 ＝M 4 ＝OH；
A combination G: m 1 ＝M 2 ＝OCH 3 ，M 3 ＝M 4 ＝OH；
Combination H: m 1 ＝M 3 ＝OCH 3 ，M 2 ＝M 4 ＝OH；
Combination I: m 1 ＝M 2 ＝OCH 3 ，M 3 ＝M 4 ＝Cl；
Combination J: m 1 ＝M 3 ＝OCH 3 ，M 2 ＝M 4 ＝Cl；
And (3) combination K: m 1 ＝M 2 ＝OCH 3 ，M 3 ＝M 4 ＝Br；
Combination L: m 1 ＝M 3 ＝OCH 3 ，M 2 ＝M 4 ＝Br；
And (3) combining M: m 1 ＝M 3 ＝OCH 3 ，M 2 ＝M 4 ＝CHO；
And (3) combining N: m 1 ＝M 2 ＝OCH 3 ，M 3 ＝M 4 ＝CHO；
A combination of O: m 1 ＝M 3 ＝OCH 3 ，M 2 ＝M 4 ＝NH 2 ；
Combination P: m 1 ＝M 2 ＝OCH 3 ，M 3 ＝M 4 ＝NH 2 。
The catalyst composition according to the present invention, in one embodiment, when said M is 1 、M 2 、M 3 、M 4 Two or more of them are each independently selected from the group consisting of hydrocarbyl radicals R 1 And alkoxy-OR 2 When adjacent radicals M 1 And M 2 And/or adjacent radicals M 3 And M 4 Are connected to each other to form a ring structure.
Examples of heteroatoms in the heteroatom-containing group of the catalyst composition according to the present invention may include, for example, O, N, S, P, si and B.
Catalyst composition according to the invention, when M 1 ＝M 3 ＝X 0 ，M 2 ＝M 4 ＝Y 0 (X 0 、Y 0 Respectively represent the above M of the present invention 1 And M 3 、M 3 And M 4 An optional group, and X 0 And Y 0 Different), the diphenylanthracene derivative may exist as the following isomers: m 1 ＝M 4 ＝X 0 ，M 2 ＝M 3 ＝Y 0 . It is to be noted that the isomers are also within the scope of the present invention.
The content of each component in the catalyst composition of the present invention is not particularly limited. In order to obtain a better quality catalyst/composite catalyst, preferably, in the catalyst composition, the content molar ratio of the magnesium alcoholate calculated as Mg, the electron donor a, the titanium-containing compound calculated as Ti, and the first organoaluminum compound calculated as Al is 1:0.001-0.1:0.1-50:0-5.
The catalyst composition of the present invention may or may not contain the first organoaluminum compound.
According to a particular embodiment of the invention, said first organoaluminium compound is contained in said catalyst composition. Preferably, the content molar ratio of the magnesium alcoholate calculated as Mg, the electron donor a, the titanium-containing compound calculated as Ti and the first organoaluminum compound calculated as Al in the catalyst composition is 1:0.002-0.05:1-5:0.8-2.2.
According to another particular embodiment of the invention, said first organoaluminium compound is absent from said catalyst composition. In this embodiment, preferably, the molar ratio of the contents of the magnesium alcoholate, the electron donor a and the titanium-containing compound, calculated as Mg, is 1:0.002-0.05:20-35. In such embodiments, the amount of titanium-containing compound used will be substantially increased, and preferably, the titanium-containing compound is divided into a first titanium-containing compound and a second titanium-containing compound (the same or different, each selected from the limitations of the invention as to the type of titanium-containing chemical) to be added at different steps during the preparation of the catalyst, preferably, the weight ratio of the first titanium-containing compound to the second titanium-containing compound is from 1.5 to 2.5:1.
according to the catalyst composition of the invention, the magnesium alcoholate may be one conventional in the art, preferably one having the general formula MgX 2 -mROH, wherein R is selected from C 1 -C 6 Alkyl, X is selected from halogen atom, m is 2.5-4; preferably, X is selected from fluorine, chlorine, bromine, more preferably X is chlorine, i.e. the magnesium alcoholate is of the formula MgCl 2 -magnesium chloride alcoholates of mROH; preferably, R is selected from C 1 -C 4 Alkyl, more preferably selected from methyl, ethyl, propyl and isopropyl.
According to the catalyst composition of the invention, preferably, the magnesium alcoholate is obtained by reacting C 1 -C 4 The molar ratio of the lower alcohol (OH) to the magnesium halide (Mg) is 2.5-4:1, heating and melting the mixture, then rapidly cooling the mixture,spherical particles containing 2.5 to 4 moles of alcohol per mole of magnesium halide are obtained. According to a particular embodiment of the invention, a non-dealcoholated magnesium chloride alcoholate is used, preferably in a ratio of 2.5 to 4 moles of alcohol per mole of magnesium chloride. The magnesium chloride alcoholate mentioned above is disclosed in CN1091748A, the disclosure of which is hereby incorporated by reference in its entirety.
