CATALYST SYSTEM FOR OLEFIN POLYMERIZATION AND USE THEREOF

Abstract

A catalyst system for olefin polymerization contains a main catalyst and a cocatalyst. The cocatalyst contains a twelve-membered ring compound represented by formula (M). The catalyst system is suitable for preparing polypropylene products having high stereoregularity and low ash, and can regulate the melt index of the products within a wide range by adjusting the amount of hydrogenation. It is also suitable for copolymerization systems to improve the copolymerization yield.

##STR00001##

Claims

1. A catalyst system for olefin polymerization, comprising a main catalyst and a cocatalyst, wherein the cocatalyst comprises a twelve-membered ring compound represented by formula (M), ##STR00020## wherein in the formula (M), R.sub.1-R.sub.16 are the same or different, each independently selected from a group consisting of hydrogen, hydroxyl, halogen, cyano, nitro, amino, amine, aldehyde, carboxyl, ketone, alkoxy and hydrocarbyl, and when two adjacent groups on a benzene ring are each selected from a group consisting of alkoxy and hydrocarbyl, the two adjacent groups may optionally form a ring with each other, the ring selected from a group consisting of a saturated or unsaturated monocyclic ring, a saturated or unsaturated polycyclic ring and a combination thereof; and wherein R.sub.17 to R.sub.24 are the same or different, each independently selected from a group consisting of hydrogen and C.sub.1-C.sub.10 hydrocarbyl, and the amine, aldehyde, carboxyl, ketone, alkoxy and hydrocarbyl may be optionally substituted by one or more substituents.

2. The catalyst system according to claim 1, characterized in that the main catalyst comprises (i) a solid catalyst component containing magnesium, titanium, halogen and an internal electron donor compound; (ii) an organic aluminum compound; and optionally (iii) an external electron donor compound.

3. The catalyst system according to claim 2, characterized in that a molar ratio of the external electron donor compound to the titanium element in the solid catalyst component is (0-500):1, preferably (0.01-200):1, and more preferably (0.1-100):1.

4. The catalyst system according to claim 1, characterized in that, in the formula (M), R.sub.1-R.sub.16 are the same or different, each independently selected from a group consisting of hydrogen, hydroxyl, halogen, cyano, nitro, amino, mono-C.sub.1-C.sub.10 alkyl amine, bis-C.sub.1-C.sub.10 alkyl amine, C.sub.1-C.sub.10 aldehyde, C.sub.1-C.sub.10 carboxyl, R.sub.aC(O)—, R.sub.aO—, C.sub.1-C.sub.20 alkyl, C.sub.2-C.sub.20 alkenyl, C.sub.2-C.sub.20 alkynyl, C.sub.3-C.sub.20 cycloalkyl, C.sub.6-C.sub.20 aryl, C.sub.7-C.sub.20 aralkyl, 4-12-membered heterocycloalkyl and C.sub.5-C.sub.20 heteroaryl, and when two adjacent groups on a benzene ring are each selected from a group consisting of R.sub.aC(O)—, R.sub.aO—, C.sub.1-C.sub.20 alkyl, C.sub.2-C.sub.20 alkenyl, C.sub.2-C.sub.20 alkynyl, C.sub.3-C.sub.20 cycloalkyl, C.sub.6-C.sub.20 aryl, C.sub.7-C.sub.20 aralkyl, 4-12-membered heterocycloalkyl and C.sub.5-C.sub.20 heteroaryl, the two adjacent groups may optionally form a ring with each other, the ring selected from a group consisting of a saturated or unsaturated monocyclic ring, a saturated or unsaturated polycyclic ring and a combination thereof, wherein R.sub.a is selected from a group consisting of C.sub.1-C.sub.20 alkyl, C.sub.2-C.sub.20 alkenyl, C.sub.2-C.sub.20 alkynyl, C.sub.3-C.sub.20 cycloalkyl, C.sub.6-C.sub.20 aryl, C.sub.7-C.sub.20 aralkyl, 4-12-membered heterocycloalkyl and C.sub.5-C.sub.20 heteroaryl; and R.sub.17 to R.sub.24 are the same or different, each independently selected from a group consisting of hydrogen, C.sub.1-C.sub.10 alkyl, C.sub.2-C.sub.10 alkenyl, C.sub.2-C.sub.10 alkynyl, C.sub.3-C.sub.8 cycloalkyl, C.sub.6-C.sub.10 aryl, C.sub.7-C.sub.20 aralkyl, 4-12-membered heterocycloalkyl and C.sub.5-C.sub.20 heteroaryl, and any one of the alkyl, alkenyl, alkynyl, cycloalkyl, aryl, aralkyl, heterocycloalkyl and heteroaryl may be optionally substituted by one or more substituents.

5. The catalyst system according to claim 1, characterized in that, in the formula (M), the substituents are selected from a group consisting of alkyl, alkoxyl, hydroxyl, halogen, cyano, nitro, amino, alkyl substituted amino, aldehyde, carboxyl and a heteroatom-containing group; preferably, the substituents are selected from a group consisting of C.sub.1-C.sub.10 alkyl, C.sub.1-C.sub.10 alkoxyl, hydroxyl, halogen, cyano, nitro, amino, mono-C.sub.1-C.sub.10 alkyl amine, bis-C.sub.1-C.sub.10 alkyl amine, C.sub.1-C.sub.10 aldehyde, C.sub.1-C.sub.10 carboxyl and a heteroatom-containing group; and more preferably, the substituents are selected from a group consisting of C.sub.1-C.sub.6 alkyl, C.sub.1-C.sub.6 alkoxyl, hydroxyl, fluorine, chlorine, bromine, iodine, cyano, nitro, amino, mono-C.sub.1-C.sub.6 alkyl amine, bis-C.sub.1-C.sub.6 alkyl amine, C.sub.1-C.sub.6 aldehyde and C.sub.1-C.sub.6 carboxyl.

