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

Abstract

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 the use thereof in an olefin polymerization reaction. The internal electron donor is at least one selected from compounds represented by structural general formula (I), wherein R1-R16 are the same or different, and are each independently selected from H, halogens, C1-C10 alkyl, cycloalkyl, alkenyl, phenyl, alkylphenyl, phenylalkyl, indenyl and benzyl, and alkyl, cycloalkyl, phenyl, alkylphenyl, phenylalkyl, indenyl and benzyl which are halogenated or substituted with N, O, S, P and Si heteroatoms, and two or more among R1-R14 can be mutually bonded into a ring or bonded into an unsaturated bond. The polymerization catalyst prepared from the internal electron donor provided in the present invention has high activity and good hydrogen response sensitivity, and obtained polymers have high isotactic indexes, low contents of xylene-soluble matters and wide molecular weight distribution.

Description

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

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

[0002] It is well known that Ziegler-Natta catalysts used for olefin polymerization consist of three components: a magnesium chloride support, an internal electron donor compound, and a titanium compound. The internal electron donor compound not only enhances the activity of the olefin polymerization catalyst but also strengthens the catalyst's stereospecificity. Without the internal electron donor compound, the catalyst's activity is significantly reduced, and the resulting polymers are unusable due to their low isotactic index.

[0003] Various compounds are widely used as internal electron donors to prepare Ziegler-Natta catalysts, such as aromatic monoester or diester compounds such as diisobutyl phthalate or ethyl benzoate used in patent document US4784983A, glycol ester compounds used in patent document CN1453298A, diether compounds used in patent document EP361494A, 1,2-phenylene aromatic diester compounds used in patent document US61141902A, and amide or amide ester compounds used in patent document CN108570120A.

[0004] In industrial production, these internal electron donor compounds each have certain defects in practical applications, such as: using aromatic diester compounds as internal electron donor catalysts has low catalytic activity; using diether compounds as internal electron donor catalysts, although the catalytic activity is high and has good hydrogen adjustment sensitivity, the relative molecular mass distribution of the resulting polymer is narrow; using 1,2-phenylene aromatic diester compounds as internal electron donor catalysts, its catalytic activity and hydrogen adjustment sensitivity are good, but the xylene solubles of the resulting polymer are relatively high; using amide or amide ester compounds as internal electron donor catalysts, the catalytic activity is low and the xylene solubles are high.

[0005] Currently, the internal electron donor compounds used in the art have some deficiencies in practical applications, so improving internal electron donor compounds has always been a research hotspot in this field. In view of this, it is of great significance to develop a new internal electron donor that can overcome the above-mentioned deficiencies of the existing technology for use in the preparation of olefin polymerization catalysts.

[0006] Summary of the Invention

[0007] In order to solve the above-mentioned technical problems, the purpose of the present invention is to provide an internal electron donor, a solid catalyst component, a polymerization catalyst and its application in olefin polymerization reaction. The polymerization catalyst prepared using the novel internal electron donor has the advantages of high activity and good hydrogen regulation sensitivity. The polymer obtained by using the catalyst in olefin polymerization reaction has the characteristics of high isotacticity, relatively low xylene soluble content and wide molecular weight distribution.

[0008] In order to achieve the above object, the present invention provides the following technical solutions:

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

[0010] In Formula 1:

[0011] R1-R 14 are the same or different and are independently selected from H, halogen, saturated or unsaturated C1-C10 straight-chain or branched alkyl, cycloalkyl, alkenyl, ester, phenyl, alkylphenyl, phenylalkyl, indenyl, benzyl, halogenated or substituted by N, O, S, P, Si heteroatoms, alkyl, cycloalkyl, phenyl, alkylphenyl, phenylalkyl, indenyl, benzyl; or are selected from heterocyclic aromatic groups; and R1-R 14 Two or more of them may be bonded to each other to form a ring or to form an unsaturated bond;

[0012] R 15 -R 16 the same or different, each independently selected from H, halogen, saturated or unsaturated C1-C10 straight-chain or branched alkyl, cycloalkyl, alkenyl, ester, phenyl, alkylphenyl, phenylalkyl, indenyl, benzyl, halogenated or substituted by N, O, S, P, Si heteroatom alkyl, cycloalkyl, phenyl, alkylphenyl, phenylalkyl, indenyl, benzyl; or selected from heterocyclic aryl;

[0013] In the above aryl, aralkyl or alkaryl groups, hydrogen atoms on the benzene ring may be optionally replaced by halogen atoms.

