Internal electron donor, solid catalyst component, polymerization catalyst and application thereof

Abstract

The invention belongs to the technical field of olefin polymerization catalysts, and particularly relates to an internal electron donor, a solid catalyst component, a polymerization catalyst and application thereof in olefin polymerization. An internal electron donor of the olefin polymerization catalyst is selected from any one of compounds shown in the following structural general formula I, and R1-R11 are the same or different and are independently selected from H, halogen, C1-C10 alkyl, naphthenic base, alkenyl and phenyl, or halogenated alkyl or substituted by heteroatoms of N, O, S, P and Si, naphthenic base, phenyl, alkylphenyl, phenylalkyl, indenyl and benzyl; two or more of R1-R9 may be bonded to each other to form a ring or to each other to form an unsaturated bond; a polymerization catalyst prepared by using the compound provided by the invention as an internal electron donor of a Ziegler-Natta catalyst has the advantages of high activity and good hydrogen regulation sensitivity, and the obtained polymer has the advantages of high isotacticity, low xylene soluble substance content and wide molecular weight distribution. # imgabs0 #

Description

Technical Field

[0001] The present invention belongs to the technical field of olefin polymerization catalysts, and particularly relates to an internal electron donor, a solid catalyst component, a polymerization catalyst and their applications in olefin polymerization reactions. Background Art

[0002] As is well known, the Ziegler-Natta catalyst for olefin polymerization consists of three parts: a magnesium chloride carrier, an internal electron donor compound, and a titanium compound. The internal electron donor compound therein can not only improve the activity of the olefin polymerization catalyst, but also enhance the stereospecificity of the catalyst. Without the internal electron donor compound in the catalyst, its activity will be greatly reduced, and the polymer prepared therefrom will be unusable due to a low isotactic index.

[0003] So far, various compounds have been widely used as internal electron donors to prepare Ziegler-Natta catalysts. For example, aromatic mono-esters or di-esters such as diisobutyl phthalate or ethyl benzoate used in the patent document US4784983A, glycol esters used in the patent document CN1453298A, succinate esters used in the patent document CN1313869A, diethers used in the patent document EP361494A, 1,2-phenylene aromatic di-esters used in the patent document US61141902A, substituted amido-benzoate compounds used in the patent documents EP15186252A / CN108570120A, etc. are all used as internal electron donors.

[0004] In industrial production, each of these internal electron donor compounds has certain defects in practical applications. For example, phthalate compounds, as plasticizer substances, have received increasing attention for their potential harm to human health, which also limits their use in Ziegler-Natta catalysts; catalysts using aromatic di-ester compounds as internal electron donors have relatively low catalytic activity; catalysts using diether compounds as internal electron donors, although having relatively high catalytic activity and good hydrogen response sensitivity, have a narrow relative molecular mass distribution of the resulting polymer; catalysts using 1,2-phenylene aromatic di-ester compounds as internal electron donors have good catalytic activity and hydrogen response sensitivity, but the xylene-soluble matter of the resulting polymer is relatively high; catalysts using substituted amido-benzoate compounds as internal electron donors have relatively low activity and high xylene-soluble matter.

[0005] Precisely because of the importance of the internal electron donor compound in the catalyst and some deficiencies of the current internal electron donor compounds in practical applications, the improvement of internal electron donor compounds has always been a research hotspot in this field.

[0006] Therefore, it is of great significance to develop a new catalyst for olefin polymerization that can overcome the above-mentioned defects of the prior art. SUMMARY OF THE INVENTION

[0007] In view of the above problems existing in the prior art, the object of the present invention is to provide an internal electron donor for an olefin polymerization catalyst, a solid catalyst component, an olefin polymerization catalyst and its application; the polymerization catalyst prepared by using this novel compound as the internal electron donor of the Ziegler-Natta catalyst has the advantages of high activity and good hydrogen response sensitivity, and the polymer obtained by using this polymerization catalyst for olefin polymerization has the characteristics of high isotacticity, relatively low xylene-soluble content and wide molecular weight distribution.

[0008] To achieve the above object, the present invention provides the following technical solutions:

[0009] In a first aspect, an internal electron donor for an olefin polymerization catalyst is provided, and the internal electron donor is selected from at least one of the compounds represented by the following general structural formula I:

[0010]

[0011] In formula I:

[0012] R1-R9 are the same or different, and each independently selected from H, halogen, saturated or unsaturated C1-C10 straight-chain alkyl or branched-chain alkyl, cycloalkyl, alkenyl, ester group, phenyl, alkylphenyl, phenylalkyl, indenyl, benzyl, halogenated or alkyl, cycloalkyl, phenyl, alkylphenyl, phenylalkyl, indenyl, benzyl substituted by N, O, S, P, Si heteroatoms; or selected from heteroaryl; and two or more of R1-R9 can be bonded to each other to form a ring or an unsaturated bond;

[0013] R 10 -R 11 are the same or different, and each independently selected from H, halogen, saturated or unsaturated C1-C10 straight-chain alkyl or branched-chain alkyl, cycloalkyl, alkenyl, ester group, phenyl, alkylphenyl, phenylalkyl, indenyl, benzyl, halogenated or alkyl, cycloalkyl, phenyl, alkylphenyl, phenylalkyl, indenyl, benzyl substituted by N, O, S, P, Si heteroatoms; or selected from heteroaryl;

[0014] In the above aryl, aralkyl or alkaryl, the hydrogen on the benzene ring can be optionally substituted by a halogen atom.

