CN114426607A - Catalyst for olefin polymerization, application thereof, olefin polymerization method and polymer - Google Patents

Catalyst for olefin polymerization, application thereof, olefin polymerization method and polymer Download PDF

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CN114426607A
CN114426607A CN202011103615.9A CN202011103615A CN114426607A CN 114426607 A CN114426607 A CN 114426607A CN 202011103615 A CN202011103615 A CN 202011103615A CN 114426607 A CN114426607 A CN 114426607A
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dimethoxypropane
compound
phosphate
electron donor
dimethyl
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CN114426607B (en
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赵瑾
夏先知
周俊领
刘月祥
谭扬
任春红
陈龙
凌永泰
李威莅
刘涛
高富堂
张天一
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Sinopec Beijing Research Institute of Chemical Industry
China Petroleum and Chemical Corp
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China Petroleum and Chemical Corp
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Abstract

The invention belongs to the field of olefin polymerization, and relates to a catalyst for olefin polymerization, an application of the catalyst, an olefin polymerization method and a polymer. The catalyst comprises: (i) a solid catalyst component; (ii) at least one alkyl aluminum compound; (iii) at least one external electron donor; wherein the solid catalyst component contains a product obtained by the reaction of a magnesium source, a titanium source and an internal electron donor; the internal electron donor contains a phosphate compound and a diether compound; the external electron donor contains a hydrocarbyl trihydrocarbyloxysilane compound, and the content of the hydrocarbyl trihydrocarbyloxysilane compound accounts for more than 60 wt% of the total amount of the external electron donor. According to the invention, through the combination of the specific external electron donor compound and the specific titanium-containing solid catalyst component, the polymer with high isotacticity can be obtained, the particle breakage is less, and the fine powder content of the polymer is low.

Description

Catalyst for olefin polymerization, application thereof, olefin polymerization method and polymer
Technical Field
The invention belongs to the field of olefin polymerization, and particularly relates to a catalyst for olefin polymerization, application of the catalyst in olefin polymerization reaction, an olefin polymerization method adopting the catalyst, and a polymer prepared by the olefin polymerization method.
Background
It is known that the Z-N catalyst systems for the polymerization of olefins generally consist of three parts, including in particular: (1) a main catalyst (solid catalyst component), (2) a cocatalyst (usually an alkylaluminium compound) and (3) an external electron donor compound. It has been developed since the advent and has become the subject of catalyst systems for commercial olefin polymerization. The development of the method mainly goes through three stages of progress of a carrier preparation process, development of an internal electron donor and improvement of an external electron donor.
The electron donor compound is one of the essential components in the catalyst component, plays a decisive role in important indexes such as polymerization activity, polymer isotacticity, polymer molecular weight and molecular weight distribution, and the olefin polymerization catalyst is continuously updated along with the development of internal and external electron donors.
As an internal electron donor for promoting the development of the Z-N catalyst, the monoacid ester of the third-generation Z-N catalyst, such as ethyl benzoate, ethyl p-ethoxybenzoate and the like, is developed into dibasic acid ester, such as di (iso) butyl phthalate and the like with good comprehensive performance of the fourth-generation Z-N catalyst. Phthalate compounds (plasticizers) are the most commonly used internal electron donors in polypropylene catalysts at present, and researches show that the phthalate compounds can cause serious damage to the growth and development of animals and reproductive systems and can also have similar influence on human beings.
The external electron donor as an important component of the Z-N catalyst system not only affects the stereoregularity of the polymer, but also affects the activity, hydrogen sensitivity and the like of the catalyst to different degrees. While a variety of compounds are known to be useful as external electron donors, such as carboxylic acids, carboxylic acid anhydrides, carboxylic acid esters, ketones, ethers, alcohols, lactones, organophosphorus compounds, and organosilicon compounds, the use of different external electron donors for a particular catalyst may result in different polymer properties. For a particular catalyst component, the selection of an appropriate external electron donor can significantly improve certain properties of the polymer product, such as isotacticity, molecular weight distribution, etc. Thus, it is highly desirable to find an external electron donor suitable for use in a particular catalyst component.
Disclosure of Invention
The inventor of the invention unexpectedly finds that when the catalyst component containing titanium, magnesium, halogen, phosphate compounds and diether compounds is adopted and an external electron donor containing hydrocarbyl trihydrocarbyloxysilane compounds is added during olefin polymerization, the prepared polymer has high isotactic index and the breakage of the polymer is obviously reduced. The present invention has been made based on this finding.
A first aspect of the present invention provides a catalyst for olefin polymerization, the catalyst comprising: (i) a solid catalyst component; (ii) at least one alkyl aluminum compound; (iii) at least one external electron donor;
wherein the solid catalyst component contains a product obtained by the reaction of a magnesium source, a titanium source and an internal electron donor; the internal electron donor contains a phosphate compound and a diether compound;
the external electron donor contains a hydrocarbyl trihydrocarbyloxysilane compound, and the content of the hydrocarbyl trihydrocarbyloxysilane compound accounts for more than 60 wt% of the total amount of the external electron donor.
A second aspect of the invention provides the use of a catalyst as described above in the polymerisation of olefins.
A third aspect of the present invention provides an olefin polymerization process comprising: contacting one or more olefins of the formula CH with the catalyst under olefin polymerization conditions2＝CH-RvWherein R isvIs hydrogen or C1～C6An alkyl group.
A fourth aspect of the present invention provides a polymer produced by the above olefin polymerization process.
