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.

Claims

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): ##STR00007## 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.sup.1 and R.sup.4 are same or different C.sub.1-C.sub.20 hydrocarbon group; R.sup.2, R.sup.3, R.sup.5-R.sup.9 are same or different, and are selected from a hydrogen atom, a halogen atom, an oxygen atom, a sulfur atom and C.sub.1-C.sub.20 hydrocarbon group; said R.sup.1-R.sup.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.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 alkaryl and C.sub.7-C.sub.20 aralkyl group; wherein any two groups of R.sup.1-R.sup.9 may be bonded to each other to form one or more spiro ring or fused ring structures, with the proviso that either D, A, R.sup.5 and R.sup.8 together do not form a benzyl ring, or that B, C, R.sup.7 and R.sup.6 together do not form a benzyl ring.

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): ##STR00008## wherein A, B, C and D are each carbon atoms and bonded to each other through a single bond, R.sup.1-R.sup.8 groups are defined as in the general formula (I), R.sup.5-R.sup.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): ##STR00009## wherein R.sub.1-R.sup.8 groups are defined as in the general formula (I), R.sup.5-R.sup.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): ##STR00010## wherein R.sup.1-R.sup.8 groups are defined as in the general formula (I).

5. 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; methy1-(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-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-1yl]-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; bi(9-methoxy carbonyl-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[0.3.0]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′-dicyclohexyl)-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-ethoxycarbonyl-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.

6. 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).sub.2, X.sub.nMg(OR).sub.2-n, MgCl.sub.2.mROH, R.sub.2-nMgX.sub.n, MgR.sub.2, MgCl.sub.2/SiO.sub.2, MgCl.sub.2/Al.sub.2O.sub.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.sub.1-C.sub.20 hydrocarbon group; and wherein said titanium compound is represented by the general formula TiXn(OR).sub.4-n, wherein R is C.sub.1-C.sub.20 hydrocarbon group, X is halogen, n=1-4.

7. A catalyst for polymerization of an olefin CH.sub.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.sub.nX.sub.(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.

8. The catalyst according to claim 7, wherein the organic aluminum compound (b) is a trialkylaluminum compound.

9. The catalyst according to claim 8, wherein the trialkylaluminum compound is selected from the group consisting of trimethylaluminum, triethylaluminum, triisobutylaluminum, tri-n-butyl aluminum, tri-n-hexyl aluminum, trioctyl aluminum.

10. The catalyst according to claim 7, wherein said external electron donor (c) is selected from a siloxane compound of the general formula R.sub.nSi(OR.sub.1).sub.4-n, wherein R and R.sub.1 are a C.sub.1-C.sub.18 hydrocarbon group which optionally includes heteroatoms; and n is an integer that satisfies 0≦n≦3.

11. A pre-polymerization catalyst for an olefin CH.sub.2═CHR polymerization, wherein R is hydrogen or a 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.

12. The pre-polymerization catalyst according to claim 11, wherein the olefin for pre-polymerization is ethylene or propylene.

Description

SPECIFIC MODES FOR CARRYING OUT THE EMBODIMENTS

[0094] The following examples further illustrating the present invention are intended to make the advantages and effects of the invention better understood, but these examples are only for illustrating the present invention and not for limiting the present invention.

[0095] Five-membered ring ether ester compounds listed in the examples are only to illustrate the present invention, and not limiting the present invention. Other compounds that are within the scope of the present invention but not mentioned in the examples, such as the six-membered ring and seven-membered ring ether ester compounds, will also have similar properties as those of compounds of the examples.

