CN110903417B - Solid catalyst component for olefin polymerization, catalyst and application thereof - Google Patents
Solid catalyst component for olefin polymerization, catalyst and application thereof Download PDFInfo
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Abstract
The invention discloses a solid catalyst component for olefin polymerization, which comprises magnesium, titanium, halogen and an electron donor, wherein the electron donor comprises a compound selected from a general formula (I). The invention also discloses a catalyst for olefin polymerization. The catalyst component and the catalyst containing the catalyst component are suitable for developing polyolefin, especially polypropylene resin.
Description
Technical Field
The invention belongs to the field of catalysts, and particularly relates to a catalyst component for olefin polymerization, a catalyst system and application thereof.
Background
It is well known that solid titanium catalyst components based on magnesium, titanium, halogen and electron donor can be used for CH2The CHR olefin polymerization reaction, particularly in the polymerization of α -olefins having 3 or more carbon atoms, can give polymers of higher yield and higher stereoregularity, in which an electron donor compound is one of indispensable components in the catalyst component, and the polyolefin catalyst is continuously updated with the development of internal electron donor compounds. At present, the internal electron donor used in industry is mainly phthalate, and the catalyst system has higher activity and high stereoregularity. Phthalates have attracted considerable attention due to their associated environmental and medical problems. Therefore, researchers in this field are all working on developing internal electron donor compounds of polyolefin catalysts that can replace phthalates.
At present, a large number of non-phthalate electron donor compounds have been disclosed, such as mono-or poly-carboxylic acid esters, anhydrides, ketones, ethers, glycol esters, amines, etc. and derivatives thereof, see patents CN1042547A, CN1143651A, CN1054139A, WO98/56830, WO98/56834, WO01/57099, WO01/63231, and WO00/55215, etc.
Most of the electron donors reported at present are oxygen, nitrogen, phosphorus and sulfur-containing compounds. In these catalytic polymerization systems, the electron donor has varying degrees of influence on the activity, stereospecificity, molecular weight distribution and polymer properties.
Disclosure of Invention
The present inventors have found through extensive experiments that by using a phosphine oxide compound having a specific structure as an electron donor in an olefin polymerization catalyst, a catalyst having excellent overall performance can be obtained, and when the catalyst is used for olefin polymerization, particularly propylene polymerization, the catalyst has good hydrogen response and the molecular weight distribution of the obtained polymer is broad.
The first aspect of the present invention provides a solid catalyst component for olefin polymerization comprising magnesium, titanium, halogen and an electron donor compound comprising a compound of the following general formula (I),
in the general formula (I),
R1is C1-C10Straight chain alkyl group of (1), C2-C10Linear alkenyl of (A), C2-C10Straight chain alkynyl of (2), C3-C12A branched hydrocarbon group of3-C12A cycloalkyl group of6-C20Aryl of (C)7-C20Of hydrocarbon aryl or C7-C20And said C is an aromatic hydrocarbon group1-C10Straight chain alkyl group of (1), C2-C10Linear alkenyl of (A), C2-C10Straight chain alkynyl of (2), C3-C12A branched hydrocarbon group of3-C12A cycloalkyl group of6-C20Aryl of (C)7-C20Of hydrocarbon aryl or C7-C20The hydrogen on the arylcarbon of (a) is optionally substituted with a heteroatom, preferably at least one heteroatom selected from halogen atoms, oxygen atoms and nitrogen atoms;
R2selected from hydrogen, halogen atoms, C1-C10Straight chain alkyl group of (1), C3-C10Branched alkyl of C1-C10Linear alkoxy of (1) and C3-C10A branched alkoxy group of (A), and said C1-C10Straight chain alkyl group of (1), C3-C10Branched alkyl of C1-C10Straight chain alkane of (2)Oxy and C3-C10The hydrogen on the branched alkoxy carbon of (a) may be optionally substituted with a heteroatom, preferably at least one heteroatom selected from a halogen atom, an oxygen atom and a nitrogen atom.
According to an embodiment of the solid catalyst component of the present invention, R1Is C1-C8Straight chain alkyl group of (1), C2-C8Linear alkenyl of (A), C2-C8Straight chain alkynyl of (2), C3-C10Branched hydrocarbon radicals (e.g. C)3-C10Alkyl of (C)3-C10Branched alkenyl of (C)3-C10Branched alkynyl of (2), C3-C10A cycloalkyl group of6-C15Aryl of (C)7-C15Of hydrocarbon aryl or C7-C15And said C is an aromatic hydrocarbon group1-C8Straight chain alkyl group of (1), C2-C8Linear alkenyl of (A), C2-C8Straight chain alkynyl of (2), C3-C10Branched alkyl of C3-C10Branched alkenyl of (C)3-C10Branched alkynyl of (2), C3-C10A cycloalkyl group of6-C15Aryl of (C)7-C15Of hydrocarbon aryl or C7-C15The hydrogen on the arylcarbon of (a) is optionally substituted with one or more heteroatoms selected from halogen atoms, oxygen atoms and nitrogen atoms.
