CN116003656B - External electron donor composition, ziegler-Natta catalyst composition and propylene polymerization process - Google Patents

External electron donor composition, ziegler-Natta catalyst composition and propylene polymerization process Download PDF

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CN116003656B
CN116003656B CN202211711360.3A CN202211711360A CN116003656B CN 116003656 B CN116003656 B CN 116003656B CN 202211711360 A CN202211711360 A CN 202211711360A CN 116003656 B CN116003656 B CN 116003656B
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electron donor
external electron
catalyst
composition
ziegler
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CN116003656A (en
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常贺飞
霍晓剑
毛满意
邓国伟
常思乔
白雪琴
武卫华
熊丽霞
任家君
李春光
黄艳刚
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Hubei Huabang Chemical Co ltd
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Abstract

The application relates to the technical field of propylene polymerization catalysis, in particular to an external electron donor composition, a Ziegler-Natta catalyst composition and a propylene polymerization method. The external electron donor composition is formed by a halogenated ether compound shown in a formula I and a C 1～C10 alkoxy silane compound according to a molar ratio of 1:99-99:1, and the Ziegler-Natta catalyst composition formed by the external electron donor composition can be applied to propylene polymerization, so that the stereospecificity of the catalyst and the isotacticity of polypropylene can be greatly improved, and the polymerization activity and the hydrogen sensitivity of the catalyst can be also improved.

Description

External electron donor composition, ziegler-Natta catalyst composition and propylene polymerization process
Technical Field
The application relates to the technical field of propylene polymerization catalysis, in particular to an external electron donor composition, a Ziegler-Natta catalyst composition and a propylene polymerization method.
Background
At present, the catalyst used in the industrial polypropylene device is mainly a MgCl 2 supported Ziegler-Natta catalyst, and because the catalyst contains diester internal electron donor, the catalyst needs to be matched with external electron donor to improve the activity and the stereoregularity of the catalyst during propylene polymerization. The main function of the external electron donor is to adjust the isotacticity of polypropylene, and in addition, the addition of the external electron donor also has a certain influence on the performances of the catalyst, such as hydrogen sensitivity, catalyst activity and the like. In the prior art, in addition to the catalyst and the cocatalyst aluminum alkyl, an appropriate amount of external electron donor is usually added in the production process to realize balance between polymerization activity and polypropylene isotacticity. To date, it has been difficult for industry to increase the polymerization activity of olefins, especially propylene, by changing the composition of the external electron donor, by simply adding a small amount of a silane compound for production.
The prior art shows that the addition of the external electron donor mainly improves the isotacticity (namely the stereospecificity of the catalyst) of the polypropylene, but has limited improvement on the activity and hydrogen sensitivity of the catalyst.
Disclosure of Invention
The inventor of the present application has found that, by using a combination of an alkoxysilane and a halogenated ether compound as an external electron donor, not only the stereoregularity of the catalyst and the isotacticity of polypropylene can be greatly improved, but also the polymerization activity and hydrogen sensitivity of the catalyst can be improved. Therefore, the embodiment of the application at least discloses the following technical scheme:
in a first aspect, the embodiment of the application discloses an external electron donor composition of a Ziegler-Natta catalyst for propylene polymerization, which comprises a first external electron donor and a second external electron donor, wherein the molar ratio of the first external electron donor to the second external electron donor is 1:99-99:1; wherein,
The first external electron donor is a halogenated ether compound with a-C-O-C-ether functional group, and the second external electron donor is a C1-C10 alkoxy silane compound;
The first external electron donor is selected from compounds shown in a formula I;
in formula I, at least one R is independently selected from the group consisting of halomethyl, haloethyl, halopropyl, haloisopropyl, halobutyl, haloisobutyl, halosec-butyl, and halotert-butyl.
In a second aspect, embodiments of the present application disclose a Ziegler-Natta catalyst composition for propylene polymerization comprising:
A carrier selected from magnesium chloride and/or magnesium ethoxide;
a first catalyst selected from titanium tetrachloride and/or titanium trichloride;
the internal electron donor is a mixture of 1, 3-diether and aromatic acid ester;
The second catalyst is aluminum alkyl;
the external electron donor composition of the first aspect;
In the Ziegler-Natta catalyst composition for propylene polymerization, the molar ratio of aluminum to titanium element is 10-1200, and the molar ratio of silicon to titanium element is 2-50.
In a third aspect, embodiments of the present application disclose a process for polymerizing propylene in the presence of hydrogen using the Ziegler-Natta catalyst composition of the second aspect to catalyze the polymerization of propylene.
Specific technical effects of the external electron donor composition, the Ziegler-Natta catalyst composition and the propylene polymerization method provided in the embodiments of the present application will be described in detail in the examples.
