CN110938160B - Catalyst system for olefin polymerization and prepolymerized catalyst composition and use thereof - Google Patents
Catalyst system for olefin polymerization and prepolymerized catalyst composition and use thereof Download PDFInfo
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
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Abstract
The present invention relates to the field of olefin polymerization catalysts, in particular to catalyst systems for olefin polymerization, prepolymerized catalyst compositions for olefin polymerization, and their use in olefin polymerization reactions. The catalyst system comprises: a solid catalyst component comprising a titanium compound, a magnesium compound, and an internal electron donor; an alkyl aluminum compound; and an external electron donor; the internal electron donor contains phthalic acid carboxylate, the external electron donor contains a lactone compound shown in a formula I, the lactone compound is used as the external electron donor, alkyl aluminum is used as a cocatalyst, and the lactone compound is matched with a solid catalyst component of which phthalic acid carboxylate is used as the internal electron donor for use.
Description
Technical Field
The present invention relates to the field of olefin polymerization catalysts, in particular to catalyst systems for olefin polymerization, prepolymerized catalyst compositions for olefin polymerization, and their use in olefin polymerization reactions.
Background
It is known that the core Ziegler-Natta catalyst used in polyolefin technology mainly comprises magnesium/titanium/halogen/internal electron donor, and the catalyst is often used in combination with aluminum alkyl and external electron donor to form a complete catalyst system. Among them, the internal electron donor and the external electron donor have been developed in recent decades from none to many, from single structure and variety to rich variety, diverse functions, excellent performance, and have made great progress in technology, and thus have gradually become important components of polyolefin catalyst technology. At present, a large number of electron donor compounds have been disclosed, such as internal electron donor mono-or polycarboxylic esters, ketones, mono-or polyethers, amines, etc. and their derivatives, external electron donor carboxylic esters, amines, silanes, aminosilanes, etc. and their derivatives.
In the current industrial production, fourth generation Ziegler-Natta catalysts are still widely used. The catalyst adopts phthalate compounds as internal electron donors and adopts alkoxy silane as external electron donors, so that the catalyst has good stereospecificity. However, such catalysts have a general hydrogen response.
At present, polyolefin products tend to be diversified in application, and for some specific application occasions, the catalyst is required to have good hydrogen regulation sensitivity and the like, and higher requirements are provided for other performances of the catalyst, such as copolymerization performance. As is known, the external electron donor has the remarkable characteristics of abundant species, flexible and controllable addition, large influence on various performances of the catalyst, and the like, so that the regulation of the overall performance of the catalyst by selecting a proper external electron donor is an important direction for the research and development of the catalyst, and when the external electron donor is selected, the improvement of the external electron donor compound on the performance of the catalyst, cost, environmental factors, and the like need to be comprehensively considered. .
Disclosure of Invention
The invention aims to provide a catalyst system for olefin polymerization, which has high hydrogen regulation sensitivity, wider polymer molecular weight distribution and better capability of copolymerizing ethylene when used for ethylene/propylene copolymerization when used for olefin polymerization.
In order to achieve the above object, one aspect of the present invention provides a catalyst system for olefin polymerization, the catalyst system comprising:
(1) a solid catalyst component comprising a titanium compound, a magnesium compound, and an internal electron donor;
(2) an alkyl aluminum compound; and
(3) an external electron donor;
wherein the internal electron donor contains phthalic acid carboxylate,
wherein the external electron donor contains a lactone compound shown as a formula I,
in formula I:
r is a group shown in a formula II,
in formula II:
2≤n≤11，R1' and RnAre all CR1”R2", wherein R1"and R2"identical or different" are each independently selected from the group consisting of a single bond, a double bond, hydrogen, a halogen atom, a straight or branched C1-C20Alkyl radical, C3-C20Cycloalkyl radical, C6-C20Aryl radical, C7-C20One of aralkyl groups.
Another aspect of the present invention provides a prepolymerized catalyst composition for olefin polymerization, said composition comprising a prepolymer obtained by polymerizing an olefin using the catalyst system as described above;
wherein the pre-polymerization multiple of the prepolymer is 0.1 to 1000g of olefin polymer per g of the solid catalyst component.
In a further aspect the present invention provides the use of a catalyst system as described above and/or a prepolymerised catalyst composition as described above in the polymerisation of olefins.
Yet another aspect of the present invention provides an olefin polymerization process comprising: contacting one or more olefins with a catalyst system as described above and/or a prepolymerized catalyst composition as described above under olefin polymerization conditions; the olefin is preferably propylene.