According to the invention, through the combination of the specific external electron donor compound and the specific titanium-containing solid catalyst component, the polymer with high isotacticity can be obtained, the particle breakage is less, and the fine powder content of the polymer is low.
Additional features and advantages of the invention will be set forth in the detailed description which follows.
Detailed Description
The following describes in detail specific embodiments of the present invention. It should be understood that the detailed description and specific examples, while indicating the present invention, are given by way of illustration and explanation only, not limitation.
The present invention provides a catalyst for olefin polymerization, comprising: (i) a solid catalyst component; (ii) at least one alkyl aluminum compound; (iii) at least one external electron donor;
wherein the solid catalyst component contains a product obtained by the reaction of a magnesium source, a titanium source and an internal electron donor; the internal electron donor contains a phosphate compound and a diether compound;
the external electron donor contains a hydrocarbyl trihydrocarbyloxysilane compound, and the content of the hydrocarbyl trihydrocarbyloxysilane compound accounts for more than 60 wt% of the total amount of the external electron donor.
According to the present invention, the total content of the phosphate compound and the diether compound is 70 to 100 wt%, more preferably 80 to 100 wt%, even more preferably 90 to 100 wt%, and most preferably 100 wt%, based on the content of the internal electron donor.
The kind of the phosphate ester compound is not particularly limited in the present invention, and may be various phosphate ester compounds that can be used as internal electron donors in catalysts for olefin polymerization, and preferably, the phosphate ester compound is at least one selected from the group consisting of phosphate ester compounds represented by formula (1),
Figure BDA0002726220060000031
in the formula (1), R13、R14And R15Each independently selected from C1-C20Straight or branched alkyl of (2), C3-C20Cycloalkyl of, C6-C20Aryl of (C)7-C20Alkylaryl or C of7-C20The aralkyl group of (1), wherein a hydrogen atom on the benzene ring in the aryl group, the alkaryl group and the aralkyl group is optionally substituted with a halogen atom; further preferred is R13、R14And R15Each independently selected from C1-C12Straight or branched alkyl of (2), C3-C12Cycloalkyl of, C6-C12Aryl of (C)7-C12Alkylaryl or C of7-C12The aralkyl group of (1), the hydrogen on the benzene ring in the aryl, alkaryl and aralkyl groupsThe atoms being optionally substituted by halogen atoms or C1-C4Alkoxy substitution of (a); further preferred is R13、R14And R15Each independently selected from C1-C4Straight or branched alkyl of (2), C3-C6Cycloalkyl of, C6-C8Aryl of (C)7-C8Alkylaryl or C of7-C8The aralkyl group of (1), wherein a hydrogen atom on the benzene ring in the aryl group, the alkaryl group and the aralkyl group is optionally substituted with a halogen atom.
Specifically, the phosphate ester compound is preferably at least one selected from the group consisting of trimethyl phosphate, triethyl phosphate, tributyl phosphate, triphenyl phosphate, tricresyl phosphate, triisopropylphenyl phosphate, trimethoxyphenyl phosphate, phenyl dimethyl phosphate, cresyl dibutyl phosphate, isopropylphenyl dimethyl phosphate, isopropylphenyl diethyl phosphate, isopropylphenyl dibutyl phosphate, phenyl dimethyl phenyl phosphate, phenyl diisopropylphenyl phosphate, p-xylyldibutyl phosphate, m-xylyldibutyl phosphate, p-diisopropylphenyl dimethyl phosphate, p-diisopropylphenyl diethyl phosphate, p-tert-butylphenyl dimethyl phosphate, and o-tolylp-di-tert-butylphenyl phosphate.
Most preferably, the phosphate ester compound is tributyl phosphate.
The kind of the diether compound is not particularly limited in the present invention, and may be any of various diether compounds that can be used as an internal electron donor of a catalyst for olefin polymerization, and preferably, the diether compound is at least one selected from diether compounds represented by formula (2),
Figure BDA0002726220060000041
in the formula (2), RⅠ、RⅡ、RⅢ、RⅣ、RⅤAnd RⅥIdentical or different, each independently selected from hydrogen, halogen atom, C1-C20Straight or branched alkyl of (2), C3-C20A cycloalkyl group of,C6-C20Aryl of (C)7-C20Aralkyl and C7-C20One of the alkylaryl groups of (1), RⅠ-RⅥThe groups can be bonded to form a ring; and R isⅦAnd RⅧOr may be the same or different and are each independently selected from C1-C20Linear or branched alkyl of (2), C3-C20Cycloalkyl radical, C6-C20Aryl radical, C7-C20Alkylaryl group, C7-C20One of aralkyl groups.