Detailed Description
In order to make the objects, technical solutions and advantages of the present application more apparent, the present application will be described in further detail with reference to the following examples. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the application. The reagents not specifically and individually described in the present application are all conventional reagents and are commercially available; methods which are not specifically described in detail are all routine experimental methods and are known from the prior art.
It should be noted that, the terms "first," "second," and the like in the description and the claims of the present application are used for distinguishing between similar objects and not necessarily for describing a particular sequential or chronological order, and are not intended to limit the essential characteristics thereof. It is to be understood that the data so used may be interchanged where appropriate such that the embodiments of the application described herein may be implemented in sequences other than those described herein. Furthermore, the terms "comprises," "comprising," and "having," and any variations thereof, are intended to cover a non-exclusive inclusion, such that a process, method, system, article, or apparatus that comprises a list of steps or elements is not necessarily limited to those steps or elements expressly listed but may include other steps or elements not expressly listed or inherent to such process, method, article, or apparatus.
In one embodiment of the application, an external electron donor composition of a Ziegler-Natta catalyst for propylene polymerization is provided, comprising a first external electron donor and a second external electron donor, wherein the molar ratio of the first external electron donor to the second external electron donor is 1:99-99:1; wherein,
The first external electron donor is a halogenated ether compound with a-C-O-C-ether functional group, and the second external electron donor is a C1-C10 alkoxy silane compound;
The first external electron donor is selected from compounds shown in a formula I;
in formula I, at least one R is independently selected from the group consisting of halomethyl, haloethyl, halopropyl, haloisopropyl, halobutyl, haloisobutyl, halosec-butyl, and halotert-butyl.
Wherein halogen such as fluorine, chlorine, bromine or iodine, the number of atoms of the "halo" is 1 to 2.
In some embodiments, the first external electron donor is selected from one of bromomethyl ether, 2-bromoethyl methyl ether, isopropyl-2-bromoethyl ether, 2-dichloroethyl ether, 2-chloroethyl propyl ether, dichloroisopropyl ether, 2-chloroethyl n-butyl ether, or tert-butyl chloromethyl ether.
In some embodiments, the second external electron donor is selected from the group consisting of cyclohexylmethyldimethoxy silane, dicyclopentyl dimethoxy silane, diisobutyldimethoxy silane, diisopropyldimethoxy silane, dicyclohexyldimethoxy silane, di-tert-butyldimethoxy silane, ethylcyclohexyldimethoxy silane, diphenyldimethoxy silane, di-n-propyldimethoxy silane, di-n-butyldimethoxy silane, cyclopentyltrimethoxy silane, n-propyltrimethoxy silane, isopropyltrimethoxy silane, n-propyltriethoxy silane, isopropyltriethoxy silane, tetraethoxy silane, tetramethoxy silane, cyclopentylpyrrole dimethoxy silane, dipyrrole dimethoxy silane, or bisperhydroisoquinoline dimethoxy silane.
In the application, when the first external electron donor or the second external electron donor is respectively used as the external electron donor to construct a catalytic system to catalyze and synthesize polypropylene, the obtained polypropylene has poorer prescribing properties than the case of combining the first external electron donor and the second external electron donor. And when the second external electron donor is independently used as the external electron donor in the propylene polymerization reaction process, the polymerization reaction is easy to generate larger static fluctuation, at least polymer agglomeration is generated, or the polymerization reaction temperature is too high, so that the reaction is not controlled. In view of this, the present application adopts the combination of the first external electron donor and the second external electron donor, which enables directional control of the catalyst activity and easy control of the reaction temperature, thereby enabling the obtained polymer to have higher isotropicity. And moreover, by adopting the combination of the first external electron donor and the second external electron donor, the electrostatic fluctuation of the reaction can be reduced, the reaction is more stable, the reaction can be controlled at a lower temperature, the energy is saved, and the production rate and the utilization efficiency of the catalyst can be improved.
In addition, the applicant has surprisingly found that when the molar ratio of the first external electron donor to the second external electron donor is between 35:65 and 65:35, it is more advantageous to improve the regulation properties of the obtained polypropylene and the like, and to prevent the polymerization temperature fluctuation and the static fluctuation, improve the control over the reaction process, and provide the production rate and the utilization efficiency of the catalyst.
In one embodiment, a Ziegler-Natta catalyst composition for propylene polymerization is provided comprising:
A carrier selected from magnesium chloride and/or magnesium ethoxide;
a first catalyst selected from titanium tetrachloride and/or titanium trichloride;
An internal electron donor selected from the group consisting of diisobutyl phthalate, di-n-butyl 2-isopropyl malonate, diethyl 2-methyl-2-isopropyl malonate, diisobutyl diisopropyl succinate, 2, 3-diisopropyl succinic acid and mixtures thereof;
The second catalyst is aluminum alkyl;
The external electron donor composition as provided in the above embodiment;
In the Ziegler-Natta catalyst composition for propylene polymerization, the molar ratio of aluminum to titanium element is 10-1200, and the molar ratio of silicon to titanium element is 2-50.
