Alkoxy magnesium supported olefin polymerization catalyst component, catalyst and application thereof

Abstract

Provided is an alkoxy magnesium supported olefin polymerization catalyst component, comprising the reaction products of the following components: at least one alkoxy magnesium compound of Mg(OR1′)N(OR2′)2-N, at least one titanium compound of general formula Ti(OR)nX4-n, at least one ortho-phenylene diester electron donor compound a, and at least one diether electron donor compound b, wherein the molar ratio of a to b is 0.05 to 20. The catalyst component has an ultrahigh polymerization activity when used for olefin polymerization, and does not require the use of an external electron donor, but can also obtain a polymer with a high isotacticity, and the resulting polymer has a relatively wide molecular weight distribution and a relatively low ash content.

Claims

1. An alkoxymagnesium supported olefin polymerization catalyst component, comprising the reaction products of the following components: 1) an alkoxymagnesium compound represented by the formula Mg(OR.sub.1′).sub.N(OR.sub.2′).sub.2-N, wherein R.sub.1′ and R.sub.2′ may be the same or different and are C.sub.1-C.sub.20 alkyl group, 0≤N≤2; 2) at least one titanium compound represented by the formula Ti(OR).sub.nX.sub.4-n, wherein R represents a C.sub.1-C.sub.4 alkyl group; X represents chlorine, bromine or iodine atom; 0≤n≤4; 3) at least one electron donor a compound and at least one electron donor b compound; wherein the electron donor a compound is selected from the group consisting of (a1) 1,2-benzenediol-1,2-dicyclohexylcarboxylate; (a2) 1,2-benzenediol-4-tert-butyl-1,2-dicyclohexylcarboxylate; (a3) 1,2-benzenediol-4-tert-butyl-1,2-di-n-hexanoate; (a4) 1,2-benzenediol-4-tert-butyl-1,2-di-n-decanoate; (a5) 1,2-benzenediol-4-tert-butyl-1,2-dilaurate; (a6) 1,2-benzenediol-4-tert-butyl-1,2-dimyristate; (a7) 1,2-benzenediol-3-methyl-5-tert-butyl-1,2-dipalmitate; (a8) 1,2-benzenediol-3-methyl-5-tert-butyl-1,2-difurancarboxylate; (a9) 1,2-benzenediol-1,2-dibenzoate; (a10) 1,2-benzenediol-4-tert-butyl-1,2-dibenzoate; (a11) 1,2-benzenediol-4-tert-butyl-1,2-di(o-chlorobenzoate); (a12) 1,2-benzenediol-4-tert-butyl-1,2-di(m-chlorobenzoate); (a13)1,2-benzenediol-4-tert-butyl-1,2-di(p-chlorobenzoate); (a14) 1,2-benzenediol-4-tert-butyl-1,2-di(p-methylbenzoate); (a15) 1,2-benzenediol-4-chloro-1,2-dibenzoate; and (a16) 1,2-benzenediol-3-methyl-5-tert-butyl-1,2-di(m-chlorobenzoate); wherein the electron donor b compound is selected from the group consisting of diethers of the formula (II): ##STR00008## wherein R, R.sup.1, R.sup.2, R.sup.3, R.sup.4 and R.sup.5 may be the same or different and represent H or linear or branched alkyl, cycloalkyl, aryl, alkaryl or aralkyl group having 1 to 18 carbon atoms; R.sup.6 and R.sup.7 may be the same or different and represent linear or branched C.sub.1-C.sub.20 alkyl group, C.sub.3-C.sub.20 cycloalkyl group, C.sub.5-C.sub.20 aryl group, C.sub.7-C.sub.20 alkaryl and C.sub.7-C.sub.20 aralkyl group; one or more groups of R, R.sup.1 to R.sup.7 may be linked to form a cyclic structure, each of which may comprise one or more heteroatom selected from the group consisting of halogen, N, O, S, P, and Si; wherein the molar ratio of the electron donor a compound to the electron donor b compound is from 0.77 to 1.54.

2. The catalyst component according to claim 1, wherein the alkoxymagnesium compound is selected from the group consisting of magnesium dimethoxide, magnesium diethoxide, magnesium dipropoxide, magnesium dibutoxide, magnesium ethoxymethoxy, magnesium ethoxypropoxy, and magnesium butoxyethoxy, which is used alone or in combination.