The invention uses phthalic acid carboxylate as internal electron donor to prepare solid catalyst component, and uses lactone compound as external electron donor and alkyl aluminum as cocatalyst, and combines with solid catalyst product component to form catalyst system, when the catalyst system is used for olefin polymerization, especially propylene polymerization, the hydrogen regulation sensitivity is good, the molecular weight of polymerization product is obviously reduced, and the molecular weight distribution of polymer is wider. And when the catalyst system is used for ethylene/propylene copolymerization, the ethylene copolymerization capability is better, which is beneficial to developing polypropylene products with high impact resistance. The lactone compound has the characteristics of low price and environmental friendliness, and has a good application prospect.
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 numerical ranges, each range between its endpoints and individual point values, and each individual point value can be combined with each other to give one or more new numerical ranges, and such numerical ranges should be construed as specifically disclosed herein.
In a first aspect of the present invention, there is provided a catalyst system for the polymerisation of olefins, the catalyst system comprising:
(1) a solid catalyst component comprising a titanium compound, a magnesium compound, and an internal electron donor;
(2) an alkyl aluminum compound; and
(3) an external electron donor;
wherein the internal electron donor contains phthalic acid carboxylate,
wherein the external electron donor contains a lactone compound shown as a formula I,
in formula I:
r is a group shown in a formula II,
in formula II:
2≤n≤11，R1' and RnAre all CR1”R2", wherein R1"and R2"identical or different" are each independently selected from the group consisting of a single bond, a double bond, hydrogen, a halogen atom, a straight or branched C1-C20Alkyl radical, C3-C20Cycloalkyl radical, C6-C20Aryl radical, C7-C20One of aralkyl groups.
According to the present invention, the phthalic acid carboxylate is preferably at least one selected from the group consisting of diethyl phthalate, dipropyl phthalate, diisobutyl phthalate, di-n-butyl phthalate, dipentyl phthalate, dihexyl phthalate, diheptyl phthalate and dioctyl phthalate; preferably, the carboxylic acid ester of phthalic acid is diisobutyl phthalate.
According to the invention, in formula II, R1"and R2"identical or different, each independently selected from the group consisting of a single bond, hydrogen, a halogen atom, a linear or branched C1、C2、C3、C4、C5、C6、C7、C8、C9、C10、C11、C12、C13、C14、C15、C16、C17、C18、C19、C20Alkyl of (C)3、C4、C5、C6、C7、C8、C9、C10、C11、C12、C13、C14、C15、C16、C17、C18、C19、C20Cycloalkyl of, C6、C7、C8、C9、C10、C11、C12、C13、C14、C15、C16、C17、C18、C19、C20Aryl of (C)7、C8、C9、C10、C11、C12、C13、C14、C15、C16、C17、C18、C19、C20One of the aralkyl groups of (1).
Preferably, R1"and R2"identical or different" are each independently selected from the group consisting of a single bond, hydrogen, straight or branched C1-C8More preferably selected from the group consisting of a single bond, hydrogen, straight or branched C1-C5Alkyl of (e.g. C)1、C2、C3、C4、C5Including, but not limited to, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, neopentyl.
According to a particular embodiment of the invention, the lactone compound is selected from the group consisting of beta-propiolactone, gamma-butyrolactone, alpha-methyl-gamma-butyrolactone, alpha-methylene-gamma-butyrolactone, alpha-ethyl-gamma-butyrolactone, alpha-butyl-gamma-butyrolactone, alpha-bromo-gamma-butyrolactone, alpha-hydroxy-gamma-butyrolactone, beta-hydroxy-gamma-butyrolactone, alpha-methyl-alpha-methoxymethyl-gamma-butyrolactone, alpha-hexyl-alpha-methoxymethyl-gamma-butyrolactone, alpha-cyclohexylmethyl-alpha-ethoxymethyl-gamma-butyrolactone, alpha-methylethoxymethyl-gamma-butyrolactone, gamma-butylolactone, and gamma-butylolactone, Alpha-cyclohexylmethyl-gamma-cyclohexyl-alpha-methoxymethyl-gamma-butyrolactone, alpha-benzyl-alpha-methoxymethyl-gamma-butyrolactone, alpha-isopropyl-alpha-methoxymethyl-gamma-butyrolactone, alpha-cyclohexyl-alpha-methoxymethyl-gamma-butyrolactone, alpha-pentyl-alpha-methoxymethyl-gamma-butyrolactone, gamma-valerolactone, gamma-caprolactone, gamma-heptolactone, gamma-octalactone, gamma-nonalactone, gamma-decalactone, gamma-undecalactone, gamma-dodecalactone, delta-butyrolactone, delta-valerolactone, delta-caprolactone, delta-heptalactone, delta-valerolactone, gamma-methyloxymethyl-gamma-butyrolactone, gamma-methyle, gamma-valerolactone, gamma-caprolactone, gamma-butylolactone, gamma-butyllactone, gamma-butyrolactone, gamma-butyllactone, gamma-valerolactone, gamma-butyllactone, gamma-valerolactone, gamma-methylvalerolactone, or a-methylvalerolactone, or a-methylvalerolact, Delta-octalactone, delta-nonalactone, delta-decalactone, delta-undecalactone, delta-dodecalactone, epsilon-caprolactone, dihydrocoumarate and gamma-angelactone.