In some embodiments, the carrier comprises magnesium chloride and magnesium ethoxide in a molar ratio of 1:99 to 99:1; the first catalyst comprises titanium tetrachloride and titanium trichloride, and the molar ratio of the titanium tetrachloride to the titanium trichloride is 1:99-99:1; the alkyl aluminum is selected from one or two of triethyl aluminum and triisobutyl aluminum.
In one embodiment, a process for polymerizing propylene is provided for catalyzing the polymerization of propylene in the presence of hydrogen using the Ziegler-Natta catalyst composition provided in the previous embodiment.
In some embodiments, the polymerization process of propylene comprises:
Adding propylene monomer, the carrier, the first catalyst, the internal electron donor, the second catalyst and the external electron donor composition into a reaction system respectively or simultaneously in the presence of hydrogen; and
And extracting polypropylene from the reaction system.
In some embodiments, the second external electron donor is added at the beginning of the reaction, and the first external electron donor is present at the time of: polymer agglomeration occurs during the polymerization reaction and/or the polymerization temperature is too high during the polymerization reaction; is added in the case of (2). In some embodiments, the second external electron donor is added at the beginning of the reaction, and the first external electron donor is added to the reaction system in batch form. Thus, the static fluctuation and the temperature fluctuation of the reaction can be reduced, the polymerization reaction is stable and is convenient to control, meanwhile, the agglomeration of the polymer can be reduced, and the reaction efficiency and the catalyst utilization rate are improved.
In some embodiments, the carrier, the first catalyst, and the internal electron donor are first processed to prepare a solid component, and the solid component, the second catalyst, the first external electron donor, and the second external electron donor are individually packaged, stored, and shipped, respectively; and
The solid component, the second catalyst, the first external electron donor and the second external electron donor are used in a polymerization reaction by being individually packaged.
The application is further described below with reference to examples. It should be noted that the following examples should not be construed as limiting the scope of the application, and any modifications made thereto do not depart from the spirit of the application.
Example 1
The present embodiment provides an external electron donor composition for a ziegler-natta catalyst for propylene polymerization, comprising: the first external electron donor is bromomethyl ether, the second external electron donor is cyclohexylmethyl dimethoxy silane, and the external electron donor composition comprises 35mol percent of bromomethyl ether and 65mol percent of cyclohexylmethyl dimethoxy silane.
The embodiment provides a Ziegler-Natta catalyst composition for propylene polymerization, which comprises a carrier, a first catalyst, an internal electron donor, a second catalyst and an external electron donor composition, wherein the carrier is a composition of 5mol% of magnesium chloride and 95mol% of ethoxymagnesium, the first catalyst is titanium tetrachloride and 75mol% of titanium trichloride in a mole ratio, the second catalyst is triethylaluminum, the internal electron donor is diisobutyl diisopropyl succinate, and the external electron donor composition is as described above.
A process for preparing a ziegler-natta catalyst composition for propylene polymerization:
1) Adding a first catalyst to the carrier under nitrogen protection conditions at-40 ℃;
2) Gradually heating to 50 ℃, adding an internal electron donor, then heating to 100 ℃, preserving heat for 1h, continuously heating to 150 ℃, stirring for 1h, and separating out solid particles;
3) The filtered solid particles are repeatedly and alternately washed by adopting a first catalyst and an inert diluent, and dried to obtain a solid component;
4) And 3) packaging, storing and transporting the solid component, the second catalyst, the first external electron donor and the second external electron donor obtained in the step 3) independently. During propylene polymerization, the Ziegler-Natta catalyst composition for propylene polymerization is formed by combining.
Propylene polymerization:
The autoclave was heated and evacuated to remove air and water, replaced with nitrogen, and repeated three times, and the solid component (3.38% Ti supported on MgCl 2 mg), the second catalyst (n (Al)/n (Ti) = 1011.2), the second external electron donor ((n (Si)/n (Ti) =28.7) were all added according to the above ratio while 50% by weight of the first external electron donor described in the above example was added, and then hydrogen (n (H2)/n (C3) =6.47 mmol/mol was introduced, and propylene was introduced again to make the total pressure in the autoclave 0.35MPa. The autoclave was closed, the autoclave temperature was raised to 70 ℃, polymerization was started, 10% of the remaining first external electron donor was added every 10 minutes, and after 2 hours of reaction, unreacted propylene was discharged to obtain polypropylene particles, and the properties of the catalyst and the particle size distribution results of the obtained polypropylene were shown in tables 1 and 2.