According to a preferred embodiment of the solid catalyst component of the invention, R1Is C1-C6Straight chain alkyl group of (1), C2-C6Linear alkenyl of (A), C2-C6Straight chain alkynyl of (2), C3-C8Branched alkyl of C3-C8Branched alkenyl of (C)3-C8Branched alkynyl of (2), C3-C8A cycloalkyl group of6-C12Aryl of (C)7-C12Of hydrocarbon aryl or C7-C12And said C is an aromatic hydrocarbon group1-C6Straight chain alkyl group of (1), C2-C6Linear alkenyl of (A), C2-C6Straight chain alkynyl of (2), C3-C8Branched alkyl of C3-C8Branched alkenyl of (C)3-C8Branched alkynyl of (2), C3-C8A cycloalkyl group of6-C12Aryl of (C)7-C12Of hydrocarbon aryl or C7-C12The hydrogen on the arylcarbon of (a) is optionally substituted with one or more heteroatoms selected from halogen atoms, oxygen atoms and nitrogen atoms.
According to a preferred embodiment of the solid catalyst component of the invention, R2Selected from hydrogen, halogen, C1-C8Straight chain alkyl group of (1), C3-C8Branched alkyl of C1-C8Linear alkoxy of (1) and C3-C8A branched alkoxy group of (a), said C1-C8Straight chain alkyl group of (1), C3-C8Branched alkyl of C1-C8Linear alkoxy of (1) and C3-C8The hydrogen on the branched alkoxy carbon of (a) is optionally substituted with one or more heteroatoms selected from halogen atoms, oxygen atoms and nitrogen atoms.
According to a preferred embodiment of the solid catalyst component of the invention, R2Selected from hydrogen, halogen, C1-C6Straight chain alkyl group of (1), C3-C6Branched alkyl of C1-C6Linear alkoxy of (1) and C3-C6A branched alkoxy group of (a), said C1-C6Straight chain alkyl group of (1), C3-C6Branched alkyl of C1-C6Linear alkoxy of (1) and C3-C6The hydrogen on the branched alkoxy carbon of (a) is optionally substituted with one or more heteroatoms selected from halogen atoms, oxygen atoms and nitrogen atoms.
According to a preferred embodiment of the solid catalyst component of the invention, R1Is C6-C12Aryl of (C)7-C12Of hydrocarbon aryl or C7-C12Is preferably phenyl, C7-C12Hydrocarbon phenyl or C7-C12More preferably phenyl, C7-C12Alkylphenyl radical of (1), C7-C12Phenylalkyl of, C7-C12Phenylalkenyl or C7-C12Optionally substituted with one or more heteroatoms selected from halogen atoms, oxygen atoms and nitrogen atoms.
The solid catalyst component according to the invention, the compound of the general formula (I) is selected from acetoxydiphenylphosphine oxide, trifluoroacetyloxydiphenylphosphine oxide, propionyloxydiphenylphosphine oxide, n-butyryloxydiphenylphosphine oxide, isobutyryloxydiphenylphosphine oxide, n-valeryloxydiphenylphosphine oxide, isovaleryloxydiphenylphosphine oxide, 2-methylbutyryloxydiphenylphosphine oxide, 2, 2-dimethylpropionyloxydiphenylphosphine oxide, n-hexanoyloxydiphenylphosphine oxide, 2-acryloyloxydiphenylphosphine oxide, benzoyloxydiphenylphosphine oxide, 4-methylbenzoyloxydiphenylphosphine oxide, 4-methoxybenzoyloxydiphenylphosphine oxide, 4-ethylbenzoyloxydiphenylphosphine oxide, 4-n-propylbenzoyloxydiphenylphosphine oxide, 4-isopropylbenzoyloxydiphenylphosphine oxide, 4-n-butylbenzoyloxybis (p-methoxyphenyl) phosphine oxide, 4-isobutylbenzoyloxydiphenylphosphine oxide, 4-tert-butylbenzoyloxydiphenylphosphine oxide, 1-naphthoyloxydiphenylphosphine oxide, cinnamoyloxybis (p-tolyl) phosphine oxide, acetoxybis (p-tolyl) phosphine oxide, trifluoroacetyloxybis (p-tolyl) phosphine oxide, propionyloxybis (p-tolyl) phosphine oxide, n-butyryloxybis (p-tolyl) phosphine oxide, isobutyryloxybis (p-tolyl) phosphine oxide, n-valeryloxybis (p-tolyl) phosphine oxide, isovaleryloxybis (p-tolyl) phosphine oxide, 2-methylbutyryloxybis (p-tolyl) phosphine oxide, 2, 2-dimethylpropionyloxybis (p-tolyl) phosphine oxide, n-hexyloxybis (p-tolyl) phosphine oxide, 2-acryloyloxybis (p-tolyl) phosphine oxide, benzoyloxybis (p-tolyl) phosphine oxide, 4-methylbenzoyloxybis (p-tolyl) phosphine oxide, 4-methoxybenzoyloxybis (p-tolyl) phosphine oxide, 4-ethylbenzoyloxybis (p-tolyl) phosphine oxide, 4-n-propylbenzoyloxybis (p-tolyl) phosphine oxide, 4-isopropylbenzoyloxybis (p-tolyl) phosphine oxide, 4-n-butylbenzoyloxybis (p-tolyl) phosphine oxide, 4-isobutylbenzoyloxybis (p-tolyl) phosphine oxide, 