Preferably, the lactone compound is at least one selected from the group consisting of gamma-decalactone, epsilon-caprolactone, gamma-dodecalactone and gamma-angelactone.
According to the invention, the solid catalyst component contains titanium, magnesium and an internal electron donor, and is a reaction product of a halogen-containing titanium compound, a halogen-containing magnesium compound and an internal electron donor. Since the present invention improves the performance of the olefin polymerization catalyst by changing the kinds of the internal electron donor and the external electron donor, the method of preparing the solid catalyst component by the above reaction in the present invention may be performed according to a method conventionally used in the art, for example, methods disclosed in CN1506384, CN1091748, CN85100997, CN102399326A, US4540679, etc., the disclosure of which is incorporated herein by reference.
According to a specific embodiment of the present invention, a titanium compound or a mixture of a titanium compound and an inert solvent (such as hexane, heptane, octane, decane, toluene, etc.) pre-cooled to-15 ℃ to-40 ℃ is mixed with a magnesium compound, the temperature of the mixture is raised to 90 ℃ to 110 ℃ in stages and maintained for 0.1 to 2 hours, and an internal electron donor is added during the raising of the temperature. Then solid-liquid separation is carried out, the obtained solid phase is treated for at least 2 times by using the titanium compound again, and is washed by using a solvent, and finally, the solid catalyst component is obtained by vacuum drying.
According to the present invention, the magnesium compound may be various magnesium compounds conventionally used in the art for preparing olefin polymerization catalysts, for example, the magnesium compound may be selected from at least one of magnesium dihalide, alkoxy magnesium, alkyl magnesium, a hydrate of magnesium dihalide, an alkoxide of magnesium dihalide, and a derivative in which one halogen atom in the molecule of magnesium dihalide is substituted with an alkoxide group or a haloalkoxide group.
According to a preferred embodiment of the invention, the magnesium compound is an alcoholate of magnesium dihalide. More preferably, the alcoholate of the magnesium dihalide has the spherical magnesium alcoholate of formula III,
MgX2·m(ROH)·nE·rH2o formula III
In formula III:
x is chlorine or bromine;
r is C1-C10Is preferably C1-C4Alkyl (e.g., methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl) of (a), m is 0.5 to 4;
e is an ether or ester electron donor compound, and n is 0-1.0;
r is 0-0.8.
According to a further preferred embodiment of the present invention, in formula III, X is chloro or bromo; r is C1-C4M is 1.5 to 3.5; n and r are both 0, and more preferably, the magnesium compound is MgCl2·m(CH3CH2OH), m is 1.5-3.5.
According to the present invention, the alcoholate of the magnesium dihalide can be prepared by referring to the methods disclosed in chinese patent applications CN1091748 and CN101050245, the relevant disclosures of which are incorporated herein by reference in their entirety. The following provides a specific preparation method of the magnesium dihalide alcohol compound:
(1) mixing anhydrous magnesium dihalide with an alcohol compound (ROH), optionally adding an ether or ester electron donor compound, and reacting at 90-140 ℃ to obtain an alcohol compound of magnesium halide;
(2) shearing the magnesium halide alcohol compound in a dispersion medium, cooling the sheared magnesium halide alcohol compound in an inert medium to obtain the spherical magnesium halide alcohol compound, and washing and drying the spherical magnesium halide alcohol compound to obtain the spherical carrier.
The mixing ratio of the anhydrous magnesium dihalide and the alcohol compound may be determined according to the actual need of the alcohol compound supported on the anhydrous magnesium dihalide.
Wherein, the dispersion medium can adopt hydrocarbon inert solvent, such as kerosene, white oil, silicone oil, paraffin oil, vaseline oil, etc. The inert medium may be selected from pentane, hexane, heptane, petroleum ether, raffinate oil, etc.
Wherein the shearing means shearing the alcoholic product of the magnesium halide by external shearing force, for example, high-speed stirring method (e.g. CN1330086), spraying method (e.g. US6020279) and super-gravity rotating bed (e.g. CN1580136A) and emulsifier method (CN1463990A) and the like.
According to the present invention, the titanium compound may be various titanium compounds conventionally used in the art for preparing olefin polymerization catalysts. Preferably, the titanium compound has a structure represented by formula IV,
Ti(OR”)4-kXkformula IV
In formula IV:
r' is C1-C20Is preferably C1-C10Is preferably C1-C5Alkyl of (a), for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, neopentyl;
x is F, Cl or Br, preferably Cl;
k is an integer of 0 to 4.