3. The catalyst component according to claim 1, wherein the titanium compound is selected from the group consisting of titanium tetrachloride, titanium tetrabromide, titanium tetraiodide, titanium tetraethoxide, titanium tetrabutoxide, ethoxy titanium trichloride, methoxy titanium trichloride, propoxy titanium trichloride, n-butoxy titanium trichloride, dimethoxy titanium dichloride, diethoxy titanium dichloride, dipropoxy titanium dichloride, di-n-butoxy titanium dichloride, trimethoxy titanium chloride, triethoxy titanium chloride, tripropoxy titanium chloride, and tri-n-butoxy titanium chloride, which may be used alone or in combination.

4. The catalyst component according to claim 1, wherein the electron donor b compound is selected from the diether compounds of the formula (IV): ##STR00009## wherein the groups R.sup.6 and R.sup.7 have the same meanings as in the formula (II), and the groups R.sup.2, R.sup.3, R.sup.4, R.sup.5 and R.sup.9 are the same or different from each other and selected from hydrogen, halogen; linear or branched C.sub.1-20 alkyl group; C.sub.3-20 cycloalkyl group, C.sub.6-20 aryl group, C.sub.7-20 alkylaryl group and C.sub.7-20 arylalkyl group, and two or more R.sup.9 groups may be bonded to each other to form a condensed cyclic structure, which is saturated or unsaturated and optionally substituted with a group selected from the group consisting of: halogen; linear or branched C.sub.1-20 alkyl group; C.sub.3-20 cycloalkyl group, C.sub.6-20 aryl group, C.sub.7-20 alkylaryl group and C.sub.7-20 arylalkyl group.

5. The catalyst component according to claim 4, wherein the electron donor b compound is selected from the diether compounds of the formula (V): ##STR00010## wherein the R.sup.8 groups are the same or different and are hydrogen, halogen, linear or branched C.sub.1-20 alkyl group; C.sub.3-20 cycloalkyl group, C.sub.6-20 aryl group, C.sub.7-20 alkylaryl group and C.sub.7-20 arylalkyl group, optionally containing one or more heteroatom selected from the group consisting of N, O, S, P, Si, and halogen as a a substituent for a carbon atom or a hydrogen atom or both; the groups R.sup.2, R.sup.3, R.sup.4, R.sup.5, R.sup.6 and R.sup.7 are defined as in the formula (IV).

6. An olefin polymerization catalyst, comprising the following components or reaction products of the following components: A) the solid catalyst component according to claim 1; B) at least one organoaluminum compound of the formula AlR.sub.nX.sub.(3-n) wherein R is hydrogen, a C.sub.1-20 hydrocarbon group; X is a halogen, and n is an integer of 0≤n≤3; C) optionally, an external electron donor compound.

7. An olefin polymerization catalyst, comprising the following components or reaction products of the following components: A) the solid catalyst component according to claim 1; B) at least one organoaluminum compound of the formula AlR.sub.nX.sub.(3-n) wherein R is hydrogen, C.sub.1-20 hydrocarbon group; X is a halogen, and n is an integer of 0≤n≤3.

8. The catalyst component according to claim 1, wherein the electron donor b compound is 9,9-dimethoxymethylfluorene or 2-isopropyl-2-isopentyl-1,3-dimethoxypropane.

