Catalyst component for olefin polymerization and application thereof

Abstract

Provided is a solid catalyst component for olefin polymerization, which comprises Mg, Ti, a halogen and an electron donor. The electron donor is selected from at least one of ring-substituted ether-acid ester compounds of the general formula (I). Also provided are a catalyst containing the solid catalyst component and the application of the catalyst in reactions of olefin polymerization, particularly in the reaction of propylene polymerization. The compound with a specific ring-substituted structure contained in the solid catalyst component of the present invention has a steric hindrance effect and a spatial configuration capable of fixing ether and acid ester functional groups, which has a positive influence on the participation thereof in the formation of an active centre of the catalyst and the improvement of the steric specificity of the catalyst. The solid catalyst component of the invention has a good activity. The polymers made therefrom have a high isotacticity.

1 . A solid catalyst component for olefin polymerization, comprising: Mg, Ti, a halogen and an electron donor, the electron donor being selected from at least one of ring-substituted ether-acid ester compounds of the general formula (I): 
       
         
           
           
               
               
           
         
         wherein, A, B, C, D, and E are each carbon atoms, or are selected from N, O and S heteroatoms; W, X, Y, Z, and m are each 0, 1 or 2; with the proviso that 
         when n is equal to 0: 
         IX) B is a nitrogen atom, A, C and D are each carbon atoms, X is 1, W, Y and Z are each 2; or 
         X) C is a nitrogen atom, A, B and D are each carbon atoms, Y is 1, W, X and Z are each 2; or 
         XI) C is an oxygen atom, A, B, and D are each carbon atoms, Y is 0, W, X and Z are each 2; or 
         XII) A and C are each oxygen atoms, W and Y are each 0, X and Z are each 2; or 
         XIII) B is an oxygen atom, A, C and D are each carbon atoms, X is 0, W, Y and Z are each 2; or 
         XIV) A, B, C and D are each carbon atoms and bonded to each other through a single bond, W, X, Y and Z are each 2; or 
         XV) A, B, C and D are each carbon atoms, B and C are bonded through a double bond, X and Y are each 1, W and Z are each 2; or 
         XVI) A, B, C and D are each carbon atoms, A and D, B and C, respectively, are bonded through a double bond, W, X, Y and Z are each 1; 
         when n is equal to 1: 
         x) D is a nitrogen atom, A, B, C, and E are each carbon atoms, Z is 1, W, X, Y, and m are each 2; or 
         xi) E is a nitrogen atom, A, B, C and D are each carbon atoms, m is 1, W, X, Y and Z are each 2; or 
         xii) E is an oxygen atom, A, B, C and D are each carbon atoms, m is 0, W, X, Y and Z are each 2; or 
         xiii) C and D are each oxygen atoms, A, B and E are each carbon atoms, Y and Z are each 0, W, X, and m are each 2; or 
         xiv) D is an oxygen atom, A, B, C, and E are each carbon atoms, Z is 0, W, X, Y, and m are each 2; or 
         xv) B is an oxygen atom, A, C, D, and E are each carbon atoms, X is 0, W, Y, Z, and m are each 2; 
         xvi) A, B, C, D, and E are each carbon atoms, W, X, Y, Z, and m are each 2; 
         xvii) A, B, C, D, and E are each carbon atoms, B and C are bonded through a double bond, X and Y are each 1, W, Z, and m are each 2; or 
         xviii) A, B, C, D, and E are each carbon atoms, A and D, B and C, respectively, are bonded through a double bond, W, X, Y and Z are each 1, m is 2; 
         when n is equal to 2: 
         A and B are each carbon atoms, W and X are each 2, C and D are each carbon atom, sulfur atom, oxygen atom or nitrogen atom, Y and Z are each 2 or 0, E represents two carbon atoms bonded through a single bond or a double bond, when the two carbon atoms of E are bonded through a double bond, m is equal to 1, and when the two carbon atoms of E are bonded through a single bond, m is equal to 2; 
         R 1  and R 4  are same or different C 1 -C 20  hydrocarbon group; R 2 , R 3 , R 5 -R 9  are same or different, and are selected from a hydrogen atom, a halogen atom, an oxygen atom, a sulfur atom and C 1 -C 20  hydrocarbon group; 
         said R 1 -R 9  optionally contain one or more R atoms as a substituent of a carbon atom, a hydrogen atom, or both, where R is a heteroatom, linear or branched C 1 -C 20  alkyl, C 3 -C 20  cycloalkyl, C 6 -C 20 -aryl, C 7 -C 20  alkaryl and C 7 -C 20  aralkyl group; wherein any two groups of R 1 -R 9  may be bonded to each other to form one or more spiro ring or fused ring structures. 
       