According to the catalyst composition of the present invention, the titanium-containing compound may be a titanium-containing compound that is conventional in the art. Preferably, the titanium-containing compound of the present invention has the formula Ti (OR) n X’ 4－n Wherein R is selected from C 1 -C 8 Hydrocarbyl, preferably selected from C 1 -C 8 Alkyl, X' is selected from halogen atoms, preferably from fluorine, chlorine and bromine, 0. Ltoreq. N.ltoreq.4. According to a preferred embodiment of the invention, the titanium-containing compound is selected from TiCl 4 、TiBr 4 、TiI 4 、Ti(OC 2 H 5 )Cl 3 、Ti(OCH 3 )Cl 3 、Ti(OC 4 H 9 )Cl 3 、Ti(OC 2 H 5 )Br 3 、Ti(OC 2 H 5 ) 2 Cl 2 、Ti(OCH 3 ) 2 Cl 2 、Ti(OCH 3 ) 2 I 2 、Ti(OC 2 H 5 ) 3 Cl、Ti(OCH 3 ) 3 Cl、Ti(OC 2 H 5 ) 3 I、Ti(OC 2 H 5 ) 4 、Ti(OC 3 H 7 ) 4 And Ti (OC) 4 H 9 ) 4 One or more of; further preferably from TiCl 4 、Ti(OC 2 H 5 )Cl 3 、Ti(OCH 3 )Cl 3 、Ti(OC 4 H 9 )Cl 3 、Ti(OC 4 H 9 ) 4 One or more of; most preferably TiCl 4 。
According to the catalyst composition of the present invention, the first organoaluminum compound may be an organoaluminum compound conventional in the art, preferably the first organoaluminum compound has the general formula AlR' a X” b H c Wherein R' is selected from C 1 -C 14 A hydrocarbon radical, X' being selected from among halogen atomsPreferably selected from fluorine, chlorine and bromine, a, b, c are each integers from 0 to 3, and a + b + c =3. According to a preferred embodiment of the present invention, the first organoaluminium compound is an alkyl aluminium compound; more preferably, the first organoaluminium compound is selected from Al (CH) 3 ) 3 、Al(CH 2 CH 3 ) 3 、Al(i-Bu) 3 、Al(n-C 6 H 13 ) 3 、AlH(CH 2 CH 3 ) 2 、AlH(i-Bu) 2 、AlCl(CH 2 CH 3 ) 2 、Al 2 Cl 3 (CH 2 CH 3 ) 3 And AlCl 2 (CH 2 CH 3 ) One or more of; further preferably selected from Al (CH) 2 CH 3 ) 3 、Al(n-C 6 H 13 ) 3 And Al (i-Bu) 3 One or more of; most preferably Al (CH) 2 CH 3 ) 3 . Wherein i-Bu means isobutyl, n-C 6 H 13 Means an n-hexyl group.
According to the catalyst composition of the present invention, the first organoaluminum compound is preferably added to the polymerization reaction in the form of a solution. The concentration of the solution is not particularly limited, but is preferably 0.5 to 2mol/L. The solvent of the solution is not particularly limited, and may be an organic solvent which does not react with the organoaluminum compound and the other materials of the present invention, and is preferably an organic solvent which satisfies the above conditions and is within the range of the inert solvent of the present invention.
According to the catalyst component of the present invention, the catalyst component may or may not contain an electron donor b.
According to the catalyst component of the present invention, preferably, the catalyst component further comprises an electron donor b, wherein the electron donor b is 0.01 to 5mol, more preferably 0.1 to 0.25mol, relative to 1mol of magnesium in the magnesium alcoholate.
According to the catalyst composition of the present invention, preferably, the electron donor b is selected from one or more of organic alcohols, organic acids, organic acid esters, organic acid halides, organic acid anhydrides, ethers, ketones, amines, phosphate esters, amides, carbonates, phenols, pyridines, haloalkylene oxides, polyolefins, polyalkylene oxides and halopolyalkylene oxides.
Further preferably, the electron donor b is selected from one or more of methyl acetate, ethyl acetate, propyl acetate, butyl acetate, n-octyl acetate, methyl benzoate, ethyl benzoate, butyl benzoate, hexyl benzoate, ethyl p-methylbenzoate, methyl naphthoate, ethyl naphthoate, methyl methacrylate, ethyl acrylate, butyl acrylate, diethyl ether, butyl ether, tetrahydrofuran, 2,2-dimethyl-1,3-diethoxypropane, methanol, ethanol, propanol, isopropanol, butanol, isooctanol, octylamine, triethylamine, acetone, butanone, cyclopentanone, 2-methylcyclopentanone, cyclohexanone, phenol, hydroquinone, ethylene oxide, propylene oxide, epichlorohydrin, trimethyl phosphate, triethyl phosphate, tripropyl phosphate, tributyl phosphate, triphenyl phosphate, trihexyl phosphate, polymethyl methacrylate, polystyrene, polyepichlorohydrin, and polyethylene oxide.