4-tert-butylbenzoyloxybis (p-tolyl) phosphine oxide, 1-naphthoyloxybis (p-tolyl) phosphine oxide, cinnamoyloxybis (p-tolyl) phosphine oxide, acetoxybis (p-chlorophenyl) phosphine oxide, trifluoroacetoxybis (p-chlorophenyl) phosphine oxide, propionyloxybis (p-chlorophenyl) phosphine oxide, n-butyryloxybis (p-chlorophenyl) phosphine oxide, isobutyryloxybis (p-chlorophenyl) phosphine oxide, n-valeryloxybis (p-chlorophenyl) phosphine oxide, isovaleryloxybis (p-chlorophenyl) phosphine oxide, 2-methylbutyryloxybis (p-chlorophenyl) phosphine oxide, 2, 2-dimethylpropionyloxybis (p-chlorophenyl) phosphine oxide, n-hexanoyloxybis (p-chlorophenyl) phosphine oxide, 2-acryloyloxybis (p-chlorophenyl) phosphine oxide, benzoyloxybis (p-chlorophenyl) phosphine oxide, phenylacetyloxybis (p-chlorophenyl) phosphine oxide, 4-methylbenzoyloxybis (p-chlorophenyl) phosphine oxide, 4-methoxybenzoyloxybis (p-chlorophenyl) phosphine oxide, 4-ethylbenzoyloxybis (p-chlorophenyl) phosphine oxide, 4-n-propylbenzoyloxybis (p-chlorophenyl) phosphine oxide, 4-isopropylbenzoyloxybis (p-chlorophenyl) phosphine oxide, 4-n-butylbenzoyloxybis (p-chlorophenyl) phosphine oxide, 4-isobutylbenzoyloxybis (p-chlorophenyl) phosphine oxide, 4-tert-butylbenzoyloxybis (p-chlorophenyl) phosphine oxide, 1-naphthoyloxybis (p-chlorophenyl) phosphine oxide and cinnamoyloxybis (p-chlorophenyl) phosphine oxide.
According to the invention, the halogen is selected from fluorine, chlorine, bromine and iodine.
According to an embodiment of the invention, the solid catalyst component comprises the reaction product of a magnesium compound, a titanium compound and a compound of general formula (I).
According to a preferred embodiment of the present invention, the molar ratio of the magnesium compound, the titanium compound and the compound of the general formula (I) is 1 (0.5-150) to (0.02-0.4).
According to a preferred embodiment of the present invention, the magnesium compound includes one or more selected from the group consisting of magnesium dihalide, alkoxy magnesium, alkyl magnesium, hydrate or alcoholate of magnesium dihalide and derivative in which one halogen atom in the molecular formula of magnesium dihalide is replaced with alkoxy or haloalkoxy. Preference is given to magnesium dihalides or alcoholates of magnesium dihalides, such as magnesium dichloride, magnesium dibromide, magnesium diiodide and alcoholates thereof.
According to a preferred embodiment of the present invention, the titanium compound comprises one or more selected from the group consisting of compounds represented by the general formula (II):
TiXm(OR1)4-m(II)
in the general formula (II), R1Is C1～C20A hydrocarbon group of (a); x is halogen; m is more than or equal to 1 and less than or equal to 4.
Examples of the titanium compound include titanium tetrachloride, titanium tetrabromide, titanium tetraiodide, tetrabutoxytitanium, tetraethoxytitanium, chlorotriethoxytitanium, dichlorodiethoxytitanium, trichloromonoethoxytitanium, and preferably titanium tetrachloride.
Specifically, the magnesium compound is soluble in a solvent system containing an organic epoxy compound and an organic phosphorus compound, and also soluble in a 1, 3-diol ester compound. Wherein the organic epoxy compound comprises at least one of an oxide, a glycidyl ether and an internal ether of aliphatic olefin with 2-8 carbon atoms, diene or halogenated aliphatic olefin or diene. Specific compounds are as follows: ethylene oxide, propylene oxide, butylene oxide, butadiene double oxide, epichlorohydrin, methyl glycidyl ether, diglycidyl ether, tetrahydrofuran.
Wherein the organophosphorus compound comprises hydrocarbyl or halohydrocarbyl esters of orthophosphoric acid or phosphorous acid, such as: trimethyl orthophosphate, triethyl orthophosphate, tributyl orthophosphate, triphenyl orthophosphate, trimethyl phosphite, triethyl phosphite, tributyl phosphite, and trityl phosphite.
The solid catalyst component of the present invention can be prepared by various methods, and the following are only a few methods for preparing the catalyst, and the preparation of the catalyst according to the present invention is not limited thereto.