Preparation of Ring-Substituted Ether-Acid Ester Compounds

Example 1 Synthesis of 9-Methoxymethyl-Fluorene Carboxylic Acid-(9)-Methyl Ester

[0096] Step A: to a 1000 mL three-necked flask were successively added 18 g sodium hydride, 50 g fluorene, 150 mL toluene under nitrogen, with mechanical stirring, the temperature was raised to 125° C. to reflux for 4 h; after cooling to 90° C., 146.1 g diethyl carbonate was slowly added dropwise to the flask over 1.5 h, then the reaction was continued for 3 h; after cooling to 20° C., a mixture of 60 g concentrated hydrochloric acid and 75 g water was slowly added dropwise, and the temperature was controlled to be no greater than 40° C.; the organic phase was separated by filtering and washed with water to neutral, followed by rotary evaporation to yield a red-brown liquid; the resulting liquid obtained by rotary evaporation, 157.4 g acetic acid and 63 g 10% hydrochloric acid were refluxed overnight; the mixture was cooled to 20° C., followed by liquid separation; 30% NaOH solution was added to the organic phase after rotary evaporation, which was adjusted to pH 8 and extracted with ethyl acetate, the aqueous phase was retained. Concentrated hydrochloric acid was added to the aqueous phase to adjust the pH to 5, which was extracted with ethyl acetate, the organic phase was retained for rotary evaporation; the products were dissolved in ethyl acetate and frozen for recrystallization; the crude products after filtration were washed with hexane to give colorless crystals of about 10 g, melting point: 228˜230° C.

[0097] Step B: to a 250 mL three-necked flask were added 2 g (9.5 mmol) 9-fluorene carboxylic acid, methanol (30 mL), concentrated sulfuric acid (0.2 mL); the mixture was heated to reflux for 2 h, cooled to room temperature, and poured into a saturated sodium bicarbonate solution, and extracted twice with ethyl acetate (30 mL*2), the combined organic phase was washed with brine (30 mL*1), evaporated under reduced pressure to give a yellow solid, followed by drying with oil pump to give 1.8 g crude products with mp 62-65° C.

[0098] Step C: to a 250 mL three-necked round bottom flask were added methanol (20 mL), metallic sodium (0.12 g, 5 mmol) and placed under ice-bath, after metallic sodium was completely dissolved until no bubble emerges, 9-fluorene carboxylic acid methyl ester (0.56 g, 2.5 mmol) was added and completely dissolved, the mixture appeared yellow and was stirred for 5 min, chloromethyl methyl ether (0.6 g, 7.5 mmol) was added therein, stirred for 30 min, poured into an aqueous solution, extracted with dichloromethane (20 mL*2) and extracted twice with ethyl acetate (50 mL*2). The combined organic phases were washed with saturated brine (50 mL*1), followed by rotary evaporation to remove liquid, the resulting crude product was washed with hexane to give the product, 126-129° C. 9-methoxymethyl-fluorene carboxylic acid-(9)-methyl ester, 1H-NMR (CDCl.sub.3) δ (ppm): 3.370 (s, 3H, ether methyl), 3.660 (s, 3H, ester methyl), 3.791 (s, 2H, methylene hydrogen), 7.313-7.345 (t, 2H, aromatic hydrogen), 7.408-7.440 (t, 2H, aromatic hydrogen), 7.707-7.745 (m, 4H, aromatic hydrogen).

Example 2 Synthesis of 9-Ethoxymethyl-Fluorene Carboxylic Acid-(9)-n-Butyl Ester

[0099] The synthetic steps were the same as those of Example 1, except that the methanol Step B was replaced by n-butanol. 1H-NMR (CDCl.sub.3) δ (ppm): 0.86 (t, 3H, hydrogen), 1.27 (m, 2H, methylene hydrogen), 1.54 (m, 2H, methylene hydrogen), 3.37 (s, 3H, ether methyl hydrogen), 3.80 (s, 2H, ether, methylene hydrogen), 4.11 (t, 2H, ester methylene hydrogen), 7.31-7.40 (t, 2H, aromatic hydrogen), 7.42-7.43 (t, 2H, aromatic hydrogen), 7.72-7.74 (m, 4H, aromatic hydrogen).

Example 3 Synthesis of 9-Methoxymethyl-Fluorene Carboxylic Acid-(9)-Isobutyl Ester

[0100] The synthetic steps were the same as those in Example 1, except that the methanol of step B was replaced by isobutanol. 1H-NMR (CDCl.sub.3) δ (ppm): 0.832-0.0845 (d, 6H, methyl hydrogen), 1.833-1.900 (m, 1H, methine hydrogen), 3.384 (s, 3H, ether methyl hydrogen), 3.821 (s, 2H, ether methylene hydrogen), 3.887-3.900 (d, 2H, ester methylene hydrogen), 7.260-7.352 (t, 2H, aromatic hydrogen), 7.408-7.440 (t, 2H, the aromatic ring hydrogen), 7.735-7.750 (m, 4H, aromatic hydrogen).

