Catalyst system for olefin polymerization and use thereof
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.
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),
wherein in the formula (M), R 1 -R 16 are the same or different, each independently selected from the 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 the group consisting of alkoxy and hydrocarbyl, the two adjacent groups may optionally form a ring with each other, the ring selected from the group consisting of a saturated or unsaturated monocyclic ring, a saturated or unsaturated polycyclic ring and a combination thereof; and wherein R 17 to R 24 are the same or different, each independently selected from the group consisting of hydrogen and C 1 -C 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 titanium element in the solid catalyst component is (0-500):1.
4. The catalyst system according to claim 1 , characterized in that,
in the formula (M), R 1 -R 16 are the same or different, each independently selected from the group consisting of hydrogen, hydroxyl, halogen, cyano, nitro, amino, mono-C 1 -C 10 alkyl amine, bis-C 1 -C 10 alkyl amine, C 1 -C 10 aldehyde, C 1 -C 10 carboxyl, R a C(O)—, R a O—, C 1 -C 20 alkyl, C 2 -C 20 alkenyl, C 2 -C 20 alkynyl, C 3 -C 20 cycloalkyl, C 6 -C 20 aryl, C 7 -C 20 aralkyl, 4-12-membered heterocycloalkyl and C 5 -C 20 heteroaryl, and when two adjacent groups on a benzene ring are each selected from the group consisting of R a C(O)—, R a O—, C 1 -C 20 alkyl, C 2 -C 20 alkenyl, C 2 -C 20 alkynyl, C 3 -C 20 cycloalkyl, C 6 -C 20 aryl, C 7 -C 20 aralkyl, 4-12-membered heterocycloalkyl and C 5 -C 20 heteroaryl, the two adjacent groups may optionally form a ring with each other, the ring selected from the group consisting of a saturated or unsaturated monocyclic ring, a saturated or unsaturated polycyclic ring and a combination thereof,
wherein R a is selected from the group consisting of C 1 -C 20 alkyl, C 2 -C 20 alkenyl, C 2 -C 20 alkynyl, C 3 -C 20 cycloalkyl, C 6 -C 20 aryl, C 7 -C 20 aralkyl, 4-12-membered heterocycloalkyl and C 5 -C 20 heteroaryl; and
R 17 to R 24 are the same or different, each independently selected from the group consisting of hydrogen, C 1 -C 10 alkyl, C 2 -C 10 alkenyl, C 2 -C 10 alkynyl, C 3 -C 8 cycloalkyl, C 6 -C 10 aryl, C 7 -C 20 aralkyl, 4-12-membered heterocycloalkyl and C 5 -C 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 the group consisting of alkyl, alkoxyl, hydroxyl, halogen, cyano, nitro, amino, alkyl substituted amino, aldehyde, carboxyl and a heteroatom-containing group.
6. The catalyst system according to claim 1 , characterized in that, in the formula (M), R 1 to R 16 are the same or different, and are each independently selected from the group consisting of hydrogen, hydroxyl, halogen, cyano, nitro, amino, mono-C 1 -C 6 alkyl amine, bis-C 1 -C 6 alkyl amine, C 1 -C 6 aldehyde, C 1 -C 6 carboxyl, R a C(O)—, R a O—, C 1 -C 6 alkyl, C 2 -C 6 alkenyl, C 2 -C 6 alkynyl, C 3 -C 6 cycloalkyl, C 6 -C 10 aryl, C 7 -C 10 aralkyl, 4-6-membered heterocycloalkyl and C 5 -C 10 heteroaryl, wherein R a is selected from the group consisting of C 1 -C 6 alkyl, C 2 -C 6 alkenyl, C 2 -C 6 alkynyl, C 3 -C 6 cycloalkyl, C 6 -C 10 aryl, C 7 -C 10 aralkyl, 4-6-membered heterocycloalkyl and C 5 -C 10 heteroaryl.
7. The catalyst system according to claim 1 , characterized in that, in the formula (M), R 1 , R 4 , R 5 , R 8 , R 9 , R 12 , R 13 and R 16 are each independently selected from the group consisting of hydrogen and C 1 -C 6 alkyl; R 2 , R 3 , R 6 , R 7 , R 10 , R 11 , R 14 and R 15 are each independently selected from the group consisting of hydroxyl, amino, halogen, C 1 -C 6 aldehyde, C 1 -C 6 alkoxyl and halogen substituted C 1 -C 6 alkoxyl.