Example 2
The present embodiment provides an external electron donor composition for a ziegler-natta catalyst for propylene polymerization, comprising: the first external electron donor is 2-bromoethyl methyl ether, the second external electron donor is cyclohexylmethyl dimethoxy silane, and the external electron donor composition comprises 35mol percent of 2-bromoethyl methyl ether and 65mol percent of cyclohexylmethyl dimethoxy silane.
The present example provides a Ziegler-Natta catalyst composition for propylene polymerization comprising a support, a first catalyst, an internal electron donor, a second catalyst and an external electron donor composition. Wherein the carrier is a composition of 5mol percent magnesium chloride and 95mol percent ethoxymagnesium, the first catalyst is titanium tetrachloride and titanium trichloride with the mol percent of 25mol percent and 75mol percent, the second catalyst is triethylaluminum, the internal electron donor is diisobutyl diisopropyl succinate, and the external electron donor composition is as described above.
The Ziegler-Natta catalyst composition for propylene polymerization and propylene polymerization were the same as in example 1.
Example 3
The present embodiment provides an external electron donor composition for a ziegler-natta catalyst for propylene polymerization, comprising: the first external electron donor is isopropyl-2-bromoethyl ether, the second external electron donor is cyclohexylmethyl dimethoxy silane, and the external electron donor composition comprises 35mol percent of isopropyl-2-bromoethyl ether and 65mol percent of cyclohexylmethyl dimethoxy silane.
The present example provides a Ziegler-Natta catalyst composition for propylene polymerization comprising a support, a first catalyst, an internal electron donor, a second catalyst and an external electron donor composition. Wherein the carrier is a composition of 5mol percent magnesium chloride and 95mol percent ethoxymagnesium, the first catalyst is titanium tetrachloride and titanium trichloride with the mol percent of 25mol percent and 75mol percent, the second catalyst is triethylaluminum, the internal electron donor is diisobutyl diisopropyl succinate, and the external electron donor composition is as described above.
The Ziegler-Natta catalyst composition for propylene polymerization and propylene polymerization were the same as in example 1.
Example 4
The present embodiment provides an external electron donor composition for a ziegler-natta catalyst for propylene polymerization, comprising: the first external electron donor is 2, 2-dichloroethyl ether, the second external electron donor is cyclohexylmethyldimethoxy silane, and the external electron donor composition comprises 35mol percent of 2, 2-dichloroethyl ether and 65mol percent of cyclohexylmethyldimethoxy silane.
The present example provides a Ziegler-Natta catalyst composition for propylene polymerization comprising a support, a first catalyst, an internal electron donor, a second catalyst and an external electron donor composition. Wherein the carrier is a composition of 5mol percent magnesium chloride and 95mol percent ethoxymagnesium, the first catalyst is titanium tetrachloride and titanium trichloride with the mol percent of 25mol percent and 75mol percent, the second catalyst is triethylaluminum, the internal electron donor is diisobutyl diisopropyl succinate, and the external electron donor composition is as described above.
The Ziegler-Natta catalyst composition for propylene polymerization and propylene polymerization were the same as in example 1.
Example 5
The present embodiment provides an external electron donor composition for a ziegler-natta catalyst for propylene polymerization, comprising: the first external electron donor is 2-chloroethyl propyl ether, the second external electron donor is cyclohexylmethyl dimethoxy silane, and the external electron donor composition comprises 35mol percent of 2-chloroethyl propyl ether and 65mol percent of cyclohexylmethyl dimethoxy silane.
The present example provides a Ziegler-Natta catalyst composition for propylene polymerization comprising a support, a first catalyst, an internal electron donor, a second catalyst and an external electron donor composition. Wherein the carrier is a composition of 5mol percent magnesium chloride and 95mol percent ethoxymagnesium, the first catalyst is titanium tetrachloride and titanium trichloride with the mol percent of 25mol percent and 75mol percent, the second catalyst is triethylaluminum, the internal electron donor is diisobutyl diisopropyl succinate, and the external electron donor composition is as described above.
The Ziegler-Natta catalyst composition for propylene polymerization and propylene polymerization were the same as in example 1.
Example 6
The present embodiment provides an external electron donor composition for a ziegler-natta catalyst for propylene polymerization, comprising: the first external electron donor is dichloroisopropyl ether, the second external electron donor is cyclohexylmethyl dimethoxy silane, and the external electron donor composition comprises 35mol percent of dichloroisopropyl ether and 65mol percent of cyclohexylmethyl dimethoxy silane.
The present example provides a Ziegler-Natta catalyst composition for propylene polymerization comprising a support, a first catalyst, an internal electron donor, a second catalyst and an external electron donor composition. Wherein the carrier is a composition of 5mol percent magnesium chloride and 95mol percent ethoxymagnesium, the first catalyst is titanium tetrachloride and titanium trichloride with the mol percent of 25mol percent and 75mol percent, the second catalyst is triethylaluminum, the internal electron donor is diisobutyl diisopropyl succinate, and the external electron donor composition is as described above.