Example 4 Synthesis of 9-Methoxymethyl-Fluorene Carboxylic Acid-(9)-Isopropyl Ester

[0101] The synthetic steps were the same as those of Example 1, except that the methanol of step B was replaced by isopropanol. 1H-NMR (CDCl.sub.3) δ (ppm): 1.179-1.191 (d, 6H, methyl hydrogen), 3.364 (s, 3H, ether methyl hydrogen), 3.768 (s, 2H, ether methylene hydrogen), 5.035-5.085 (m, 1H, methine hydrogen), 7.303-7.335 (t, 2H, aromatic hydrogen), 7.392-7.409 (t, 2H, aromatic hydrogen), 7.716-7.733 (m, 4H, aromatic ring hydrogen).

Example 5 Synthesis of 9-Methoxymethyl-Fluorene Carboxylic Acid-(9)-Ethyl Ester

[0102] Synthetic steps were the same as those of Example 1, except that the methanol of step B was replaced by ethanol. 1H-NMR (CDCl.sub.3) δ (ppm): 1.17-1.20 (t, 3H, methyl hydrogen), 3.37 (s, 3H, hydrogen methyl ether), 3.791 (s, 2H, ether methylene hydrogen), 4.14-4.19 (m, 2H, ester methylene hydrogen), 7.26-7.42 (t, 2H, aromatic hydrogen), 7.42-7.44 (t, 2H, aromatic hydrogen), 7.73-7.74 (m, 4H, aromatic ring hydrogen).

Example 6 Synthesis of 9-ethoxymethyl-fluorene carboxylic acid-(9) methyl ester

[0103] The synthetic steps were the same as those of Example 1, except that the chloromethyl methyl ether of step C of was replaced by chloromethyl ether. 1H-NMR (CDCl.sub.3) δ (ppm): 1.11-1.18 (t, 3H, ether methyl hydrogen), 3.40-3.46 (m, 2H, ether methylene hydrogen), 3.66 (s, 3H, ester methyl hydrogen), 3.65-3.79 (s, 2H, ether methylene hydrogen), 7.31-7.34 (t, 2H, aromatic hydrogen), 7.40-7.44 (t, 2H, aromatic hydrogen), 7.70-7.74 (m, 4H, aromatic hydrogen).

Example 7 Synthesis of 9-Ethoxymethyl-Fluorene Carboxylic Acid-(9)-Ethyl Ester

[0104] The synthetic steps were the same as those of Example 1, except that the methanol of step B was replaced by ethanol, and chloromethyl methyl ether of Step C was replaced by chloromethyl ether. 1H-NMR (CDCl.sub.3) δ (ppm): 1.13-1.17 (t, 3H, ether methyl hydrogen), 1.30-1.34 (t, 3H, ester methyl hydrogen), 3.40-3.46 (m, 2H, ether methylene hydrogens), 3.90 (s, 2H, ether methylene hydrogen), 4.12-4.16 (m, 2H, ester methylene hydrogen), 7.26-7.40 (t, 2H, aromatic hydrogen), 7.41-7.43 (t, 2H, aromatic hydrogen), 7.72-7.74 (m, 4H, aromatic hydrogen).

Example 8 Synthesis of 1-Benzyloxymethyl-1-Methoxyacyl-2,5-Cyclopentadiene

[0105] The synthetic step was the same as Step c of Example 1, except that the chloromethyl methyl ether of Step C was replaced by chloromethyl benzyl ether, and 9-fluorene carboxylic acid methyl ester was replaced by cyclohexa-2,5-diene-carboxylic acid methyl ester. 1H-NMR (CDCl.sub.3) δ (ppm): 2.62-2.64 (m, 1H, cyclohexadiene hydrogen), 3.63-3.67 (s, 3H, ester methyl hydrogen), 3.77-3.79 (s, 2H, ether methylene hydrogen), 4.60-4.66 (s, 2H, ether methylene hydrogen), 3.90 (s, 2H, ether methylene hydrogen), 5.58-5.62 (d, 2H, cyclohexadiene hydrogen), 5.64-5.70 (m, 2H, cyclohexadiene hydrogen), 7.16-7.20 (m, 5H, aromatic hydrogen).