[0015] In some embodiments, in formula I, R 10 -R 11 are each independently phenyl, tert-butyl, ethoxy.

[0016] In some embodiments, in Formula I, for R4 and R5, R6 and R7, R8 and R9, preferably R4, R6, and R8 are hydrogen.

[0017] According to the internal electron donor provided by the present invention, in some embodiments, the internal electron donor is selected from at least one of the compounds represented by the following general structural formula (II):

[0018]

[0019] In Formula (II):

[0020] R1-R6 are the same or different and each independently selected from H, halogen, saturated or unsaturated C1-C10 linear alkyl or branched alkyl, cycloalkyl, alkenyl, ester group, phenyl, alkylphenyl, phenylalkyl, indenyl, benzyl, halogenated or alkyl, cycloalkyl, phenyl, alkylphenyl, phenylalkyl, indenyl, benzyl substituted with N, O, S, P, Si heteroatoms; or selected from heteroaryl; two or more of R1-R6 may be bonded to each other to form a ring or an unsaturated bond;

[0021] R7-R8 are the same or different and each independently selected from H, halogen, saturated or unsaturated C1-C10 linear alkyl or branched alkyl, cycloalkyl, alkenyl, ester group, phenyl, alkylphenyl, phenylalkyl, indenyl, benzyl, halogenated or alkyl, cycloalkyl, phenyl, alkylphenyl, phenylalkyl, indenyl, benzyl substituted with N, O, S, P, Si heteroatoms; or selected from heteroaryl.

[0022] According to the internal electron donor provided by the present invention, in some embodiments, in Formula (II), R7-R8 are each independently selected from phenyl, tert-butyl or ethoxy.

[0023] In a second aspect, there is provided a solid catalyst component for olefin polymerization, which comprises: a titanium compound, a magnesium compound and at least one internal electron donor selected as described above.

[0024] In some embodiments, the preparation method of the solid catalyst component is: contacting and reacting a precursor of a magnesium compound, a titanium compound with at least one of the internal electron donors to obtain the solid catalyst component; wherein,

[0025] The precursor of the magnesium compound is selected from the general formula X n Mg(OR) 2-nAt least one of the compounds shown, the compounds shown by the general formula MgCl2·mROH, the mixture of MgCl2 / SiO2, the mixture of MgCl2 / Al2O3, and the mixture of magnesium halide and titanium alkoxide; wherein, m is 0.1-6 (for example, 0.2, 0.5, 0.8, 1, 2, 3, 4, 5), 0≦n≦2 (for example, n is 0, 1, 2), X is a halogen (for example, fluorine, chlorine, bromine), and R is hydrogen or a C1-C8 hydrocarbon group (for example, methyl, ethyl, n-propyl, n-butyl, isobutyl, 1-pentyl, 1-hexyl);

[0026] The general formula of the titanium compound is TiX n (OR) 4-n , wherein, R is a C1-C20 hydrocarbon group, X is a halogen, and n = 1-4 (such as, 1, 2, 3, 4).

[0027] In some embodiments, the titanium compound can be but not limited to titanium tetrachloride, titanium tetrabromide, titanium tetraiodide or alkyl titanium halide, and the alkyl titanium halide can be selected from, for example, methoxy titanium trichloride, ethoxy titanium trichloride, propoxy titanium trichloride, n-butoxy titanium trichloride, dimethoxy titanium dichloride, diethoxy titanium dichloride, dipropoxy titanium dichloride, di-n-butoxy titanium dichloride, trimethoxy titanium chloride, triethoxy titanium chloride, tripropoxy titanium chloride or tri-n-butoxy titanium chloride. One or more of these alkyl titanium halides can be used in combination.

[0028] In the present invention, the magnesium compound is well-known in the art and will not be elaborated here. For example, the magnesium compound is a precursor derived from a magnesium compound.

[0029] In the present invention, the preparation method and specific process of the solid catalyst component can be conventional operations in the art and will not be elaborated here.

[0030] In the solid catalyst component, the content or dosage of the internal electron donor can be a conventional selection in the art.

[0031] In a third aspect, a polymerization catalyst for the polymerization of olefins (the general formula of olefins is CH2=CHR, wherein R is hydrogen or a C1-C12 hydrocarbon group) is provided, and the polymerization catalyst is a product obtained by reacting the following raw material components:

[0032] (a) At least one of the solid catalyst components as described above;

[0033] (b) At least one organic aluminum compound shown by the general formula AlR n X (3-n) , wherein, R is hydrogen or a C1-C20 hydrocarbon group; X is a halogen, and n is an integer of 0≦n≦3;

[0034] (c) At least one of the general formula Rn Si(OR 1 ) 4-n The siloxane compound shown (as an external electron donor compound), in the formula, R and R 1 are the same or different and each independently is a C1-C18 hydrocarbon group, a halogenated hydrocarbon group or a substituent containing 1-10 carbon atoms and optional heteroatoms (such as N, O, S, P); n is an integer of 0≦n≦3.