6. The catalyst system according to claim 1, characterized in that, in the formula (M), R.sub.1 to R.sub.16 are the same or different, and are each independently selected from a group consisting of hydrogen, hydroxyl, halogen, cyano, nitro, amino, mono-C.sub.1-C.sub.6 alkyl amine, bis-C.sub.1-C.sub.6 alkyl amine, C.sub.1-C.sub.6 aldehyde, C.sub.1-C.sub.6 carboxyl, R.sub.aC(O)—, R.sub.aO—, C.sub.1-C.sub.6 alkyl, C.sub.2-C.sub.6 alkenyl, C.sub.2-C.sub.6 alkynyl, C.sub.3-C.sub.6 cycloalkyl, C.sub.6-C.sub.10 aryl, C.sub.1-C.sub.10 aralkyl, 4-6-membered heterocycloalkyl and C.sub.5-C.sub.10 heteroaryl, wherein R.sub.a is selected from a group consisting of C.sub.1-C.sub.6 alkyl, C.sub.2-C.sub.6 alkenyl, C.sub.2-C.sub.6 alkynyl, C.sub.3-C.sub.6 cycloalkyl, C.sub.6-C.sub.10 aryl, C.sub.1-C.sub.10 aralkyl, 4-6-membered heterocycloalkyl and C.sub.5-C.sub.10 heteroaryl; preferably, R.sub.1 to R.sub.16 are selected from a group consisting of hydrogen, hydroxyl, amino, halogen, C.sub.1-C.sub.6 aldehyde, C.sub.1-C.sub.6 alkoxyl and halogen substituted C.sub.1-C.sub.6 alkoxyl; and preferably, R.sub.1 to R.sub.16 are not hydrogen at the same time.

7. The catalyst system according to claim 1, characterized in that, in the formula (M), R.sub.1, R.sub.4, R.sub.5, R.sub.8, R.sub.9, R.sub.12, R.sub.13 and R.sub.16 are each independently selected from a group consisting of hydrogen and C.sub.1-C.sub.6 alkyl; R.sub.2, R.sub.3, R.sub.6, R.sub.7, R.sub.10, R.sub.11, R.sub.14 and R.sub.15 are each independently selected from a group consisting of hydroxyl, amino, halogen, C.sub.1-C.sub.6 aldehyde, C.sub.1-C.sub.6 alkoxyl and halogen substituted C.sub.1-C.sub.6 alkoxyl.

8. The catalyst system according to claim 1, characterized in that, in the formula (M), R.sub.17 to R.sub.24 are each independently selected from a group consisting of hydrogen and C.sub.1-C.sub.10 alkyl, preferably selected from a group consisting of hydrogen and C.sub.1-C.sub.6 alkyl, and more preferably selected from a group consisting of hydrogen and C.sub.1-C.sub.4 alkyl.

9. The catalyst system according to claim 1, characterized in that, the twelve-membered ring compound represented by the formula (M) is represented by formula (N), ##STR00021## and preferably, the twelve-membered ring compound represented by the formula (M) is selected from one or more of the following compounds: Compound A: in the formula (N), R.sub.2═R.sub.3═R.sub.6═R.sub.7═R.sub.10═R.sub.11═R.sub.14═R.sub.15═OCH.sub.3; Compound B: in the formula (N), R.sub.2═R.sub.3═R.sub.6═R.sub.7═R.sub.10═R.sub.11═R.sub.14═R.sub.15═OCH.sub.2CH.sub.3; Compound C: in the formula (N), R.sub.2═R.sub.3═R.sub.6═R.sub.7═R.sub.10═R.sub.11═R.sub.14═R.sub.15═OCH.sub.2CH.sub.2CH.sub.3; Compound D: in the formula (N), R.sub.2═R.sub.3═R.sub.6═R.sub.7═R.sub.10═R.sub.11═R.sub.14═R.sub.15═OCH(CH.sub.3).sub.2; Compound E: in the formula (N), R.sub.2═R.sub.3═R.sub.6═R.sub.7═R.sub.10═R.sub.11═R.sub.14═R.sub.15═OCH.sub.2CH.sub.2CH.sub.2CH.sub.3; Compound F: in the formula (N), R.sub.2═R.sub.6═R.sub.10═R.sub.14═OCH.sub.3 and R.sub.3═R.sub.7═R.sub.11═R.sub.15═OCH.sub.2CH.sub.3; Compound G: in the formula (N), R.sub.2═R.sub.6═R.sub.10═R.sub.14═OCH.sub.3 and R.sub.3═R.sub.7═R.sub.11═R.sub.15═OCH.sub.2CH.sub.2CH.sub.3; Compound H: in the formula (N), R.sub.2═R.sub.6═R.sub.10═R.sub.14═OCH.sub.3 and R.sub.3═R.sub.7═R.sub.11═R.sub.15═OCH.sub.2CH.sub.2CH.sub.2CH.sub.3; Compound I: in the formula (N), R.sub.2═R.sub.3═R.sub.6═R.sub.7═R.sub.10═R.sub.11═R.sub.14═R.sub.15═OH; Compound J: in the formula (N), R.sub.2═R.sub.6═R.sub.10═R.sub.14═OCH.sub.3 and R.sub.3═R.sub.7═R.sub.11═R.sub.15═OH; Compound K: in the formula (N), R.sub.2═R.sub.6═R.sub.10═R.sub.14═OCH.sub.3 and R.sub.3═R.sub.7═R.sub.11═R.sub.15═NH.sub.2; Compound L: in the formula (N), R.sub.2═R.sub.6═R.sub.10═R.sub.14═OCH.sub.3 and R.sub.3═R.sub.7═R.sub.11═R.sub.15═Cl; Compound M: in the formula (N), R.sub.2═R.sub.6═R.sub.10═R.sub.14═OCH.sub.3 and R.sub.3═R.sub.7═R.sub.11═R.sub.15═Br; Compound N: in the formula (N), R.sub.2═R.sub.6═R.sub.10═R.sub.14═OCH.sub.3 and R.sub.3═R.sub.7═R.sub.11═R.sub.15═I; Compound O: in the formula (N), R.sub.2═R.sub.6═R.sub.10═R.sub.14═OCH.sub.3 and R.sub.3═R.sub.7═R.sub.11═R.sub.15═CHO; Compound P: in the formula (N), R.sub.2═R.sub.6═R.sub.10═R.sub.14═OCH.sub.3 and R.sub.3═R.sub.7═R.sub.11═R.sub.15═OCH.sub.2CH.sub.2CH.sub.2Br; Compound Q: in the formula (N), R.sub.2═R.sub.3═R.sub.6═R.sub.7═R.sub.10═R.sub.11═R.sub.14═R.sub.15═OCH.sub.2CH.sub.2Cl; and Compound R: in the formula (N), R.sub.2═R.sub.6═R.sub.10═R.sub.14═OH and R.sub.3═R.sub.7═R.sub.11═R.sub.15═OCH.sub.2CH.sub.3.