The method comprises the following steps: the catalyst was prepared as disclosed in patent CN 1506384. Firstly, mixing a magnesium compound and an organic alcohol compound with an inert solvent according to a molar ratio of 2-5, heating to 120-150 ℃, and reacting for 1-5 hours according to a magnesium/anhydride molar ratio of 5-10 and a magnesium/silicon molar ratio of 20-50. And then adding the alcohol compound cooled to room temperature into the titanium compound solution precooled to the temperature of minus 15 to minus 40 ℃ according to the molar ratio of titanium to magnesium of 20 to 50, heating to the temperature of 90 to 110 ℃, adding a compound selected from the compounds represented by the formula (I) according to the molar ratio of magnesium to ester of 2 to 10, reacting for 1 to 3 hours at the temperature of 100 to 130 ℃, and filtering to separate solid particles. And adding the solid particles into the titanium compound solution according to the molar ratio of titanium to magnesium of 20-50, stirring, reacting at 100-130 ℃ for 1.5-3 hours, and filtering to separate out the solid particles. And finally, washing the solid particles by using an inert solvent at the temperature of 50-80 ℃, and drying to obtain the catalyst.
The second method comprises the following steps: the preparation method is disclosed in patent CN85100997, firstly, a magnesium compound is dissolved in a solvent system composed of an organic epoxy compound, an organic phosphorus compound and an inert diluent to form a uniform solution, then the uniform solution is mixed with a titanium compound, and a solid is precipitated in the presence of a precipitation assistant; the solid is treated with a compound selected from the group consisting of compounds of formula (I) to be supported on the solid, and if necessary, the solid is treated with a titanium tetrahalide and an inert diluent, wherein the precipitation aid is one of an organic acid anhydride, an organic acid, an ether, a ketone, an ester, or a mixture thereof. The method specifically comprises the following steps: acetic anhydride, phthalic anhydride, succinic anhydride, maleic anhydride, pyromellitic dianhydride, acetic acid, propionic acid, butyric acid, acrylic acid, methacrylic acid, acetone, methyl ethyl ketone, benzophenone, methyl ether, ethyl ether, propyl ether, butyl ether, pentyl ether, succinate, malonate, glutarate, 2, 4-pentanediol ester, 3, 5-heptanediol ester, and the like.
The components are calculated by each mole of magnesium halide, 0.2-10 moles of organic epoxy compound, 0.1-3 moles of organic phosphorus compound, 0-1.0 mole of precipitation assistant, 0.5-150 moles of titanium compound and 0.02-0.5 mole of compound in the general formula (I).
The third method comprises the following steps: the catalyst component was prepared according to the method disclosed in patent CN 1091748. The magnesium chloride alcoholate melt is stirred and dispersed at a high speed in a dispersing agent system of white oil and silicone oil to form emulsion, and the emulsion is discharged into cooling liquid to be rapidly cooled and shaped to form the magnesium chloride alcoholate microspheres. The cooling liquid is inert hydrocarbon solvent with low boiling point, such as petroleum ether, pentane, hexane, heptane, etc. The obtained magnesium chloride alcoholate microspheres are washed and dried to form spherical carriers, and the molar ratio of alcohol to magnesium chloride is 2-3, preferably 2-2.5. The particle size of the carrier is 10 to 300 microns, preferably 30 to 150 microns.
Treating the spherical carrier with excessive titanium tetrachloride at low temperature, gradually raising the temperature, adding electron donor during the treatment, treating with inert solvent, and drying to obtain solid powdered spherical catalyst. The molar ratio of titanium tetrachloride to magnesium chloride is 20-200, preferably 30-60; the initial treatment temperature is-30 to 0 ℃, preferably-25 to-20 ℃; the final treatment temperature is 80-136 ℃, preferably 100-130 ℃.
The spherical catalyst obtained has the following characteristics: 1.5-3.0% of titanium (weight), 6.0-20.0% of ester, 52-60% of chlorine, 10-20% of magnesium, 1-6% of inert solvent and more than 250m of specific surface area of catalyst2/g。
The method four comprises the following steps: or adding dialkoxy magnesium into aromatic hydrocarbon compound, stirring to form suspension; treating the suspension with tetravalent titanium chloride at-20-100 ℃, reacting at 0-130 ℃, adding an electron donor at-20-130 ℃ for reaction in the process, and washing the obtained solid with an aromatic hydrocarbon compound; then treating the solid catalyst in an aromatic hydrocarbon solvent at the temperature of 0-130 ℃, then treating the solid catalyst with tetravalent titanium chloride, finally washing the solid catalyst with an inert solvent, and draining the solid catalyst to obtain the solid catalyst. Wherein, 0.5 to 100mol of tetravalent titanium chloride is used for each mol of dialkyl magnesium, and 0.01 to 10mol of electron donor is used.
The method five comprises the following steps: with TiCl4Or halogenating a magnesium dialkoxide compound such as magnesium dialkoxide or diaryloxide with TiCl at 80-130 deg.C4Or the aromatic hydrocarbon solution thereof, may be subjected to one or more treatments, and the compound of the formula (I) is added in one or more of such treatments.