[0035] In some embodiments, in the organoaluminum compound shown by the general formula AlR n X (3-n) , R is hydrogen or a C1-C12 hydrocarbon group.

[0036] In some embodiments, the organoaluminum compound may be an alkylaluminum compound, which is a trialkylaluminum compound, preferably selected from one or more of trimethylaluminum, triethylaluminum, triisobutylaluminum, tri-n-butylaluminum, tri-n-hexylaluminum and trioctylaluminum.

[0037] In the olefin polymerization catalyst, the amount of the organoaluminum compound used as the cocatalyst can be a conventional choice in the art. The ratio between the solid catalyst component and the organoaluminum compound (calculated as the Ti / Al molar ratio), for example, is 1:5 to 1:400.

[0038] In some embodiments, in the siloxane compound shown by the general formula R n Si(OR 1 ) 4-n , R and R 1 are each independently a C1-C18 alkyl group, a C3-C18 cycloalkyl group, a C6-C18 aryl group, or a C1-C18 halogenated alkyl group.

[0039] The siloxane compound may specifically include but not be limited to tetramethoxysilane, tetraethoxysilane (TEOS), dimethyldimethoxysilane, dimethyldiethoxysilane, methyl tert-butyl dimethoxysilane, methyl isopropyl dimethoxysilane, diphenoxydimethoxysilane, vinyltrimethoxysilane, methylcyclohexyldimethoxysilane, ethylcyclohexyldimethoxysilane, di-n-propyl dimethoxysilane, diisopropyl dimethoxysilane, di-n-butyl dimethoxysilane, diisobutyl dimethoxysilane, di-tert-butyl dimethoxysilane, dicyclopentyldimethoxysilane (D donor), cyclopentyltrimethoxysilane, isopropyltrimethoxysilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, ethyltriethoxysilane, diethylaminotriethoxysilane, cyclohexylpyrrolidinedimethoxysilane, bis(pyrrolidine)-dimethoxysilane, bis(perhydroisoquinoline)dimethoxysilane, 2-ethylpiperidinyl-2-tert-butyl dimethoxysilane, (1,1,1-trifluoro-2-propyl)-2-ethylpiperidinyl dimethoxysilane, and (1,1,1-trifluoro-2-propyl)-methyldimethoxysilane, etc. It may preferably be selected from one or more of dicyclopentyldimethoxysilane (D donor), methylcyclohexyldimethoxysilane, diisopropyl dimethoxysilane, diisobutyl dimethoxysilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, tetraethoxysilane (TEOS), and diethylaminotriethoxysilane.

[0040] In the olefin polymerization catalyst, the amount of the siloxane compound as the external electron donor component can be conventionally selected in the art and will not be elaborated here.

[0041] In a fourth aspect, there is provided an application of the polymerization catalyst as described above in an olefin polymerization reaction.

[0042] In the present invention, the olefin (the general formula of the olefin is CH2=CHR, where R is hydrogen or a C1-C12 hydrocarbon group) polymerization reaction may be a copolymerization of ethylene and an α-olefin monomer, or a homopolymerization of an olefin monomer. The method of the olefin polymerization reaction can be achieved by conventional operations in the art and will not be elaborated here.

[0043] Compared with the prior art, the beneficial effects of the technical solution of the present invention are at least as follows: The present invention uses a hydrogenated 8-hydroxyquinoline derivative as the internal electron donor. The polymerization catalyst prepared by using this novel compound as the internal electron donor of the Ziegler-Natta catalyst has the advantages of high activity and good hydrogen response sensitivity; when this catalyst is applied to an olefin polymerization reaction, the obtained polymer has the characteristics of high isotacticity, relatively low xylene-soluble content, and broad molecular weight distribution. Detailed Embodiments

[0044] To be able to understand the technical features and content of the present invention in detail, the preferred embodiments of the present invention will be described in more detail below. Although the preferred embodiments of the present invention are described in the examples, it should be understood that the present invention can be implemented in various forms and should not be limited by the embodiments set forth herein.

[0045] Unless otherwise specified, the experimental procedures used in the following examples are all conventional methods.

[0046] The materials, reagents, etc. used in the following examples can all be obtained through commercial channels.

[0047] Among them, the information of some raw materials is as follows:

[0048] Internal donor C1, DNBP (dibutyl phthalate), commercially available;

[0049] Internal donor C2 (which can be named 3-methyl-5-tert-butyl-1,2-bis(benzoyl)benzene diol ester according to the structure shown in Table 1 or 2), commercially available from Beijing Innochem Science & Technology Co., Ltd.;

[0050] Internal donor C3 (which can be named phenyl 2-(N-methylbenzamido)benzoate according to the structure shown in Table 1 or 2), commercially available from Beijing Innochem Science & Technology Co., Ltd.;

[0051] Internal donors ID1 to ID6 are all self-made, and their respective structural formulas are shown in Table 1 or Table 2.