10. The catalyst system according to claim 1, characterized in that the internal electron donor compound is selected from one or more of a diether compound, an alcohol ester compound, an aromatic carboxylic acid ester compound, a succinate compound or a ketone compound.

11. The catalyst system according to claim 10, characterized in that, the alcohol ester compound is a glycol ester compound represented by formula B, ##STR00022## wherein, in the formula B, R.sub.1 and R.sub.2 are the same or different, each independently selected from a group consisting of C.sub.1-C.sub.20 alkyl, C.sub.2-C.sub.20 alkenyl, C.sub.3-C.sub.20 cycloalkyl, C.sub.6-C.sub.20 aryl, C.sub.7-C.sub.20 alkaryl, C.sub.7-C.sub.20 aralkyl and C.sub.10-C.sub.20 fused ring aryl, and preferably each independently selected from a group consisting of C.sub.1-C.sub.10 alkyl, C.sub.2-C.sub.10 alkenyl, C.sub.3-C.sub.10 cycloalkyl, C.sub.6-C.sub.10 aryl, C.sub.7-C.sub.10 alkaryl, C.sub.7-C.sub.10 aralkyl and C.sub.10-C.sub.15 fused ring aryl, the alkyl, alkenyl, cycloalkyl, aryl, alkaryl, aralkyl and fused ring aryl optionally substituted by one or more substituents selected from a group consisting of C.sub.1-C.sub.10 alkyl, C.sub.1-C.sub.10 alkoxyl, hydroxyl, halogen, cyano, nitro, amino, mono-C.sub.1-C.sub.6 alkyl amine, bis-C.sub.1-C.sub.6 alkyl amine, aldehyde, carboxyl and a heteroatom; and M is a divalent linking group, preferably selected from a group consisting of C.sub.1-C.sub.20 alkylene, C.sub.3-C.sub.20 cycloalkylene and C.sub.6-C.sub.20 arylene, the alkylene, cycloalkylene and/or arylene substituted by a substituent selected from a group consisting of C.sub.1-C.sub.20 alkyl, C.sub.1-C.sub.20 alkoxyl and halogen, the substituent optionally bonded to form one or more rings, and a carbon atom or/and a hydrogen atom in M optionally substituted by a nitrogen, oxygen, sulfur, silicon, phosphorus or halogen atom; the diether compound is a 1,3-diether compound represented by formula E, ##STR00023## wherein, in the formula E, R.sup.I, R.sup.II, R.sup.III, R.sup.IV, R.sup.V and R.sup.VI are the same or different, and are each independently selected from a group consisting of hydrogen, halogen, C.sub.1-C.sub.20 alkyl, C.sub.3-C.sub.20 cycloalkyl, C.sub.6-C.sub.20 aryl, C.sub.7-C.sub.20 aralkyl and C.sub.7-C.sub.20 alkaryl; R.sup.VII and R.sup.VIII are the same or different, and are each independently selected from a group consisting of C.sub.1-C.sub.20 alkyl, C.sub.3-C.sub.20 cycloalkyl, C.sub.6-C.sub.20 aryl, C.sub.7-C.sub.20 aralkyl and C.sub.7-C.sub.20 alkaryl, wherein any one of the alkyl, alkenyl, alkynyl, cycloalkyl, aryl, aralkyl and alkaryl may be optionally substituted by one or more substituents which are selected from a group consisting of hydroxyl, halogen, cyano, nitro, amino, mono-C.sub.1-C.sub.10 alkyl amine, bis-C.sub.1-C.sub.10 alkyl amine, aldehyde, carboxyl and a heteroatom; or, two or more of R.sup.I, R.sup.II, R.sup.III, R.sup.IV, R.sup.V and R.sup.VI are bonded to each other to form a saturated or unsaturated monocyclic or polycyclic ring, such as a fluorene ring; a structure of the aromatic carboxylic acid ester compound is as shown in formula F: ##STR00024## wherein, in the formula F, each R.sub.3 is the same or different, which is independently C.sub.1-C.sub.8 alkyl, C.sub.5-C.sub.10 cycloalkyl, C.sub.6-C.sub.15 aryl, C.sub.7-C.sub.15 alkaryl or C.sub.7-C.sub.15 aralkyl, and hydrogen on carbon of the C.sub.1-C.sub.8 alkyl, C.sub.3-C.sub.10 branched alkyl, C.sub.5-C.sub.10 cycloalkyl, C.sub.6-C.sub.15 aryl, C.sub.7-C.sub.15 alkaryl or C.sub.7-C.sub.15 aralkyl may be optionally substituted by a substituent selected from a group consisting of an alkane and a halogen atom, and preferably substituted by one or more substituents selected from a group consisting of C.sub.1-C.sub.6 alkyl, a fluorine atom, a chlorine atom, a bromine atom and an iodine atom; and R.sub.4-R.sub.7 may be the same or different, which are hydrogen, halogen, C.sub.1-C.sub.6 alkyl, C.sub.5-C.sub.10 cycloalkyl, C.sub.6-C.sub.20 aryl, C.sub.7-C.sub.20 alkaryl or C.sub.7-C.sub.20 aralkyl, and hydrogen on carbon of the C.sub.1-C.sub.8 alkyl, C.sub.5-C.sub.10 cycloalkyl, C.sub.6-C.sub.15 aryl, C.sub.7-C.sub.15 alkaryl or C.sub.7-C.sub.15 aralkyl may be optionally substituted by a substituent selected from a group consisting of an alkane and a halogen atom, and preferably substituted by one or more substituents selected from a group consisting of C.sub.1-C.sub.6 alkyl, a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom; and a structure of the succinate compound is as shown in formula G, ##STR00025## wherein, in the formula G, R.sub.1 and R.sub.2 are the same or different, each independently selected from a group consisting of a C.sub.1-C.sub.20 alkyl group, a C.sub.3-C.sub.20 cycloalkyl group, a C.sub.6-C.sub.20 aryl group, a C.sub.7-C.sub.20 arylalkyl group or a C.sub.7-C.sub.20 alkylaryl group, and optionally containing a heteroatom; and R.sub.3, R.sub.4, R.sub.5 and R.sub.6 are the same or different, each independently selected from a group consisting of hydrogen, a C.sub.1-C.sub.20 alkyl group, a cycloalkyl group, an aryl group, an arylalkyl group or an alkylaryl group, and optionally containing a heteroatom, and groups may be connected to form a ring.