The Ziegler-Natta catalyst composition for propylene polymerization and propylene polymerization were the same as in example 1.
Example 7
The present embodiment provides an external electron donor composition for a ziegler-natta catalyst for propylene polymerization, comprising: the first external electron donor is 2-chloroethyl n-butyl ether, the second external electron donor is cyclohexylmethyl dimethoxy silane, and the external electron donor composition comprises 35mol percent of 2-chloroethyl n-butyl ether and 65mol percent of cyclohexylmethyl dimethoxy silane.
The present example provides a Ziegler-Natta catalyst composition for propylene polymerization comprising a support, a first catalyst, an internal electron donor, a second catalyst and an external electron donor composition. Wherein the carrier is a composition of 5mol percent magnesium chloride and 95mol percent ethoxymagnesium, the first catalyst is titanium tetrachloride and titanium trichloride with the mol percent of 25mol percent and 75mol percent, the second catalyst is triethylaluminum, the internal electron donor is diisobutyl diisopropyl succinate, and the external electron donor composition is as described above.
The Ziegler-Natta catalyst composition for propylene polymerization and propylene polymerization were the same as in example 1.
Example 8
The present embodiment provides an external electron donor composition for a ziegler-natta catalyst for propylene polymerization, comprising: the first external electron donor is tert-butyl chloromethyl ether, the second external electron donor is cyclohexylmethyl dimethoxy silane, and the external electron donor composition comprises 35mol percent of tert-butyl chloromethyl ether and 65mol percent of cyclohexylmethyl dimethoxy silane.
The present example provides a Ziegler-Natta catalyst composition for propylene polymerization comprising a support, a first catalyst, an internal electron donor, a second catalyst and an external electron donor composition. Wherein the carrier is a composition of 5mol percent magnesium chloride and 95mol percent ethoxymagnesium, the first catalyst is titanium tetrachloride and titanium trichloride with the mol percent of 25mol percent and 75mol percent, the second catalyst is triethylaluminum, the internal electron donor is diisobutyl diisopropyl succinate, and the external electron donor composition is as described above.
The Ziegler-Natta catalyst composition for propylene polymerization and propylene polymerization were the same as in example 1.
Example 9
The present embodiment provides an external electron donor composition for a ziegler-natta catalyst for propylene polymerization, comprising: the first external electron donor is dichloroisopropyl ether, the second external electron donor is cyclohexylmethyl dimethoxy silane, and the external electron donor composition comprises 55mol percent of dichloroisopropyl ether and 45mol percent of cyclohexylmethyl dimethoxy silane.
The present example provides a Ziegler-Natta catalyst composition for propylene polymerization comprising a support, a first catalyst, an internal electron donor, a second catalyst and an external electron donor composition. Wherein the carrier is a composition of 5mol percent magnesium chloride and 95mol percent ethoxymagnesium, the first catalyst is titanium tetrachloride and titanium trichloride with the mol percent of 25mol percent and 75mol percent, the second catalyst is triethylaluminum, the internal electron donor is diisobutyl diisopropyl succinate, and the external electron donor composition is as described above.
The Ziegler-Natta catalyst composition for propylene polymerization and propylene polymerization were the same as in example 1.
Example 10
The present embodiment provides an external electron donor composition for a ziegler-natta catalyst for propylene polymerization, comprising: the first external electron donor is dichloroisopropyl ether, the second external electron donor is cyclohexylmethyl dimethoxy silane, and the external electron donor composition comprises 65mol percent of dichloroisopropyl ether and 35mol percent of cyclohexylmethyl dimethoxy silane.
The present example provides a Ziegler-Natta catalyst composition for propylene polymerization comprising a support, a first catalyst, an internal electron donor, a second catalyst and an external electron donor composition. Wherein the carrier is a composition of 5mol percent magnesium chloride and 95mol percent ethoxymagnesium, the first catalyst is titanium tetrachloride and titanium trichloride with the mol percent of 25mol percent and 75mol percent, the second catalyst is triethylaluminum, the internal electron donor is diisobutyl diisopropyl succinate, and the external electron donor composition is as described above.
The Ziegler-Natta catalyst composition for propylene polymerization and propylene polymerization were the same as in example 1.
Example 11
The present embodiment provides an external electron donor composition for a ziegler-natta catalyst for propylene polymerization, comprising: the first external electron donor is dichloroisopropyl ether, the second external electron donor is cyclohexylmethyl dimethoxy silane, and the external electron donor composition comprises 65mol percent of dichloroisopropyl ether and 35mol percent of cyclohexylmethyl dimethoxy silane.