     
     
         2 . The solid catalyst component for olefin polymerization according to  claim 1 , wherein the compounds of the general formula (I) are of the following general formula (II): 
       
         
           
           
               
               
           
         
         wherein A, B, C and D are each carbon atoms and bonded to each other through a single bond, R 1 -R 8  groups are defined as in the general formula (I), R 5 -R 8  groups are same or different groups. 
       
     
     
         3 . The solid catalyst component for olefin polymerization according to  claim 2 , wherein the compounds of the general formula (II) are of the following general formula (III): 
       
         
           
           
               
               
           
         
         wherein R 1 -R 8  groups are defined as in the general formula (I), R 5 -R 8  groups are same or different groups. 
       
     
     
         4 . The solid catalyst component for olefin polymerization according to  claim 1 , wherein the compounds of the general formula (I) are of the following general formula (IV): 
       
         
           
           
               
               
           
         
         wherein R 1 -R 8  groups are defined as in the general formula (I). 
       
     
     
         5 . The solid catalyst component for olefin polymerization according to  claim 1 , wherein the compounds of the general formula (IV) are of the following general formula (V): 
       
         
           
           
               
               
           
         
         wherein R 1 -R 8  groups are defined as in the general formula (I), R′ are same or different, and selected from hydrogen, a halogen atom, linear or branched C 1 -C 20  alkyl, C 3 -C 20  cycloalkyl, C 6 -C 20  aryl, C 7 -C 20  alkaryl and C 7 -C 20  aralkyl. 
       
     
     