[0014] In some embodiments, in Formula I, R 15 -R 16 Each is independently selected from phenyl, butyl or ethoxy.

[0015] In some embodiments, the internal electron donor is selected from at least one of the compounds represented by the following structural formula (II):

[0016] In formula (II):

[0017] R1-R8 are the same or different and are independently selected from H, halogen, saturated or unsaturated C1-C10 linear or branched alkyl, cycloalkyl, alkenyl, ester, phenyl, alkylphenyl, phenylalkyl, indenyl, benzyl, halogenated or substituted by N, O, S, P, Si heteroatoms, alkyl, cycloalkyl, phenyl, alkylphenyl, phenylalkyl, indenyl, benzyl; or selected from heterocyclic aromatic groups; two or more of R1-R8 may be bonded to each other to form a ring or to form an unsaturated bond;

[0018] R9-R 10 the same or different, each independently selected from H, halogen, saturated or unsaturated C1-C10 straight-chain alkyl or branched alkyl, cycloalkyl, alkenyl, ester group, phenyl, alkylphenyl, phenylalkyl, indenyl, benzyl, halogenated or substituted by N, O, S, P, Si heteroatom alkyl, cycloalkyl, phenyl, alkylphenyl, phenylalkyl, indenyl, benzyl; or selected from heterocyclic aromatic groups.

[0019] In some embodiments, in formula (II), R9-R 10 Each is independently selected from phenyl, butyl or ethoxy.

[0020] In a second aspect, a solid catalyst component for olefin polymerization is provided, comprising: a titanium compound, a magnesium compound, and at least one internal electron donor selected from the above.

[0021] In some embodiments, the solid catalyst component is prepared by contacting and reacting a precursor of a magnesium compound and a titanium compound with at least one internal electron donor to obtain the solid catalyst component; wherein,

[0022] The precursor of the magnesium compound is selected from the general formula X n Mg(OR) 2-n At least one of the compounds shown, compounds of the general formula MgCl2·mROH, mixtures of MgCl2 / SiO2, mixtures of MgCl2 / Al2O3, and mixtures of magnesium halide and titanium alkoxide, wherein m is 0.1-6 (e.g., 0.2, 0.5, 0.8, 1, 2, 3, 4, 5), 0≦n≦2 (e.g., n is 0, 1, 2), X is a halogen (e.g., fluorine, chlorine, bromine), and R is hydrogen or a C1-C8 hydrocarbon group (e.g., methyl, ethyl, propyl, n-butyl, isobutyl, 1-pentyl, 1-hexyl, 1-heptyl);

[0023] 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 (e.g., 1, 2, 3, 4).

[0024] In some embodiments, the titanium compound may be, but is not limited to, titanium tetrachloride, titanium tetrabromide, titanium tetraiodide, or an alkyl titanium halide. The alkyl titanium halide may be selected from, for example, methoxytitanium trichloride, ethoxytitanium trichloride, propoxytitanium trichloride, n-butoxytitanium trichloride, dimethoxytitanium dichloride, diethoxytitanium dichloride, dipropoxytitanium dichloride, di-n-butoxytitanium dichloride, trimethoxytitanium chloride, triethoxytitanium chloride, tripropoxytitanium chloride, or tri-n-butoxytitanium chloride. One or more of these alkyl titanium halides may be used in combination.

[0025] In the present invention, the magnesium compound is well known in the art and will not be described in detail herein. For example, the magnesium compound may be a precursor derived from a magnesium compound.

[0026] In the present invention, the method and specific process for preparing the solid catalyst component may be conventional operations in the art and will not be described in detail here.

[0027] In the solid catalyst component, the content or amount of the internal electron donor can be selected according to conventional methods in the art.