In a second aspect the present invention provides a process for the preparation of a catalyst, wherein the process comprises the steps of:
(1) First mixing a magnesium alcoholate with a first component group selected from one of the following options in a first inert solvent at a temperature of-20 ℃ to obtain a first mixture:
option one, an electron donor a, an optional first organoaluminum compound and an optional electron donor b,
option two, a first organoaluminum compound and optionally an electron donor b, and
option three, at least a portion of the titanium-containing compound;
(2) Carrying out a first contact reaction on the first mixture at the temperature of 50-85 ℃, and carrying out first solid-liquid separation on the reacted materials;
(3) Second mixing the solid obtained in step (2) with a second component group in a second inert solvent at a temperature of-20 ℃ to obtain a second mixture, wherein the second component group is a component except the magnesium alcoholate and the first component group in the catalyst composition of the first aspect of the invention;
(4) And carrying out a second contact reaction on the second mixture at the temperature of 50-85 ℃.
The materials used in the process for preparing the catalyst according to the second aspect of the present invention are selected and used in the same amounts as in the catalyst composition according to the first aspect of the present invention, and will not be described herein again. It should be noted that, according to one embodiment of the present invention, when the organoaluminum compound is added in the preparation method (i.e., when the organoaluminum compound is contained in the catalyst composition of the first aspect), preferably, the at least part of the titanium-containing compound is the entire titanium-containing compound; according to another embodiment of the present invention, when no organoaluminum compound is added in the preparation process (i.e. when no organoaluminum compound is contained in the catalyst composition of the first aspect), preferably, said at least part of the titanium-containing compound is said first titanium-containing compound in said catalyst composition, and the rest of the titanium-containing compound is said second titanium-containing compound in said catalyst composition, which is added in step (3).
In step (1) and step (3), the inert solvent (including the first inert solvent and the second inert solvent, each independently selected) may be any of various organic solvents that do not react with the material in the method of the present invention, for example, one or more of saturated aliphatic hydrocarbon compounds and aromatic hydrocarbon compounds that do not react with the material in the method of the present invention. The inventors of the present invention found that a specific inert solvent has a good effect on the quality of the resulting catalyst, preferably, the first inert solvent and the second inert solvent are each independently selected from one or more of isobutane, hexane, heptane, cyclohexane, naphtha, raffinate, hydrogenated gasoline, kerosene, benzene, toluene, and xylene. According to a particular embodiment of the invention, the first inert solvent and the second inert solvent are each independently selected from one or more of toluene, n-hexane and cyclohexane.
In step (1), the temperature of the first mixing is in the range of-20 ℃ to 20 ℃ as described above, preferably in the range of-20 ℃ to 0 ℃, more preferably in the range of-5 ℃ to-10 ℃.
In step (1), preferably, the first mixing process comprises: the magnesium alcoholate is first dispersed in the first inert solvent to obtain a suspension, which is then mixed with the first component group.
In the present invention, the first organoaluminum compound is preferably added in a slow manner, preferably at a uniform rate over 0.5 to 3 hours, without distinction in the large and small test runs, for example, in the form of a dropwise addition in the laboratory, in the form of a continuous batch in the industrial production, and the addition is carried out with stirring.
In the present invention, the titanium-containing compound is preferably added slowly, preferably at a uniform rate over 0.5 to 3 hours, without distinction from the pilot scale, for example, dropwise in the laboratory, continuously in the industrial process, with stirring.
In step (2), the temperature of the first contact reaction is preferably 55 to 75 ℃, more preferably 55 to 65 ℃.
In the step (2), the time of the first contact reaction may be 0.5 to 5 hours, preferably 2 to 4 hours.
In step (2), the first solid-liquid separation process may be performed in a manner conventional in the art, for example, the reaction mass is stopped from stirring, the suspension is allowed to stand to separate layers, the supernatant is removed, and the solid is washed with an inert solvent.
In step (3), the temperature of the second mixing is in the range of-20 ℃ to 20 ℃ as described above, so as to obtain the catalyst of the present invention, and in a preferred case, the temperature of the second mixing is in the range of-10 ℃ to 5 ℃, more preferably in the range of-5 ℃ to 2 ℃.
In step (4), the temperature of the second contact reaction is preferably 55 to 75 ℃, more preferably 55 to 65 ℃.
In the step (4), the time of the second contact reaction may be 0.5 to 5 hours, preferably 1 to 3 hours.
The catalyst of the invention can be obtained after the second contact reaction. The process for the preparation of the catalyst of the present invention may also comprise conventional work-up procedures, such as carrying out a second solid-liquid separation. The second solid-liquid separation may be carried out in a manner conventional in the art, for example, by stopping stirring the reaction mass, allowing the suspension to stand to separate into layers, removing the supernatant, washing the solid with an inert solvent, transferring the solid to a chromatography funnel with an inert solvent (e.g., hexane), and blow-drying with an inert gas (e.g., high purity nitrogen) to obtain the catalyst.
In a third aspect, the present invention provides a catalyst prepared by the method of the second aspect of the present invention.
The catalyst of the invention presents solid spheres with better fluidity.