         6 . The solid catalyst component for olefin polymerization according to  claim 1 , wherein said compounds of the general formula group (I) are selected from the group consisting of the following compounds:
 five-membered ring ether-acid ester compounds:   ethyl 1-(1,1-vinyldioxyethyl)cyclopentane-1-carboxylate; ethyl 2-(1-methoxycyclopentane)-2-methoxy acetate; methyl 1-(methoxymethyl)cyclopentane carboxylate; methyl 1-(benzyloxymethyl)cyclohexyl carboxylate; ethyl 1-(4,4,6-trimethyl-[1,3]azapyran-2-yl)-cyclopentyl carboxylate; methyl 2-chloro-methoxyethyl-1-cyclopentyl carboxylate; bi(cyclohexyl carboxylic acid methyl ester)methyl methyl ether; ethyl 2-benzyloxy-(1,1-vinyldioxyethyl)cyclopentyl carboxylate; dimethyl-1-methoxybicyclo[2.2.2]oct-8-ene-2,6-dicarboxylic acid methyl ester; 1-methoxybicyclo[2.2.2]oct-9-ane, trimethyl-1-methoxybicyclo[2.2.1]heptane-2,6,10-tricarboxylate; 1-methoxy-1-cyclopentane carboxylic acid ethyl ester-3-phenyl-propylene; 2-benzyloxymethyl-2-ethoxycarbonyl-1-(tetrahydropyran-2-oxy)oxocyclopentane; 2-benzyloxy-2-ethoxycarbonyl-cyclopentanol; methyl 1-(1-methoxyethyl)cyclopentane carboxylate; 2-methyl-2-(1-cyclopentyl carboxylic acid ethyl ester-1-yl)-4-methylene-1,3-oxopropane; methyl-(3,4-dihydro-1H-isopyran-1-yl) cyclopentyl carboxylate; ethyl 1-(methoxymethyl)cyclopentane carboxylate; methyl-1-(ethoxymethyl)cyclopentane carboxylate; 2-benzyloxymethyl-1-cyclopentanonecarboxylic acid ethyl ester; methyl 1-benzyloxymethyl-pyrrolidine-2-carboxylate; methyl-hexahydro-2,2,7-trimethyl-6-oxo[1,3]dioxo[5,4-b]pyrrole-4a-carboxylate; methyl-2-benzyloxymethyl-5-carbonylpyrrolidine-2-carboxylate; methyl-1-(4-chlorophenyl)-3-(methoxymethyl)-4,5-dicarbonylpyrrole-3-carboxylate; methyl 3-methoxymethyl-pyrrolidine-3-carboxylate; 1-tert-butoxycarbonylmethyl-3-methoxymethyl-pyrrolidine-3-carboxylate; methyl 1-benzyl-3-methoxymethyl-pyrrolidine-3-carboxylate; 2-ethoxymethyl-pyrrolidine-1,2-dicarboxylic acid 1-tert-butyl ester 2-methyl ester; 2-isopropoxymethyl-pyrrolidine-1,2-dicarboxylic acid 1-tert butyl ester 2-ethyl ester; methyl 3-methoxymethyl-1-(3-methylphenyl)-4,5-dicarbonylpyrrolidine-3-carboxylate; methyl 3-methoxy-1-(4-fluorophenyl)-4,5-dicarbonylpyrrolidine-3-carboxylate; methyl 3-methoxymethyl-1-(4-bromophenyl)-4,5-dicarbonylpyrrolidine-3-carboxylate; methyl 1-(4-hydroxyphenyl)-3-methoxymethyl-4,5-dicarbonylpyrrolidine-3-carboxylate; ethyl 3-ethoxymethyl-1-phenyl-4,5-dicarbonylpyrrolidine-3-carboxylate; ethyl 3-ethoxymethyl-1-(3-methylphenyl)-4,5-dicarbonylpyrrolidine-3-carboxylate; ethyl 3-methoxymethyl-2-carbonyl-tetrahydrofuran-3-carboxylate; ethyl 3-isopropoxymethyl-2-carbonyl-tetrahydrofuran-3-carboxylate; ethyl 1-(4,4,6-trimethyl-[1,3]oxazin-2-yl)-cyclopentyl carboxylate; methyl-3-ethyl-2-[(2-trimethylsilylethoxy) methoxymethyl]1,4-dioxaspiro[4.4]nonane-2-carboxylate; methyl 5-oxo-phenyl-2-deoxy-4-methoxycarbonyl-D-pentofuranoside; 2-benzyloxymethyl-3-(2-methoxyvinyl)-2-methoxycarbonyl-1,4-oxaspiro[4.4]nonane; 4-pentenyl-5-O-benzyl-2-deoxy-4-methoxycarbonyl-D-pentofuranoside; methyl 