Preparation of Solid Catalyst Component

[0106] Preparation of the catalysts in Examples was carried out in the protective atmosphere of high purity nitrogen. Specific examples were provided as follows.

Example 9

[0107] To a 500 ml fully nitrogen-purged five-necked flask equipped with a stirrer were added 10 g diethoxy magnesium and 80 mL toluene to prepare a suspension, and then 20 mL titanium tetrachloride was added dropwise at −15° C., after addition was completed the system was slowly warmed to 10° C. after 60 mL titanium tetrachloride was added dropwise, then slowly warmed to 80° C. and then, 2.8 g 9-methoxymethyl-fluorene carboxylic acid-(9)-methyl ester was added, and then the temperature of the system was raised up to 120° C. and maintained constant for 2 hours, then the liquid was cleaned by filter pressing and filtered, the resulting solid was washed 3 times with 120 mL titanium tetrachloride at 125° C. The resulting solid was washed two times at 60° C. and two times at room temperature with 150 mL hexane; after removal of the liquid by filtration and drying the solid, 10.43 g solid powder, i.e. solid catalyst component, was obtained. Analytical results of the solid showed that the titanium content was 3.90 (wt) %, fluorene ether ester content was 16.27 (wt) %.

Example 10

[0108] To a 500 ml fully nitrogen-purged five-necked flask equipped with a stirrer were added 10 g MgCl.sub.2.2.5C.sub.2H.sub.5OH microspheres and 150 mL titanium tetrachloride to prepare a suspension, and then the system was kept at −15° C. for 1 hour and warmed to 80° C., 1.5 g 9-methoxymethyl-fluorene carboxylic acid-(9)-methyl ester was added, and then the system continued to warm up to 110° C. and maintained the temperature constant for 1 hour, then the liquid was cleaned by filter pressing and filtered, the resulting solid was washed 3 times with 120 mL titanium tetrachloride at 125° C. The resulting solid was washed four times with 150 mL hexane at 60° C., after filtering to remove the liquid and drying the solid, 5.61 g solid powder was obtained, i.e. solid catalyst component. Analytical results of the solid component showed that the titanium content was 3.23 (wt) %, fluorene ether ester content was 23.7 (wt) %.

Example 11

[0109] 7.1 g anhydrous magnesium chloride, 38 mL decane and 35 mL 2-ethylhexanol were reacted at 130° C. for 2 hours to form a homogeneous solution. 1.7 g phthalic anhydride was added to the solution, and stirred for 1 hour at 130° C. to completely dissolve phthalic anhydride in the homogeneous solution. The resulting homogeneous solution was cooled to room temperature and was dropwise added to 200 mL titanium tetrachloride kept at −20° C. over 1 hour; After addition was completed, the mixed solution was heated to 110° C. over 4 hours, when the temperature reached 110° C., 5 g 9-methoxymethyl-fluorene carboxylic acid-(9)-methyl ester was added, the mixture was stirred at that temperature for 2 hours. After reaction, the solid portion was collected by hot filtration. The solid portion was suspended in 275 mL titanium tetrachloride and reacted at 110° C. for 2 hours. After the reaction, the solid was collected by hot filtration, sufficiently washed with decane and hexane at 110° C., followed by suction filtration to give a solid catalyst component. Analytical results of the solid component showed that the titanium content was 2.6 (wt) %, and the content of fluorene ether ester was 14.6 (wt) %.