[0028] In a third aspect, there is provided a polymerization catalyst for the polymerization of olefins (the olefin is CH2=CHR, wherein R is hydrogen or a hydrocarbon group containing 1 to 12 carbon atoms), which is the product of the reaction of the following raw material components:

[0029] (a) at least one solid catalyst component as described above;

[0030] (b) at least one of the general formula AlR n X (3-n) The organoaluminum compound shown in the formula, wherein R is hydrogen or a C1-C20 hydrocarbon group; X is a halogen, and n is an integer of 0≦n≦3;

[0031] (c) at least one of the general formula R n Si(OR 1 ) 4-n The siloxane compound shown in the formula, wherein R and R 1 The same or different, each independently being 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.

[0032] In some embodiments, the general formula AlR n X (3-n) In the organoaluminum compound shown, R is hydrogen or a C1-C12 hydrocarbon group.

[0033] In some embodiments, the organoaluminum compound can be an alkylaluminum compound selected from trialkylaluminum compounds, preferably one or more selected from trimethylaluminum, triethylaluminum, triisobutylaluminum, tri-n-butylaluminum, tri-n-hexylaluminum and trioctylaluminum.

[0034] In the olefin polymerization catalyst, the amount of the organoaluminum compound used as a cocatalyst can be selected conventionally in the art. The ratio between the solid catalyst component and the organoaluminum compound (i.e., Ti / Al molar ratio) is, for example, 1:5 to 1:400.

[0035] In some embodiments, the general formula R n Si(OR 1 ) 4-n In the siloxane compound shown, R and R 1 Each is independently a C1-C18 alkyl group, a C3-C18 cycloalkyl group, a C6-C18 aryl group, or a C1-C18 haloalkyl group.

[0036] The siloxane compound may specifically include but is not limited to tetramethoxysilane, tetraethoxysilane (TEOS), dimethyldimethoxysilane, dimethyldiethoxysilane, methyl tert-butyldimethoxysilane, methylisopropyldimethoxysilane, diphenoxydimethoxysilane, vinyltrimethoxysilane, methylcyclohexyldimethoxysilane, ethylcyclohexyldimethoxysilane, di-n-propyldimethoxysilane, diisopropyldimethoxysilane, di-n-butyldimethoxysilane, diisobutyldimethoxysilane, di-tert-butyldimethoxysilane, dicyclopentyldimethoxysilane (D donor), cyclopentyltrimethoxysilane, isopropyltrimethoxysilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, ethyltriethoxysilane, diethylaminotriethoxysilane, cyclohexylpyrrolidinedimethoxysilane, bis(pyrrolidine)-dimethoxysilane, bis(perhydroisoquinolinyl)dimethoxysilane, 2-ethylpiperidinyl-2-tert-butyldimethoxysilane, (1,1,1-trifluoro-2-propyl)-2-ethylpiperidinyldimethoxysilane, and (1,1,1-trifluoro-2-propyl)-methyldimethoxysilane. It may be preferably selected from one or more of dicyclopentyldimethoxysilane (D donor), methylcyclohexyldimethoxysilane, diisopropyldimethoxysilane, diisobutyldimethoxysilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, tetraethoxysilane (TEOS) and diethylaminotriethoxysilane.

[0037] The amount of the siloxane compound used as the external electron donor component in the olefin polymerization catalyst can be selected according to conventional methods in the art and will not be described in detail here.

[0038] In a fourth aspect, a method for preparing the polymerization catalyst is provided.

[0039] In the present invention, the olefin (olefin has the general formula CH2=CHR, wherein R is hydrogen or a C1-C12 hydrocarbon group) polymerization reaction can be a copolymerization of ethylene and an α-olefin monomer, or a homopolymerization of the olefin monomer. The olefin polymerization method can be carried out by conventional operations in the art and will not be described in detail here.

[0040] Compared to existing technologies, the technical solution of the present invention has at least the following advantages: the polymerization catalyst prepared by using hydrogenated 1,10-phenanthroline derivatives as internal electron donors exhibits excellent catalytic activity and hydrogen sensitivity. Furthermore, when the catalyst prepared by using such internal electron donors is applied to olefin polymerization, the resulting polypropylene has a wider molecular weight distribution, higher isotacticity, and relatively lower xylene-soluble content. DETAILED DESCRIPTION

[0041] In order 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 embodiments, 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.

[0042] Unless otherwise specified, the experimental procedures used in the following examples are conventional methods.

[0043] The materials and reagents used in the following examples can all be obtained from commercial sources.