12. The catalyst system according to claim 2, characterized in that, the external electron donor compound is selected from one or more of a silane compound, an ester compound, an ether compound or a ketone compound.

13. The catalyst system according to claim 12, characterized in that, a structure of the silane compound is shown in formula D: ##STR00026## wherein in the formula D, R.sub.1 to R.sub.4 are the same or different, each independently selected from a group consisting of hydrogen, C.sub.1-C.sub.10 alkyl, C.sub.2-C.sub.10 alkenyl, C.sub.1-C.sub.10 alkoxyl, C.sub.2-C.sub.10 enyloxy, C.sub.2-C.sub.10 alkynyl, C.sub.2-C.sub.10 ynoxy, C.sub.3-C.sub.10 cycloalkyl, C.sub.6-C.sub.15 aryl, C.sub.3-C.sub.10 cycloalkoxyl, C.sub.6-C.sub.15 aryloxyl and amino, wherein the alkyl, alkenyl, alkynyl, alkoxyl, enyloxy, ynoxy, cycloalkyl, aryl, cycloalkoxyl, aryloxyl and amino may be optionally substituted by one or more substituents selected from a group consisting of halogen, C.sub.1-C.sub.6 alkyl, C.sub.3-C.sub.6 cycloalkyl, C.sub.6-C.sub.10 aryl and amino; and the ether compound is the 1,3-diether compound represented by the formula E, ##STR00027## wherein, in the formula E, R.sup.I, R.sup.II, R.sup.III, R.sup.IV, R.sup.V and R.sup.VI are the same or different, and are each independently selected from a group consisting of hydrogen, halogen, C.sub.1-C.sub.20 alkyl, C.sub.3-C.sub.20 cycloalkyl, C.sub.6-C.sub.20 aryl, C.sub.7-C.sub.20 aralkyl and C.sub.7-C.sub.20 alkaryl; R.sup.VII and R.sup.VIII are the same or different, and are each independently selected from a group consisting of C.sub.1-C.sub.20 alkyl, C.sub.3-C.sub.20 cycloalkyl, C.sub.6-C.sub.20 aryl, C.sub.7-C.sub.20 aralkyl and C.sub.7-C.sub.20 alkaryl, wherein any one of the alkyl, alkenyl, alkynyl, cycloalkyl, aryl, aralkyl and alkaryl may be optionally substituted by one or more substituents which are selected from a group consisting of hydroxyl, halogen, cyano, nitro, amino, mono-C.sub.1-C.sub.10 alkyl amine, bis-C.sub.1-C.sub.10 alkyl amine, aldehyde, carboxyl and a heteroatom; or, two or more of R.sup.I, R.sup.II, R.sup.III, R.sup.IV, R.sup.V and R.sup.VI are bonded to each other to form a saturated or unsaturated monocyclic or polycyclic ring, such as a fluorene ring.

14. The catalyst system according to claim 2, characterized in that, a molar ratio of the twelve-membered ring compound represented by the formula (M) to the external electron donor compound is 1:100-100:1, preferably 1:50-50:1, and more preferably 1:20-20:1.

15. The catalyst system according to claim 2, characterized in that, the organic aluminum compound is an alkyl aluminum compound; preferably, a general formula of the alkyl aluminum compound is AlR.sub.3, wherein each R is independently selected from a group consisting of hydrogen, halogen, C.sub.1-C.sub.20 alkyl, C.sub.1-C.sub.20 alkoxyl or halogenated C.sub.1-C.sub.20 alkyl, and at least one of three Rs is C.sub.1-C.sub.20 alkyl; more preferably, the general formula of the alkyl aluminum compound is AlR.sub.3, wherein each R is independently selected from a group consisting of hydrogen, halogen, C.sub.1-C.sub.10 alkyl, C.sub.1-C.sub.10 alkoxyl or halogenated C.sub.1-C.sub.10 alkyl, and at least one of the three Rs is C.sub.1-C.sub.10 alkyl; and further preferably, the alkyl aluminum compound is one or more of triethyl aluminum, tri-n-propyl aluminum, tri-isopropyl aluminum, tri-n-butyl aluminum, tri-isobutyl aluminum, tri-n-hexyl aluminum, tri-n-octyl aluminum, diethyl aluminum monohydrogen, diisobutyl aluminum monohydrogen, diethyl aluminum chloride, diisobutyl aluminum chloride, ethyl aluminum dichloride, Al(n-C.sub.6H.sub.13).sub.3 and Al(n-C.sub.8H.sub.17).sub.3.

16. The catalyst system according to claim 2, characterized in that, a molar ratio of the twelve-membered ring compound represented by the formula (M) to the organic aluminum compound in terms of aluminum is 1:(0.1-500), and preferably 1:(1-200); and a molar ratio of the solid catalyst component in terms of the titanium element to the organic aluminum compound in terms of aluminum is 1:(5-5000), and preferably 1:(20-2000).

17. A prepolymerized catalyst composition for olefin polymerization, which comprises the catalyst system according to claim 1 and a prepolymer obtained by the olefin prepolymerization, preferably a prepolymerization multiple of the prepolymer being 0.1-1000 g olefin polymer/g solid catalyst component.

18. A method for olefin polymerization, comprising: polymerizing an olefin having a general formula of CH.sub.2═CHR in the presence of the catalyst system according to claim 1, wherein R is hydrogen or C.sub.1-C.sub.8 alkyl, and preferably hydrogen or C.sub.1-C.sub.6 alkyl.