In a fourth aspect, the present invention provides a composite catalyst comprising the following components:
component one, the catalyst of the third aspect of the present invention;
component two, a second organoaluminum compound having the formula AlR " d X”’ 3-d Wherein R' is selected from hydrogen and C l -C 20 X' is a halogen atom, and d satisfies 0 < d.ltoreq.3.
According to the composite catalyst of the present invention, the molar ratio of the second component calculated as Al to the first component calculated as Ti is preferably 5 to 500:1, more preferably 20 to 200:1, more preferably 50 to 100:1.
the composite catalyst according to the invention is characterized in that said formula AlR " d X”’ 3-d Wherein R' may be selected from hydrogen and C l -C 20 A hydrocarbyl group, preferably selected from alkyl, aralkyl and aryl groups; x' "may be a halogen atom, preferably chlorine or bromine.
According to the composite catalyst of the present invention, the second organoaluminium compound is preferably an alkylaluminium compound, more preferably chosen from Al (CH) 3 ) 3 、Al(CH 2 CH 3 ) 3 、Al(i-Bu) 3 、AlH(CH 2 CH 3 ) 2 、AlH(i-Bu) 2 、AlCl(CH 2 CH 3 ) 2 、Al 2 Cl 3 (CH 2 CH 3 ) 3 And AlCl 2 (CH 2 CH 3 ) More preferably Al (CH) 2 CH 3 ) 3 And/or Al (i-Bu) 3 . Wherein i-Bu means isobutyl.
According to the composite catalyst of the present invention, the second organoaluminum compound is preferably added to the polymerization reaction in the form of a solution. The concentration of the solution is not particularly limited, and is, for example, 0.1 to 2mol/L.
According to the composite catalyst of the invention, the component I and the component II can be simply mixed in a physical mode, and can be mixed and added into the reaction together before the polymerization reaction, or can be added into the reaction respectively in the reaction process. The first component and the second component can be matched with each other to achieve good catalytic effect.
In a fifth aspect, the present invention provides an olefin polymerization process, wherein the olefin polymerization process comprises: in the presence of the composite catalyst according to the fourth aspect of the present invention, homopolymerization or copolymerization of olefins is carried out.
The composite catalyst of the present invention may be used in homopolymerization of ethylene and copolymerization of ethylene and alpha-olefin. The homopolymerization of ethylene and the copolymerization of ethylene with alpha-olefins may be carried out in a manner conventional in the art.
According to the polymerization process of the present invention, preferably, the olefin is of the formula CH 2 ＝CHR 0 Wherein R is 0 Selected from hydrogen, C 1 -C 6 Alkyl and C 1 -C 6 Aryl group of (1).
According to the polymerization method of the present invention, for example, in the copolymerization, the α -olefin may be selected from one or more of propylene, butene, pentene, hexene, octene, and 4-methyl-1-pentene.
According to the polymerization method of the present invention, the polymerization method may be carried out by liquid phase polymerization or gas phase polymerization.
When the liquid phase polymerization mode is employed, the liquid phase polymerization medium may include: and an inert solvent such as a saturated aliphatic hydrocarbon or an aromatic hydrocarbon, e.g., isobutane, hexane, heptane, cyclohexane, naphtha, raffinate, hydrogenated gasoline, kerosene, benzene, toluene, xylene, etc., preferably toluene, n-hexane, or cyclohexane.
When the liquid phase homopolymerization mode is adopted, the reaction conditions may include: hydrogen 0.1-0.7MPa, olefin monomer 0.15-1MPa (gauge pressure), polymerization temperature 70-90 deg.C, and polymerization time 1-10h.
According to the polymerization process of the present invention, hydrogen can be used as a molecular weight regulator in order to regulate the molecular weight of the final polymer.
The present invention will be described in detail below by way of examples.
Example 1
(1) Preparation of the catalyst composition
The following materials were prepared:
magnesium alcoholate: mgCl on spherical support 2 ·2.6C 2 H 5 OH (same as below, available from Oda division of Beijing, a petrochemical catalyst, china) 6.0g (based on MgCl 2 ·2.6C 2 H 5 OH molecular weight 215, reduced to 0.028 mol);
inert solvent: toluene, 100mL;
a first organoaluminum compound: 1.2M Triethylaluminum in 50mL hexane (calculated as C) 6 H 15 0.06mol of Al, and the mol ratio of Al to Mg is 2.14
Electron donor a: diphenylanthracene derivatives (M in formula (I)) 1 ＝M 2 ＝M 3 ＝M 4 ＝OCH 3 ) 0.3g (according to C) 30 H 26 O 4 Molecular weight 450.52, converted to 0.00067mol, in a molar ratio to Mg of 0.024);
a titanium-containing compound: titanium tetrachloride, 8ml (based on TiCl) 4 The molecular weight is 189.679 and the density is 1.726g/cm 3 Reduced to 0.073mol, in a molar ratio to Mg of 2.6.