5-O-benzyl-3-O-(t-butyldimethylsilane)-2-deoxy-4-methoxycarbonyl-D-pentofuranoside; 1-(2-benzyloxymethyl-3-hydroxy-2-methoxycarbonyl-5-tetrahydrofuran)thymine; 4-N-acetyl-1-(2-benzyloxymethyl-3-hydroxy-2-methoxycarbonyl-5-tetrahydrofuran)cytosine; 4-N-acetyl-5-O-benzyl-2-deoxy-4-methoxycarbonyl-cytosine; methyl-3,3-dimethyl-8-[5-methyl-2(1-H), 4-(3H)-dioxopyridine-1-yl]-2,4-dioxabicyclo[4.3.0]non-6-carboxylate; methyl-1-(4-methoxybenzyl)-2-benzyloxymethyl-3-hydroxy-3-methyl-4-methylene-5-pyrrolidin-2-carbaldehyde; methyl 2-(hydroxymethoxymethyl)1-methoxy-5-carbonylpyrrolidin-2-carboxylate; ethyl (2-cyclopentyl-[1,3]dioxolan-2-)-1-ethyl-2-oxa-2,3-dihydro-1H-indole-3-carboxylate; benzyloxycarbonyl-thioprolyl-thioproline diethyl acetal; benzyloxycarbonyl-thioprolyl-thioproline dibutyl acetal; benzyloxycarbonyl-thiprolyl-thioproline dimethyl acetal; methyl-2-(benzyloxymethyl)-3-hydroxy-4-methylene-5-carbonylpyrrolidine-2-carboxylate; 1-tert-butyl-2-methyl-2-(benzyloxymethyl)-5-oxo-pyrrolidine-1,2-dicarboxylate; methyl-2-benzyloxymethyl-3-tertbutyldimethylsilyloxy-4-methyl-5-carbonylpyrrolidine-2-carboxylate; 1-tert-butyl-2-methyl-2(benzyloxymethyl)-3-hydroxy-4-methylene-5-oxopyrrolidine-1,2-dicarboxylate; 5-tert-butyl-6-methyl-6-(benzyloxymethyl)-2-methyl-4-oxohexahydro-5H-pyrrolo[3,4-d]oxazole-5,6-dicarboxylate; methyl-1-(3,4-dihydro-1H-isobenzo-1-yl)cyclopentane carboxylate; tert-butyl-1-(1-ethoxy-3-phenyl-allyl)-2-carbonylcyclopentane carboxylate; 1-tert-butyl-2-methyl-2 (benzyloxymethyl)pyridine-1,2-dicarboxylate; N-(t-butoxycarbonyl)-α-(methoxymethyl) proline ethyl ester; N-(t-butoxycarbonyl)-α-(t-butylmethyl)proline ethyl ester; 1-tert-butyl-2-methyl-2-(benzyloxymethyl)pyrrolidine-1,2-dicarboxylate; methyl 3-benzyloxymethyl-1-(2,6-dimethylphenyl)-5-oxo-pyrrolidine-3-carboxylate; ethyl 1-benzyl-2-(diethoxymethyl)pyrrolidine-2-carboxylate; methyl 2-benzyloxymethyl-1-methyl-pyrrolidine-2-carboxylate;   9-methoxymethyl-fluorene carboxylic acid-(9)-methyl ester; 9-ethoxymethyl-fluorene carboxylic acid-(9)-methyl ester; 9-methoxymethyl-fluorene carboxylic acid-(9)-ethyl ester; 9-methoxymethyl-fluorene carboxylic acid-(9)-n-butyl ester; 9-methoxymethyl-fluorene carboxylic acid-(9)-isobutyl ester; 9-methoxymethyl-fluorene carboxylic acid-(9)-isopropyl ester; 9-ethoxymethyl-fluorene carboxylic acid-(9)-ethyl ester; 9-ethoxymethyl-fluorene carboxylic acid-(9)-n-butyl ester; 9-ethoxymethyl-fluorene carboxylic acid-(9)-isobutyl ester; 9-ethoxymethyl-fluorene carboxylic acid-(9)-isopropyl ester; bi(9-methoxycarbonyl-fluoren-9-yl)-ether; methyl 3-[1-[2-(indol-3-yl)-1-oxo-ethyl]]-2-methoxy-3-azabicyclo[3.2.1]oct-6-ene-7-ethyl-1-carboxylate; methyl-2-methoxydibenzobicyclo-[3.2.1]octadien-1-carboxylate; methyl-benzyloxymethyl-2-cyclopent-2-ene-1-carboxylate; methyl-4-[(tert-butoxycarbonyl)amino]-1-ethoxymethyl-cyclopent-2-ene-1-carboxylate; 8-benzyloxy-1-ethoxycarbonyl-5,7,7-trimethyl-2-(propan-2-ylidene)bicyclo[3.3.0]oct-2-ene; methyl-1,1-bis(hydroxymethyl)-3-methoxy-1,2,3,3a,6,6a-hexahydropentene-3a-carboxylate; methyl-1-(t-butyldimethylsiloxymethyl)-1-di(hydroxymethyl)-3-methoxy-1,2,3,3a,6,6a-hexahydropentene-3a-carboxylate; methyl 