[0052] Substituted or unsubstituted 8-hydroxy-1,2,3,4-tetrahydroquinoline, benzoyl chloride, o-methylbenzoyl chloride, ethoxycarbonyl chloride, etc. are all purchased from Beijing Innochem Science & Technology Co., Ltd.

[0053] According to the structure shown in Table 1 or 2, the internal donors used in each example can be named as follows:

[0054] Internal donor ID1 can be named: N-benzoyl-8-benzoyloxy-1,2,3,4-tetrahydroquinoline;

[0055] Internal donor ID2 can be named: N-benzoyl-7-methyl-8-benzoyloxy-1,2,3,4-tetrahydroquinoline;

[0056] Internal donor ID3 can be named: N-benzoyl-5-tert-butyl-7-methyl-8-benzoyloxy-1,2,3,4-tetrahydroquinoline;

[0057] Internal donor ID4 can be named: N-benzoyl-5-adamantyl-7-methyl-8-benzoyloxy-1,2,3,4-tetrahydroquinoline;

[0058] The internal donor ID5 can be named as: N-o-methylbenzoyl-8-o-methylbenzoyloxy-1,2,3,4-tetrahydroquinoline;

[0059] The internal donor ID6 can be named as: N-ethoxycarbonyl-8-ethoxycarbonyloxy-1,2,3,4-tetrahydroquinoline.

[0060] Preparation of internal electron donor

[0061] Preparation Example 1:

[0062] The synthesis method of the internal donor ID1 is as follows: Add 14.9 g (100 mmol) of 8-hydroxy-1,2,3,4-tetrahydroquinoline into a 250 mL single-necked flask, then add 100 mL of tetrahydrofuran and 40 mL (300 mmol) of triethylamine. Then, under the condition of an ice-water bath, slowly drop 23 mL (200 mmol) of benzoyl chloride into the reaction solution of the flask. After the dropping is completed, react at room temperature for 3 h. Then filter the reactants, concentrate the obtained mother liquor, wash the obtained solid with 50 mL of methanol for 3 times, and then recrystallize with ethyl acetate to obtain 31.3 g of the ID1 product, with a yield of 87%.

[0063] Preparation Example 2:

[0064] The synthesis method of the internal donor ID2 refers to Example 1, the only difference being that 8-hydroxy-1,2,3,4-tetrahydroquinoline is replaced by 7-methyl-8-hydroxy-1,2,3,4-tetrahydroquinoline.

[0065] Preparation Example 3:

[0066] The synthesis method of the internal donor ID3 refers to Example 1, the only difference being that 8-hydroxy-1,2,3,4-tetrahydroquinoline is replaced by 5-tert-butyl-7-methyl-8-hydroxy-1,2,3,4-tetrahydroquinoline.

[0067] Preparation Example 4:

[0068] The synthesis method of the internal donor ID4 refers to Example 1, the only difference being that 8-hydroxy-1,2,3,4-tetrahydroquinoline is replaced by 5-adamantyl-7-methyl-8-hydroxy-1,2,3,4-tetrahydroquinoline.

[0069] Preparation Example 5:

[0070] The synthesis method of the internal donor ID5 refers to Example 1, the only difference being that benzoyl chloride is replaced by o-methylbenzoyl chloride.

[0071] Preparation Example 6:

[0072] The synthesis method of internal electron donor ID6 refers to Example 1, with the only difference being that benzoyl chloride is replaced by ethoxycarbonyl chloride.

[0073] Preparation of catalyst and polymer

[0074] Catalyst Preparation Example 1:

[0075] In a 250 ml reactor with a six-port custom-made and filtration function and equipped with stirring, after being fully replaced with nitrogen, 2.2 g of diethoxymagnesium and 50 mL of chlorobenzene were added. Then, while maintaining the temperature at -10°C, 100 mL of a titanium tetrachloride / chlorobenzene solution (volume ratio of the two is 1:1) was added dropwise. After that, the system was slowly heated to 90°C. At this time, 1.8 g of internal electron donor ID1 dissolved in chlorobenzene was injected into the reactor using a syringe. The system was continued to be heated to 110°C and then kept at a constant temperature for 1 hour. Then, the mother liquor was filtered clean. 100 mL of the titanium tetrachloride / chlorobenzene solution (volume ratio of the two is 1:1) was added dropwise again, and the reaction was carried out at a constant temperature of 110°C for 1 hour. The mother liquor was filtered clean again. Finally, 100 mL of the titanium tetrachloride / chlorobenzene solution (volume ratio of the two is 1:1) was added dropwise again, and the reaction was carried out at a constant temperature of 110°C for 0.5 hour. The obtained mother liquor was filtered clean, the obtained solid was washed with 100 mL of n-heptane, and the washing was repeated three times. The n-heptane was filtered off and the product was dried to obtain a solid powder, which is the prepared solid catalyst component 1.