Example 12

[0110] To a 500 ml fully nitrogen-purged five-necked flask equipped with a stirrer were added 10 g anhydrous magnesium chloride, 150 mL toluene, 17 mL epichlorohydrin and 16 mL tributyl phosphate at the room temperature, warmed to 50° C. with stirring and maintained for 2 hours until the solid was completely dissolved, and then 2.40 g phthalic anhydride was added, the reaction was maintained for 1 hour. The solution was cooled to −25° C., 110 mL titanium tetrachloride was dropwise added over 1 hour, the temperature was slowly raised to 80° C., in the heating process, the solid was precipitated stepwise. 5 g 9-methoxymethyl-fluorene carboxylic acid-(9)-methyl ester was added and the reaction was maintained at 80° C. for 1 hour. The resulting sold after filtration was washed twice with 200 mL toluene, and then 120 mL toluene and 80 mL titanium tetrachloride were added, the temperature was raised to 110° C. and maintained for 2 hours, then the liquid was cleaned by filter pressing, and the treatment was repeated one time. The resulting solid after filtration was washed one time with 100 mL dichloroethane, four times with hexane, and dried to give 10.2 g solid powder, i.e. the solid catalyst component. Analytical results of the solid component showed that the titanium content after analysis was 5.16 (wt) %, and the fluorene ether ester content was 17.46 (wt) %.

Examples 13-19

[0111] Preparation steps of catalyst component were the same as described in Example 9, except that the 9-methoxymethyl-fluorene carboxylic acid-(9)-methyl ester was replaced by 9-methoxy-fluorene carboxylic acid-(9)-n-butyl ester, 9-methoxy-methyl-fluorene carboxylic acid-(9)-isobutyl ester, 9-methoxy-fluorene carboxylic acid-(9)-isopropyl ester, 9-methoxy-methyl-fluorene carboxylic acid-(9)-ethyl ester, 9-ethoxymethyl-fluorene carboxylic acid-(9)-methyl ester, 9-ethoxymethyl-fluorene carboxylic acid-(9)-ethyl ester, or 1-benzyloxymethyl-1-methoxyacyl-2,5-cyclopentadiene, respectively.

Examples 20-26

[0112] Preparation steps of catalyst component were the same as described in Example 10, except that the 9-methoxymethyl-fluorene carboxylic acid-(9)-methyl ester was replaced by 9-methoxy-fluorene carboxylic acid-(9)-n-butyl ester, 9-methoxy-methyl-fluorene carboxylic acid-(9)-isobutyl ester, 9-methoxy-fluorene carboxylic acid-(9)-isopropyl ester, 9-methoxy-methyl-fluorene carboxylic acid-(9)-ethyl ester, 9-ethoxymethyl-fluorene carboxylic acid-(9)-methyl ester, 9-ethoxymethyl-fluorene carboxylic acid-(9)-ethyl ester, or 1-benzyloxymethyl-1-methoxyacyl-2,5-cyclopentadiene, respectively.

Examples 27-28

[0113] Preparation steps of catalyst component were the same as described in Example 11, except that the 9-methoxymethyl-fluorene carboxylic acid-(9)-methyl ester was replaced by 9-methoxy-fluorene carboxylic acid-(9)-n-butyl ester or 9-methoxy-fluorene carboxylic acid-(9)-ethyl ester, respectively.

Polymerization

[0114] Polymerization evaluation was made by using a solid catalyst as the catalyst component for olefin polymerization:

[0115] To a 5 L fully nitrogen-purged stainless steel reactor were added 5 mL solution of triethylaluminum in hexane at a concentration of 0.5 mol/L and 1 mL solution of methyl cyclohexyl dimethoxy silane (CMMS) in hexane at a concentration of 0.1 mol/L and 10 mg prepared catalyst, 10 mL hexane was added to rinse the feed lines, and then 2 L hydrogen (standard state) and 2.5 L purified propylene were added, the reaction was controlled at 20° C. to prepolymerize for 5 minutes, the temperature was raised to 70° C., and at this temperature the polymerization reaction was carried out for 1 hour. After the reaction, the reactor was cooled and the stirring was stopped, the reaction product was discharged and dried to obtain a polymer. (Bulk density of the polymer measured by JB/T 2412-2008 method, isotacticity measured by JB/T 3682-2000 method.)