Preferably, the titanium compound is selected from at least one of titanium tetrachloride, titanium tetrabromide, titanium tetraiodide, tetrabutoxytitanium, tetraethoxytitanium, chlorotris butoxytitanium, dichlorodibutoxytitanium, trichloro monobutoxytitanium, chlorotriethoxytitanium, dichlorodiethoxytitanium, trichloro-monoethoxytitanium and titanium trichloride; more preferably, the titanium compound is titanium tetrachloride.
According to a preferred embodiment of the present invention, the weight ratio of the titanium element, the magnesium element and the internal electron donor in the solid catalyst component is 1: (5-25): (2-15).
According to the invention, the alkylaluminum compound has the general formula AlR3R are identical or different C1-C8In the alkyl group of (1), one or two alkyl groups may be substituted with halogen, and one or more alkyl aluminum groups may be used in combination. The alkyl aluminum compound is preferably triethyl aluminum, tripropyl aluminum, triisobutyl aluminum, tri-n-butyl aluminum, tri-n-hexyl aluminum, tri-n-octyl aluminum, alkyl aluminum chloride, or the like.
According to the invention, it is preferred that in said catalyst system the molar ratio of the catalyst component, calculated as titanium element, to the aluminium of the alkylaluminium compound is 1: (5-1000), preferably 1: (20-500).
According to the present invention, it is preferred that in the catalyst system, the molar ratio of the external electron donor to the aluminum in the alkyl aluminum compound is 1: (0.1-200); preferably 1: (1-100).
According to a second aspect of the present invention, there is provided a prepolymerized catalyst composition for olefin polymerization, characterized in that said composition comprises a prepolymer obtained by polymerizing an olefin using the catalyst system as described above;
wherein the pre-polymerization multiple of the prepolymer is 0.1 to 1000g of olefin polymer per g of the solid catalyst component.
According to the invention, a "prepolymerized catalyst" refers to a catalyst which has undergone a polymerization step with a relatively low degree of conversion. In the present invention, the prepolymerization can be carried out using the same α -olefin as the olefin used for the polymerization, and the olefin to be subjected to the prepolymerization is preferably propylene. In particular, it is particularly preferred to carry out the prepolymerization with propylene or a mixture thereof with one or more alpha-olefins in a molar amount of up to 20%. Preferably, the conversion degree (prepolymerization multiple) of the prepolymerized catalyst component is about 0.2 to 500g of the olefin polymer per gram of the solid catalyst component, and more preferably 0.5 to 20g of the olefin polymer per gram of the solid catalyst component.
According to the invention, the prepolymerization conditions can be carried out at temperatures of-20 to 80 ℃, preferably 0 to 50 ℃, in liquid or 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.
In the present invention, to prepare a polymer of 0.1 to 1000g of an olefin polymer per g of a solid catalyst component, preferably 0.2 to 500g of an olefin polymer per g of a solid catalyst component, more preferably 0.5 to 20g of an olefin polymer per g of a solid catalyst component, it is particularly preferred that the prepolymerization of the catalyst of the present invention with an olefin is carried out independently in a batch operation, and the polymerization pressure is preferably 0.01 to 5 MPa.
According to a third aspect of the present invention there is provided the use of a catalyst system as described above and/or a prepolymerised catalyst composition as described above in the polymerisation of olefins.
According to a fourth aspect of the present invention, there is provided an olefin polymerisation process comprising: contacting one or more olefins with a catalyst system as described above and/or a prepolymerized catalyst composition as described above under olefin polymerization conditions; the olefin is preferably propylene.
According to the present invention, both the above catalyst system and the prepolymerized catalyst composition of the present invention can be used in the homopolymerization of olefins, preferably propylene, or in the copolymerization with other olefins.
Thus, the present invention also provides a process for the polymerisation of olefins, the process comprising: the olefin is polymerized under the action of the above-mentioned catalyst system or the above-mentioned prepolymerized catalyst composition.
According to the invention, the olefin has the general formula CH2Wherein R is hydrogen or C1-C12Alkyl or aryl of (a). Preferably, the olefin is selected from the group consisting of ethylene, propylene, 1-butene, 4-methyl-1-pentene and 1-hexene, more preferably, the olefin is propylene.
According to the invention, the catalyst system can be directly added into a reactor for a polymerization process, or the catalyst system and olefin are prepolymerized to obtain a prepolymerized catalyst which is then added into the reactor for polymerization.