More preferably, the diether compound is selected from the group consisting of 2- (2-ethylhexyl) -1, 3-dimethoxypropane, 2-isopropyl-1, 3-dimethoxypropane, 2-butyl-1, 3-dimethoxypropane, 2-sec-butyl-1, 3-dimethoxypropane, 2-cyclohexyl-1, 3-dimethoxypropane, 2-phenyl-1, 3-dimethoxypropane, 2- (2-phenylethyl) -1, 3-dimethoxypropane, 2- (2-cyclohexylethyl) -1, 3-dimethoxypropane, 2- (p-chlorophenyl) -1, 3-dimethoxypropane, 2- (diphenylmethyl) -1, 3-dimethoxypropane, 2-dicyclohexyl-1, 3-dimethoxypropane, 2-dicyclopentyl-1, 3-dimethoxypropane, 2-diethyl-1, 3-dimethoxypropane, 2-dipropyl-1, 3-dimethoxypropane, 2-diisopropyl-1, 3-dimethoxypropane, 2-dibutyl-1, 3-dimethoxypropane, 2-methyl-2-propyl-1, 3-dimethoxypropane, 2-methyl-2-benzyl-1, 3-dimethoxypropane, 2-methyl-2-ethyl-1, 3-dimethoxypropane, 2-dimethyl-2-propyl-dimethoxypropane, 2-dimethyl-propyl-1, 3-dimethoxypropane, 2-dimethyl-propyl-2-propyl-dimethoxypropane, 2-propyl-dimethyl-1, 3-dimethoxypropane, 2-dimethyl-propyl-1, 2-dimethyl-1, 3-dimethoxypropane, 2-dimethyl-propyl-1, 2-dimethyl-1, 3-dimethoxypropane, 2-dimethyl-propyl-dimethyl-1, 2-dimethyl-propyl-dimethyl-propyl, 2, and the same, 2, 2-methyl-2-isopropyl-1, 3-dimethoxypropane, 2-methyl-2-phenyl-1, 3-dimethoxypropane, 2-methyl-2-cyclohexyl-1, 3-dimethoxypropane, 2-bis (2-cyclohexylethyl) -1, 3-dimethoxypropane, 2-methyl-2-isobutyl-1, 3-dimethoxypropane, 2-methyl-2- (2-ethylhexyl) -1, 3-dimethoxypropane, 2-diisobutyl-1, 3-dimethoxypropane, 2-diphenyl-1, 3-dimethoxypropane, 2-dibenzyl-1, 3-dimethoxypropane, 2-bis (cyclohexylmethyl) -1, 3-dimethoxypropane, 2-isobutyl-2-isopropyl-1, 3-dimethoxypropane, 2- (1-methylbutyl) -2-isopropyl-1, 3-dimethoxypropane, 2-isopropyl-2-isoamyl-1, 3-dimethoxypropane, 2-phenyl-2-isopropyl-1, 3-dimethoxypropane, 2-phenyl-2-sec-butyl-1, 3-dimethoxypropane, 2-benzyl-2-isopropyl-1, 3-dimethoxypropane, 2-cyclopentyl-2-isopropyl-1, at least one of 3-dimethoxypropane, 2-cyclopentyl-2-sec-butyl-1, 3-dimethoxypropane, 2-cyclohexyl-2-isopropyl-1, 3-dimethoxypropane, 2-cyclohexyl-2-sec-butyl-1, 3-dimethoxypropane, 2-isopropyl-2-sec-butyl-1, 3-dimethoxypropane, 2-cyclohexyl-2-cyclohexylmethyl-1, 3-dimethoxypropane and 9, 9-dimethoxymethylfluorene.
Most preferably, the diether compounds are 2-isopropyl-2-isoamyl-1, 3-dimethoxypropane and 9, 9-dimethoxymethylfluorene.
In the present invention, the phosphate compound and the diether compound are used as the internal electron donor, and the molar ratio of the phosphate compound to the diether compound is preferably controlled to be 0.02-0.30: 1, and further preferably controlled in the range of 0.03 to 0.25: 1, more preferably controlled in the range of 0.04 to 0.20: 1. this can further effectively improve the hydrogen response and stereospecificity of the catalyst.
According to the present invention, it is preferable to control the phosphorus content in the catalyst component not to be excessively high, for example, to be not more than 0.08% by weight in the catalyst component.
In the present invention, the magnesium source may be various magnesium-containing compounds that can be used in catalysts for olefin polymerization, for example, the magnesium source may be magnesium halide, alcoholate of magnesium, or haloalcoholate and magnesium halide adduct support, and the like; the magnesium halide may be, for example, magnesium chloride and/or magnesium bromide; the alcoholate of magnesium may be, for example, diethoxymagnesium; the haloalcoholate of magnesium may be, for example, magnesium ethoxychloride; the types of the magnesium halide adduct carrier are well known to those skilled in the art, for example, the magnesium halide adduct carriers disclosed in CN1091748A, CN101050245A, CN101486722A, 201110142357.X, 201110142156.X and 201110142024.7, etc., and the relevant contents of these patent publications are incorporated into the present invention by reference.
According to the invention, the titanium source may be chosen conventionally in the art, for example, it may be of the general formula Ti (OR')3-aZaAnd Ti (OR')4-bZbShown are combined withAt least one of the above compounds, wherein R' is C1-C20Is preferably C1-C12More preferably C1-C6Z is halogen, a is an integer of 1 to 3, b is an integer of 1 to 4. Preferably, the titanium source is one or more of titanium tetrachloride, titanium tetrabromide, titanium tetraiodide, tributoxy titanium chloride, dibutoxy titanium dichloride, butoxytitanium trichloride, triethoxy titanium chloride, diethoxy titanium dichloride, ethoxy titanium trichloride, and titanium trichloride.
In the present invention, the term "halogen" includes, but is not limited to, F, Cl, Br or I.
The content of magnesium, titanium and the internal electron donor in the solid catalyst component is not particularly limited, and may be any content of the solid catalyst component conventional in the art, preferably, the content of magnesium element is 2 to 16 parts by weight, preferably 3 to 12 parts by weight, and more preferably 4 to 10 parts by weight, per part by weight of titanium element; the content of the internal electron donor is 2 to 16 parts by weight, preferably 3 to 14 parts by weight, and more preferably 4 to 12 parts by weight.