9. The catalyst component according to claim 1, wherein: (A) the electron donor a compound is 1,2-benzenediol-1,2-dicyclohexylcarboxylate, the electron donor b compound is 9,9-dimethoxymethylfluorene, and the molar ratio of the electron donor a compound to the electron donor b compound is 1.54; or (B) the electron donor a compound is 1,2-benzenediol-4-tert-butyl-1,2-dicyclohexylcarboxylate, the electron donor b compound is 9,9-dimethoxymethylfluorene, and the molar ratio of the electron donor a compound to the electron donor b compound is 1.32; or (C) the electron donor a compound is 1,2-benzenediol-4-tert-butyl-1,2-di-n-hexanoate, the electron donor b compound is 9,9-dimethoxymethylfluorene, and the molar ratio of the electron donor a compound to the electron donor b compound is 1.40; or (D) the electron donor a compound is 1,2-benzenediol-4-tert-butyl-1,2-di-n-decanoate, the electron donor b compound is 9,9-dimethoxymethylfluorene, and the molar ratio of the electron donor a compound to the electron donor b compound is 1.07; or (E) the electron donor a compound is 1,2-benzenediol-4-tert-butyl-1,2-dilaurate, the electron donor b compound is 9,9-dimethoxymethylfluorene, and the molar ratio of the electron donor a compound to the electron donor b compound is 0.96; or (F) the electron donor a compound is 1,2-benzenediol-4-tert-butyl-1,2-dimyristate, the electron donor b compound is 9,9-dimethoxymethylfluorene, and the molar ratio of the electron donor a compound to the electron donor b compound is 0.87; or (G) the electron donor a compound is 1,2-benzenediol-3-methyl-5-tert-butyl-1,2-dipalmitate, the electron donor b compound is 9,9-dimethoxymethylfluorene, and the molar ratio of the electron donor a compound to the electron donor b compound is 0.77; or (H) the electron donor a compound is 1,2-benzenediol-4-tert-butyl-1,2-dibenzoate, the electron donor b compound is 9,9-dimethoxymethylfluorene, and the molar ratio of the electron donor a compound to the electron donor b compound is 1.36; or (I) the electron donor a compound is 1,2-benzenediol-4-tert-butyl-1,2-di(o-chlorobenzoate), the electron donor b compound is 9,9-dimethoxymethylfluorene, and the molar ratio of the electron donor a compound to the electron donor b compound is 1.18; or (J) the electron donor a compound is 1,2-benzenediol-4-tert-butyl-1,2-di(m-chlorobenzoate), the electron donor b compound is 9,9-dimethoxymethylfluorene, and the molar ratio of the electron donor a compound to the electron donor b compound is 1.18; or (K) the electron donor a compound is 1,2-benzenediol-4-tert-butyl-1,2-di(p-chlorobenzoate), the electron donor b compound is 9,9-dimethoxymethylfluorene, and the molar ratio of the electron donor a compound to the electron donor b compound is 1.18; or (L) the electron donor a compound is 1,2-benzenediol-4-tert-butyl-1,2-di(p-methylbenzoate), the electron donor b compound is 9,9-dimethoxymethylfluorene, and the molar ratio of the electron donor a compound to the electron donor b compound is 1.33; or (M) the electron donor a compound is 1,2-benzenediol-4-chloro-1,2-dibenzoate, the electron donor b compound is 9,9-dimethoxymethylfluorene, and the molar ratio of the electron donor a compound to the electron donor b compound is 1.44; or (N) the electron donor a compound is 1,2-benzenediol-3-methyl-5-tert-butyl-1,2-di(m-chlorobenzoate), the electron donor b compound is 9,9-dimethoxymethylfluorene, and the molar ratio of the electron donor a compound to the electron donor b compound is 1.11; or (O) the electron donor a compound is 1,2-benzenediol-4-tert-butyl-1,2-dibenzoate, the electron donor b compound is 9,9-dimethoxymethylfluorene, and the molar ratio of the electron donor a compound to the electron donor b compound is 1.02.

Description

EMBODIMENTS

(1) The invention will be described in detail below by way of examples, but the invention is not limited thereto.

(2) The terms used herein is for the purpose of illustration of the specific examples and not intend to limit the invention. Unless otherwise defined, all terms (including technical and scientific terms) used herein are understood the same way by those of ordinary skill in the art. It must also be made clear that, terms such as those generally defined in a dictionary should be interpreted as having a consistent meaning in the context of the present specification and the related art, and should not be interpreted in an idealized or too formalized way, except explicitly defined herein.

(3) The procedures for preparing the catalyst in the examples were all carried out under the protection of high purity nitrogen.

(4) Determination of Polymer Isotacticity

(5) It was determined by heptane extraction (extraction with boiling heptane for 6 hours). Two grams of dried polymer sample was placed in an extractor and extracted with boiling heptane for 6 hours. The ratio of the weight of the polymer (g) obtained by drying the residue to constant weight to 2 was isotacticity.

(6) Determination of Molecular Weight Distribution of Polymer

(7) It was determined by PL-220 gel permeation chromatography using trichlorobenzene as a solvent at 150° C. (standard: polystyrene, flow rate 1.0 mL/min, column: 3×Plgel 10 um M1Xed-B 300×7.5 nm).

(8) Determination of Polymer Ash Content

(9) It was determined according to GB/T 9345.1-2008.