19. A method for olefin polymerization, comprising: polymerizing an olefin having a general formula of CH.sub.2═CHR in the presence of the prepolymerized catalyst composition according to claim 17, wherein R is hydrogen or C.sub.1-C.sub.8 alkyl, and preferably hydrogen or C.sub.1-C.sub.6 alkyl

20. The method for olefin polymerization according to claim 18, wherein R is hydrogen or C.sub.1-C.sub.8 alkyl, and preferably hydrogen or C.sub.1-C.sub.6 alkyl. wherein the olefin is selected from one or more of ethylene, propylene, 1-butene, 4-methyl-1-pentene, and 1-hexene.

Description

DETAILED DESCRIPTION OF THE EMBODIMENTS

[0144] The embodiments of the invention will be explained in details with reference to examples, but those skilled in the art will understand that the following examples are only used to illustrate the invention and should not be regarded as limiting the scope of the invention. If specific conditions are not indicated in an example, it shall be carried out in accordance with conventional conditions or conditions recommended by the manufacturer. If the manufacturer is not indicated for the reagents or instruments used, they are all conventional products that may be purchased commercially.

[0145] Test Methods:

[0146] 1. Polymerization activity of the catalyst: it is obtained by dividing the amount of the polymer obtained in a certain period of time (in kg) with the amount of the catalyst added (in g).

[0147] 2. Weight average molecular weight: it is measured by high temperature sol permeation chromatography with reference to the standard GB/T 36214.4-2018.

[0148] 3. Isotactic index of the polymer: it is performed with reference to the standard GB/T 2412-2008.

[0149] 4. Ethylene content: it is measured by Fourier Infrared Spectrometer VERTEX70.

Preparation Example 1

[0150] A mixed solution of 3,4-dimethoxybenzhydrol (5 g)/dichloromethane (20 mL) was dropwise added to a dichloromethane (200 mL) solution of trifluoroacetic acid (25 mL). After the dropwise addition was completed, the reaction continued in the ice bath for 4 hours. The reaction solution was neutralized with a sodium hydroxide solution. The organic phase was separated followed by complete drainage. The resulting product was washed with water and an organic solvent many times, and was recrystallized in chloroform (80 mL)/benzene (30 mL) to obtain 2.5 g of compound A.

##STR00015##

Preparation Example 2

[0151] This preparation example is used to illustrate the preparation of a magnesium compound. Anhydrous magnesium chloride and ethanol were mixed according to the molar ratio of 1:2.6, and the temperature was raised to 120° C. to perform the reaction so as to form a magnesium chloride alcoholate melt. The resulting melt was stirred in the dispersion media white oil and silicone oil at high speed and was then put into the cooled hexane to form spherical magnesium chloride alcoholate particles. The resulting particles were washed and dried to obtain a spherical magnesium chloride alcoholate carrier.

Preparation Example 3

[0152] This preparation example is used to illustrate the preparation of a solid catalyst component.

[0153] In a 300 ml glass reaction flask with stirring which had been fully displaced by high-purity nitrogen, 100 ml of titanium tetrachloride was added followed by cooling to −20° C. 8 g of the spherical magnesium chloride alcoholate prepared in the Preparation Example 2 was added followed by slowly raising the temperature to 110° C. In the temperature raising process, 6 mmol of 2-isopropyl-2-isopentyl-1,3-dimethoxypropane was added as an internal electron donor. After the temperature was kept at 110° C. for 0.5 h, the liquid was filtered off, and titanium tetrachloride was added for the treatment twice. Then, washing with hexane was performed five times. After drying in vacuum, titanium-containing solid catalyst component Z1 with titanium content of 2.4 wt % was obtained.

Preparation Example 4

[0154] This preparation example is used to illustrate the preparation of a solid catalyst component.

[0155] In a 300 ml glass reaction flask with stirring which had been fully displaced by high-purity nitrogen, 100 ml of titanium tetrachloride was added followed by cooling to −20° C. 8 g of the spherical magnesium chloride alcoholate prepared in the Preparation Example 2 was added followed by slowly raising the temperature to 110° C. In the temperature raising process, 3 mmol of 2,4-pentanediol dibenzoate and 3 mmol of 2-isopropyl-2-isopentyl-1,3-dimethoxypropane were added as internal electron donors. After the temperature was kept at 110° C. for 0.5 h, the liquid was filtered off, and titanium tetrachloride was added for the treatment twice. Then, washing with hexane was performed five times. After drying in vacuum, titanium-containing solid catalyst component Z2 with titanium content of 2.7 wt % was obtained.

Preparation Example 5

[0156] This preparation example is used to illustrate the preparation of a solid catalyst component.

[0157] In a reactor which had been fully displaced by high-purity nitrogen, 6.0 g of magnesium chloride, 119 ml of toluene, 5 ml of epichlorohydrin and 15.6 ml of tributyl phosphate (TBP) were added successively. The temperature was raised to 50° C. with stirring, then continue stirring at 50° C. for 2.5 hours, and the solid was completely dissolved. 1.7 g of phthalic anhydride was added, then continue stirring at 50° C. for 1 hour. The solution was cooled to below −25° C. 70 ml of TiCl.sub.4 was dropwise added within 1 hour and the temperature was slowly raised to 80° C. In the temperature raising process, a solid was gradually precipitated. 6 mmol of 3-methyl-2,4-pentanediol dibenzoate was added as an internal electron donor, and the temperature was maintained for 1 hour. After filtration, 80 ml of toluene was added and washing was performed twice to obtain a solid precipitate. Then, 60 ml of toluene and 40 ml of TiCl.sub.4 were added, and the temperature was raised to 100° C. The treatment was performed for 2 hours. After the filtrate was drained off, 60 ml of toluene and 40 ml of TiCl.sub.4 were added again, and the temperature was raised to 100° C. The treatment was performed for 2 hours. The filtrate was drained off 60 ml of toluene was added. Washing was performed 3 times in a boiling state. 60 ml of hexane was then added. Washing was performed twice in a boiling state. 60 ml of hexane was added. After washing was performed twice at room temperature, solid catalyst component Z3 with titanium content of 2.5 wt % was obtained.