In the present invention, the alkylaluminum compound may be various alkylaluminum compounds conventionally used in the art, for example, the alkylaluminum compound may be selected from the group consisting of AlR16R16′R16"at least one of the compounds shown, wherein R16、R16' and R16Each independently is C1-C8And at least one of alkyl or halogen of (A) is C1-C8And, the hydrogen on the alkyl group is optionally substituted with halogen. Said C is1-C8Specific examples of the alkyl group of (a) may include, but are not limited to: methyl, ethyl, propyl, n-butyl, isobutyl, pentyl, hexyl, n-heptyl, n-octyl and the halogen may be fluorine, chlorine, bromine, iodine. In particular, the alkylaluminum compound can be chosen, for example, from triethylaluminum, triisobutylaluminum, tri-n-butylaluminum, tri-n-hexylaluminum, diethylaluminum monochloride, diisobutylaluminum monochloride, di-n-butylaluminum monochloride, di-n-hexylaluminum monochloride, ethylaluminum dichloride, isobutylaluminum dichloride, dichloroaluminumOne or more of mono-n-butylaluminum and di-n-hexylaluminum dichloride.
According to the present invention, it is preferable that the external electron donor comprises at least one of the hydrocarbyl trihydrocarbyloxysilanes represented by formula (3);
Figure BDA0002726220060000071
in the formula (3), R1-R4Are the same or different and are each selected from C1-C20Alkyl of (C)3-C20Cycloalkyl radical, C6-C20Aryl or C of7-C20Preferably selected from C1-C10Alkyl of (C)3-C10Cycloalkyl radical, C6-C10Aryl or C of7-C10The alkyl, aryl, aralkyl or alkaryl group optionally having one or more substituents selected from the group consisting of hetero atom, C1-C6Alkyl and C1-C6Preferably at least one of oxygen, nitrogen and halogen.
Specifically, the hydrocarbyl trialkoxysilane compound is preferably at least one selected from the group consisting of propyltrimethoxysilane, butyltrimethoxysilane, isobutyltrimethoxysilane, phenyltrimethoxysilane, cyclopentyltrimethoxysilane, ethylpiperidinyltrimethoxysilane, propyltriethoxysilane, isopentyltriethoxysilane, isooctyltriethoxysilane, and decyltrimethoxysilane.
According to a more preferred embodiment of the present invention, the external electron donor further comprises at least one dihydrocarbyl silane compound represented by formula (4);
(R5)(R6)Si(OR7)(OR8) Formula (4)
In the formula (4), R5、R6、R7And R8Each independently selected from C1-C20Optionally containing heteroatoms; preferably R5、R6Each independently selected from C1-C10Straight or branched alkyl of (2), C3-C20Cycloalkyl of, C6-C20Aryl of (C)7-C20Alkylaryl or C of7-C20Aralkyl optionally containing heteroatoms; r7、R8Each independently selected from C1-C10Linear or branched alkyl, optionally containing heteroatoms; the hetero atom is preferably at least one of oxygen, nitrogen and halogen, and more preferably halogen.
Specifically, the dihydrocarbyldihydrocarbyloxysilane compound is preferably at least one selected from the group consisting of cyclohexylmethyldimethoxysilane, diisopropyldimethoxysilane, di-n-butyldimethoxysilane, diisobutyldimethoxysilane, diphenyldimethoxysilane, methyl-t-butyldimethoxysilane, dicyclopentyldimethoxysilane, 2-ethylpiperidinyl-2-t-butyldimethoxysilane, (1,1, 1-trifluoro-2-propyl) -2-ethylpiperidinyldimethoxysilane and (1,1,1-, trifluoro-2-propyl) -methyldimethoxysilane.
According to the present invention, the amount of the hydrocarbyl trihydrocarbyl oxysilane compound is preferably 60 wt% or more of the total amount of the external electron donor, and the sum of the amounts of the hydrocarbyl trihydrocarbyl hydrocarbyloxysilane compound and the dihydrocarbyl hydrocarbyloxysilane compound is preferably 80 to 100 wt%, preferably 90 to 100 wt%, of the total amount of the external electron donor.
More preferably, the molar ratio of the hydrocarbyl trihydrocarbyl hydrocarbyloxysilane compound to the dihydrocarbyl dihydrocarbyloxysilane compound is controlled to be 1-20: 1, preferably 2 to 10: 1.
according to the invention, the alkyl aluminium compound may be used in amounts conventional in the art. Preferably, the solid catalyst component, calculated as titanium element, and the alkylaluminium compound, calculated as aluminium element, are used in a molar ratio of 1: 1-2000, preferably 1: 20-500; the external electron donor is used in an amount of 0.002 to 1.0 mole, preferably 0.01 to 0.5 mole, per mole of aluminum in the alkylaluminum compound.
The catalyst of the invention can be applied to olefin polymerization reaction.
The invention specifically provides an olefin polymerization method, which comprises the following steps: contacting one or more olefins of the formula CH with the catalyst under olefin polymerization conditions2＝CH-RvWherein R isvIs hydrogen or C1～C6An alkyl group; the olefin is preferably propylene and/or ethylene.
In the polymerization process, the compound external electron donor compounds can be added respectively, simultaneously or at different stages of the polymerization.