[0044] Among them, some raw material information is as follows:

[0045] Internal electron donor C1, DNBP (di-n-butyl phthalate), commercially available;

[0046] Internal electron donor C2 (based on the structure shown in Table 1 or 2, it can be named: 2-(N-methylbenzamido)-phenyl benzoate) was purchased from Beijing Yinuokai Technology Co., Ltd.

[0047] Internal electron donor C3 (based on the structure shown in Table 1 or 2, it can be named: 1,2-dibenzamide) was purchased from Beijing Yinuokai Technology Co., Ltd.

[0048] Internal electron donor C4 (based on the structure shown in Table 1 or 2, it can be named: 1,2-bis[(N-tert-butyl)benzoyl]phenylenediamine) was purchased from Beijing Yinuokai Technology Co., Ltd.

[0049] Internal electron donors ID1 to ID5 were all self-made, and their corresponding structural formulas are shown in Table 1 or Table 2.

[0050] Substituted or unsubstituted 2,3,4,7,8,9-hexahydro-1,10-phenanthroline, benzoyl chloride, o-methylbenzoyl chloride, and methoxycarbonyl chloride were purchased from Beijing Inokai Technology Co., Ltd.

[0051] Based on the structures shown in Table 1 or 2, the internal electron donors ID1 to ID5 can be named as follows:

[0052] Internal electron donor ID1, CAS No.: 1464216-94-1, can be named: 1,10-di(benzoyl)-2,3,4,7,8,9-hexahydro-1,10-phenanthroline;

[0053] Internal electron donor ID2 can be named as: 1,10-di(o-methylbenzoyl)-2,3,4,7,8,9-hexahydro-1,10-phenanthroline;

[0054] Internal electron donor ID3 can be named as: 1,10-bis(methoxycarbonyl)-2,3,4,7,8,9-hexahydro-1,10-phenanthroline;

[0055] Internal electron donor ID4 can be named as: 1,10-bis(methoxycarbonyl)-5-adamantyl-2,3,4,7,8,9-hexahydro-1,10-phenanthroline;

[0056] The internal electron donor ID5 can be named: 1,10-di(benzoyl)-5-adamantyl-2,3,4,7,8,9-hexahydro-1,10-phenanthroline.

[0057] Preparation of internal electron donors

[0058] Preparation Example 1:

[0059] The synthesis method of the internal electron donor ID1 is as follows: 18.8 g (100 mmol) of 2,3,4,7,8,9-hexahydro-1,10-phenanthroline is added to a 250 mL single-necked flask, followed by 100 mL of tetrahydrofuran and 40 mL (300 mmol) of triethylamine. Then, 23 mL (200 mmol) of benzoyl chloride is slowly dripped into the reaction solution in the flask under ice-water bath conditions. After the addition is complete, the reaction is carried out at room temperature for 3 hours. After that, the reactant is filtered, and the obtained mother liquor is concentrated. The obtained solid is washed with 50 mL of methanol for 3 times, and then recrystallized from ethyl acetate to finally obtain 36.4 g of ID1 product with a yield of 92%.

[0060] Preparation Example 2:

[0061] The synthesis method of internal electron donor ID2 is similar to that of Example 1, except that benzoyl chloride is replaced by o-methylbenzoyl chloride.

[0062] Preparation Example 3:

[0063] The synthesis method of internal electron donor ID3 is similar to that of Example 1, except that benzoyl chloride is replaced by methoxycarbonyl chloride.

[0064] Preparation Example 4:

[0065] The synthesis method of internal electron donor ID4 is similar to that of Example 1, except that 2,3,4,7,8,9-hexahydro-1,10-phenanthroline is replaced by 5-adamantyl-2,3,4,7,8,9-hexahydro-1,10-phenanthroline, and benzoyl chloride is replaced by methoxycarbonyl chloride.

[0066] Preparation Example 5:

[0067] The synthesis method of internal electron donor ID5 refers to Example 1, except that 2,3,4,7,8,9-hexahydro-1,10-phenanthroline is replaced by 5-adamantyl-2,3,4,7,8,9-hexahydro-1,10-phenanthroline.