1,1-bis(benzyloxymethyl)-3-methoxy-1,2,3,3a,6,6a-hexahydropentene-3a-carboxylate; 1,2,3,4,5-pentamer (methoxycarbonyl)-5-(methoxy methyl)cyclopentadiene;   six-membered ring ether acid-ester compounds:   methyl benzyloxymethyl-cyclohexyl carboxylate; ethyl 8-benzyloxymethyl-1,4-dioxo-spiro[4.5]decane-8-carboxylate; 2-benzyloxymethyl-2-ethoxycarbonylcyclohexanol; 2-benzyloxymethyl-2-ethoxycarbonyl-1-(tetrahydrofuran-2-yl)oxycyclohexane; methyl 4-(1,3-dioxolan-2-yl)-(1,1′-di cyclohexyl)-4-carboxylate; ethyl-1-(benzyloxymethyl)-4,4-difluorocyclohexanecarboxylate; ethyl 6-methoxymethyl-1,4-dioxaspiro[4.5]decane-6-carboxylate; 2-methoxymethyl-2-ethoxycarbonyl-6-methyl cyclohexanol; ethyl 1-diethoxymethyl-cyclohexylcarboxylate; methyl methoxychloromethyl-cyclohexylcarboxylate; spiro[bicyclo[3.3.1]nonane-2,2′-[1.3]dioxa-2,2′-[1.3]dioxolane]1-butyric acid methyl ester; ethyl 1-benzyloxymethyl-4-dimethoxycyclohexyl-carboxylate; ethyl benzyloxymethyl-4-methoxycyclohexyl-carboxylate; ethyl-4-methyl-1-methoxymethyl-4-trimethylsiloxycyclohexyl carboxylate; methyl 1-methoxymethyl-cyclohexylcarboxylate; methyl 1-(3,4-dihydro-1H-isobenzo-1-yl) cyclopentyl carboxylate; tert-butyl-4-hydroxy-1-(methoxymethyl)cyclohexane carboxylate; tert-butyl-4-(tert-butyldimethylsiloxy)-1-(methoxymethyl)cyclohexane carboxylate; tert-butyl-4-(5-aminopyridine-2-oxy)-1-(methoxymethyl)cyclohexane carboxylate; tert-butyl-1-methoxymethyl-4-(5-nitropyridin-2-oxy)cyclohexanecarboxylate; ethyl 1-(2-methoxy-ethoxymethyl)-cyclohexyl carboxylate; ethyl 4,4-difluoro-1-(methoxymethyl)cyclohexyl carboxylate; 4-benzyloxymethyl-piperidine-1,4-dicarboxylic acid 1-tert-butyl ester 4-ethyl ester; ethyl 4-benzyloxymethyl-piperidine-4-carboxylate; ethyl 1-((benzyloxymethyl)methyl)2-oxocyclohexane carboxylate; 2-benzyloxymethyl-2-ethoxycarbonyl cyclohexanol; 2-benzyloxymethyl-2-ethoxycarbonyl-1-(tetrahydropyran-2-yl)-oxy-cyclohexane; ethyl 4-methoxymethylpiperidine-4-carboxylate; methyl 5-methoxyethyl-2-phenyl-[1.3]dioxan-5-carboxylate; ethyl 2-oxacyclohexan-oxo-furo-[1.3]dithiane-2-carboxylate; diethyl-3-phenyl-6,6-(ethylenedioxy)-2-oxo-3-azabicyclo[3.3.1]nonane-1,5-dicarboxylate; methyltetrahydro-(3,4-dihydro-1H-isobenzo-1-yl)-2H-pyran-4-carboxylate; methyltetrahydro-(3,4-dihydro-1H-isobenzo-1-yl)-2H-pyran-4-carboxylate; methyl 1-(3,4-dihydro-1H-isobenzo-1-yl)cyclohexanecarboxylate; methylenetetrahydro-3,4-dihydro-5-methyl-1H-isobenzo-1-yl)-2H-2-pyran-4-carboxylate; ethyl 4,4-difluoro-1-(methoxymethyl)cyclohexane carboxylate; ethyl 2-(methoxymethyl)tetrahydro-2H-pyran-2-carboxylate; 3-methoxymethyl-3-ethoxy carbonyl-1-methyl-cyclohexen(1); methyl-2,3,3a,4,5,7a-hexahydro-3,3a-dimethyl-1,5-bi-[2-(trimethylethoxysilane-oxy]indene-7a-carboxylate; 1-benzyloxymethyl-1-methoxycarbonyl-2,5-cyclohexene;   seven-membered ring ether-ester compounds:   methyl 4-benzyl-7-methoxy-3-oxo-3,4-dihydro-2H-1,5-benzothia-4-carboxylate; methyl 4-benzyloxymethyl-3-(4-methoxybenzyl)-5-methyl-7-oxo-6-oxa-3-aza-bicyclo[3.2.0]heptane-4-carboxylate.   
     