The method for mixing the solid catalyst component, the at least one alkyl aluminum compound and the at least one external electron donor is not particularly limited, and when the catalyst is used for olefin polymerization, the solid catalyst component, the alkyl aluminum compound and the external electron donor can be added into a polymerization reactor respectively, or can be added into the polymerization reactor after being mixed, or can be added into the polymerization reactor after olefin prepolymerization by adopting a prepolymerization method known in the industry.
The improvement of the present invention is that a new catalyst system for olefin polymerization is used, and the specific kind of olefin, the polymerization method and conditions of olefin can be selected conventionally in the field.
According to the present invention, the polymerization of the olefin can be carried out according to the existing methods, specifically, under the protection of inert gas, in liquid phase monomer or inert solvent containing polymerized monomer, or in gas phase, or by gas-liquid phase combined polymerization process. The polymerization temperature may be generally 0 to 150 ℃ and preferably 60 to 90 ℃. The pressure of the polymerization reaction may be normal pressure or higher; for example, it may be in the range of 0.01 to 10MPa, preferably 0.01 to 5MPa, and more preferably 0.1 to 4 MPa. The pressure in the present invention is a gauge pressure. During the polymerization, hydrogen may be added to the reaction system as a polymer molecular weight regulator to regulate the molecular weight and melt index of the polymer. In addition, in the polymerization process of the olefin, the kinds and amounts of the inert gas and the solvent may be conventionally selected in the art, and the present invention is not particularly limited thereto.
The invention also provides a polymer prepared by the olefin polymerization method. The polymer has high isotacticity, less particle breakage and low fine powder content.
The present invention will be further described with reference to the following examples, but the scope of the present invention is not limited to these examples.
Polymer isotactic index: and (2) measuring by adopting a heptane extraction method, specifically, taking a 2g dried polymer sample, placing the sample in an extractor, extracting the sample by using boiling heptane for 6 hours, and then drying the residue to constant weight, wherein the ratio of the weight (g) of the obtained polymer to 2 is the isotactic index.
Particle size distribution of the polymer: the method adopts an electric screening instrument for determination, a screen adopts a standard inspection screen (specification model: phi 200), and a manufacturer: beijing Yan Sen Tengda mechanical device, Inc.
Example 1
This example illustrates the catalysts for olefin polymerization provided by the present invention.
(1) Preparation of the catalyst component
In a 300ml glass reaction flask, 90ml of titanium tetrachloride was added and cooled to-20 ℃, 37mmol of magnesium halide carrier (prepared as disclosed in example 1 of CN 1330086A) as magnesium element was added thereto, then the temperature was raised to 110 ℃, and during the raising of the temperature, 0.9mmol of tributyl phosphate and 7.8mmol of 2-isopropyl-2-isopentyl-1, 3-dimethoxypropane were added, and after maintaining at 110 ℃ for 30min, the liquid was filtered, washed with titanium tetrachloride, then with hexane, and dried under vacuum to obtain catalyst component Cat-1.
(2) Catalyst preparation and liquid phase bulk polymerization of propylene
In a 5L stainless steel autoclave, 1ml of a hexane solution of triethylaluminum (concentration: 0.5mmol/ml), 0.1ml of a hexane solution of n-propyltrimethoxysilane (concentration: 0.1mmol/ml) and 7mg of the above catalyst component Cat-1 were successively charged under a nitrogen atmosphere to the autoclave, to obtain catalyst C-1. The autoclave was closed and 1L of hydrogen (standard volume) and 2.3L of liquid propylene were added. The temperature is raised to 70 ℃, after 1 hour of reaction, the temperature is reduced, the pressure is relieved, the material is discharged, the obtained propylene homopolymer is weighed and analyzed after being dried, and the results are shown in table 1.
Example 2
This example illustrates the catalysts for olefin polymerization provided by the present invention.
A catalyst component, a catalyst and a liquid phase bulk polymerization of propylene were prepared in the same manner as in example 1 except that 0.1ml of a hexane solution of n-propyltriethoxysilane (concentration of 0.1mmol/ml) was added at the time of polymerization, and the results are shown in Table 1.
Example 3
This example illustrates the catalysts for olefin polymerization provided by the present invention.
A catalyst component, a catalyst and propylene liquid phase bulk polymerization were prepared by following the procedure of example 1 except that 0.1ml of a hexane solution of n-propyltrimethoxysilane and cyclohexylmethyldimethoxysilane mixed was added at the time of polymerization (total concentration of silane compounds was 0.1mmol/ml, molar ratio of n-propyltrimethoxysilane: cyclohexylmethyldimethoxysilane was 3:1), and the results are shown in Table 1.
Example 4
This example illustrates the catalysts for olefin polymerization provided by the present invention.
A catalyst component, a catalyst and propylene liquid phase bulk polymerization were prepared by following the procedure of example 1 except that 0.2ml of a hexane solution of n-propyltrimethoxysilane and cyclohexylmethyldimethoxysilane mixed was added at the time of polymerization (total concentration of silane compounds was 0.1mmol/ml, molar ratio of n-propyltrimethoxysilane: cyclohexylmethyldimethoxysilane was 3:1), and the results are shown in Table 1.
Example 5
This example illustrates the catalysts for olefin polymerization provided by the present invention.
A catalyst component was prepared according to the method of example 1 except that 1.3mmol of tributyl phosphate and 7.1mmol of 2-isopropyl-2-isopentyl-1, 3-dimethoxypropane were added during the temperature increase to obtain a catalyst component Cat-2.