(2) Preparation of the catalyst
A. Sequentially adding the magnesium alcoholate and the inert solvent into a reactor which is fully replaced by high-purity nitrogen, and cooling to-10 ℃ under stirring; then dropwise adding the first organic aluminum compound, and then adding the electron donor a;
B. the mixture obtained in step A was warmed to 60 ℃ and the reaction was maintained for 3 hours. Stirring was stopped, the suspension was allowed to settle, the supernatant was removed quickly, and the precipitate was washed several times with toluene and hexane in succession.
C. Adding 120ml of hexane into the precipitate obtained in the step B, cooling the system to 0 ℃, slowly dropwise adding the titanium-containing compound, then heating to 60 ℃, and reacting for 2 hours.
D. Stopping stirring, standing, quickly layering the suspension, pumping out supernatant, washing the precipitate twice with hexane, transferring the precipitate into a chromatography funnel through hexane, and drying the precipitate with high-purity nitrogen to obtain a solid spherical catalyst with good fluidity, which is recorded as S1.
Comparative example 1
The procedure is as in example 1, except that no diphenylanthracene derivative is added.
The final catalyst was designated as D1.
Comparative example 2
The catalyst was prepared as follows:
4.0g of MgCl on a spherical support are added in sequence to a reactor which is fully replaced by high-purity nitrogen 2 ·3.0C 2 H 5 OH, hexane 150ml, was cooled to-10 ℃ with stirring, 60ml of a hexane solution of triethylaluminum (triethylaluminum: 1.2M) and 1ml of n-octyl acetate, 1ml of ethyl benzoate were added dropwise, followed by warming to 50 ℃ and maintaining the reaction for 3 hours. Stirring was stopped, the suspension was allowed to settle, the suspension was quickly separated, the supernatant was removed, and the precipitate was washed twice with hexane at room temperature. 150ml of hexane was added, the system was cooled to 0 ℃ and 6ml of titanium tetrachloride was slowly added dropwise, after which the temperature was raised to 60 ℃ to react for 2 hours. Stopping stirring, standing, quickly demixing the suspension, pumping out the supernatant, washing the precipitate twice with hexane, transferring the precipitate into a chromatography funnel through hexane, and drying the precipitate with high-purity nitrogen to obtain the catalyst which is recorded as D2.
Comparative example 3
The catalyst was prepared as follows:
in a reactor fully replaced by high-purity nitrogen, 5.0g of MgCl as spherical carrier is added in turn 2 ·3.0C 2 H 5 OH and toluene 100ml, cooling to-10 ℃ with stirring, dropping 60ml titanium tetrachloride, then heating to 40 ℃, adding 3ml ethyl benzoate, continuing to heat to 85 ℃, and maintaining the reaction for 3 hours. Stirring was stopped, the suspension was allowed to settle, the supernatant was removed quickly, and the precipitate was washed several times with toluene and hexane in succession. 150ml of toluene was added, the system was cooled to 0 ℃ and 30ml of titanium tetrachloride was slowly added dropwise, followed by heating to 85 ℃ and reaction for 2 hours. Stopping stirring, standing, quickly layering the suspension, pumping out supernatant, washing the precipitate twice with hexane, transferring the precipitate into a chromatography funnel through hexane, and drying the precipitate with high-purity nitrogen to obtain the catalyst which is recorded as D3.
Example 2
(1) Preparation of the catalyst composition
The following materials were prepared:
magnesium alcoholate: mgCl on spherical support 2 ·2.6C 2 H 5 OH,6.0g (according to MgCl) 2 ·2.6C 2 H 5 OH molecular weight 215, reduced to 0.028 mol);
inert solvent: toluene, 120mL;
a first organoaluminum compound: 50mL of 0.56M triethylaluminum in hexane (calculated as C) 6 H 15 0.028mol of Al, 1:1 mol of molar ratio to Mg)
Electron donor a: diphenylanthracene derivatives (M in formula (I)) 1 ＝M 2 ＝M 3 ＝M 4 ＝OCH 3 ) 0.025g (according to C) 30 H 26 O 4 Molecular weight 450.52, converted to 0.000056mol, in a molar ratio to Mg of 0.002;
a titanium-containing compound: titanium tetrachloride, 15.4ml (based on TiCl) 4 The molecular weight is 189.679 and the density is 1.726g/cm 3 Reduced to 0.14mol, and a molar ratio to Mg of 5:1).
(2) Preparation of the catalyst
A. Sequentially adding the magnesium alcoholate and the inert solvent into a reactor which is fully replaced by high-purity nitrogen, and cooling to-10 ℃ under stirring; then dropwise adding the titanium-containing compound;
B. the mixture obtained in step A was warmed to 60 ℃ and the reaction was maintained for 3 hours. Stirring was stopped, the suspension was allowed to settle, the supernatant was removed quickly, and the precipitate was washed several times with toluene and hexane in succession.
C. And D, adding 120ml of hexane into the precipitate obtained in the step B, cooling the system to 0 ℃, slowly dropwise adding the first organic aluminum compound and the electron donor a, heating to 60 ℃, and reacting for 2 hours.