[0068] Preparation of catalysts and polymers

[0069] Catalyst Preparation Example 1:

[0070] In a 250ml reactor with a 6-mouth custom-made stirring and filtering function, after sufficient nitrogen replacement, 2.2g of diethoxymagnesium and 50mL of chlorobenzene were added, and then 100mL of titanium tetrachloride / chlorobenzene solution (the volume ratio of the two was 1:1) was added dropwise at -10°C. The system was then slowly heated to 90°C. At this time, 1.5g of internal electron donor ID1 dissolved in chlorobenzene was injected into the reactor with a syringe, and the system was continued to be heated to 110°C and kept at this temperature for 1 hour. The mother liquid was then filtered clean and continued to be dripped. 100 mL of titanium tetrachloride / chlorobenzene solution (volume ratio of 1:1) was added, and the mixture was kept at a constant temperature for 1 hour at 110°C. The resulting mother liquid was filtered clean again. Finally, 100 mL of titanium tetrachloride / chlorobenzene solution (volume ratio of 1:1) was added dropwise again, and the mixture was kept at a constant temperature for 0.5 hour at 110°C. The resulting mother liquid was filtered clean, and the resulting 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 was the prepared solid catalyst component 1.

[0071] The titanium content, internal electron donor content and internal electron donor structural formula of the solid catalyst component 1 are shown in Table 1-2 below.

[0072] Olefin polymerization example a1:

[0073] The propylene polymerization process was carried out on a 2L stainless steel polymerization reactor in the laboratory:

[0074] Step 1: First, purge the reactor with purified nitrogen (water <1 ppm, oxygen <1 ppm); then, add 0.55 L of liquid propylene and 0.2 g of hydrogen in sequence at room temperature, and heat the system to 70°C;

[0075] Step 2: Before the reactor temperature reaches 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 solid catalyst component 1 prepared above (i.e., the ZN catalyst containing the internal electron donor ID1) are pre-complexed for 5 minutes. When the reactor temperature reaches 70°C, the pre-complexed mixture is injected into the reactor and the reaction timer is started;

[0076] Step 3: After the reaction has continued for 60 minutes, the materials are discharged, the temperature is lowered, and the reaction is stopped; the polypropylene resin in the reactor is taken out and vacuum-dried at 30° C. for 2 hours to obtain a polypropylene product.

[0077] The obtained polypropylene product was subjected to performance testing, and the test results are shown in Table 2.

[0078] Olefin polymerization example b1:

[0079] The propylene polymerization process was carried out on a 2L stainless steel polymerization reactor in the laboratory:

[0080] Step 1: First, purge the reactor with purified nitrogen (water <1 ppm, oxygen <1 ppm); then, add 0.55 L of liquid propylene and 1.2 g of hydrogen in sequence at room temperature, and heat the system to 70°C;

[0081] Step 2: Before the reactor temperature reaches 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 solid catalyst component 1 prepared above (i.e., the ZN catalyst containing the internal electron donor ID1) are pre-complexed for 5 minutes. When the reactor temperature reaches 70°C, the pre-complexed mixture is injected into the reactor and the reaction timer is started;

[0082] Step 3: After the reaction has continued for 60 minutes, the materials are discharged, the temperature is lowered, and the reaction is stopped; the polypropylene resin in the reactor is taken out and vacuum-dried at 30° C. for 2 hours to obtain a polypropylene product.

[0083] The obtained polypropylene product was subjected to performance testing, and the test results are shown in Table 2.

[0084] Catalyst Preparation Example 2:

[0085] The preparation method of the solid catalyst component was similar to that of Catalyst Preparation Example 1, except that the internal electron donor ID1 was replaced by ID2. The remaining steps were the same as those of Example 1. Solid catalyst component 2 (i.e., a ZN catalyst containing the internal electron donor ID2) was obtained.

[0086] The titanium content, internal electron donor content and internal electron donor structural formula in the solid catalyst component 2 are shown in Table 1-2 below.

[0087] Olefin polymerization example a2:

[0088] The propylene polymerization process refers to polymerization example a1, except that the solid catalyst component 1 (i.e., the ZN catalyst containing the internal electron donor ID1) is replaced by the solid catalyst component 2 (i.e., the ZN catalyst containing the internal electron donor ID2) in the polymerization experiment.