(10) ##STR00006##

(11) TABLE-US-00001 TABLE 1 Structure of formula (I) Compound No. Name of internal electron donor a compound R.sup.1, R.sup.2, R.sup.3, R.sup.4 R.sup.I, R.sup.II a1 1,2-benzenediol-1,2-dicyclohexylcarboxylate all H R.sup.I, R.sup.II are C.sub.6H.sub.11 a2 1,2-benzenediol-4-tert-butyl-1,2-dicyclohexylcarboxylate R.sup.2 is .sup.tC.sub.4H.sub.10, the rest is all H R.sup.I, R.sup.II are C.sub.6H.sub.11 a3 1,2-benzenediol-4-tert-butyl-1,2-di-n-hexanoate R.sup.2 is .sup.tC.sub.4H.sub.10, the rest is all H R.sup.I, R.sup.II are C.sub.5H.sub.11 a4 1,2-benzenediol-4-tert-butyl-1,2-di-n-decanoate R.sup.2 is .sup.tC.sub.4H.sub.10, the rest is all H R.sup.I, R.sup.II are C.sub.9H.sub.19 a5 1,2-benzenediol-4-tert-butyl-1,2-dilaurate R.sup.2 is .sup.tC.sub.4H.sub.10, the rest is all H R.sup.I, R.sup.II are C.sub.11H.sub.23 a6 1,2-benzenediol-4-tert-butyl-1,2-dimyristate R.sup.2 is .sup.tC.sub.4H.sub.10, the rest is all H R.sup.I, R.sup.II are C.sub.13H.sub.27 a7 1,2-benzenediol-3-methyl-5-tert-butyl-1,2-dipalmitate R.sup.1 is .sup.tCH.sub.3, R.sup.3 is R.sup.I, R.sup.II are .sup.tC.sub.4H.sub.10, R.sup.2, R.sup.3 are H C.sub.15H.sub.31 a8 1,2-benzenediol-3-methyl-5-tert-butyl-1,2-difurancarboxylate R.sup.1 is .sup.tCH.sub.3, R.sup.3 is R.sup.I, R.sup.II are .sup.tC.sub.4H.sub.10, R.sup.2, R.sup.3 are H C.sub.5H.sub.3O

(12) ##STR00007##

(13) TABLE-US-00002 TABLE 2 Structure of formula (III) Compound No. Name of internal electron donor a compound R.sup.1-R.sup.4 R.sup.5-R.sup.14 a9 1,2-benzenediol-1,2-dibenzoate are all H are all H a10 1,2-benzenediol-4-tert-butyl-1,2-dibenzoate R.sup.2 is .sup.tC.sub.4H.sub.10, are all H the rest is all H a11 1,2-benzenediol-4-tert-butyl-1,2-di(o-chlorobenzoate) R.sup.2 is .sup.tC.sub.4H.sub.10, R.sup.7 and R.sup.12 is Cl, the rest is all H the rest is all H a12 1,2-benzenediol-4-tert-butyl-1,2-di(m-chlorobenzoate) R.sup.2 is .sup.tC.sub.4H.sub.10, R.sup.6 and R.sup.11 is the rest is all H Cl, the rest is all H a13 1,2-benzenediol-4-tert-butyl-1,2-di(p-chlorobenzoate) R.sup.2 is .sup.tC.sub.4H.sub.10, R.sup.5 and R.sup.10 the rest is all H is Cl, the rest is all H a14 1,2-benzenediol-4-tert-butyl-1,2-di(p-methylbenzoate) R.sup.2 is .sup.tC.sub.4H.sub.10, R.sup.7 and R.sup.12 is CH.sub.3, the rest is all H the rest is all H a15 1,2-benzenediol-4-chloro-1,2-dibenzoate R.sup.2 is Cl, are all H the rest is all H a16 1,2-benzenediol-3-methyl-5-tert-butyl-1,2-di(m-chlorobenzoate) R.sup.1 is .sup.tCH.sub.3, R.sup.6 and R.sup.11 is Cl, R.sup.3 is .sup.tC.sub.4H.sub.10, the rest is all H R.sup.2, R.sup.3 are all H

EXAMPLE 1

(14) In a four-necked flask equipped with a stirrer, a reflux condenser was installed and connected to a cumulative gas meter. 70.8 mL of anhydrous ethanol and 1.26 g of iodine were added after the entire reaction apparatus was fully purged with nitrogen. 6 g of magnesium was added thereto after the iodine was dissolved, and the mixture was heated to reflux temperature of ethanol with stirring, and 47 mL of anhydrous ethanol and 6 g of magnesium powder were added every 10 minutes from the start of reflux to a total of 3 times. The liquid viscosity began to rise sharply about 1-2 hours after the completion of the third addition. At this time, 240 mL of ethanol was added to the reaction system, and the reaction was continued until hydrogen gas was no longer generated at the end of the reaction. The entire reaction time was about 6 hours. The remaining liquid was filtered off under pressure, and the filtrate was washed three times with 1200 mL of toluene to give diethoxymagnesium.