According to the invention, the olefin polymerization can be carried out according to known polymerization methods, in liquid or gas phase, or in a combination of liquid and gas phase polymerization stages, or using conventional techniques such as slurry processes, gas phase fluidized beds, etc. Preferred polymerisation conditions include a temperature of from 0 to 150 ℃ for a period of from 0.5 to 5 hours and a pressure of from 0.01 to 10MPa, more preferably a temperature of from 60 to 90 ℃ for a period of from 0.5 to 2 hours and a pressure of from 0.05 to 1.5 MPa.
According to the invention, the polymerization can be carried out in the presence of a solvent. Wherein the concentration of the catalyst system in the solvent may be 0.1X 10 in terms of the titanium element in the solid catalyst component-5-5×10-5Mol/l, preferably 0.5X 10-5-2×10-5Mol/l.
The present invention will be described in detail below by way of examples. In the following examples of the present invention,
1. weight average molecular weight (M)w): measured by high temperature sol-gel chromatography with reference to standard GB/T36214.4-2018.
2. Molecular weight distribution (weight average molecular weight M)wNumber average molecular weight Mn): measured by high temperature sol-gel chromatography with reference to standard GB/T36214.4-2018.
3. Ethylene content in the polymer (wt%): measured by fourier infrared spectrometer VERTEX 70.
Preparation example 1
This preparation example is illustrative of the preparation of a magnesium compound
Mixing anhydrous magnesium chloride and ethanol according to a molar ratio of 1:2.6, heating to 120 ℃ for reaction to generate magnesium chloride alcoholate melt, stirring at a high speed in white oil and silicone oil as dispersion media, then putting into cooled hexane to form spherical magnesium chloride alcoholate particles, washing and drying to obtain a spherical carrier MgCl2·2.6C2H5OH。
Preparation example 2
This preparation example is intended to illustrate the preparation of the solid catalyst component
Adding into a 500ml glass reaction bottle100ml of titanium tetrachloride were charged, and 8g of the spherical magnesium chloride alcoholate (MgCl) prepared in preparation example 1 were added with stirring2·2.6C2H5OH), the temperature was raised to 120 ℃ and 3.9mmol of diisobutylphthalate was added during the temperature rise, and the mixture was held at 120 ℃ for 1 hour and filtered. To the solid phase obtained by the filtration, 100ml of titanium tetrachloride was added, and the mixture was stirred at 120 ℃ for 0.5 hour and filtered. The solid phase obtained by filtration was washed with 100ml of hexane and dried under vacuum to obtain a solid catalyst component.
Examples 1 to 5 and comparative example 1
This example illustrates the catalyst system provided by the present invention and its applications
Purging with nitrogen at high temperature in a 48-channel parallel pressure reactor (reaction volume 20ml) (PPR), and cooling to normal temperature; replacing the reactor with propylene at normal temperature, and filling propylene with a certain pressure and a certain amount of hydrogen; filling propylene gas to about 1MPa, and adding 6ml of liquid propylene; several 1ml glass bottles were placed on a shaking table and filled with triethylaluminium (calculated as aluminium): external electron donors in table 1: the solid catalyst component prepared in preparation example 2 (by titanium element) is sequentially added with triethyl aluminum, an external electron donor and a heptane solution of the solid catalyst component in a molar ratio of 500:25:1 to prepare a mixed solution; automatically extracting a certain amount of mixed liquid by using a needle head and injecting the mixed liquid into the reactor; the temperature is raised to 70 ℃ for reaction for 1 hour.
The polymer was discharged and weighed using a weighing apparatus provided in the PPR, and the weight average molecular weight and the width of the molecular weight distribution of the polymer were measured, and the results are shown in Table 1.
TABLE 1
Note: C-Donor: cyclohexyl methyl dimethoxy silane
Examples 6 to 10 and comparative example 2
This example illustrates the catalyst system provided by the present invention and its applications
In a 48-channel parallel pressure reactor (reaction volume 20ml) (PPR), nitrogen is adopted for high-temperature purging, and the temperature is cooled to normal temperature; replacing the reactor with propylene at normal temperature, and filling propylene with a certain pressure and a certain amount of hydrogen; filling propylene gas to about 1MPa, and adding 6ml of liquid propylene; several 1ml glass bottles were placed on a shaking table and filled with triethylaluminium (calculated as aluminium): external electron donors in table 2: the solid catalyst component prepared in preparation example 2 (by titanium element) is sequentially added with triethyl aluminum, an external electron donor and a heptane solution of the solid catalyst component in a molar ratio of 500:25:1 to prepare a mixed solution; automatically extracting a certain amount of mixed liquid by using a needle head and injecting the mixed liquid into the reactor; heating to 70 ℃ and reacting for 40 minutes; the reactor is emptied, mixed gas with the mol ratio of 1 to 1 of ethylene/propylene is introduced, the temperature is raised to 80 ℃, the reaction pressure is controlled to be 0.7MPa, and the reaction is carried out for 20 minutes.