D. Stopping stirring, standing, quickly layering the suspension, pumping out supernatant, washing the precipitate twice with hexane, transferring the precipitate into a chromatography funnel through hexane, and drying the precipitate with high-purity nitrogen to obtain a solid spherical catalyst with good fluidity, which is recorded as S2.
Example 3
(1) Preparation of the catalyst composition
The following materials were prepared:
magnesium alcoholate: mgCl on spherical support 2 ·3.0C 2 H 5 OH,5.0g (according to MgCl) 2 ·3.0C 2 H 5 OH molecular weight 233.42, 0.021 mol);
inert solvent: toluene, 120mL;
electron donor a: diphenylanthracene derivatives (M in formula (I)) 1 ＝M 2 ＝M 3 ＝M 4 ＝OCH 3 ) 0.47g (according to C) 30 H 26 O 4 Molecular weight 450.52, converted to 0.00105mol, in a 0.05 to Mg molar ratio;
a first titanium-containing compound: titanium tetrachloride, 45ml (based on TiCl) 4 The molecular weight is 189.679 and the density is 1.726g/cm 3 0.41mol, and the molar ratio of Mg to the Mg is 20);
a second titanium-containing compound: titanium tetrachloride, 20ml (based on TiCl) 4 The molecular weight is 189.679 and the density is 1.726g/cm 3 The conversion is 0.18mol, and the molar ratio to Mg is 9:1).
(2) Preparation of the catalyst
A. Sequentially adding the magnesium alcoholate and the inert solvent into a reactor which is fully replaced by high-purity nitrogen, and cooling to-5 ℃ under stirring; then dropwise adding a first titanium-containing compound;
B. the mixture obtained in step a was warmed to 85 ℃ and the reaction was maintained for 2 hours. Stirring was stopped, the suspension was allowed to settle, the supernatant was removed quickly, and the precipitate was washed several times with toluene and hexane in succession.
C. And D, adding 120ml of toluene into the precipitate obtained in the step B, cooling the system to 0 ℃, slowly dropwise adding the second titanium-containing compound and the electron donor a, then heating to 85 ℃, and reacting for 2 hours.
D. Stopping stirring, standing, quickly layering the suspension, pumping out supernatant, washing the precipitate twice with hexane, transferring the precipitate into a chromatography funnel through hexane, and drying the precipitate with high-purity nitrogen to obtain a solid spherical catalyst with good fluidity, which is recorded as S3.
Examples 4 to 18
The procedure is as in example 1, except that the diphenylanthracene derivatives used in examples 4-19 are each changed to the combination B-combination P as described in the specification, and the molar amounts used are the same as in example 1. The solid spherical catalyst with good fluidity is obtained and is respectively marked as S4B, S5C, S6D, S7E, S8F, S9G, S10H, S11I, S12J, S13K, S L, S15M, S16 zxft 9843O, S P.
Example 19
The procedure is as in example 1, except that the diphenylanthracene derivative used: m in the formula (I) 1 ＝M 2 ＝M 3 ＝M 4 ＝OCH 3 0.023g (according to C) 30 H 26 O 4 Molecular weight 450.52, 0.00005mol converted, molar ratio to Mg 0.001.
The solid catalyst finally obtained is denoted as S19.
Example 20
The procedure is as in example 1, except that the diphenylanthracene derivative used: m in the formula (I) 1 ＝M 2 ＝M 3 ＝M 4 ＝OCH 3 1.13g (according to C) 30 H 26 O 4 Molecular weight 450.52, 0.0025mol, 0.1 molar ratio to Mg.
The solid catalyst finally obtained is denoted as S20.
Examples 21 to 24
The process is carried out as in example 1, except that the electron donor b is added during the preparation in the following order:
example 21b: in step B, 1mL of ethyl benzoate (as per C) was added together with the electron donor a 9 H 10 O 2 Molecular weight 150.17, density 1.05g/mL, 0.007mol converted, molar ratio to Mg 0.25. Finally, a solid spherical catalyst with good fluidity is obtained and is marked as S21b.
Example 22b: in step B, 1mL of trihexyl phosphate (as per C) was added with electron donor a 18 H 39 O 4 Molecular weight of P350.4736, density 0.95g/mL, 0.0028mol converted, molar ratio to Mg 0.1. Finally, a solid spherical catalyst with good fluidity is obtained and is marked as S22b.
Example 23b: in step C, triethylamine, 2mL (as per C) was added together with the titanium-containing compound 6 H 15 N molecular weight 101.19, density 0.728g/mL, reduced to 0.014mol, molar ratio to Mg 0.5. Finally, a solid spherical catalyst with good fluidity is obtained and is marked as S23b.
Example 24b: in step C, 0.25mL of cyclopentanone (according to C) was added together with the titanium-containing compound 5 H 8 O molecular weight 84.12, density 0.951g/mL, reduced to 0.0028mol, and molar ratio to Mg 0.01. Finally, a solid spherical catalyst with good fluidity is obtained and is marked as S24b.