[0089] Olefin polymerization example b2:

[0090] The propylene polymerization process refers to polymerization example b1, except that the solid catalyst component 1 (i.e., the ZN catalyst containing the internal electron donor ID1) is replaced by the solid catalyst component 2 (i.e., the ZN catalyst containing the internal electron donor ID2) in the polymerization experiment.

[0091] The obtained polypropylene product was subjected to performance testing, and the test results are shown in Table 2.

[0092] Catalyst Preparation Example 3:

[0093] The preparation method of the solid catalyst component was similar to that of Catalyst Preparation Example 1, except that the internal electron donor ID1 was replaced by ID3. The remaining steps were the same as those of Example 1. Solid catalyst component 3 (i.e., a ZN catalyst containing the internal electron donor ID3) was obtained.

[0094] The titanium content, internal electron donor content and internal electron donor structural formula in the solid catalyst component 3 are shown in Table 1-2 below.

[0095] Olefin polymerization example a3:

[0096] The propylene polymerization process refers to polymerization example a1, except that the solid catalyst component 1 (i.e., the ZN catalyst containing the internal electron donor ID1) is replaced by the solid catalyst component 3 (i.e., the ZN catalyst containing the internal electron donor ID3) in the polymerization experiment.

[0097] Olefin polymerization example b3:

[0098] The propylene polymerization process refers to polymerization example b1, except that the solid catalyst component 1 (i.e., the ZN catalyst containing the internal electron donor ID1) is replaced by the solid catalyst component 3 (i.e., the ZN catalyst containing the internal electron donor ID3) in the polymerization experiment.

[0099] The obtained polypropylene product was subjected to performance testing, and the test results are shown in Table 2.

[0100] Catalyst Preparation Example 4:

[0101] The preparation method of the solid catalyst component was similar to that of Catalyst Preparation Example 1, except that the internal electron donor ID1 was replaced by ID4. The remaining steps were the same as those of Example 1. Solid catalyst component 4 (i.e., a ZN catalyst containing internal electron donor ID4) was obtained.

[0102] The titanium content, internal electron donor content and internal electron donor structural formula of the solid catalyst component 4 are shown in Table 1-2 below.

[0103] Olefin polymerization example a4:

[0104] The propylene polymerization process refers to polymerization example a1, except that the solid catalyst component 1 (i.e., the ZN catalyst containing the internal electron donor ID1) is replaced by the solid catalyst component 4 (i.e., the ZN catalyst containing the internal electron donor ID4) in the polymerization experiment.

[0105] Olefin polymerization example b4:

[0106] The propylene polymerization process refers to polymerization example b1, except that the solid catalyst component 1 (i.e., the ZN catalyst containing the internal electron donor ID1) is replaced by the solid catalyst component 4 (i.e., the ZN catalyst containing the internal electron donor ID4) in the polymerization experiment.

[0107] The obtained polypropylene product was subjected to performance testing, and the test results are shown in Table 2.

[0108] Catalyst Preparation Example 5:

[0109] The preparation method of the solid catalyst component was similar to that of Catalyst Preparation Example 1, except that the internal electron donor ID1 was replaced by ID5. The remaining steps were the same as those of Example 1. Solid catalyst component 5 (i.e., a ZN catalyst containing internal electron donor ID5) was obtained.

[0110] The titanium content, internal electron donor content and internal electron donor structural formula of the solid catalyst component 5 are shown in Table 1-2 below.

[0111] Olefin polymerization example a5:

[0112] The propylene polymerization process refers to polymerization example a1, except that the solid catalyst component 1 (i.e., the ZN catalyst containing the internal electron donor ID1) is replaced by the solid catalyst component 5 (i.e., the ZN catalyst containing the internal electron donor ID5) in the polymerization experiment.

[0113] Olefin polymerization example b5:

[0114] The propylene polymerization process refers to polymerization example b1, except that the solid catalyst component 1 (i.e., the ZN catalyst containing the internal electron donor ID1) is replaced by the solid catalyst component 5 (i.e., the ZN catalyst containing the internal electron donor ID5) in the polymerization experiment.

[0115] The obtained polypropylene product was subjected to performance testing, and the test results are shown in Table 2.

[0116] Catalyst Preparation Comparative Example 1:

[0117] The preparation method of the solid catalyst component refers to Catalyst Preparation Example 1, except that the internal electron donor ID1 is replaced by C1; the remaining steps are the same as Example 1. A solid catalyst component 1' (ie, a ZN catalyst containing the internal electron donor C1) is prepared.