The polymer was discharged and the ethylene content of the polymer was determined and the results are shown in Table 2.
TABLE 2
| Examples | External electron donor | Amount of hydrogenation (NL 10)-3) | Ethylene content (wt%) |
| Example 6 | Gamma-caprolactone | 20 | 12.7 |
| Example 7 | Gamma-dodecalactone | 20 | 12.6 |
| Example 8 | Epsilon-caprolactone | 20 | 12.8 |
| Example 9 | Gamma-angelic lactone | 20 | 13.0 |
| Example 10 | Gamma-decalactone | 20 | 12.1 |
| Comparative example 2 | C-Donor | 20 | 8.8 |
Note: C-Donor: cyclohexyl methyl dimethoxy silane
As can be seen from tables 1 and 2, the molecular weight of the polymer prepared by the catalyst with the addition of the internal ester and the external electron Donor is significantly reduced, which indicates that the hydrogen regulation sensitivity of the catalyst with the internal ester as the external electron Donor is improved and the molecular weight distribution of the polymer obtained by catalysis is wider compared with that of C-Donor; and when the catalyst system is used for ethylene/propylene copolymerization, the ethylene copolymerization capability is better, which is beneficial to developing polypropylene products with high impact resistance. The better hydrogen regulation sensitivity of the catalyst enables the melt index of the product to be more easily regulated within a limited hydrogenation range, and is also beneficial to the improvement of subsequent processing performance.
The preferred embodiments of the present invention have been described above in detail, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, many simple modifications can be made to the technical solution of the invention, including combinations of various technical features in any other suitable way, and these simple modifications and combinations should also be regarded as the disclosure of the invention, and all fall within the scope of the invention.
Claims (60)
1. A catalyst system for the polymerization of olefins, the catalyst system comprising:
(1) a solid catalyst component comprising a titanium compound, a magnesium compound, and an internal electron donor;
(2) an alkyl aluminum compound; and
(3) an external electron donor;
wherein the internal electron donor contains phthalic acid carboxylate,
wherein the external electron donor contains a lactone compound, and the lactone compound is gamma-angelica lactone.
2. The catalyst system according to claim 1, wherein the carboxylic acid ester of phthalic acid is selected from at least one of diethyl phthalate, dipropyl phthalate, diisobutyl phthalate, di-n-butyl phthalate, dipentyl phthalate, dihexyl phthalate, diheptyl phthalate and dioctyl phthalate.
3. The catalyst system of claim 2, wherein the carboxylic acid ester of phthalic acid is diisobutyl phthalate.
4. The catalyst system according to any one of claims 1-3, wherein the solid catalyst component is a reaction product of a titanium compound, a magnesium compound and the internal electron donor.
5. The catalyst system according to any one of claims 1 to 3, wherein the magnesium compound is at least one selected from the group consisting of magnesium dihalides, alkoxy magnesium, alkyl magnesium, hydrates of magnesium dihalides, alcoholates of magnesium dihalides, and derivatives in which one halogen atom in the magnesium dihalide molecule is substituted with an hydrocarbyloxy group or a halohydrocarbyloxy group.
6. The catalyst system according to claim 5, wherein the magnesium compound is an alcoholate of magnesium dihalide.
7. The catalyst system of claim 6, wherein the alcoholate of a magnesium dihalide has a spherical magnesium alcoholate of formula III,
MgX2·m(ROH)·nE·rH2o formula III
In formula III:
x is chlorine or bromine;
r is C1-C10M is 0.5 to 4;
e is an ether or ester electron donor compound, and n is 0-1.0;
r is 0-0.8.
8. Catalyst system according to claim 7, wherein the magnesium compound is MgCl2·m(CH3CH2OH)。
9. The catalyst system according to claim 4, wherein the magnesium compound is at least one selected from the group consisting of magnesium dihalides, alkoxy magnesium, alkyl magnesium, hydrates of magnesium dihalides, alcoholates of magnesium dihalides, and derivatives in which one halogen atom in the magnesium dihalide molecule is substituted with hydrocarbyloxy group or halohydrocarbyloxy group.
10. The catalyst system of claim 9, wherein the magnesium compound is an alcoholate of a magnesium dihalide.
11. The catalyst system of claim 10, wherein the alcoholate of a magnesium dihalide has a spherical magnesium alcoholate of formula III,
MgX2·m(ROH)·nE·rH2o formula III
In formula III:
x is chlorine or bromine;
r is C1-C10M is 0.5 to 4;
e is an ether or ester electron donor compound, and n is 0-1.0;
r is 0-0.8.