[0076] The titanium content, internal electron donor content, and the structural formula of the internal electron donor in this solid catalyst component 1 are shown in Table 1-2 below.

[0077] Olefin Polymerization Example a1:

[0078] The propylene polymerization process was carried out on a 2 L stainless steel polymerization kettle in the laboratory:

[0079] Step 1, first, the reaction kettle was purged with purified nitrogen (water < 1 ppm, oxygen < 1 ppm); then, 0.55 L of liquid propylene and 0.2 g of hydrogen were sequentially added at room temperature, and the system was heated to 70°C.

[0080] Step 2, before the temperature of the reaction kettle reached 70°C, 0.75 ml of a 1 M heptane solution of triethylaluminum, 1.1 ml of a 0.05 M hexane solution of D-donor, and 6 mg of the above-prepared solid catalyst component 1 (i.e., the Z-N catalyst containing internal electron donor ID1) were pre-complexed for 5 min. When the reaction kettle reached 70°C, the pre-complexed mixture was injected into the reaction kettle and the reaction timing was started.

[0081] Step 3, after the reaction for 60 min, the materials were emptied, the temperature was lowered, and the reaction was stopped; after the polypropylene resin in the reaction kettle was taken out, it was vacuum-dried at 30°C for 2 h to obtain a polypropylene product.

[0082] The obtained polypropylene product was subjected to performance tests, and the test results are shown in Table 2.

[0083] Olefin polymerization example b1:

[0084] The propylene polymerization process was carried out on a 2L stainless steel polymerization kettle in the laboratory:

[0085] Step 1: First, purge the reaction kettle with refined nitrogen (water < 1 ppm, oxygen < 1 ppm); then sequentially add 0.55 L of liquid propylene and 1.2 g of hydrogen at room temperature, and heat the system to 70 °C.

[0086] Step 2: Before the temperature of the reaction kettle reached 70 °C, 0.75 ml of a heptane solution of 1 M triethylaluminum, 1.1 ml of a hexane solution of 0.05 M D-donor, and 6 mg of the above-prepared solid catalyst component 1 (i.e., the Z-N catalyst containing internal electron donor ID1) were pre-complexed for 5 min, and then the pre-complexed mixture was injected into the reaction kettle when the reaction kettle reached 70 °C and the reaction timing was started.

[0087] Step 3: After the reaction for 60 min, vent the materials, cool down, and stop the reaction; after taking out the polypropylene resin in the reaction kettle, vacuum dry it at 30 °C for 2 h to obtain the polypropylene product.

[0088] The obtained polypropylene product was subjected to performance tests, and the test results are shown in Table 2.

[0089] Catalyst preparation example 2:

[0090] The preparation method of the solid catalyst component refers to catalyst preparation example 1, the difference being that the internal electron donor ID1 was replaced with ID2. The remaining steps were the same as in example 1. The solid catalyst component 2 (i.e., the Z-N catalyst containing internal electron donor ID2) was prepared.

[0091] The titanium content, internal electron donor content, and the structural formula of the internal electron donor in the solid catalyst component 2 are shown in Table 1-2 below.

[0092] Olefin polymerization example a2:

[0093] The propylene polymerization process refers to polymerization example a1, the difference being that in the polymerization experiment, the solid catalyst component 1 (i.e., the Z-N catalyst containing internal electron donor ID1) was replaced with the solid catalyst component 2 (i.e., the Z-N catalyst containing internal electron donor ID2).

[0094] Olefin polymerization example b2:

[0095] The propylene polymerization process refers to polymerization Example b1, with the difference that in the polymerization experiment, solid catalyst component 1 (i.e., the Ziegler-Natta catalyst containing internal electron donor ID1) was replaced by solid catalyst component 2 (i.e., the Ziegler-Natta catalyst containing internal electron donor ID2).

[0096] The obtained polypropylene product was subjected to performance testing, and the test results are shown in Table 2.

[0097] Catalyst Preparation Example 3:

[0098] The preparation method of the solid catalyst component refers to Catalyst Preparation Example 1, with the difference that internal electron donor ID1 was replaced by ID3. The remaining steps were the same as in Example 1. Solid catalyst component 3 (i.e., the Ziegler-Natta catalyst containing internal electron donor ID3) was obtained.

[0099] The titanium content, internal electron donor content, and internal electron donor structural formula in solid catalyst component 3 are shown in Table 1-2 below.

[0100] Olefin Polymerization Example a3:

[0101] The propylene polymerization process refers to Polymerization Example a1, with the difference that in the polymerization experiment, solid catalyst component 1 (i.e., the Ziegler-Natta catalyst containing internal electron donor ID1) was replaced by solid catalyst component 3 (i.e., the Ziegler-Natta catalyst containing internal electron donor ID3).

[0102] Olefin Polymerization Example b3:

[0103] The propylene polymerization process refers to Polymerization Example b1, with the difference that in the polymerization experiment, solid catalyst component 1 (i.e., the Ziegler-Natta catalyst containing internal electron donor ID1) was replaced by solid catalyst component 3 (i.e., the Ziegler-Natta catalyst containing internal electron donor ID3).