Application example
The catalysts S1 to S24b and D1 to D2 obtained in the above examples 1 to 24 and comparative examples 1 to 2 were polymerized in the following manner:
a stainless steel reaction kettle with the volume of 2L is fully replaced by high-purity nitrogen, 1L of hexane and 1.0ml of triethyl aluminum with the concentration of 1M are added, then the solid catalyst (containing 0.6mg of titanium) prepared by the method is added, the temperature is raised to 70 ℃, hydrogen is introduced to ensure that the pressure in the kettle reaches 0.28MPa, then ethylene is introduced to ensure that the total pressure in the kettle reaches 0.73MPa (gauge pressure), and the polymerization product is obtained after 2 hours of polymerization at the temperature of 80 ℃.
Test example
The following tests were performed, respectively, and the test results are shown in table 1.
1. Catalytic Activity of polymerization (10) 4 gPE/gcat): thoroughly drying and weighing the powder obtained by polymerization; dividing the mass of the powder by the mass of the composite catalyst added into the polymerization kettle (the total mass of the prepared catalyst and triethyl aluminum in application examples) to obtain the catalytic activity of the composite catalyst;
2. determination of the melt index of the polymerization product (MI, g/10 min): the temperature was 190 ℃ and the load was 2.16Kg, measured according to ASTM D1238-99.
TABLE 1
As can be seen from the results in Table 1, the catalytic activity of the composite catalyst of the present invention for olefin polymerization can reach 2.7X 10 4 gPE/gcat is higher than that, and in a preferred embodiment, can reach 3.0X 10 4 gPE/gcat is higher than that, and in a further preferred embodiment, may be 3.5X 10 4 More than gPE/gcat. As can be seen by comparing example 1 with comparative example 1, when the diphenylanthracene derivative was not contained, the catalytic activity was significantly decreased, and the melt index of the polymer product obtained was significantly increased.
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 various technical features being combined 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 (18)
1. A catalyst composition comprising a magnesium alkoxide, a titanium-containing compound, an electron donor a selected from compounds of the general formula (I):
wherein, in the catalyst composition, the content molar ratio of the magnesium alcoholate calculated as Mg, the electron donor a, the titanium-containing compound calculated as Ti and the first organoaluminum compound calculated as Al is 1:0.001-0.1:0.1-15:0 to 5;
wherein, in the formula (I), M 1 、M 2 、M 3 And M 4 Selected from the following combinations:
combination A: m is a group of 1 ＝M 2 ＝M 3 ＝M 4 ＝OCH 3 ；
Combination B: m 1 ＝M 2 ＝M 3 ＝M 4 ＝OCH 2 CH 3 ；
And (3) combination C: m is a group of 1 ＝M 2 ＝M 3 ＝M 4 ＝OCH 2 CH 2 CH 3 ；
Combination D: m 1 ＝M 2 ＝OCH 3 ，M 3 ＝M 4 ＝OCH 2 CH 3 ；
Combination E: m 1 ＝M 3 ＝OCH 3 ，M 2 ＝M 4 ＝OCH 2 CH 3 ；
And (3) combination F: m 1 ＝M 2 ＝M 3 ＝M 4 ＝OH；
A combination G: m 1 ＝M 2 ＝OCH 3 ，M 3 ＝M 4 ＝OH；
Combination H: m 1 ＝M 3 ＝OCH 3 ，M 2 ＝M 4 ＝OH；
Combination I: m 1 ＝M 2 ＝OCH 3 ，M 3 ＝M 4 ＝Cl；
Combination J: m 1 ＝M 3 ＝OCH 3 ，M 2 ＝M 4 ＝Cl；
And (3) combination K: m 1 ＝M 2 ＝OCH 3 ，M 3 ＝M 4 ＝Br；
Combination L: m 1 ＝M 3 ＝OCH 3 ，M 2 ＝M 4 ＝Br；
And (3) combining M: m 1 ＝M 3 ＝OCH 3 ，M 2 ＝M 4 ＝CHO；
And (3) combining N: m is a group of 1 ＝M 2 ＝OCH 3 ，M 3 ＝M 4 ＝CHO；
Combination O: m is a group of 1 ＝M 3 ＝OCH 3 ，M 2 ＝M 4 ＝NH 2 ；
And (3) combination P: m is a group of 1 ＝M 2 ＝OCH 3 ，M 3 ＝M 4 ＝NH 2 。
2. The catalyst composition of claim 1, wherein the magnesium alkoxide compound has the formula MgX 2 -mROH, wherein R is selected from C 1 -C 6 Alkyl, X is selected from halogen atoms, and m is 2.5-4.0.
3. Catalyst composition according to claim 2, wherein the magnesium alcoholate has the general formula MgCl 2 -mROH。
4. The catalyst composition of any one of claims 1-3, wherein the titanium-containing compound has the general formula Ti (OR) n X’ 4－n Wherein R is selected from C 1 -C 8 A hydrocarbon group, X' is selected from halogen atoms, and 0. Ltoreq. N.ltoreq.4.