The present example provides a Ziegler-Natta catalyst composition for propylene polymerization comprising a support, a first catalyst, an internal electron donor, a second catalyst and an external electron donor composition. Wherein the carrier is a composition of 5mol percent magnesium chloride and 95mol percent ethoxymagnesium, the first catalyst is titanium tetrachloride and titanium trichloride with the mol percent of 25mol percent and 75mol percent, the second catalyst is triethylaluminum, the internal electron donor is diisobutyl diisopropyl succinate, and the external electron donor composition is as described above.
The Ziegler-Natta catalyst composition for propylene polymerization and propylene polymerization were the same as in example 1. Wherein the addition amount of the second external electron donor is n (Si)/n (Ti) =10.
Example 12
The present embodiment provides an external electron donor composition for a ziegler-natta catalyst for propylene polymerization, comprising: the first external electron donor is dichloroisopropyl ether, the second external electron donor is cyclohexylmethyl dimethoxy silane, and the external electron donor composition comprises 65mol percent of dichloroisopropyl ether and 35mol percent of cyclohexylmethyl dimethoxy silane.
The present example provides a Ziegler-Natta catalyst composition for propylene polymerization comprising a support, a first catalyst, an internal electron donor, a second catalyst and an external electron donor composition. Wherein the carrier is a composition of 5mol percent magnesium chloride and 95mol percent ethoxymagnesium, the first catalyst is titanium tetrachloride and titanium trichloride with the mol percent of 25mol percent and 75mol percent, the second catalyst is triethylaluminum, the internal electron donor is diisobutyl diisopropyl succinate, and the external electron donor composition is as described above.
The Ziegler-Natta catalyst composition for propylene polymerization and propylene polymerization were the same as in example 1. Wherein the addition amount of the second external electron donor is n (Si)/n (Ti) =50.
Example 13
The present embodiment provides an external electron donor composition for a ziegler-natta catalyst for propylene polymerization, comprising: the first external electron donor is dichloroisopropyl ether and 2, 2-dichloroethyl ether, the second external electron donor is cyclohexylmethyl dimethoxy silane, and the external electron donor composition comprises 45mol percent of dichloroisopropyl ether, 20mol percent of 2, 2-dichloroethyl ether and 35mol percent of cyclohexylmethyl dimethoxy silane.
The present example provides a Ziegler-Natta catalyst composition for propylene polymerization comprising a support, a first catalyst, an internal electron donor, a second catalyst and an external electron donor composition. Wherein the carrier is a composition of 5mol percent magnesium chloride and 95mol percent ethoxymagnesium, the first catalyst is titanium tetrachloride and titanium trichloride with the mol percent of 25mol percent and 75mol percent, the second catalyst is triethylaluminum, the internal electron donor is diisobutyl diisopropyl succinate, and the external electron donor composition is as described above.
The Ziegler-Natta catalyst composition for propylene polymerization and propylene polymerization were the same as in example 1.
Comparative example 1
This comparative example provides an external electron donor composition for a ziegler-natta catalyst for propylene polymerization, said external electron donor composition comprising only bromomethyl methyl ether.
This comparative example provides a ziegler-natta catalyst composition for propylene polymerization comprising a support, a first catalyst, an internal electron donor, a second catalyst, and an external electron donor composition. Wherein the carrier is a composition of 5mol percent magnesium chloride and 95mol percent ethoxymagnesium, the first catalyst is titanium tetrachloride and titanium trichloride with the mol percent of 25mol percent and 75mol percent, the second catalyst is triethylaluminum, the internal electron donor is diisobutyl diisopropyl succinate, and the external electron donor composition is as described above.
A process for preparing a ziegler-natta catalyst composition for propylene polymerization:
1) Adding a first catalyst to the carrier under nitrogen protection conditions at-40 ℃;
2) Gradually heating to 50 ℃, adding an internal electron donor, then heating to 100 ℃, preserving heat for 1h, continuously heating to 150 ℃, stirring for 1h, and separating out solid particles;
3) The filtered solid particles are repeatedly and alternately washed by adopting a first catalyst and an inert diluent, and dried to obtain a solid component;
4) And (3) packaging the solid component obtained in the step (3), the second catalyst and the external electron donor respectively and independently, storing and transporting. During propylene polymerization, the Ziegler-Natta catalyst composition for propylene polymerization is formed by combining.
Propylene polymerization:
the autoclave was heated and evacuated to remove air and water, replaced with nitrogen gas, repeated three times, and the solid component (3.38% Ti supported on MgCl 2 mg), the second catalyst (n (Al)/n (Ti) = 1011.2), the external electron donor ((n (-O-)/n (Ti) =28.7), i.e., the molar ratio of ether bond to titanium was 28.7) were all added according to the above ratio, and then hydrogen gas (n (H2)/n (C3) =6.47 mmol/mol was introduced, and propylene was introduced to make the total pressure in the autoclave 0.35MPa. The autoclave was closed, the autoclave temperature was raised to 70 ℃ and after 2 hours of reaction, unreacted propylene was discharged to obtain polypropylene particles, and the properties of the catalyst and the particle size distribution results of the obtained polypropylene were shown in tables 1 and 2.