[0118] The titanium content, internal electron donor content and internal electron donor structural formula of the solid catalyst component 1' are shown in Table 1-2 below.

[0119] Olefin polymerization comparative example a1':

[0120] The propylene polymerization process refers to the polymerization example a1, except that the solid catalyst component 1 (ie, the ZN catalyst containing the internal electron donor ID1) is replaced by the solid catalyst component 1' (ie, the ZN catalyst containing the internal electron donor C1) in the polymerization experiment.

[0121] Olefin polymerization comparative example b1':

[0122] The propylene polymerization process refers to the polymerization example b1, except that the solid catalyst component 1 (ie, the ZN catalyst containing the internal electron donor ID1) is replaced by the solid catalyst component 1' (ie, the ZN catalyst containing the internal electron donor C1) in the polymerization experiment.

[0123] The obtained polypropylene product was subjected to performance testing, and the test results are shown in Table 2.

[0124] Catalyst Preparation Comparative Example 2:

[0125] The preparation method of the solid catalyst component is similar to that of Example 1, except that the internal electron donor ID1 is replaced by C2. The remaining steps are the same as Example 1. A solid catalyst component 2' (ie, a ZN catalyst containing the internal electron donor C2) is obtained.

[0126] The titanium content, internal electron donor content and internal electron donor structural formula of the solid catalyst component 2' are shown in Table 1-2 below.

[0127] Olefin polymerization comparative example a2':

[0128] The propylene polymerization process refers to the polymerization example a1, except that the solid catalyst component 1 (ie, the ZN catalyst containing the internal electron donor ID1) is replaced by the solid catalyst component 2' (ie, the ZN catalyst containing the internal electron donor C2) in the polymerization experiment.

[0129] Olefin polymerization comparative example b2':

[0130] The propylene polymerization process refers to Polymerization Example 1, except that the solid catalyst component 1 (ie, the ZN catalyst containing the internal electron donor ID1) is replaced by the solid catalyst component 2' (ie, the ZN catalyst containing the internal electron donor C2) in the polymerization experiment.

[0131] The obtained polypropylene product was subjected to performance testing, and the test results are shown in Table 2.

[0132] Catalyst Preparation Comparative Example 3:

[0133] The preparation method of the solid catalyst component is similar to that of Catalyst Preparation Example 1, except that the internal electron donor ID1 is replaced by C3. The remaining steps are the same as those of Example 1. A solid catalyst component 3' (ie, a ZN catalyst containing the internal electron donor C3) is obtained.

[0134] The titanium content, internal electron donor content and internal electron donor structural formula of the solid catalyst component 3' are shown in Table 1-2 below.

[0135] Olefin polymerization comparative example a3':

[0136] The propylene polymerization process refers to the polymerization example a1, except that the solid catalyst component 1 (ie, the ZN catalyst containing the internal electron donor ID1) is replaced by the solid catalyst component 3' (ie, the ZN catalyst containing the internal electron donor C3) in the polymerization experiment.

[0137] Olefin polymerization comparative example b3':

[0138] The propylene polymerization process refers to the polymerization example b1, except that the solid catalyst component 1 (ie, the ZN catalyst containing the internal electron donor ID1) is replaced by the solid catalyst component 3' (ie, the ZN catalyst containing the internal electron donor C3) in the polymerization experiment.

[0139] The obtained polypropylene product was subjected to performance testing, and the test results are shown in Table 2.

[0140] Catalyst Preparation Comparative Example 4:

[0141] The solid catalyst component was prepared as described in Example 1, except that the internal electron donor ID1 was replaced with C4. The remaining steps were the same as in Example 1, yielding a solid catalyst component 4' (ie, a ZN catalyst containing the internal electron donor C4).

[0142] The titanium content, internal electron donor content and internal electron donor structural formula of the solid catalyst component 4' are shown in Table 1-2 below.

[0143] Olefin polymerization comparative example a4':

[0144] The propylene polymerization process refers to the polymerization example a1, except that the solid catalyst component 1 (ie, the ZN catalyst containing the internal electron donor ID1) is replaced by the solid catalyst component 4' (ie, the ZN catalyst containing the internal electron donor C4) in the polymerization experiment.