The method six: the catalyst was prepared according to the method disclosed in patent US 4540679. The transition metal compound (preferably tetravalent titanium compound), alkoxy magnesium compound and electron donor are reacted in an inert solvent according to a certain proportion, wherein the molar ratio of the transition metal element to the magnesium element is at least 0.5:1, the dosage of the electron donor compound (I) is at most 1.0 mol per gram of titanium atom, the inert solvent is required to be conveniently removed, dehydration, deoxidation and gas which is easy to poison the catalyst are required to be removed, the reaction is carried out at the temperature of-10-170 ℃, and the reaction time is from several minutes to several hours.
The preparation method of the catalyst also comprises the steps of forming an emulsion by a magnesium compound, an electron donor and the like in a diluent, adding a titanium compound to fix the emulsion to obtain a spherical solid, and then treating the spherical solid to obtain the solid catalyst component.
In a second aspect the present invention provides a catalyst for the polymerisation of olefins comprising the reaction product of:
component a, the solid catalyst component according to the first aspect of the present invention;
component b, an alkyl aluminum compound; and
optionally component c, an external electron donor compound.
According to a preferred embodiment of the present invention, the external electron donor compound comprises a compound represented by the general formula (III):
R2 kSi(OR3)4-k(III)
in the general formula (III), k is more than or equal to 0 and less than or equal to 3; r2Is an alkyl, cycloalkyl, aryl, haloalkyl, amino, halogen or hydrogen atom; r3Is alkyl, cycloalkyl, aryl, haloalkyl or amino.
The external electron donor compound may be specifically selected from triethylaluminum, tripropylaluminum, tri-n-butylaluminum, triisobutylaluminum, tri-n-octylaluminum, triisobutylaluminum, diethylaluminum monohydrochloride, diisobutylaluminum monohydrochloride, diethylaluminum monochloride, diisobutylaluminum monochloride, ethylaluminum sesquichloride and ethylaluminum dichloride, preferably triethylaluminum and triisobutylaluminum.
For the application of olefin polymers with high stereoregularity, an external electron donor compound is added, for example, the general formula R2 kSi(OR3)4-kIn the formula, k is more than or equal to 0 and less than or equal to 3, R2And R3Is the same or different alkyl, cycloalkyl, aryl, haloalkyl, R2And may be a halogen or hydrogen atom. For example: trimethylmethoxysilane, trimethylethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, phenyltriethoxysilane, phenyltrimethoxysilane, vinyltrimethoxysilane, cyclohexylmethyldimethoxysilane, methyl-tert-butyldimethoxysilane, preferably cyclohexylmethyldimethoxysilane, diphenyldimethoxysilane.
According to a preferred embodiment of the present invention, the molar ratio of component a, component b and component c is 1 (5-1000) to (0-500) in terms of titanium to aluminum to silicon; preferably 1 (25-100) to (25-100).
The third aspect of the present invention provides a prepolymerized catalyst for olefin polymerization, comprising the solid catalyst component according to the first aspect of the present invention and/or a prepolymer obtained by prepolymerizing the catalyst according to the second aspect of the present invention with an olefin, wherein the prepolymerization multiple of the prepolymer is 0.1 to 1000g of olefin polymer/g of catalyst component; the prepolymerized olefin is ethylene, propylene and/or butene.
In a fourth aspect, the present invention provides a process for the polymerization of olefins having the general formula CH, in the presence of the solid catalyst component according to the first aspect of the present invention and/or the catalyst according to the second aspect of the present invention and/or the prepolymerized catalyst according to the third aspect of the present invention2Wherein R is hydrogen or C1～C6Alkyl groups of (a); the olefin is preferably ethylene, propylene and/or 1-butene.
The olefin polymerization reaction of the present invention is carried out according to a known polymerization method, and may be carried out in a liquid phase or a gas phase, or may be carried out in an operation combining liquid phase and gas phase polymerization stages. Homopolymerization of propylene and/or copolymerization of other olefins is carried out using conventional techniques such as slurry processes, gas phase fluidized beds, etc., wherein the olefin is selected from ethylene, propylene, 1-butene, 4-methyl-1-pentene and 1-hexene, especially propylene. The following reaction conditions are preferably employed: the polymerization temperature is 0-150 ℃, preferably 60-90 ℃.
The catalyst of the present invention may be added directly to the reactor for use in the polymerization process. Alternatively, the catalyst may be prepolymerized before being fed into the first polymerization reactor. In the present invention, "prepolymerized catalyst" means a catalyst which has undergone a polymerization step at a relatively low degree of conversion. According to the invention, the pre-polymerization catalyst comprises a pre-polymer obtained by pre-polymerizing the solid catalyst component and olefin, and the pre-polymerization multiple is 0.1-1000 g of olefin polymer/g of the solid catalyst component.
The prepolymerization can be carried out using the same α -olefin as the aforementioned olefin, wherein the olefin to be subjected to the prepolymerization is preferably ethylene or propylene. In particular, it is particularly preferred to carry out the prepolymerization with ethylene or a mixture of one or more alpha-olefins in a remaining amount of up to 20 mol%. Preferably, the degree of conversion of the prepolymerized catalyst component is about 0.2 to 500 g polymer/g solid catalyst component.