[0104] The obtained polypropylene product was subjected to performance testing, and the test results are shown in Table 2.

[0105] Catalyst Preparation Example 4:

[0106] The preparation method of the solid catalyst component refers to Catalyst Preparation Example 1, with the difference that internal electron donor ID1 was replaced by ID4. The remaining steps were the same as in Example 1. Solid catalyst component 4 (i.e., the Ziegler-Natta catalyst containing internal electron donor ID4) was obtained.

[0107] The titanium content, internal electron donor content, and internal electron donor structural formula in solid catalyst component 4 are shown in Table 1-2 below.

[0108] Olefin Polymerization Example a4:

[0109] The propylene polymerization process refers to polymerization Example a1, with the difference that in the polymerization experiment, solid catalyst component 1 (i.e., the Z-N catalyst containing internal electron donor ID1) is replaced by solid catalyst component 4 (i.e., the Z-N catalyst containing internal electron donor ID4).

[0110] Olefin polymerization Example b4:

[0111] The propylene polymerization process refers to polymerization Example b1, with the difference that in the polymerization experiment, solid catalyst component 1 (i.e., the Z-N catalyst containing internal electron donor ID1) is replaced by solid catalyst component 4 (i.e., the Z-N catalyst containing internal electron donor ID4).

[0112] The obtained polypropylene product was subjected to performance testing, and the test results are shown in Table 2.

[0113] Catalyst preparation Example 5:

[0114] The preparation method of the solid catalyst component refers to Catalyst preparation Example 1, with the difference that internal electron donor ID1 is replaced by ID5. The remaining steps are the same as in Example 1. Solid catalyst component 5 (i.e., the Z-N catalyst containing internal electron donor ID5) was prepared.

[0115] The titanium content, internal electron donor content, and the structural formula of the internal electron donor in solid catalyst component 5 are shown in Table 1-2 below.

[0116] Olefin polymerization Example a5:

[0117] The propylene polymerization process refers to polymerization Example a1, with the difference that in the polymerization experiment, solid catalyst component 1 (i.e., the Z-N catalyst containing internal electron donor ID1) is replaced by solid catalyst component 5 (i.e., the Z-N catalyst containing internal electron donor ID5).

[0118] Olefin polymerization Example b5:

[0119] The propylene polymerization process refers to polymerization Example b1, with the difference that in the polymerization experiment, solid catalyst component 1 (i.e., the Z-N catalyst containing internal electron donor ID1) is replaced by solid catalyst component 5 (i.e., the Z-N catalyst containing internal electron donor ID5).

[0120] The obtained polypropylene product was subjected to performance testing, and the test results are shown in Table 2.

[0121] Catalyst preparation Example 6:

[0122] The preparation method of the solid catalyst component refers to Preparation Example 1 of the catalyst, with the difference that the internal electron donor ID1 is replaced by ID6. The remaining steps are the same as those in Example 1. The solid catalyst component 6 (i.e., the Z-N catalyst containing the internal electron donor ID6) was obtained.

[0123] For the titanium content, internal electron donor content and the structural formula of the internal electron donor in the solid catalyst component 6, please refer to Table 1-2 below.

[0124] Olefin Polymerization Example a6:

[0125] The propylene polymerization process refers to Polymerization Example a1, with the difference that in the polymerization experiment, the solid catalyst component 1 (i.e., the Z-N catalyst containing the internal electron donor ID1) is replaced by the solid catalyst component 6 (i.e., the Z-N catalyst containing the internal electron donor ID6).

[0126] Olefin Polymerization Example b6:

[0127] The propylene polymerization process refers to Polymerization Example b1, with the difference that in the polymerization experiment, the solid catalyst component 1 (i.e., the Z-N catalyst containing the internal electron donor ID1) is replaced by the solid catalyst component 6 (i.e., the Z-N catalyst containing the internal electron donor ID6).

[0128] The obtained polypropylene product was subjected to performance testing. The test results are shown in Table 2.

[0129] Catalyst Preparation Comparative Example 1:

[0130] The preparation method of the solid catalyst component refers to Preparation Example 1 of the catalyst, with the difference that the internal electron donor ID1 is replaced by C1. The remaining steps are the same as those in Example 1. The solid catalyst component 1' (i.e., the Z-N catalyst containing the internal electron donor C1) was obtained.

[0131] For the titanium content, internal electron donor content and the structural formula of the internal electron donor in the solid catalyst component 1', please refer to Table 1-2 below.

[0132] Olefin Polymerization Comparative Example a1':

[0133] The propylene polymerization process refers to Polymerization Example a1, with the difference that in the polymerization experiment, the solid catalyst component 1 (i.e., the Z-N catalyst containing the internal electron donor ID1) is replaced by the solid catalyst component 1' (i.e., the Z-N catalyst containing the internal electron donor C1).