5. Catalysis according to claim 4Agent composition, wherein the titanium-containing compound is selected from TiCl 4 、TiBr 4 、TiI 4 、Ti(OC 2 H 5 )Cl 3 、Ti(OCH 3 )Cl 3 、Ti(OC 4 H 9 )Cl 3 、Ti(OC 2 H 5 )Br 3 、Ti(OC 2 H 5 ) 2 Cl 2 、Ti(OCH 3 ) 2 Cl 2 、Ti(OCH 3 ) 2 I 2 、Ti(OC 2 H 5 ) 3 Cl、Ti(OCH 3 ) 3 Cl、Ti(OC 2 H 5 ) 3 I、Ti(OC 2 H 5 ) 4 、Ti(OC 3 H 7 ) 4 And Ti (OC) 4 H 9 ) 4 One or more of (a).
6. The catalyst composition of any one of claims 1 to 3, wherein the first organoaluminum compound has the general formula AlR' a X” b H c Wherein R' is selected from C 1 -C 14 A hydrocarbon group, X' is selected from halogen atoms, a, b and c are all integers of 0-3, and a + b + c =3.
7. The catalyst composition of claim 6, wherein the first organoaluminum compound is selected from Al (CH) 3 ) 3 、Al(CH 2 CH 3 ) 3 、Al(i-Bu) 3 、Al(n-C 6 H 13 ) 3 、AlH(CH 2 CH 3 ) 2 、AlH(i-Bu) 2 、AlCl(CH 2 CH 3 ) 2 、Al 2 Cl 3 (CH 2 CH 3 ) 3 And AlCl 2 (CH 2 CH 3 ) One or more of (a).
8. The catalyst composition of any one of claims 1-3, wherein the catalyst composition further comprises an electron donor b selected from one or more of organic alcohols, organic acids, organic acid esters, organic acid halides, organic acid anhydrides, ethers, ketones, amines, phosphate esters, amides, carbonates, phenols, pyridines, haloalkylene oxides, polyolefins, polyalkylene oxides, and halopolyalkylene oxides.
9. The catalyst composition of claim 8, wherein the electron donor b is 0.01 to 5mol with respect to 1mol of magnesium in the magnesium alcoholate.
10. The catalyst composition of claim 8, wherein the electron donor b is selected from one or more of methyl acetate, ethyl acetate, propyl acetate, butyl acetate, n-octyl acetate, methyl benzoate, ethyl benzoate, butyl benzoate, hexyl benzoate, ethyl p-methylbenzoate, methyl naphthoate, ethyl naphthoate, methyl methacrylate, ethyl acrylate, butyl acrylate, diethyl ether, butyl ether, tetrahydrofuran, 2,2-dimethyl-1,3-diethoxypropane, methanol, ethanol, propanol, butanol, isooctanol, octylamine, triethylamine, acetone, butanone, cyclopentanone, 2-methylcyclopentanone, cyclohexanone, phenol, hydroquinone, ethylene oxide, propylene oxide, epichlorohydrin, trimethyl phosphate, triethyl phosphate, tripropyl phosphate, tributyl phosphate, triphenyl phosphate, trihexyl phosphate, polymethyl methacrylate, polystyrene, polyepichlorohydrin, and polyethylene oxide.
11. The catalyst composition of claim 10, wherein the electron donor b is isopropanol.
12. A method of preparing a catalyst, comprising the steps of:
(1) First mixing a magnesium alcoholate with a first component group selected from one of the following options in a first inert solvent at a temperature of-20 ℃ to obtain a first mixture:
option one, an electron donor a, an optional first organoaluminum compound, and an optional electron donor b,
option two, a first organoaluminum compound and optionally an electron donor b, and
option three, at least a portion of the titanium-containing compound;
(2) Carrying out a first contact reaction on the first mixture at the temperature of 50-85 ℃, and carrying out first solid-liquid separation on the reacted materials;
(3) Second mixing the solid obtained in step (2) with a second component group in a second inert solvent at a temperature of-20 ℃ to obtain a second mixture, wherein the second component group is the component except the magnesium alcoholate and the first component group in the catalyst composition of any one of claims 1-11;
(4) And carrying out a second contact reaction on the second mixture at the temperature of 50-85 ℃.
13. A catalyst prepared by the method of claim 12.
14. A composite catalyst, characterized in that the composite catalyst comprises the following components:
component one, the catalyst of claim 13;
component two, a second organoaluminum compound having the general formula AlR " d X”’ 3-d Wherein R' is selected from hydrogen and C l -C 20 X' is a halogen atom, and d is 0 < d.ltoreq.3.
15. The composite catalyst of claim 14, wherein the molar ratio of the second component, calculated as Al, to the first component, calculated as Ti, is from 5 to 500:1.
16. the composite catalyst of claim 15, wherein the molar ratio of the second component, calculated as Al, to the first component, calculated as Ti, is 20-200:1.
17. an olefin polymerization process, comprising: homopolymerization or copolymerization of olefins in the presence of the composite catalyst according to any of claims 14 to 16.
18. The process of claim 17 wherein the olefin is of the formula CH 2 ＝CHR 0 Wherein R is 0 Selected from hydrogen, C 1 -C 6 Alkyl and C 6 Aryl group of (1).
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