The prepolymerization step can be carried out at a temperature of-20 to 80 ℃, preferably 0 to 50 ℃, in a liquid or in a gas phase. The pre-polymerization step may be carried out in-line as part of a continuous polymerization process or separately in a batch operation. For the preparation of polymers in amounts of 0.5 to 20g/g of catalyst component, batch prepolymerization of the catalyst of the invention with ethylene is particularly preferred. The polymerization pressure is 0.01 to 10 MPa.
The catalysts of the invention are also suitable for the production of polyethylene and copolymers of ethylene with alpha-olefins, such as propylene, butene, pentene, hexene, 4-methyl-1-pentene.
It is worth pointing out that the invention can obtain the catalyst with excellent comprehensive performance by adopting the novel internal electron donor compound, when the catalyst is used for propylene polymerization, the catalyst has good hydrogen regulation sensitivity, and the obtained polypropylene resin has wide molecular weight distribution.
Detailed Description
The present invention will be described in detail with reference to examples, but the present invention is not limited to the examples.
The following examples are given for the purpose of illustrating the invention and are not to be construed as limiting the invention.
Test method
Polymer isotactic index II: as determined by heptane extraction (6 hours of heptane boil extraction): a2 g sample of the dried polymer was extracted with boiling heptane in an extractor for 6 hours, and the ratio of the weight (g) of the polymer to 2, which was obtained by drying the residue to a constant weight, was defined as the isotactic index.
Melt index MI: measured using a melt index apparatus at 230 ℃ under a pressure of 2.16kg according to ASTM D1238-99 Standard test method for measuring thermoplastic melt flow Rate with an extrusion plastometer.
Molecular weight distribution MWD (MWD ═ M) of polymerw/Mn): the measurement was carried out by Waters Alliance GPC2000 from Waters corporation using 1,2, 4-trichlorobenzene as a solvent and styrene as a standard.
Synthesis of Compounds
The synthesis is carried out according to the description of the document Oxidation von Aroyl (diphenylyl) phosphane-Darstellung und Eigenschaften von Aroyl (diphenylyl) phosphane oxide, chem.Ber., 112, 1456 to 1463(1979) and the following formula.
Example 1
Preparation of solid catalyst component: 4.8g of magnesium chloride, 95mL of toluene, 4mL of epichlorohydrin and 12.5mL of tributyl phosphate are sequentially added into a reactor fully replaced by high-purity nitrogen, the temperature is raised to 50 ℃ under stirring, the temperature is maintained for 2.5 hours, the solid is completely dissolved, 1.4g of phthalic anhydride is added, and the temperature is maintained for 1 hour. Cooling the solution to below-25 ℃, and dripping TiCl in 1h4And (3) slowly heating to 80 ℃ to gradually separate out solids in the heating process, adding 5mmol of synthesized electron donor compound isovaleryl oxy di (p-methoxyphenyl) phosphine oxide, maintaining the temperature for 1h, filtering, and washing with 70mL of toluene for 2 times to obtain solid precipitates. Then 60mL of toluene and TiCl were added440mL of the mixture is heated to 110 ℃, and vitamin C is addedThe same procedure was repeated for 2h, followed by washing with 70mL of toluene at 110 ℃ for 3 times each of 10min, and then with 60mL of hexane for 2 times. A solid catalyst component is obtained.
Polymerization of propylene: the dry 250mL three-neck flask was fully replaced with nitrogen and propylene, 100mL heptane was added under a slight positive pressure, the mixture was heated to 70 ℃ and then a predetermined amount of AlEt was added3And CHMMS, adding the catalyst prepared above at the temperature, keeping the temperature for reacting for 1h, and stopping the reaction by using ethanol. The polymer was washed with absolute ethanol and dried under vacuum to give a polymer. The catalyst had an activity of 213gPP/(gTi. h), an isotactic index of 94.3%, a melt index of 10.1g/10min and a molecular weight distribution of 10.6.
Example 2
The procedure is as in example 1, except that isovaleryloxybis (p-methoxyphenyl) phosphine oxide is replaced by butyryloxybis (p-tolyl) phosphine oxide. The catalyst activity was 189gPP/(gTi.h), the isotactic index was 93.8%, the melt index was 12.9g/10min, and the molecular weight distribution was 11.5.
Example 3
The procedure is as in example 1, except that isovaleryloxybis (p-methoxyphenyl) phosphine oxide is replaced by p-isopropylbenzoyloxybis (p-chlorophenyl) phosphine oxide. The catalyst had an activity of 287gPP/(gTi.h), an isotactic index of 96.2%, a melt index of 9.8g/10min and a molecular weight distribution of 9.7.
Example 4
The procedure is as in example 1, except that isovaleryloxybis (p-methoxyphenyl) phosphine oxide is replaced by phenylacetyloxydiphenylphosphine oxide. The catalyst has an activity of 256gPP/(gTi.h), an isotactic index of 95.7%, a melt index of 8.2g/10min and a molecular weight distribution of 10.8.
Example 5
The procedure is as in example 1, except that isovaleryloxybis (p-methoxyphenyl) phosphine oxide is replaced by p-n-butylbenzoyloxybis (m-chlorophenyl) phosphine oxide. The catalyst activity was 304gPP/(gTi.h), the isotactic index was 97.0%, the melt index was 8.9g/10min, and the molecular weight distribution was 9.5.