[0134] Olefin Polymerization Comparative Example b1':

[0135] The propylene polymerization process was carried out with reference to Polymerization Example b1, except that in the polymerization experiment, solid catalyst component 1 (i.e., the Ziegler-Natta catalyst containing internal electron donor ID1) was replaced with solid catalyst component 1' (i.e., the Ziegler-Natta catalyst containing internal electron donor C1).

[0136] The obtained polypropylene product was subjected to performance testing, and the test results are shown in Table 2 below.

[0137] Catalyst Preparation Comparative Example 2:

[0138] The preparation method of the solid catalyst component was carried out with reference to Catalyst Preparation Example 1, except that the internal electron donor ID1 was replaced with C2. The remaining steps were the same as those in Example 1. Solid catalyst component 2' (i.e., the Ziegler-Natta catalyst containing internal electron donor C2) was obtained.

[0139] The titanium content, internal electron donor content and the structural formula of the internal electron donor in solid catalyst component 2' are shown in Table 1-2 below.

[0140] Olefin Polymerization Comparative Example a2':

[0141] The propylene polymerization process was carried out with reference to Polymerization Example a1, except that in the polymerization experiment, solid catalyst component 1 (i.e., the Ziegler-Natta catalyst containing internal electron donor ID1) was replaced with solid catalyst component 2' (i.e., the Ziegler-Natta catalyst containing internal electron donor C2).

[0142] Olefin Polymerization Comparative Example b2':

[0143] The propylene polymerization process was carried out with reference to Polymerization Example b1, except that in the polymerization experiment, solid catalyst component 1 (i.e., the Ziegler-Natta catalyst containing internal electron donor ID1) was replaced with solid catalyst component 2' (i.e., the Ziegler-Natta catalyst containing internal electron donor C2).

[0144] The obtained polypropylene product was subjected to performance testing, and the test results are shown in Table 2 below.

[0145] Catalyst Preparation Comparative Example 3:

[0146] The preparation method of the solid catalyst component was carried out with reference to Catalyst Preparation Example 1, except that the internal electron donor ID1 was replaced with C3. The remaining steps were the same as those in Example 1. Solid catalyst component 3' (i.e., the Ziegler-Natta catalyst containing internal electron donor C3) was obtained.

[0147] The titanium content, internal electron donor content and the structural formula of the internal electron donor in solid catalyst component 3' are shown in Table 1-2 below.

[0148] Olefin Polymerization Comparative Example a3':

[0149] The propylene polymerization process refers to polymerization example a1, with the difference that in the polymerization experiment, solid catalyst component 1 (i.e., the Z-N catalyst containing internal electron donor ID1) is replaced by solid catalyst component 3' (i.e., the Z-N catalyst containing internal electron donor C3).

[0150] Olefin polymerization comparative example b3':

[0151] The propylene polymerization process refers to polymerization example b1, with the difference that in the polymerization experiment, solid catalyst component 1 (i.e., the Z-N catalyst containing internal electron donor ID1) is replaced by solid catalyst component 3' (i.e., the Z-N catalyst containing internal electron donor C3).

[0152] The obtained polypropylene product was subjected to performance testing, and the test results are shown in Table 2.

[0153] For the polymers obtained in each polymerization example and comparative example, performance testing was carried out according to the following testing methods:

[0154] 1. Melt flow rate MFR: Detected in accordance with ASTM D1238;

[0155] 2. Isotacticity: Detected using the fully automatic xylene solubles analyzer (CRYSTEX QC) from Polymer Char; the isotacticity value is 1 minus the measured xylene solubles content;

[0156] 3. Molecular weight and its distribution: Detected using the high-temperature gel permeation chromatograph (GPC-IR6) from Polymer Char;

[0157] 4. Catalyst activity: Well-known to those skilled in the art, it can be calculated as the ratio of the mass of the obtained product to the mass of the added catalyst or other calculation methods are also acceptable.

[0158] Table 1

[0159]

[0160]

[0161] Table 2

[0162]

[0163]

[0164] The experimental results in the above table show that when a catalyst using a hydrogenated 8-hydroxyquinoline derivative as an internal electron donor is used for propylene polymerization, the catalyst has the characteristics of high polymerization activity and sensitive hydrogen response. The polymer prepared has a high isotacticity and a wide molecular weight distribution. Under the same preparation process conditions, a catalyst using an ortho-hydrogenated 8-hydroxyquinoline derivative as an internal electron donor is more sensitive to hydrogen response than catalysts prepared from other uncyclized aromatic amine compounds, and the isotacticity of the polymer prepared is also higher. In addition, the molecular weight distribution of the polypropylene obtained in the present invention is generally wider than that of the polypropylene obtained using a phthalate catalyst.

[0165] The embodiments of the present invention have been described above. The above description is exemplary and not exhaustive, and is not limited to the disclosed embodiments. Many modifications and variations are obvious to those of ordinary skill in the art without departing from the gist of the present invention.