Preparation Example 6

[0158] This preparation example is used to illustrate the preparation of magnesium alkoxide.

[0159] After a 16 L pressure-resistant reactor with a stirrer was fully displaced with nitrogen, 10 L of ethanol, 300 mL of 2-ethylhexanol, 11.2 g of iodine, 8 g of magnesium chloride and 640 g of magnesium powder were added to the reactor. While stirring, the system was heated to 75° C. and refluxed for the reaction until no more hydrogen was discharged. The reaction was stopped. The mixture was washed with 3 L of ethanol, filtered, and dried to obtain magnesium alkoxide.

Preparation Example 7

[0160] This preparation example is used to illustrate the preparation of a solid catalyst component.

[0161] 10 g of the magnesium alkoxide compound of the Preparation Example 6, 50 mL of toluene, 3 mmol of 2,3-diisopropyl diethyl succinate and 3 mmol of 3,5-heptanediol dibenzoate were taken and formulated into a suspension. In a 300 mL reaction kettle that had been repeatedly displaced by high-purity nitrogen, 40 mL of toluene and 60 mL of titanium tetrachloride were added. The temperature was raised to 80° C., and then the formulated suspension was added to the kettle. The temperature was kept constant for 1 hour, and was slowly raised to 110° C. The temperature was kept constant for 2 hours. After pressure filtration, a mixed solution of 78 mL of toluene and 52 mL of titanium tetrachloride was added followed by the stirring treatment at 110° C. for 1 hour. Such treatment was carried out 3 times. After pressure filtration, washing with hexane was performed 4 times in 150 mL each time. The pressure filtration and drying were performed to obtain solid catalyst component Z4 with titanium content of 2.5 wt %.

Preparation Example 8

[0162] A mixed solution of 3,4-diethoxybenzyl alcohol (5.8 g)/dichloromethane (20 mL) was dropwise added to a dichloromethane (200 mL) solution of trifluoroacetic acid (25 mL). After the dropwise addition was completed, the reaction continued in the ice bath for 4 hours. The reaction solution was neutralized with a sodium hydroxide solution. The organic phase was separated followed by complete drainage. The resulting product was washed with water and an organic solvent many times, and was recrystallized in chloroform (80 mL)/benzene (30 mL) to obtain 1.5 g of compound B.

##STR00016##

Preparation Example 9

[0163] A mixed solution of 3-methoxy-4-bromopropoxybenzyl alcohol (7 g)/dichloromethane (20 mL) was dropwise added to a dichloromethane (200 mL) solution of trifluoroacetic acid (25 mL). After the dropwise addition was completed, the reaction continued in the ice bath for 4 hours. The reaction solution was neutralized with a sodium hydroxide solution. The organic phase was separated followed by complete drainage. The resulting product was washed with water and an organic solvent many times, and was recrystallized in chloroform (80 mL)/benzene (30 mL) to obtain 1.7 g of compound P.

##STR00017##

Preparation Example 10

[0164] A diethyl ether solution (100 mL) containing P.sub.2O.sub.5 (57.5 g) was stirred and dropwise added to a mixed solution of 3-iodo-4-methoxybenzhydrol (23 g)/diethyl ether. In reflux, stirring is stopped. 3 days later, the diethyl ether was spin-dried. The resulting product was dissolved in dichloromethane and passed through the column. After the filtrate was spin-dried, the resulting product was recrystallized with a mixed solution of diethyl ether/dichloromethane (95/5) to obtain 1.3 g of compound N.

##STR00018##

Preparation Example 11

[0165] 2 mL of a toluene solution containing n-BuLi (5 mmol of n-BuLi) was added to 25 mL of a THF solution (containing 0.5 g of the compound N) at −80° C. After 1 hour, the reaction solution was heated to 0° C. After stirred at room temperature for 1 hour, the reaction solution was quickly cooled to −70° C. 2 mL of ethyl chloroformate was added. The reaction solution was returned to the room temperature and stirred for 3 hours. The remaining n-BuLi was neutralized with NH.sub.4Cl. The organic phase was extracted with ethyl acetate, and 0.14 g of compound O was obtained after drying.

##STR00019##

Example 1

[0166] 4 mNL (mNL represents a milli standard liter) of hydrogen was added to a 48-channel parallel pressure reactor (the reaction volume is 20 ml). The reactor was filled with propylene gas to 1 MPa, and 5 ml of liquid propylene was added. According to the triethylaluminum (in terms of the aluminum element): compound A: solid catalyst component Z1 (in terms of the titanium element) molar ratio of 500:20:1, triethylaluminum, compound A, and a heptane solution of the solid catalyst component Z1 were added successively and formulated into a mixed solution. A certain amount of the mixed solution (containing 0.02 mg of the solid catalyst component) was taken and injected into the reactor. The reaction was performed at 70° C. for 1 hour.

[0167] The resulting product was discharged, and the weight of the polymer was weighed. The activity of the catalyst was obtained by calculation. Meanwhile, the isotactic index of the polymer was measured. The results are shown in Table 1.

Example 2

[0168] It is basically the same as Example 1, except that the amount of hydrogenation is 20 mNL. The results are shown in Table 1.

Example 3

[0169] It is basically the same as Example 1, except that the compound A is replaced with equimolar compound P. The results are shown in Table 1.

Example 4

[0170] It is basically the same as Example 2, except that the compound A is replaced with equimolar compound N. The results are shown in Table 1.

Comparative Example 1

[0171] It is basically the same as Example 1, except that the compound A is not added. The results are shown in Table 1.

Comparative Example 2

[0172] It is basically the same as Example 2, except that the compound A is not added. The results are shown in Table 1.

Comparative Example 3

[0173] It is basically the same as Example 2, except that the compound A is replaced with equimolar

[0174] C-Donor. The results are shown in Table 1.

Example 5

[0175] It is basically the same as Comparative Example 3, except that compound A in an equimolar amount with the C-Donor is additionally added. The results are shown in Table 1.

Comparative Example 4

[0176] It is basically the same as Example 1, except that the compound A is replaced with equimolar Donor 1. The results are shown in Table 1.