Liquid phase bulk polymerization of propylene was carried out in the same manner as in example 1 except that 0.2ml of a hexane solution of n-propyltriethoxysilane and dicyclopentyldimethoxysilane (total concentration of silane compounds: 0.1mmol/ml, molar ratio of n-propyltriethoxysilane: dicyclopentyldimethoxysilane: 4:1) was added at the time of polymerization, and the results are shown in Table 1.
Example 6
This example illustrates the catalysts for olefin polymerization provided by the present invention.
A catalyst component, a catalyst and propylene liquid phase bulk polymerization were prepared by following the procedure of example 5 except that 0.1ml of a hexane solution of n-propyltriethoxysilane and dicyclopentyldimethoxysilane mixed was added at the time of polymerization (total concentration of silane compounds was 0.1mmol/ml, molar ratio of n-propyltriethoxysilane: dicyclopentyldimethoxysilane was 6:1), and the results are shown in Table 1.
Comparative example 1
This comparative example serves to illustrate a catalyst referenced for olefin polymerization.
A catalyst component, a catalyst and a liquid phase bulk polymerization of propylene were prepared in the same manner as in example 1 except that 0.1ml of cyclohexylmethyldimethoxysilane (concentration: 0.1mmol/ml) was added at the time of polymerization, and the results are shown in Table 1.
Comparative example 2
This comparative example serves to illustrate a catalyst referenced for olefin polymerization.
A catalyst component, a catalyst and a liquid phase bulk polymerization of propylene were prepared in the same manner as in example 1 except that 0.1ml of dicyclopentyldimethoxysilane (concentration: 0.1mmol/ml) was added at the time of polymerization, and the results are shown in Table 1.
Comparative example 3
This comparative example serves to illustrate a catalyst referenced for olefin polymerization.
The catalyst component, the catalyst and the liquid phase bulk polymerization of propylene were prepared according to the method of example 1, except that the catalyst component Cat-1 was replaced with a DQC catalyst component (the internal electron donor was diisobutylphthalate) purchased from the international Oddar catalyst division, petrochemical industries, Ltd.
TABLE 1
Examples Isotactic index (wt%) of polymer <250μm(wt％)
Example 1 98.5 0.7
Example 2 98.3 0.6
Example 3 98.9 0.5
Example 4 99.3 0.6
Example 5 99.0 0.7
Example 6 98.7 0.6
Comparative example 1 97.6 1.3
Comparative example 2 97.4 1.5
Comparative example 3 87.8 1.9
As can be seen from the results of the examples and comparative examples in Table 1, when the internal electron donor in the catalyst component contains both the phosphate compound and the diether compound, and the external electron donor is a hydrocarbyl trihydrocarbyloxysilane compound or a mixture of a hydrocarbyl trihydrocarbyloxysilane compound and a dihydrocarbyldihydrocarbyloxysilane compound, the stereospecificity of the catalyst can be effectively improved, the breakage of the polymer can be reduced, and the prepared polymer has a high isotactic index and a small amount of fine powder.
Having described embodiments of the present invention, the foregoing description is intended to be exemplary, not exhaustive, and not limited to the embodiments disclosed. Many modifications and variations will be apparent to those of ordinary skill in the art without departing from the scope and spirit of the described embodiments.
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.

Claims (16)

1. A catalyst for the polymerization of olefins, characterized in that the catalyst comprises: (i) a solid catalyst component; (ii) at least one alkyl aluminum compound; (iii) at least one external electron donor;
wherein the solid catalyst component contains a product obtained by the reaction of a magnesium source, a titanium source and an internal electron donor; the internal electron donor contains a phosphate compound and a diether compound;
the external electron donor contains a hydrocarbyl trihydrocarbyloxysilane compound, and the content of the hydrocarbyl trihydrocarbyloxysilane compound accounts for more than 60 wt% of the total amount of the external electron donor.
2. The catalyst according to claim 1, wherein the total content of the phosphate compound and the diether compound is 70 to 100 wt%, preferably 80 to 100 wt%, more preferably 90 to 100 wt%, and most preferably 100 wt% based on the content of the internal electron donor.
3. The catalyst according to claim 1, wherein the phosphate ester compound is at least one selected from the group consisting of phosphate ester compounds represented by formula (1),
Figure FDA0002726220050000011
in the formula (1), R13、R14And R15Each independently selected from C1-C20Straight or branched alkyl of (2), C3-C20Cycloalkyl of, C6-C20Aryl of (C)7-C20Alkylaryl or C of7-C20The aralkyl group of (1), wherein a hydrogen atom on the benzene ring in the aryl group, the alkaryl group and the aralkyl group is optionally substituted with a halogen atom; further preferred is R13、R14And R15Each independently selected from C1-C12Straight or branched alkyl of (2), C3-C12Cycloalkyl of, C6-C12Aryl of (C)7-C12Alkylaryl or C of7-C12The aryl group, the alkylaryl group and the arylalkyl group wherein the hydrogen atom on the benzene ring is optionally substituted with a halogen atom or C1-C4Alkoxy substitution of (a); further preferred is R13、R14And R15Each independently selected from C1-C4Straight or branched alkyl of (2), C3-C6Cycloalkyl of, C6-C8Aryl of (C)7-C8Alkylaryl or C of7-C8The aralkyl group of (1), wherein a hydrogen atom on the benzene ring in the aryl group, the alkaryl group and the aralkyl group is optionally substituted with a halogen atom;
preferably, the phosphate ester compound is at least one selected from the group consisting of trimethyl phosphate, triethyl phosphate, tributyl phosphate, triphenyl phosphate, tricresyl phosphate, triisopropylphenyl phosphate, trimethoxyphenyl phosphate, phenyl dimethyl phosphate, tolyl dibutyl phosphate, isopropylphenyl dimethyl phosphate, isopropylphenyl diethyl phosphate, isopropylphenyl dibutyl phosphate, phenyl dimethyl phenyl phosphate, phenyl diisopropylphenyl phosphate, p-xylylene dibutyl phosphate, m-xylylene dibutyl phosphate, p-diisopropylphenyl dimethyl phosphate, p-diisopropylphenyl diethyl phosphate, p-tert-butylphenyl dimethyl phosphate and o-tolylp-di-tert-butylphenyl phosphate.