Example 6
The procedure is as in example 1, except that isovaleryloxybis (p-methoxyphenyl) phosphine oxide is replaced by cinnamoyloxydiphenylphosphine oxide. The catalyst had an activity of 287gPP/(gTi.h), an isotactic index of 96.0%, a melt index of 10.0g/10min and a molecular weight distribution of 9.9.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.
Claims (19)
1. A solid catalyst component for olefin polymerization, which comprises magnesium, titanium, halogen and an electron donor compound, wherein the electron donor compound comprises a compound shown in the following general formula (I),
in the general formula (I),
R1is C1-C10Straight chain alkyl group of (1), C2-C10Linear alkenyl of (A), C2-C10Straight chain alkynyl of (2), C3-C12A branched hydrocarbon group of3-C12A cycloalkyl group of6-C20Aryl of (C)7-C20Of hydrocarbon aryl or C7-C20And said C is an aromatic hydrocarbon group1-C10Straight chain alkyl group of (1), C2-C10Linear alkenyl of (A), C2-C10Straight chain alkynyl of (2), C3-C12A branched hydrocarbon group of3-C12A cycloalkyl group of6-C20Aryl of (C)7-C20Of hydrocarbon aryl or C7-C20The hydrogen on the arylcarbon of (a) is optionally substituted with a heteroatom;
R2selected from hydrogen, halogenAtom, C1-C10Straight chain alkyl group of (1), C3-C10Branched alkyl of C1-C10Linear alkoxy of (1) and C3-C10A branched alkoxy group of (A), and said C1-C10Straight chain alkyl group of (1), C3-C10Branched alkyl of C1-C10Linear alkoxy of (1) and C3-C10The hydrogen on the branched alkoxy carbon of (a) may optionally be substituted with a heteroatom.
2. The solid catalyst component according to claim 1, characterized in that the heteroatom is selected from at least one of a halogen atom, an oxygen atom and a nitrogen atom.
3. The solid catalyst component according to claim 1 in which R is1Is C1-C8Straight chain alkyl group of (1), C2-C8Linear alkenyl of (A), C2-C8Straight chain alkynyl of (2), C3-C10A branched hydrocarbon group of3-C10A cycloalkyl group of6-C15Aryl of (C)7-C15Of hydrocarbon aryl or C7-C15And said C is an aromatic hydrocarbon group1-C8Straight chain alkyl group of (1), C2-C8Linear alkenyl of (A), C2-C8Straight chain alkynyl of (2), C3-C10Branched alkyl of C3-C10Branched alkenyl of (C)3-C10Branched alkynyl of (2), C3-C10A cycloalkyl group of6-C15Aryl of (C)7-C15Of hydrocarbon aryl or C7-C15The hydrogen on the arylcarbon of (a) is optionally substituted with one or more heteroatoms selected from halogen atoms, oxygen atoms and nitrogen atoms.
4. The solid catalyst component according to claim 1 in which R is1Is C1-C6Straight chain alkyl group of (1), C2-C6Linear alkenyl of (A), C2-C6OfAlkynyl, C3-C8A branched hydrocarbon group of3-C8A cycloalkyl group of6-C12Aryl of (C)7-C12Of hydrocarbon aryl or C7-C12And said C is an aromatic hydrocarbon group1-C6Straight chain alkyl group of (1), C2-C6Linear alkenyl of (A), C2-C6Straight chain alkynyl of (2), C3-C8A branched hydrocarbon group of3-C8A cycloalkyl group of6-C12Aryl of (C)7-C12Of hydrocarbon aryl or C7-C12The hydrogen on the arylcarbon of (a) is optionally substituted with one or more heteroatoms selected from halogen atoms, oxygen atoms and nitrogen atoms.
5. The solid catalyst component according to any one of claims 1 to 4 in which R is2Selected from hydrogen, halogen, C1-C8Straight chain alkyl group of (1), C3-C8Branched alkyl of C1-C8Linear alkoxy of (1) and C3-C8A branched alkoxy group of (a), said C1-C8Straight chain alkyl group of (1), C3-C8Branched alkyl of C1-C8Linear alkoxy of (1) and C3-C8The hydrogen on the branched alkoxy carbon of (a) is optionally substituted with one or more heteroatoms selected from halogen atoms, oxygen atoms and nitrogen atoms.
6. The solid catalyst component according to any one of claims 1 to 4 in which R is2Selected from hydrogen, halogen, C1-C6Straight chain alkyl group of (1), C3-C6Branched alkyl of C1-C6Linear alkoxy of (1) and C3-C6A branched alkoxy group of (a), said C1-C6Straight chain alkyl group of (1), C3-C6Branched alkyl of C1-C6Linear alkoxy of (1) and C3-C6The hydrogen on the branched alkoxy carbon of (a) is optionally substituted by one or more hetero atoms selected from halogen, oxygen and nitrogen atomsAnd (4) subsubstitution.
7. The solid catalyst component according to claim 5 in which R is1Is C6-C12Aryl of (C)7-C12Of hydrocarbon aryl or C7-C12Is optionally substituted with one or more heteroatoms selected from halogen atoms, oxygen atoms and nitrogen atoms.