Comparative example 2
This comparative example provides an external electron donor composition for a ziegler-natta catalyst for propylene polymerization, said external electron donor composition comprising only 2-bromoethyl methyl ether.
The Ziegler-Natta catalyst composition for propylene polymerization and propylene polymerization comparative example 1.
Comparative example 3
This comparative example provides an external electron donor composition for a Ziegler-Natta catalyst for propylene polymerization, comprising only isopropyl-2-bromoethyl ether.
The Ziegler-Natta catalyst composition for propylene polymerization and propylene polymerization comparative example 1.
Comparative example 4
This comparative example provides an external electron donor composition for a Ziegler-Natta catalyst for propylene polymerization comprising only 2, 2-dichloroethyl ether.
The Ziegler-Natta catalyst composition for propylene polymerization and propylene polymerization comparative example 1.
Comparative example 5
This comparative example provides an external electron donor composition for a Ziegler-Natta catalyst for propylene polymerization comprising only 2-chloroethyl propyl ether.
The Ziegler-Natta catalyst composition for propylene polymerization and propylene polymerization comparative example 1.
Comparative example 6
This comparative example provides an external electron donor composition for a ziegler-natta catalyst for propylene polymerization, said external electron donor composition comprising only dichloroisopropyl ether.
The Ziegler-Natta catalyst composition for propylene polymerization and propylene polymerization comparative example 1.
Comparative example 7
This comparative example provides an external electron donor composition for a Ziegler-Natta catalyst for propylene polymerization comprising only 2-chloroethyl n-butyl ether.
The Ziegler-Natta catalyst composition for propylene polymerization and propylene polymerization comparative example 1.
Comparative example 8
This comparative example provides an external electron donor composition for a ziegler-natta catalyst for propylene polymerization comprising only t-butyl chloromethyl ether.
The Ziegler-Natta catalyst composition for propylene polymerization and propylene polymerization comparative example 1.
Comparative example 9
This comparative example provides an external electron donor composition for a ziegler-natta catalyst for propylene polymerization comprising only cyclohexylmethyldimethoxysilane.
The Ziegler-Natta catalyst composition for propylene polymerization and propylene polymerization comparative example 1.
Table 1 shows the properties of the Ziegler-Natta catalyst compositions for propylene polymerization provided in examples 1 to 12 and comparative examples 1 to 9, respectively, wherein:
the polymerization activity in KgPP/(gcat.h) was calculated as follows:
Polymerization Activity = yield of polymer (Kg/h)/catalyst (Cat. G)
The melt index (MFR) of the polypropylene was determined according to test Standard ASTM D1238, test conditions being 2.16Kg,230℃and melt index in g/10min.
Degree of isotacticity: according to GB/T2546.1-2006, n-heptane extraction method is used for measurement, a Soxhlet extractor is used, about 2g of polypropylene sample is placed in the Soxhlet extractor, boiling heptane is used for extraction for 6 hours, the residual polypropylene is dried to constant weight, and the ratio of the residual polypropylene to the polypropylene added for the first time is isotacticity.
The electrostatic fluctuation is detected by adopting an electrostatic probe connected to the reaction kettle and an electrostatic detector connected with the electrostatic probe, and the method is concretely referred to the "Unipol polypropylene process reactor electrostatic fluctuation analysis and treatment [ J ] plastics industry, volume 50, 3 rd phase".
The temperature fluctuation detection is carried out by adopting a temperature probe connected to the reaction kettle and a temperature detector connected with the temperature probe.
As can be seen from Table 1, the activity of the catalyst in the examples of the present application is higher than that in the comparative examples, the electrostatic fluctuation value DeltaV in the reaction vessel is less than 20V, the temperature fluctuation value DeltaT is less than 5 ℃, and the reaction vessel is free of PP sticking material after detection.
Table 1 shows that each of comparative examples 1 to 9 uses either the first external donor or the second external donor alone as the external donor in the Ziegler-Natta catalyst composition for propylene polymerization, so that the isotacticity and melt index of the produced polypropylene are relatively low, as compared with example 6; particularly, the static fluctuation value and the temperature fluctuation value in the reaction kettle are increased, and meanwhile, polymer agglomeration exists in the reaction kettle, so that the extraction of reactants is inconvenient.
As can be seen from table 1, the catalyst composition according to example 13 was used to prepare polypropylene having high isotacticity and melt index, and had high polymerization activity, and the effect of suppressing static electricity was most remarkable, and the reaction temperature was stable and the reaction process was stable.