12. The catalyst system according to claim 11, wherein the magnesium compound is MgCl2·m(CH3CH2OH)。
13. The catalyst system of any of claims 1-3, 6-12, wherein the titanium compound has a structure represented by formula IV,
Ti(OR’’)4-kXkformula IV
In formula IV:
r' is C1-C20Alkyl groups of (a);
x is F, Cl or Br;
k is an integer of 0 to 4.
14. The catalyst system according to claim 13, wherein the titanium compound is at least one selected from the group consisting of titanium tetrachloride, titanium tetrabromide, titanium tetraiodide, tetrabutoxytitanium, tetraethoxytitanium, chlorotris butoxytitanium, dichlorodibutoxytitanium, trichloro-monobutoxytitanium, chlorotriethoxytitanium, dichlorodiethoxytitanium, trichloro-monoethoxytitanium, and titanium trichloride.
15. The catalyst system according to claim 14, wherein the titanium compound is titanium tetrachloride.
16. The catalyst system of claim 4, wherein the titanium compound has a structure represented by formula IV,
Ti(OR’’)4-kXkformula IV
In formula IV:
r' is C1-C20Alkyl groups of (a);
x is F, Cl or Br;
k is an integer of 0 to 4.
17. The catalyst system according to claim 16, wherein the titanium compound is at least one selected from the group consisting of titanium tetrachloride, titanium tetrabromide, titanium tetraiodide, tetrabutoxytitanium, tetraethoxytitanium, chlorotris butoxytitanium, dichlorodibutoxytitanium, trichloro-monobutoxytitanium, chlorotriethoxytitanium, dichlorodiethoxytitanium, trichloro-monoethoxytitanium, and titanium trichloride.
18. The catalyst system of claim 17, wherein the titanium compound is titanium tetrachloride.
19. The catalyst system of claim 5, wherein the titanium compound has a structure represented by formula IV,
Ti(OR’’)4-kXkformula IV
In formula IV:
r' is C1-C20Alkyl groups of (a);
x is F, Cl or Br;
k is an integer of 0 to 4.
20. The catalyst system according to claim 19, wherein the titanium compound is at least one selected from the group consisting of titanium tetrachloride, titanium tetrabromide, titanium tetraiodide, tetrabutoxytitanium, tetraethoxytitanium, chlorotris butoxytitanium, dichlorodibutoxytitanium, trichloro-monobutoxytitanium, chlorotriethoxytitanium, dichlorodiethoxytitanium, trichloro-monoethoxytitanium, and titanium trichloride.
21. The catalyst system of claim 20, wherein the titanium compound is titanium tetrachloride.
22. The catalyst system according to any one of claims 1-3, 6-12, 14-21, wherein the alkyl aluminum compound is selected from at least one of triethylaluminum, tripropylaluminum, triisobutylaluminum, tri-n-butylaluminum, tri-n-hexylaluminum, tri-n-octylaluminum, and alkylaluminum chloride.
23. The catalyst system according to claim 4, wherein the alkyl aluminum compound is selected from at least one of triethylaluminum, tripropylaluminum, triisobutylaluminum, tri-n-butylaluminum, tri-n-hexylaluminum, tri-n-octylaluminum, and alkylaluminum chloride.
24. The catalyst system according to claim 5, wherein the alkyl aluminum compound is selected from at least one of triethylaluminum, tripropylaluminum, triisobutylaluminum, tri-n-butylaluminum, tri-n-hexylaluminum, tri-n-octylaluminum, and alkylaluminum chloride.
25. The catalyst system according to claim 13, wherein the alkyl aluminum compound is selected from at least one of triethylaluminum, tripropylaluminum, triisobutylaluminum, tri-n-butylaluminum, tri-n-hexylaluminum, tri-n-octylaluminum, and alkylaluminum chloride.
26. The catalyst system according to any one of claims 1 to 3, 6 to 12, 14 to 21, and 23 to 25, wherein the weight ratio of the titanium element, the magnesium element, and the internal electron donor in the solid catalyst component is 1: (5-25): (2-15).
27. The catalyst system according to claim 4, wherein the weight ratio of the titanium element, the magnesium element and the internal electron donor in the solid catalyst component is 1: (5-25): (2-15).
28. The catalyst system according to claim 5, wherein the weight ratio of the titanium element, the magnesium element and the internal electron donor in the solid catalyst component is 1: (5-25): (2-15).
29. The catalyst system of claim 13, wherein the weight ratio of the titanium element, the magnesium element and the internal electron donor in the solid catalyst component is 1: (5-25): (2-15).
30. The catalyst system of claim 22, wherein the weight ratio of the titanium element, the magnesium element and the internal electron donor in the solid catalyst component is 1: (5-25): (2-15).