8. The solid catalyst component according to claim 5 in which R is1Is phenyl, C7-C12Hydrocarbon phenyl or C7-C12Optionally substituted with one or more heteroatoms selected from halogen atoms, oxygen atoms and nitrogen atoms.
9. The solid catalyst component according to claim 5 in which R is1Is phenyl, C7-C12Alkylphenyl radical of (1), C7-C12Phenylalkyl of, C7-C12Phenylalkenyl or C7-C12Optionally substituted with one or more heteroatoms selected from halogen atoms, oxygen atoms and nitrogen atoms.
10. The solid catalyst component according to any of claims 1 to 4, characterized in that it comprises the reaction product of a magnesium compound, a titanium compound and a compound of general formula (I).
11. The solid catalyst component according to claim 10 in which the molar ratio of the magnesium compound, the titanium compound and the compound of formula (I) is from 1 (0.5 to 150) to (0.02 to 0.4).
12. The solid catalyst component according to claim 10, characterized in that the magnesium compound comprises one or more selected from the group consisting of magnesium dihalides, alkoxy magnesium, alkyl magnesium, hydrates or alcoholates of magnesium dihalides and derivatives of magnesium dihalides of which one halogen atom of the formula is replaced by an alkoxy group or a haloalkoxy group; and/or
The titanium compound includes one or more selected from compounds represented by the general formula (II):
TiXm(OR1)4-m (II)
in the general formula (II), R1Is C1～C20A hydrocarbon group of (a); x is halogen; m is more than or equal to 1 and less than or equal to 4.
13. A catalyst for the polymerization of olefins comprising the reaction product of:
component a, a solid catalyst component according to any one of claims 1 to 12;
component b, an alkyl aluminum compound; and
optionally component c, an external electron donor compound.
14. The catalyst of claim 13, wherein the external electron donor compound comprises a compound of formula (III):
R2 kSi(OR3)4-k (III)
in the general formula (III), k is more than or equal to 0 and less than or equal to 3; r2Is an alkyl, cycloalkyl, aryl, haloalkyl, amino, halogen or hydrogen atom; r3Is alkyl, cycloalkyl, aryl, haloalkyl or amino.
15. The catalyst of claim 13 or 14 wherein the molar ratio of component a, component b and component c is 1 (5-1000) to (0-500) in terms of titanium to aluminum to silicon.
16. The catalyst according to claim 13 or 14, wherein the molar ratio of component a, component b and component c is 1 (25-100) to (25-100) in terms of titanium, aluminum and silicon.
17. A prepolymerized catalyst for olefin polymerization comprising the solid catalyst component according to any one of claims 1 to 12 and/or a prepolymer obtained by prepolymerizing the catalyst according to any one of claims 13 to 16 with an olefin, wherein the prepolymer has a prepolymerization multiple of 0.1 to 1000g of olefin polymer per g of catalyst component; the prepolymerized olefin is ethylene, propylene and/or butene.
18. A process for the polymerization of olefins having the general formula CH in the presence of a solid catalyst component according to any of claims 1 to 12, a catalyst according to any of claims 13 to 16 and/or a prepolymerized catalyst according to claim 172Wherein R is hydrogen or C1～C6Alkyl group of (1).
19. The process of claim 18, wherein the olefin is ethylene, propylene and/or 1-butene.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006500410A (en) * | 2002-09-24 | 2006-01-05 | ビーエーエスエフ アクチェンゲゼルシャフト | Method for producing acylphosphine oxide |
| CN102597122A (en) * | 2009-10-30 | 2012-07-18 | 株式会社钟化 | Curable composition |
| WO2017123527A1 (en) * | 2016-01-14 | 2017-07-20 | Revlon Consumer Products Corporation | Nail composition with capped oligomers |
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- 2018-09-14 CN CN201811074778.1A patent/CN110903417B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006500410A (en) * | 2002-09-24 | 2006-01-05 | ビーエーエスエフ アクチェンゲゼルシャフト | Method for producing acylphosphine oxide |
| CN102597122A (en) * | 2009-10-30 | 2012-07-18 | 株式会社钟化 | Curable composition |
| WO2017123527A1 (en) * | 2016-01-14 | 2017-07-20 | Revlon Consumer Products Corporation | Nail composition with capped oligomers |
Non-Patent Citations (3)
| Title |
|---|
| Copper-catalyzed oxidative dehydrogenative coupling of carboxylic acids with H-phosphonates:an efficient and practical approach to acyl phosphate esters;Hong Fu;《Org.Chem.Front》;20171231(第4期);第1777-1780页 * |
| Oxidation von Aroyl(diphenyl)phosphanen-Darstellung und Eigenschaften von Aroyl(diphenyl)phosphanoxide;E.Lindner;《Chem.Ber.》;19791231;第1456-1463页 * |
| 双(2,4,6-三甲基苯甲酰基)苯基氧化膦的合成及其光引发性能研究;刘娜;《中国优秀硕士学位论文全文数据库（电子期刊）》;20160331;B014-371 * |
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