8. The catalyst system according to claim 1 , characterized in that, in the formula (M), R 17 to R 24 are each independently selected from the group consisting of hydrogen and C 1 -C 10 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),
10. The catalyst system according to claim 2 , 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 and 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,
wherein, in the formula B, R 1 and R 2 are the same or different, each independently selected from the group consisting of C 1 -C 20 alkyl, C 2 -C 20 alkenyl, C 3 -C 20 cycloalkyl, C 6 -C 20 aryl, C 7 -C 20 alkaryl, C 7 -C 20 aralkyl and C 10 -C 20 fused ring aryl, the alkyl, alkenyl, cycloalkyl, aryl, alkaryl, aralkyl and fused ring aryl optionally substituted by one or more substituents selected from the group consisting of C 1 -C 10 alkyl, C 1 -C 10 alkoxyl, hydroxyl, halogen, cyano, nitro, amino, mono-C 1 -C 6 alkyl amine, bis-C 1 -C 6 alkyl amine, aldehyde, carboxyl and a heteroatom; and M is a divalent linking group;
the diether compound is a 1,3-diether compound represented by formula E,
wherein, in the formula E, R I , R II , R III , R IV , R V and R VI are the same or different, and are each independently selected from the group consisting of hydrogen, halogen, C 1 -C 20 alkyl, C 3 -C 20 cycloalkyl, C 6 -C 20 aryl, C 7 -C 20 aralkyl and C 7 -C 20 alkaryl; R VII and R VIII are the same or different, and are each independently selected from the group consisting of C 1 -C 20 alkyl, C 3 -C 20 cycloalkyl, C 6 -C 20 aryl, C 7 -C 20 aralkyl and C 7 -C 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 the group consisting of hydroxyl, halogen, cyano, nitro, amino, mono-C 1 -C 10 alkyl amine, bis-C 1 -C 10 alkyl amine, aldehyde, carboxyl and a heteroatom; or, two or more of R I , R II , R III , R IV , R V and R VI are bonded to each other to form a saturated or unsaturated monocyclic or polycyclic ring;
a structure of the aromatic carboxylic acid ester compound is as shown in formula F:
wherein, in the formula F, each R 3 is the same or different, which is independently C 1 -C 8 alkyl, C 5 -C 10 cycloalkyl, C 6 -C 15 aryl, C 7 -C 15 alkaryl or C 7 -C 15 aralkyl, and hydrogen on carbon of the C 1 -C 8 alkyl, C 3 -C 10 branched alkyl, C 5 -C 10 cycloalkyl, C 6 -C 15 aryl, C 7 -C 15 alkaryl or C 7 -C 15 aralkyl may be optionally substituted by a substituent selected from the group consisting of an alkane and a halogen atom; and R 4 -R 7 may be the same or different, which are hydrogen, halogen, C 1 -C 6 alkyl, C 5 -C 10 cycloalkyl, C 6 -C 20 aryl, C 7 -C 20 alkaryl or C 7 -C 20 aralkyl, and hydrogen on carbon of the C 1 -C 8 alkyl, C 5 -C 10 cycloalkyl, C 6 -C 15 aryl, C 7 -C 15 alkaryl or C 7 -C 15 aralkyl may be optionally substituted by a substituent selected from the group consisting of an alkane and a halogen atom; and
a structure of the succinate compound is as shown in formula G,
wherein, in the formula G, R 1 and R 2 are the same or different, each independently selected from the group consisting of a C 1 -C 20 alkyl group, a C 3 -C 20 cycloalkyl group, a C 6 -C 20 aryl group, a C 7 -C 20 arylalkyl group or a C 7 -C 20 alkylaryl group, and optionally containing a heteroatom; and R 3 , R 4 , R 5 and R 6 are the same or different, each independently selected from the group consisting of hydrogen, a C 1 -C 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 and 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:
wherein in the formula D, R 1 to R 4 are the same or different, each independently selected from the group consisting of hydrogen, C 1 -C 10 alkyl, C 2 -C 10 alkenyl, C 1 -C 10 alkoxyl, C 2 -C 10 enyloxy, C 2 -C 10 alkynyl, C 2 -C 10 _ynoxy, C 3 -C 10 cycloalkyl, C 6 -Cis aryl, C 3 -C 10 cycloalkoxyl, C 6 -C 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 the group consisting of halogen, C 1 -C 6 alkyl, C 3 -C 6 cycloalkyl, C 6 -C 10 aryl and amino; and
the ether compound is a 1,3-diether compound represented by formula E,
wherein, in the formula E, R I , R II , R III , R IV , R V and R VI are the same or different, and are each independently selected from the group consisting of hydrogen, halogen, C 1 -C 20 alkyl, C 3 -C 20 cycloalkyl, C 6 -C 20 aryl, C 7 -C 20 _aralkyl and C 7 -C 20 alkaryl; R VII and R VIII are the same or different, and are each independently selected from the group consisting of C 1 -C 20 alkyl, C 3 -C 20 cycloalkyl, C 6 -C 20 aryl, C 7 -C 20 aralkyl and C 7 -C 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 the group consisting of hydroxyl, halogen, cyano, nitro, amino, mono-C 1 -C 10 alkyl amine, bis-C 1 -C 10 alkyl amine, aldehyde, carboxyl and a heteroatom; or, two or more of R I , R II , R III , R IV , R V and R VI and are bonded to each other to form a saturated or unsaturated monocyclic or polycyclic 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.
15. The catalyst system according to claim 2 , characterized in that, the organic aluminum compound is an alkyl aluminum compound.
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
a molar ratio of the solid catalyst component in terms of titanium element to the organic aluminum compound in terms of aluminum is 1:(5-5000).
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.
18. A method for olefin polymerization, comprising: polymerizing an olefin having a general formula of CH 2 ═CHR in the presence of the catalyst system according to claim 1 , wherein R is hydrogen or C 1 -C 8 alkyl.
19. A method for olefin polymerization, comprising: polymerizing an olefin having a general formula of CH 2 ═CHR in the presence of the prepolymerized catalyst composition according to claim 17 , wherein R is hydrogen or C 1 -C 8 alkyl.
20. The method for olefin polymerization according to claim 18 , wherein R is hydrogen or C 1 -C 8 alkyl, wherein the olefin is selected from one or more of ethylene, propylene, 1-butene, 4-methyl-1-pentene, and 1-hexene.
21. The catalyst system according to claim 3 , characterized in that the molar ratio of the external electron donor compound to titanium element in the solid catalyst component is (0.01-200):1.
22. The catalyst system according to claim 5 , characterized in that, in the formula (M), the substituents are selected from the group consisting of C 1 -C 10 alkyl, C 1 -C 10 alkoxyl, hydroxyl, halogen, cyano, nitro, amino, mono-C 1 -C 10 alkyl amine, bis-C 1 -C 10 alkyl amine, C 1 -C 10 aldehyde, C 1 -C 10 carboxyl and a heteroatom-containing group.
23. The catalyst system according to claim 6 , characterized in that, in the formula (M), R 1 to R 16 are selected from the group consisting of hydrogen, hydroxyl, amino, halogen, C 1 -C 6 aldehyde, C 1 -C 6 alkoxyl and halogen substituted C 1 -C 6 alkoxyl.