Example 6

[0177] It is basically the same as Comparative Example 4, except that compound B in an equimolar amount with the Donor 1 is additionally added. The results are shown in Table 1.

Example 7

[0178] It is basically the same as Example 6, except that the solid catalyst component is replaced from Z1 to Z2, and the Donor 1 is replaced with equimolar C-Donor. The results are shown in Table 1.

Comparative Example 5

[0179] It is basically the same as Example 7, except that the compound B is not added. The results are shown in Table 1.

Example 8

[0180] It is basically the same as Example 7, except that the solid catalyst component is replaced from Z2 to Z4, and the amount of hydrogenation is changed to 20 mNL. The results are shown in Table 1.

Comparative Example 6

[0181] It is basically the same as Example 8, except that the compound B is not added. The results are shown in Table 1.

TABLE-US-00001 TABLE 1 Solid External Amount of Isotactic catalyst electron hydrogenation Activity index Example component donor Cocatalyst (mNL) (kgPP/gCat) (%) Example 1 Z1 — Compound A 4 65 98.7 Example 2 Z1 — Compound A 20 69 95.9 Example 3 Z1 — Compound P 4 68 97.6 Example 4 Z1 — Compound N 20 69 95.8 Comparative Z1 — — 4 56 96.5 Example 1 Comparative Z1 — — 20 63 95.3 Example 2 Example 5 Z1 C-Donor Compound A 20 72 96.3 Comparative Z1 C-Donor — 20 47 96.0 Example 3 Example 6 Z1 Donor 1 Compound B 4 65 98.9 Comparative Z1 Donor 1 — 4 41 97.5 Example 4 Example 7 Z2 C-Donor Compound B 4 115 97.1 Comparative Z2 C-Donor — 4 77 97.0 Example 5 Example 8 Z4 C-Donor Compound B 20 47 95.8 Comparative Z4 C-Donor — 20 35 95.5 Example 6 Note: C-Donor: cyclohexylmethyldimethoxysilane; Donor 1: 2-isopropyl-2-isopentyl-1,3-dimethoxypropane.

[0182] It can be seen from Table 1 that for the catalyst system with or without an external electron donor, when it is used in the polymerization of propylene, the addition of the twelve-membered ring compound represented by the formula (M) as a cocatalyst can significantly improve the activity of the catalyst. In addition, the isotactic index of the polymerization product has also been improved.

Example 9

[0183] It is basically the same as Example 1, except that the compound A is replaced with equimolar compound B. The results are shown in Table 2.

Comparative Example 7

[0184] It is basically the same as Example 1, except that the compound A is replaced with equimolar C-Donor. The results are shown in Table 2.

Example 10

[0185] It is basically the same as Example 2, except that a part of the compound A is replaced with equimolar C-Donor. In this example, the molar ratio of the compound A to the C-Donor is 1:1. The results are shown in Table 2.

Example 11

[0186] It is basically the same as Example 2, except that a part of the compound A is replaced with equimolar C-Donor. In this example, the molar ratio of the compound A to the C-Donor is 1:9. The results are shown in Table 2.

Example 12

[0187] It is basically the same as Example 10, except that the compound A is replaced with equimolar compound B. The results are shown in Table 2.

Example 13

[0188] It is basically the same as Example 12, except that the C-Donor is replaced with equimolar Donor 1, and the amount of hydrogenation is changed to 4 mNL. The results are shown in Table 2.

Example 14

[0189] It is basically the same as Example 2, except that the solid catalyst component is replaced from Z1 to Z2. The results are shown in Table 2.

Example 15

[0190] It is basically the same as Example 10, except that the solid catalyst component is replaced from Z1 to Z2. The results are shown in Table 2.

Example 16

[0191] It is basically the same as Example 9, except that the solid catalyst component is replaced from Z1 to Z2. The results are shown in Table 2.

Example 17

[0192] It is basically the same as Example 16, except that the amount of hydrogenation is changed to 20 mNL. The results are shown in Table 2.

Example 18

[0193] It is basically the same as Example 13, except that the solid catalyst component is replaced from Z1 to Z2, and the Donor 1 is replaced with equimolar C-Donor. The results are shown in Table 2.

Example 19

[0194] It is basically the same as Example 18, except that the amount of hydrogenation is changed to 20 mNL. The results are shown in Table 2.

Comparative Example 8

[0195] It is basically the same as Comparative Example 5, except that the amount of hydrogenation is changed to 20 mNL. The results are shown in Table 2.

Example 20

[0196] It is basically the same as Example 9, except that the solid catalyst component is replaced from Z1 to Z3. The results are shown in Table 2.

Example 21

[0197] It is basically the same as Example 20, except that the amount of hydrogenation is changed to 20 mNL. The results are shown in Table 2.

Example 22

[0198] It is basically the same as Example 21, except that the compound B is replaced with equimolar compound O. The results are shown in Table 2.

Comparative Example 9

[0199] It is basically the same as Example 20, except that the compound B is replaced with equimolar C-Donor. The results are shown in Table 2.

Comparative Example 10

[0200] It is basically the same as Comparative Example 9, except that the amount of hydrogenation is changed to 20 mNL. The results are shown in Table 2.

Example 23

[0201] It is basically the same as Example 21, except that the solid catalyst component is replaced from Z3 to Z4. The results are shown in Table 2.

Example 24

[0202] It is basically the same as Example 12, except that the solid catalyst component is replaced from Z1 to Z4. The results are shown in Table 2.