31. The catalyst system according to any one of claims 1-3, 6-12, 14-21, 23-25, 27-30, wherein the molar ratio of titanium in the solid catalyst component to aluminum in the alkyl aluminum compound is 1: (5-1000).
32. The catalyst system according to claim 31, wherein the molar ratio of titanium in the solid catalyst component to aluminum in the alkyl aluminum compound is 1: (20-500).
33. The catalyst system according to claim 4, wherein the molar ratio of titanium in the solid catalyst component to aluminum in the aluminum alkyl compound is 1: (5-1000).
34. The catalyst system according to claim 33, wherein the molar ratio of titanium in the solid catalyst component to aluminum in the alkyl aluminum compound is 1: (20-500).
35. The catalyst system according to claim 5, wherein the molar ratio of titanium in the solid catalyst component to aluminum in the alkyl aluminum compound is 1: (5-1000).
36. The catalyst system according to claim 35, wherein the molar ratio of titanium in the solid catalyst component to aluminum in the alkyl aluminum compound is 1: (20-500).
37. The catalyst system according to claim 13, wherein the molar ratio of titanium in the solid catalyst component to aluminum in the alkyl aluminum compound is 1: (5-1000).
38. The catalyst system according to claim 37, wherein the molar ratio of titanium in the solid catalyst component to aluminum in the alkyl aluminum compound is 1: (20-500).
39. The catalyst system according to claim 22, wherein the molar ratio of titanium in the solid catalyst component to aluminum in the alkyl aluminum compound is 1: (5-1000).
40. The catalyst system according to claim 39, wherein the molar ratio of titanium in the solid catalyst component to aluminum in the alkyl aluminum compound is 1: (20-500).
41. The catalyst system according to claim 26, wherein the molar ratio of titanium in the solid catalyst component to aluminum in the alkyl aluminum compound is 1: (5-1000).
42. The catalyst system according to claim 41, wherein the molar ratio of titanium in the solid catalyst component to aluminum in the alkyl aluminum compound is 1: (20-500).
43. The catalyst system of any one of claims 1-3, 6-12, 14-21, 23-25, 27-30, 32-42, wherein the molar ratio of the external electron donor to aluminum in the alkylaluminum compound is 1: (0.1-200).
44. The catalyst system of claim 43, wherein the molar ratio of the external electron donor to aluminum in the alkyl aluminum compound is 1: (1-100).
45. The catalyst system according to claim 4, wherein the molar ratio of the external electron donor to the aluminium in the alkylaluminium compound is 1: (0.1-200).
46. The catalyst system of claim 45, wherein the molar ratio of the external electron donor to aluminum in the alkyl aluminum compound is 1: (1-100).
47. The catalyst system according to claim 5, wherein the molar ratio of the external electron donor to the aluminum in the alkylaluminum compound is 1: (0.1-200).
48. The catalyst system of claim 47, wherein the molar ratio of the external electron donor to aluminum in the alkyl aluminum compound is 1: (1-100).
49. The catalyst system of claim 13, wherein the molar ratio of the external electron donor to aluminum in the alkyl aluminum compound is 1: (0.1-200).
50. The catalyst system of claim 49, wherein the molar ratio of the external electron donor to aluminum in the alkyl aluminum compound is 1: (1-100).
51. The catalyst system of claim 22, wherein the molar ratio of the external electron donor to aluminum in the alkyl aluminum compound is 1: (0.1-200).
52. The catalyst system of claim 51, wherein the molar ratio of the external electron donor to aluminum in the alkyl aluminum compound is 1: (1-100).
53. The catalyst system of claim 26, wherein the molar ratio of the external electron donor to aluminum in the alkyl aluminum compound is 1: (0.1-200).
54. The catalyst system of claim 53, wherein the molar ratio of the external electron donor to aluminum in the alkyl aluminum compound is 1: (1-100).
55. The catalyst system of claim 31, wherein the molar ratio of the external electron donor to aluminum in the alkyl aluminum compound is 1: (0.1-200).
56. The catalyst system of claim 55, wherein the molar ratio of the external electron donor to aluminum in the alkylaluminum compound is 1: (1-100).
57. A prepolymerized catalyst composition for the polymerization of olefins comprising a prepolymer obtained by polymerizing olefins using the catalyst system according to any of claims 1 to 56;
wherein the pre-polymerization multiple of the prepolymer is 0.1 to 1000g of olefin polymer per g of the solid catalyst component.
58. Use of the catalyst system of any one of claims 1 to 56 and/or the prepolymerized catalyst composition of claim 57 in the polymerization of olefins.
59. A process for the polymerization of olefins, the process comprising: contacting one or more olefins with the catalyst system of any of claims 1 to 56 and/or the prepolymerized catalyst composition of claim 57 under olefin polymerization conditions.
60. The process of claim 59, wherein the olefin is propylene.
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