4. The catalyst according to claim 1, wherein the diether-based compound is at least one compound selected from diether-based compounds represented by formula (2),
Figure FDA0002726220050000021
in the formula (2), RⅠ、RⅡ、RⅢ、RⅣ、RⅤAnd RⅥIdentical or different, each independently selected from hydrogen, halogen atom, C1-C20Straight or branched alkyl of (2), C3-C20Cycloalkyl of, C6-C20Aryl of (C)7-C20Aralkyl and C7-C20One of the alkylaryl groups of (1), RⅠ-RⅥThe groups can be bonded to form a ring; and R isⅦAnd RⅧOr may be the same or different and are each independently selected from C1-C20Linear or branched alkyl of (2), C3-C20Cycloalkyl radical, C6-C20Aryl radical, C7-C20Alkylaryl group, C7-C20One of aralkyl groups;
preferably, the diether compound is selected from the group consisting of 2- (2-ethylhexyl) -1, 3-dimethoxypropane, 2-isopropyl-1, 3-dimethoxypropane, 2-butyl-1, 3-dimethoxypropane, 2-sec-butyl-1, 3-dimethoxypropane, 2-cyclohexyl-1, 3-dimethoxypropane, 2-phenyl-1, 3-dimethoxypropane, 2- (2-phenylethyl) -1, 3-dimethoxypropane, 2- (2-cyclohexylethyl) -1, 3-dimethoxypropane, 2- (p-chlorophenyl) -1, 3-dimethoxypropane, 2- (diphenylmethyl) -1, 3-dimethoxypropane, 2-dicyclohexyl-1, 3-dimethoxypropane, 2-dicyclopentyl-1, 3-dimethoxypropane, 2-diethyl-1, 3-dimethoxypropane, 2-dipropyl-1, 3-dimethoxypropane, 2-diisopropyl-1, 3-dimethoxypropane, 2-dibutyl-1, 3-dimethoxypropane, 2-methyl-2-propyl-1, 3-dimethoxypropane, 2-methyl-2-benzyl-1, 3-dimethoxypropane, 2-methyl-2-ethyl-1, 3-dimethoxypropane, 2-dimethyl-2-propyl-dimethoxypropane, 2-dimethyl-propyl-1, 3-dimethoxypropane, 2-dimethyl-propyl-2-propyl-dimethoxypropane, 2-propyl-dimethyl-1, 3-dimethoxypropane, 2-dimethyl-propyl-1, 2-dimethyl-1, 3-dimethoxypropane, 2-dimethyl-propyl-1, 2-dimethyl-1, 3-dimethoxypropane, 2-dimethyl-propyl-dimethyl-1, 2-dimethyl-propyl-dimethyl-propyl, 2, and the same, 2, 2-methyl-2-isopropyl-1, 3-dimethoxypropane, 2-methyl-2-phenyl-1, 3-dimethoxypropane, 2-methyl-2-cyclohexyl-1, 3-dimethoxypropane, 2-bis (2-cyclohexylethyl) -1, 3-dimethoxypropane, 2-methyl-2-isobutyl-1, 3-dimethoxypropane, 2-methyl-2- (2-ethylhexyl) -1, 3-dimethoxypropane, 2-diisobutyl-1, 3-dimethoxypropane, 2-diphenyl-1, 3-dimethoxypropane, 2-dibenzyl-1, 3-dimethoxypropane, 2-bis (cyclohexylmethyl) -1, 3-dimethoxypropane, 2-isobutyl-2-isopropyl-1, 3-dimethoxypropane, 2- (1-methylbutyl) -2-isopropyl-1, 3-dimethoxypropane, 2-isopropyl-2-isoamyl-1, 3-dimethoxypropane, 2-phenyl-2-isopropyl-1, 3-dimethoxypropane, 2-phenyl-2-sec-butyl-1, 3-dimethoxypropane, 2-benzyl-2-isopropyl-1, 3-dimethoxypropane, 2-cyclopentyl-2-isopropyl-1, at least one of 3-dimethoxypropane, 2-cyclopentyl-2-sec-butyl-1, 3-dimethoxypropane, 2-cyclohexyl-2-isopropyl-1, 3-dimethoxypropane, 2-cyclohexyl-2-sec-butyl-1, 3-dimethoxypropane, 2-isopropyl-2-sec-butyl-1, 3-dimethoxypropane, 2-cyclohexyl-2-cyclohexylmethyl-1, 3-dimethoxypropane and 9, 9-dimethoxymethylfluorene.
5. The catalyst according to claim 1, wherein the molar ratio of the phosphate compound to the diether compound is 0.02-0.30: 1, preferably 0.03 to 0.25: 1, more preferably 0.04 to 0.20: 1.