Claims

1. An internal electron donor for an olefin polymerization catalyst, characterized in that, The internal electron donor is selected from at least one of the compounds represented by the following general structural formula I: In formula I: R1-R9 are the same or different and each independently selected from H, halogen, saturated or unsaturated C1-C10 straight-chain or branched-chain alkyl, cycloalkyl, alkenyl, ester group, phenyl, alkylphenyl, phenylalkyl, indenyl, benzyl, halogenated or alkyl, cycloalkyl, phenyl, alkylphenyl, phenylalkyl, indenyl, benzyl substituted by N, O, S, P, Si heteroatoms; or selected from heteroaryl; and two or more of R1-R9 may be bonded to each other to form a ring or an unsaturated bond; R 10 -R 11 Same or different, each independently selected from H, halogen, saturated or unsaturated straight-chain or branched C1-C10 alkyl, cycloalkyl, alkenyl, ester group, phenyl, alkylphenyl, phenylalkyl, indenyl, benzyl, alkyl, cycloalkyl, phenyl, alkylphenyl, phenylalkyl, indenyl, benzyl that are halogenated or substituted by heteroatoms N, O, S, P, Si; or selected from heteroaryl; In the above aryl, aralkyl or alkaryl, the hydrogen on the benzene ring may optionally be substituted by a halogen atom.

2. The internal electron donor according to claim 1, wherein The internal electron donor is selected from at least one of the compounds represented by the following general structural formula (II): In formula (II): R1-R6 are the same or different and each independently selected from H, halogen, saturated or unsaturated C1-C10 straight-chain or branched-chain alkyl, cycloalkyl, alkenyl, ester group, phenyl, alkylphenyl, phenylalkyl, indenyl, benzyl, halogenated or alkyl, cycloalkyl, phenyl, alkylphenyl, phenylalkyl, indenyl, benzyl substituted by N, O, S, P, Si heteroatoms; or selected from heteroaryl; two or more of R1-R6 may be bonded to each other to form a ring or an unsaturated bond; R7-R8 are the same or different and each independently selected from H, halogen, saturated or unsaturated C1-C10 straight-chain or branched-chain alkyl, cycloalkyl, alkenyl, ester group, phenyl, alkylphenyl, phenylalkyl, indenyl, benzyl, halogenated or alkyl, cycloalkyl, phenyl, alkylphenyl, phenylalkyl, indenyl, benzyl substituted by N, O, S, P, Si heteroatoms; or selected from heteroaryl.

3. The internal electron donor according to claim 2, characterized in that, In formula (II), R7-R8 are each independently selected from phenyl, tert-butyl or ethoxy.

4. A solid catalyst component for olefin polymerization, characterized in that, It includes: a titanium compound, a magnesium compound and at least one internal electron donor selected from any one of claims 1-3.

5. The solid catalyst component according to claim 4, characterized in that, The preparation method of the solid catalyst component is: contacting and reacting a precursor of a magnesium compound, a titanium compound with at least one of the internal electron donors to obtain the solid catalyst component; wherein, The precursor of the magnesium compound is selected from the general formula X n Mg(OR) 2-n The compounds shown, the compounds shown by the general formula MgCl2·mROH, the mixture of MgCl2 / SiO2, the mixture of MgCl2 / Al2O3, and at least one of the mixture of magnesium halide and titanium alkoxide; wherein, m is 0.1-6, 0≦n≦2, X is a halogen, and R is hydrogen or a C1-C8 hydrocarbon group; The general formula of the titanium compound is TiX n (OR) 4-n , where R is a C1-C20 hydrocarbon group, X is a halogen, and n = 1-4.

6. A polymerization catalyst for olefin polymerization, characterized in that, The polymerization catalyst is a product of the reaction of the following raw material components: (a) at least one solid catalyst component as described in claim 4 or 5; (b) at least one organoaluminum compound of the general formula AlR n X (3-n) as shown, wherein R is hydrogen or a C1-C20 hydrocarbon group; X is a halogen, and n is an integer from 0 ≦ n ≦ 3; (c) At least one siloxane compound of the general formula R n Si(OR 1 ) 4-n as shown, where R and R 1 are the same or different and each independently is a C1-C18 hydrocarbyl group, a halogenated hydrocarbyl group or a substituent containing 1-10 carbon atoms and optionally heteroatoms; n is an integer of 0 ≦ n ≦ 3.

7. The polymerization catalyst according to claim 6, wherein General formula AlR n X (3-n) In the organoaluminum compound shown, R is hydrogen or a C1-C12 hydrocarbon group.

8. The polymerization catalyst according to claim 6 or 7, characterized in that, The organoaluminum compound is a trialkylaluminum compound, preferably selected from one or more of trimethylaluminum, triethylaluminum, triisobutylaluminum, tri-n-butylaluminum, tri-n-hexylaluminum and trioctylaluminum.

9. The polymerization catalyst according to any one of claims 6-8, characterized in that, General formula R n Si(OR 1 ) 4-n In the siloxane compound shown, R and R 1 are each independently an alkyl group having 1 to 18 carbon atoms, a cycloalkyl group having 3 to 18 carbon atoms, an aryl group having 6 to 18 carbon atoms, or a haloalkyl group having 1 to 18 carbon atoms.

10. Use of the polymerization catalyst according to any one of claims 6-9 in an olefin polymerization reaction.

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