[0145] Olefin polymerization comparative example b4':

[0146] The propylene polymerization process refers to the polymerization example b1, except that the solid catalyst component 1 (ie, the ZN catalyst containing the internal electron donor ID1) is replaced by the solid catalyst component 4' (ie, the ZN catalyst containing the internal electron donor C4) in the polymerization experiment.

[0147] The obtained polypropylene product was subjected to performance testing, and the test results are shown in Table 2.

[0148] The polymers obtained in each embodiment and comparative example were tested for performance according to the following test methods:

[0149] 1. Melt flow rate (MFR): tested according to ASTM D1238;

[0150] 2. Isotacticity: The isotacticity is determined by using a fully automatic xylene soluble content analyzer (CRYSTEX QC) from Polymer Char. The isotacticity value is 1 minus the measured xylene soluble content.

[0151] 3. Molecular weight and its distribution: detected by high temperature gel permeation chromatography (GPC-IR6) of Polymer Char Company;

[0152] 4. Catalyst activity: This is well known to those skilled in the art and can be calculated by dividing the mass of the product obtained by the mass of the added catalyst or by other calculation methods.

[0153] Table 1

[0154] Table 2

[0155] The polymerization results in the above table show that when the polymerization catalyst prepared by using hydrogenated 1,10-phenanthroline derivatives as internal electron donors is used for propylene polymerization, the catalyst has excellent catalytic activity and hydrogen modulation sensitivity.

[0156] Under the same preparation process, the catalyst prepared using hydrogenated 1,10-phenanthroline derivatives as internal electron donors exhibits superior catalytic activity and hydrogen sensitivity compared to other catalysts using unannulated aromatic amine compounds as internal electron donors. The resulting polymers also exhibit higher isotacticity. Furthermore, when the catalyst prepared using this internal electron donor is used in olefin polymerization, the resulting polypropylene exhibits a broader molecular weight distribution than the polypropylene obtained when a phthalate ester catalyst is used as the internal electron donor.

[0157] While various embodiments of the present invention have been described above, the above description is intended to be illustrative, not exhaustive, and not limited to the disclosed embodiments. Many modifications and variations will be apparent to those skilled in the art without departing from the scope and spirit of the described embodiments.

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-R 14 Same or different, 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-R 14 among them may be bonded to each other to form a ring or an unsaturated bond; R 15 -R 16 Same or different, 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, alkyl, cycloalkyl, phenyl, alkylphenyl, phenylalkyl, indenyl, benzyl which are halogenated or substituted by heteroatoms such as N, O, S, P, Si; or selected from heteroaryl; In the aryl, aralkyl or alkaryl as described above, the hydrogen on the benzene ring may optionally be substituted by a halogen atom.

2. The internal electron donor according to claim 1, characterized in that, 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-R8 are the same or different and are each independently selected from H, halogen, a saturated or unsaturated straight-chain or branched-chain C1-C10 alkyl group, a cycloalkyl group, an alkenyl group, an ester group, a phenyl group, an alkylphenyl group, a phenylalkyl group, an indenyl group, a benzyl group, an alkyl group, a cycloalkyl group, a phenyl group, an alkylphenyl group, a phenylalkyl group, an indenyl group, a benzyl group that is halogenated or substituted by heteroatoms such as N, O, S, P, Si; or are selected from a heteroaryl group; two or more of R1-R8 may be bonded to each other to form a ring or an unsaturated bond; R9-R 10 identical or different, 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, alkyl, cycloalkyl, phenyl, alkylphenyl, phenylalkyl, indenyl, benzyl which are halogenated or substituted by N, O, S, P, Si heteroatoms; or selected from heteroaryl groups.

3. The internal electron donor according to claim 2, characterized in that, In formula (II), R9-R 10 are each independently selected from phenyl, 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 method for preparing 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, thereby obtaining 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, where 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, It 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, where R is hydrogen or a C1-C20 hydrocarbon group; X is a halogen, and n is an integer with 0 ≦ n ≦ 3; (c) at least one general formula R n Si(OR 1 ) 4-n wherein the siloxane compound shown, 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; 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 represented by the formula, 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 selected from trialkylaluminum compounds, 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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