     
         7 . The solid catalyst component according to  claim 1 , which is the reaction product of a titanium compound, a magnesium compound, and a ring-substituted ether-acid ester compound selected from the general formula (I), wherein a precursor of said magnesium compound is selected from at least one of: Mg(OR) 2 , X n Mg(OR) 2-n , MgCl 2 .mROH, R 2-n MgX n , MgR 2 , MgCl 2 /SiO 2 , MgCl 2 /Al 2 O 3 , or mixture of magnesium halide and titanium alkoxide, wherein m is a number from 0.1 to 6, 0<n<2, X is halogen, R is hydrogen or C 1 -C 20  hydrocarbon group; and wherein said titanium compound is represented by the general formula TiXn(OR) 4-n , wherein R is C 1 -C 20  hydrocarbon group, X is halogen, n=1-4. 
     
     
         8 . (canceled) 
     
     
         9 . (canceled) 
     
     
         10 . A catalyst for polymerization of an olefin CH 2 ═CHR, wherein R is hydrogen or hydrocarbon group having 1-12 carbon atoms, comprising: the reaction product of the following substances:
 (a) a solid catalyst component according to  claim 1 ; 
 (b) at least one organic aluminum compound of the general formula AlR n X (3-n) , wherein R is hydrogen or a hydrocarbon group having 1-20 carbon atoms; X is halogen, n is an integer of 0≦n≦3; and optionally, 
 (c) at least one external electron donor compound. 
 
     
     
         11 . The catalyst according to  claim 10 , wherein the organic aluminum compound (b) is a trialkylaluminum compound. 
     
     
         12 . The catalyst according to  claim 11 , wherein the trialkylaluminum compound is selected from the group consisting of trimethylaluminum, triethylaluminum, triisobutylaluminum, tri-n-butyl aluminum, tri-n-hexyl aluminum, trioctyl aluminum. 
     
     
         13 . The catalyst according to  claim 10 , wherein said external electron donor (c) is selected from a siloxane compound of the general formula R n Si(OR 1 ) 4-n , wherein R and R 1  are a C 1 -C 18  hydrocarbon group which optionally includes heteroatoms; and n is an integer that satisfies 0≦n≦3. 
     
     
         14 . A pre-polymerization catalyst for an olefin CH 2 ═CHR polymerization, wherein R is hydrogen or hydrocarbon group having 1 to 12 carbon atoms, comprising: a prepolymer obtained by pre-polymerization of the solid catalyst component according to  claim 1  and the olefin. 
     
     
         15 . The pre-polymerization catalyst according to  claim 14 , characterized in that the olefin for pre-polymerization is ethylene or propylene. 
     
     
         16 . (canceled) 
     
     
         17 . (canceled)