24. The catalyst system according to claim 9 , characterized in that, 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 2 ═R 3 ═R 6 ═R 7 ═R 10 ═R 11 ═R 14 ═R 15 ═OCH 3 ;
Compound B: in the formula (N), R 2 ═R 3 ═R 6 ═R 7 ═R 10 ═R 11 ═R 14 ═R 15 ═OCH 2 CH 3 ;
Compound C: in the formula (N), R 2 ═R 3 ═R 6 ═R 7 ═R 10 ═R 11 ═R 14 ═R 15 ═OCH 2 CH 2 CH 3 ;
Compound D: in the formula (N), R 2 ═R 3 ═R 6 ═R 7 ═R 10 ═R 11 ═R 14 ═R 15 ═OCH(CH 3 ) 2 ;
Compound E: in the formula (N), R 2 ═R 3 ═R 6 ═R 7 ═R 10 ═R 11 ═R 14 ═R 15 ═OCH 2 CH 2 CH 2 CH 3 ;
Compound F: in the formula (N), R 2 ═R 6 ═R 10 ═R 14 ═OCH 3 and R 3 ═R 7 ═R 11 ═R 15 ═OCH 2 CH 3 ;
Compound G: in the formula (N), R 2 ═R 6 ═R 10 ═R 14 ═OCH 3 and R 3 ═R 7 ═R 11 ═R 15 ═OCH 2 CH 2 CH 3 ;
Compound H: in the formula (N), R 2 ═R 6 ═R 10 ═R 14 ═OCH 3 and R 3 ═R 7 ═R 11 ═R 15 ═OCH 2 CH 2 CH 2 CH 3 ;
Compound I: in the formula (N), R 2 ═R 3 ═R 6 ═R 7 ═R 10 ═R 11 ═R 14 ═R 15 ═OH;
Compound J: in the formula (N), R 2 ═R 6 ═R 10 ═R 14 ═OCH 3 and R 3 ═R 7 ═R 11 ═R 15 ═OH;
Compound K: in the formula (N), R 2 ═R 6 ═R 10 ═R 14 ═OCH 3 and R 3 ═R 7 ═R 11 ═R 15 ═NH 2 ;
Compound L: in the formula (N), R 2 ═R 6 ═R 10 ═R 14 ═OCH 3 and R 3 ═R 7 ═R 11 ═R 15 ═Cl;
Compound M: in the formula (N), R 2 ═R 6 ═R 10 ═R 14 ═OCH 3 and R 3 ═R 7 ═R 11 ═R 15 ═Br;
Compound N: in the formula (N), R 2 ═R 6 ═R 10 ═R 14 ═OCH 3 and R 3 ═R 7 ═R 11 ═R 15 ═I;
Compound O: in the formula (N), R 2 ═R 6 ═R 10 ═R 14 ═OCH 3 and R 3 ═R 7 ═R 11 ═R 15 ═CHO;
Compound P: in the formula (N), R 2 ═R 6 ═R 10 ═R 14 ═OCH 3 and R 3 ═R 7 ═R 11 ═R 15 ═OCH 2 CH 2 CH 2 Br;
Compound Q: in the formula (N), R 2 ═R 3 ═R 6 ═R 7 ═R 10 ═R 11 ═R 14 ═R 15 ═OCH 2 CH 2 Cl; and
Compound R: in the formula (N), R 2 ═R 6 ═R 10 ═R 14 ═OH and R 3 ═R 7 ═R 11 ═R 15 ═OCH 2 CH 3 .
25. The catalyst system according to claim 11 , characterized in that,
wherein, in the formula B, R 1 and R 2 each independently selected from the group consisting of C 1 -C 10 alkyl, C 2 -C 10 alkenyl, C 3 -C 10 cycloalkyl, C 6 -C 10 aryl, C 7 -C 10 alkaryl, C 7 -C 10 aralkyl and C 10 -C 15 fused ring aryl; and/or M is selected from the group consisting of C 1 -C 20 alkylene, C 3 -C 20 cycloalkylene and C 6 -C 20 arylene, the alkylene, cycloalkylene and/or arylene substituted by a substituent selected from the group consisting of C 1 -C 20 alkyl, C 1 -C 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;
and/or wherein, in the formula E, two or more of R I , R II , R III , R IV , R V and R VI are bonded to each other to form a fluorene ring.
26. The catalyst system according to claim 15 , characterized in that, a general formula of the alkyl aluminum compound is AlR 3 , wherein each R is independently selected from the group consisting of hydrogen, halogen, C 1 -C 20 alkyl, C 1 -C 20 alkoxyl or halogenated C 1 -C 20 alkyl, and at least one of three Rs is C 1 -C 20 alkyl.
27. The catalyst system according to claim 26 , characterized in that, the general formula of the alkyl aluminum compound is AlR 3 , wherein each R is independently selected from the group consisting of hydrogen, halogen, C 1 -C 10 alkyl, C 1 -C 10 alkoxyl or halogenated C 1 -C 10 alkyl, and at least one of the three Rs is C 1 -C 10 alkyl.
28. The catalyst system according to claim 17 , characterized in that, a prepolymerization multiple of the prepolymer being 0.1-1000 g olefin polymer/g solid catalyst component.