TABLE-US-00002 TABLE 2 Molar ratio of cocatalyst: Solid External external Amount of Isotactic Weight-average catalyst electron electron hydrogenation Activity index molecular weight Example component donor Cocatalyst donor (mNL) (kgPP/gCat) (%) (ten thousand) Example 9 Z1 — Compound B — 4 70 97.8 58 Comparative Z1 C-Donor — — 4 42 97.6 61 Example 7 Example 10 Z1 C-Donor Compound A 1:1 20 78 96.5 42 Example 11 Z1 C-Donor Compound A 1:9 20 70 96.2 43 Example 12 Z1 C-Donor Compound B 1:1 20 96 95.8 36 Comparative Z1 C-Donor — — 20 47 96.0 45 Example 3 Example 13 Z1 Donor 1 Compound B 1:1 4 60 98.7 58 Comparative Z1 Donor 1 — — 4 41 97.5 60 Example 4 Example 14 Z2 — Compound A — 20 103 96.2 37 Example 15 Z2 C-Donor Compound A 1:1 20 109 96.6 44 Example 16 Z2 — Compound B — 4 82 96.7 80 Example 17 Z2 — Compound B — 20 119 95.3 45 Example 18 Z2 C-Donor Compound B 1:1 4 113 97.1 70 Example 19 Z2 C-Donor Compound B 1:1 20 120 95.8 46 Comparative Z2 C-Donor — — 4 77 97.0 82 Example 5 Comparative Z2 C-Donor — — 20 86 96.4 48 Example 8 Example 20 Z3 — Compound B — 4 45 98.8 78 Example 21 Z3 — Compound B — 20 50 98.0 57 Example 22 Z3 — Compound O — 20 43 97.5 55 Comparative Z3 C-Donor — — 4 35 98.5 84 Example 9 Comparative Z3 C-Donor — — 20 37 97.8 60 Example 10 Example 23 Z4 — Compound B — 20 51 95.4 50 Example 24 Z4 C-Donor Compound B 1:1 20 44 96.0 52 Comparative Z4 C-Donor — — 20 35 95.5 56 Example 6 Note: C-Donor: cyclohexylmethyldimethoxysilane; Donor 1: 2-isopropyl-2-isopentyl-1,3-dimethoxypropane.

[0203] It can be seen from Table 2 that when the catalyst system provided by the invention is used for olefin polymerization, especially propylene polymerization, the stereospecificity, catalytic activity and hydrogen modulation sensitivity are all relatively good. Compared with a catalyst system containing a silane compound or a diether compound as an external electron donor, the catalyst system containing a twelve-membered ring compound represented by the formula (M) as a cocatalyst has improved hydrogen modulation sensitivity, significantly improved polymerization activity, and a relatively good isotactic index of the polymer. When the silane compound or the diether compound is added to the catalyst system as an external electron donor, the isotactic index of the product is further improved. According to the above characteristics of the catalyst provided by the invention, the catalyst system provided by the invention is particularly suitable for preparing a polypropylene product with high stereoregularity and low ash, and the melt index of the product may be adjusted in a relatively wide range by adjusting the amount of hydrogenation.

Example 25

[0204] A 48-channel parallel pressure reactor (the reaction volume is 20 ml) was displaced with hydrogen. The reactor was filled with propylene gas to 1 MPa, and 5 ml of liquid propylene was added. According to the triethylaluminum (in terms of the aluminum element): compound A: solid catalyst component (in terms of the titanium element) molar ratio of 250:25:1, triethylaluminum, compound A, and a heptane solution of the solid catalyst component Z1 were added successively and formulated into a mixed solution. A certain amount of the mixed solution (containing 0.02 mg of the solid catalyst component) was taken and injected into the reactor. The reaction was performed at 70° C. for 40 minutes. The system was displaced with a mixture of ethylene and propylene (the volume ratio of ethylene and propylene is 1:1), and the reaction was performed at 80° C. with a controlled pressure of 0.7 Mpa for 20 minutes.

[0205] The resulting product was discharged, and the weight of the polymer was weighed. The activity of the catalyst was obtained by calculation. Meanwhile, the ethylene content of the polymer was measured. The results are shown in Table 3.

Comparative Example 11

[0206] It is basically the same as Example 25, except that the compound A is replaced with equimolar C-donor. The results are shown in Table 3.

Example 26

[0207] It is basically the same as Example 25, except that a part of the compound A is replaced with equimolar C-Donor. In this example, the molar ratio of the compound A to the C-Donor is 1:1. The results are shown in Table 3.

Example 27

[0208] It is basically the same as Example 26, except that the molar ratio of the compound A to the C-Donor is 1:9. The results are shown in Table 3.

Example 28

[0209] It is basically the same as Example 25, except that the solid catalyst component Z1 is replaced with solid catalyst component Z2. The results are shown in Table 3.

Example 29

[0210] The only difference from Example 28 lies in that the compound A is replaced with equimolar compound B. The results are shown in Table 3.

Comparative Example 12

[0211] The only difference from Example 28 lies that the compound A is replaced with equimolar C-donor. The results are shown in Table 3.

TABLE-US-00003 TABLE 3 Molar ratio of cocatalyst: Solid External external Ethylene catalyst electron electron Activity content Example component donor Cocatalyst donor (kgPP/gCat) (wt %) Example 25 Z1 — Compound A — 60 6.3 Comparative Z1 C-Donor — — 42 6.4 Example 11 Example 26 Z1 C-Donor Compound A 1:1 80 6.3 Example 27 Z1 C-Donor Compound A 1:9 76 6.3 Example 28 Z2 — Compound A — 80 4.6 Example 29 Z2 — Compound B — 100 4.5 Comparative Z2 C-Donor — — 62 4.7 Example 12 Note: C-Donor: cyclohexylmethyldimethoxysilane; the ethylene content refers to content of a —CH.sub.2CH.sub.2— unit derived from an ethylene monomer in the polymer.

[0212] It can be seen from Table 3 that when the catalyst system provided by the invention is used for olefin copolymerization, especially ethylene and propylene copolymerization, compared with C-Donor as an external electron donor, the ethylene content of the copolymer obtained from the catalyst system containing the twelve-membered ring represented by the formula (M) as a cocatalyst, is equivalent, and the polymerization activity is improved. According to the above characteristics of the catalyst provided by the invention, the catalyst system provided by the invention is also suitable for a copolymerization system to improve the copolymerization yield.

[0213] It should be noted that the above-mentioned examples are only used to explain the invention, and do not constitute any limitation to the invention. The invention may be modified within the scope of the claims of the invention as stipulated, and the invention may be revised without departing from the scope and spirit of the invention. Although the invention described therein relates to specific methods, materials and examples, it does not mean that the invention is limited to the specific examples disclosed therein. On the contrary, the invention can be extended to all other methods and use with the same function.