TABLE 1 physical Properties of Ziegler-Natta catalyst compositions for propylene polymerization
Further, the relative molecular mass of the Polymer and its distribution index were measured by using a gel permeation chromatograph PL-GPC220 of Polymer lab, UK, 1,2, 4-trichlorobenzene as a solvent, a flow rate of 1.0mL/min, a mass concentration of 1mg/mL, and polystyrene as a standard. The fractions of the polymer particles were sieved with a standard sieve, then weighed separately and the mass fractions of the fractions were calculated to obtain the particle size distribution. Bulk density was measured by reference to ASTM D1895-1969.
As shown in Table 2, the polymer bulk densities provided by examples 1 to 13 of the present application were higher than those of comparative examples 1 to 9 and the weight average molecular weights were also higher than those of comparative examples 1 to 9, indicating that propylene polymerization using the Ziegler-Natta catalyst compositions provided by examples 1 to 13, respectively, could give polypropylene of a higher weight average molecular weight. And the molecular weight distribution index was lower than that of comparative examples 1 to 9, indicating that the polypropylene particles prepared in examples 1 to 13 were more concentrated in molecular weight and more concentrated in particle size, since the polymer particles exceeding 75 μm were also more than those of comparative examples 1 to 9.
In addition, as can be seen from tables 1 and 2, the catalyst composition provided in example 13 was used to obtain polypropylene having high isotacticity and melt index, high polymerization activity, most remarkable static suppression effect, and stable reaction temperature, compared with other examples, so that the polymer particles prepared were larger in molecular weight, more concentrated in molecular weight distribution, more regular in polymer particles, and higher in product quality.
TABLE 2 Polymer Properties
Comprehensive analysis shows that the embodiment 1-13 adopts the combination of the first external electron donor and the second external electron donor as the external electron donor in the Ziegler-Natta catalyst composition for olefin polymerization, has high polymerization activity, stable polymerization process, difficult generation of static fluctuation, difficult agglomeration and difficult wall hanging of a polymerization product, ensures long-term stable operation of polymerization production, and has the advantages of less polymer fine powder, moderate stacking density and reasonable particle size distribution. The catalyst system has wide application range and is suitable for propylene polymerization in various processes.
The present application is not limited to the above-mentioned embodiments, and any changes or substitutions that can be easily understood by those skilled in the art within the technical scope of the present application are intended to be included in the scope of the present application.

Claims (5)

1. A ziegler-natta catalyst composition for propylene polymerization comprising:
A carrier, the carrier being a composition of 5 mole percent magnesium chloride and 95 mole percent magnesium ethoxide;
A first catalyst which is a composition of 25 mole percent titanium tetrachloride and 75 mole percent titanium trichloride;
an internal electron donor which is diisobutyl diisopropyl succinate;
A second catalyst, wherein the second catalyst is triethylaluminum; and
An external electron donor composition;
wherein, in the Ziegler-Natta catalyst composition for propylene polymerization, the molar ratio of aluminum to titanium element is 10-1200, and the molar ratio of silicon to titanium element is 2-50;
wherein the external electron donor composition comprises a first external electron donor and a second external electron donor, and the molar ratio of the first external electron donor to the second external electron donor is 35:65 to 65:35; wherein,
The first external electron donor is selected from at least one of bromomethyl ether, 2-bromoethyl methyl ether, isopropyl-2-bromoethyl ether, 2-dichloroethyl ether, 2-chloroethyl propyl ether, dichloroisopropyl ether, 2-chloroethyl n-butyl ether or tert-butyl chloromethyl ether;
The second external electron donor is cyclohexylmethyl dimethoxy silane.
2. A process for the polymerization of propylene, characterized in that propylene is catalyzed by the ziegler-natta catalyst composition according to claim 1 in the presence of hydrogen.
3. The polymerization process of claim 2, comprising:
Adding propylene monomer, the carrier, the first catalyst, the internal electron donor, the second catalyst and the external electron donor composition into a reaction system respectively or simultaneously in the presence of hydrogen; and
And extracting polypropylene from the reaction system.
4. A polymerization process according to claim 3, wherein the second external electron donor is added at the beginning of the reaction, and the first external electron donor is added in the presence of "polymer agglomeration during the polymerization and/or too high a polymerization temperature during the polymerization"; or alternatively
The second external electron donor is added at the beginning of the reaction, and the first external electron donor is added to the reaction system in a batch form.
5. The polymerization process of claim 4, wherein the carrier, the first catalyst, the internal electron donor are first processed to prepare a solid component, and the solid component, the second catalyst, the first external electron donor, and the second external electron donor are individually packaged, stored, and shipped, respectively; and
The solid component, the second catalyst, the first external electron donor and the second external electron donor are used in a polymerization reaction by being individually packaged.
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