TABLE-US-00001 TABLE 1 Catalyst performance Activity Bulk Example internal electron donor titanium Kg/gCat .Math. isotacticity density No. type wt % wt % h.sup.−1 % g/cm.sup.3 9 9-methoxymethyl-fluorene carboxylic 16.27 3.90 64.0 97.6 0.385 acid-(9)-methyl ester 10 9-methoxymethyl-fluorene carboxylic 23.7 3.23 76.7 98.0 0.353 acid-(9)-methyl ester 11 9-methoxymethyl-fluorene carboxylic 14.6 2.60 52.6 97.5 0.361 acid-(9)-methyl ester 12 9-methoxymethyl-fluorene carboxylic 17.46 5.16 45.8 97.2 0.380 acid-(9)-methyl ester 13 9-methoxymethyl-fluorene carboxylic 12.44 3.14 76.0 98.2 0.413 acid-(9)-n-butyl ester 14 9-methoxymethyl-fluorene carboxylic 11.00 2.10 49.0 98.0 0.396 acid-(9)-isobutyl ester 15 9-methoxymethyl-fluorene carboxylic 7.28 4.05 52.0 97.9 0.373 acid-(9)-isopropyl ester 16 9-methoxymethyl-fluorene carboxylic 16.92 3.34 52.0 98.0 0.382 acid-(9)-ethyl ester 17 9-ethoxymethyl-fluorene carboxylic 21.32 2.66 55.0 98.4 0.373 acid-(9)-methyl ester 18 9-ethoxymethyl-fluorene carboxylic 16.71 2.93 46.0 98.9 0.388 acid-(9)-ethyl ester 19 1-benzoxymethyl-1-methoxyacyl- 10.20 3.25 32.0 97.1 0.387 2,5-cyclopentadiene 20 9-methoxymethyl-fluorene carboxylic 22.00 3.10 49.0 97.6 0.360 acid-(9)-n-butyl ester 21 9-methoxymethyl-fluorene carboxylic 13.60 2.68 55.7 97.5 0.403 acid-(9)-isobutyl ester 22 9-methoxymethyl-fluorene carboxylic 19.16 3.43 55.0 97.3 0.415 acid-(9)-isopropyl ester 23 9-methoxymethyl-fluorene carboxylic 23.40 2.88 59.0 98.9 0.375 acid-(9)-ethyl ester 24 9-ethoxymethyl-fluorene carboxylic 16.60 2.75 62.0 98.0 0.4028 acid-(9)-methyl ester 25 9-ethoxymethyl-fluorene carboxylic 13.42 3.14 54.0 98.2 0.356 acid-(9)-ethyl ester 26 1-benzoxymethyl-1-methoxyacyl-2,5- 13.22 3.51 35.0 97.7 0.379 cyclopentadiene 27 9-methoxymethyl-fluorene carboxylic 18.77 4.18 38.4 97.4 0.338 acid-(9)-n-butyl ester 28 9-methoxymethyl-fluorene carboxylic 16.54 3.91 30.5 95.2 0.380 acid-(9)-ethyl ester

[0116] The polymerization results of the above table show that, using fluorenyl ether-acid ester selected from ring-substituted an ether-acid ester compounds as internal electron donor and using catalysts obtained according to four different catalyst preparation processes for propylene polymerization, high activity level can be achieved, and the polypropylene prepared under the standard polymerization conditions with the aid of methylcyclohexyl dimethoxysilane external electron donor has an isotacticity generally higher than 97%, indicating that the type of compounds can be used as the internal electron donor to be used in a variety of typical catalyst preparation routes, allowing the catalysts to have excellent performance for polymerization and obtain a high catalytic activity and a polypropylene product having high isotacticity.

[0117] Although the above has described the present invention with the general and specific embodiments in detail, on the basis of the present invention, it is obvious for those skilled in this art to make certain modifications or improvements. Therefore, these modifications or improvements made without departing from the spirit of the present invention belong to the scope of the invention as claimed.

INDUSTRIAL APPLICABILITY

[0118] The present invention provides 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 is a catalyst containing the solid catalyst component and the application of the catalyst in olefin polymerization reactions, 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 is capable of determining the spatial configuration of ether and acid ester functional groups, which has a positive influence on the formation of an active center of the catalyst and the improvement of the stereospecificity of the catalyst. The present invention has industrial applicability.