6. the catalyst of claim 1, wherein the external electron donor comprises at least one of hydrocarbyl trihydrocarbyloxysilane compounds represented by formula (3);
Figure FDA0002726220050000041
in the formula (3), R1-R4Are the same or different and are each selected from C1-C20Alkyl of (C)3-C20Cycloalkyl radical, C6-C20Aryl or C of7-C20Preferably selected from C1-C10Alkyl of (C)3-C10Cycloalkyl radical, C6-C10Aryl or C of7-C10The alkyl, aryl, aralkyl or alkaryl group optionally having one or more substituents selected from the group consisting of hetero atom, C1-C6Alkyl and C1-C6Preferably at least one of oxygen, nitrogen and halogen;
the hydrocarbyl trihydrocarbyloxysilane compound is preferably at least one member selected from the group consisting of propyltrimethoxysilane, butyltrimethoxysilane, isobutyltrimethoxysilane, phenyltrimethoxysilane, cyclopentyltrimethoxysilane, ethylpiperidinyltrimethoxysilane, propyltriethoxysilane, isopentyltriethoxysilane, isooctyltriethoxysilane, and decyltrimethoxysilane.
7. The catalyst of claim 6, wherein the external electron donor further comprises at least one dihydrocarbyl oxysilane compound of formula (4); the sum of the contents of the hydrocarbyl trihydrocarbyloxysilane compound and the dihydrocarbyldihydrocarbyloxysilane compound is 80-100 wt%, preferably 90-100 wt% of the total amount of the external electron donor;
(R5)(R6)Si(OR7)(OR8) Formula (4)
In the formula (4), R5、R6、R7And R8Each independently selected from C1-C20Optionally containing heteroatoms; preferably R5、R6Each independently selected from C1-C10Straight or branched alkyl of (2), C3-C20Cycloalkyl of, C6-C20Aryl of (C)7-C20Alkylaryl or C of7-C20Aralkyl optionally containing heteroatoms; r7、R8Each independently selected from C1-C10Linear or branched alkyl, optionally containing heteroatoms; the heteroatom is preferably at least one of oxygen, nitrogen and halogen;
the dihydrocarbyldihydrocarbyloxysilane compound is preferably at least one selected from the group consisting of cyclohexylmethyldimethoxysilane, diisopropyldimethoxysilane, di-n-butyldimethoxysilane, diisobutyldimethoxysilane, diphenyldimethoxysilane, methyl-t-butyldimethoxysilane, dicyclopentyldimethoxysilane, 2-ethylpiperidinyl-2-t-butyldimethoxysilane, (1,1, 1-trifluoro-2-propyl) -2-ethylpiperidinyldimethoxysilane and (1,1,1-, trifluoro-2-propyl) -methyldimethoxysilane.
8. The catalyst of claim 7, wherein the molar ratio of the hydrocarbyl trihydrocarbyl hydrocarbyloxysilane compound to the dihydrocarbyl dihydrocarbyloxysilane compound is from 1 to 20: 1, preferably 2 to 10: 1.
9. the catalyst of claim 1, wherein the magnesium source is at least one of a magnesium halide, an alcoholate of magnesium, or a haloalcoholate and a magnesium halide adduct support; the titanium source is of the general formula Ti (OR')3-aZaAnd Ti (OR')4-bZbAt least one of the compounds shown, wherein R' is C1-C20Is preferably C1-C12More preferably C1-C6Z is halogen, a is an integer of 1 to 3, b is an integer of 1 to 4.
10. The catalyst according to claim 1, wherein the solid catalyst component contains the magnesium element in an amount of 2 to 16 parts by weight, preferably 3 to 12 parts by weight, and more preferably 4 to 10 parts by weight, per part by weight of the titanium element; the content of the internal electron donor is 2 to 16 parts by weight, preferably 3 to 14 parts by weight, and more preferably 4 to 12 parts by weight.
11. The catalyst according to claim 1, in which the alkylaluminum compound is chosen from the general formula AlR16R16′R16"wherein R is at least one of the compounds represented by16、R16' and R16Each independently is C1-C8And at least one of alkyl or halogen of (A) is C1-C8And, the hydrogen on the alkyl group is optionally substituted with halogen.
12. The catalyst according to claim 1, in which the solid catalyst component, expressed as titanium element, and the alkylaluminium compound, expressed as aluminium element, are used in a molar ratio of 1: 1-2000, preferably 1: 20-500; the external electron donor is used in an amount of 0.002 to 1.0 mole, preferably 0.01 to 0.5 mole, per mole of aluminum in the alkylaluminum compound.
13. Use of a catalyst according to any one of claims 1 to 12 in the polymerisation of olefins.
14. An olefin polymerization process, comprising: contacting one or more olefins of the general formula CH with the catalyst of any of claims 1-12 under olefin polymerization conditions2＝CH-RvWherein R isvIs hydrogen or C1-C6An alkyl group; the olefin is preferably propylene and/or ethylene.
15. The olefin polymerization process according to claim 14, wherein the polymerization reaction temperature is from 0 to 150 ℃, preferably from 60 to 90 ℃; the pressure of the polymerization reaction is normal pressure or higher, preferably 0.01 to 10MPa, more preferably 0.01 to 5MPa, and still more preferably 0.1 to 4 MPa.
16. A polymer produced by the olefin polymerization process of claim 14 or 15.
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