(15) A suspension was prepared by adding 10 g of the above-prepared diethoxymagnesium and 80 mL of toluene at −10° C. to 500 ml of a 5-neck flask with a stirrer fully purged with nitrogen, and then 20 mL of titanium tetrachloride was dropwise added at −10° C. After completion of the addition, the system was slowly heated to 10° C. and 60 mL of titanium tetrachloride was added dropwise, then the system was slowly heated to 80° C., and 3 g of electron donor a1 and 1.5 g of 9,9-dimethoxymethylfluorene were added. Thereafter, the temperature was further raised to 120° C. and maintained for 2 hours, then the solution was filtered under pressure until the liquid was filtered off. The obtained solid was washed three times with 120 mL of titanium tetrachloride at 120° C., washed three times with 150 mL of hexane at 60° C., washed three times at room temperature, followed by filtering off the liquid. The resulting solid was dried to give a solid powder, ie. solid catalyst component CAT-1.

EXAMPLES 2-16

(16) The catalyst component was prepared in the same manner as in Example 1, except that the internal electron donor compound was sequentially changed to 3 g a2-a16 and 1.5 g of 9,9-bismethoxymethylfluorene to give solid catalyst components CAT-2-16, respectively. The results obtained are shown in Table 3.

EXAMPLE 17

(17) The catalyst component was prepared in the same manner as in Example 1, except that the internal electron donor compound was sequentially changed to 3 g of a10 and 2 g of 9,9-bismethoxymethylfluorene to give a solid catalyst component CAT-17.

EXAMPLE 18

(18) The catalyst component was prepared in the same manner as in Example 1, except that the internal electron donor compound was sequentially changed to 3 g a10 and 1 g of 2-isopropyl-2-isopentyl-1,3-dimethoxypropane to give a solid catalyst CAT-18.

EXAMPLE 19

(19) In a four-necked flask equipped with a stirrer, a reflux condenser was installed and connected to a cumulative gas meter. After the entire reaction apparatus was sufficiently replaced with nitrogen, 50 mL of anhydrous anaerobic ethanol and 0.55 g of iodine were added to the vessel. After the iodine was dissolved, 6 g of metallic magnesium was added thereto, and the temperature was raised to the reflux temperature of ethanol with stirring, and 90 mL of anhydrous ethanol and 9 g of magnesium powder were added every 10 minutes from the start of the reflux to a total of three times. The liquid viscosity began to rise sharply about 1-2 hours after the completion of the third addition (at this time, the reaction rate can be calculated to be about 85% by the amount of hydrogen generated), and then 150 mL of ethanol was added to the reaction system, and the reaction was continued until hydrogen gas was no longer generated at the end of the reaction. The entire reaction time is about 6 hours and a suspension containing a white solid powder was obtained. The suspension was placed in an autoclave, stirred at 145° C., 1.4 MPa for 3 hours, and dried by pressure filtration to give a carrier Mg(OEt).sub.2.

(20) A suspension was prepared by adding 10 g of the above-prepared diethoxymagnesium and 80 mL of toluene at −10° C. to 500 ml of 5-neck flask with a stirrer fully purged with nitrogen, and then 20 mL of titanium tetrachloride was dropwise added at −10° C. After completion of the addition, the system was slowly heated heated to 10° C., and 60 mL of titanium tetrachloride was added dropwise, then the system was slowly heated to 80° C., and 3 g of electron donor compound a10 and 2 g 9,9-dimethoxymethylfluorene were added. Thereafter, the temperature was further raised to 120° C. and maintained for 2 hours, then the solution was filtered under pressure until the liquid was filtered off, and the obtained solid was washed three times with 120 mL of titanium tetrachloride at 120° C., washed three times with 150 mL of hexane at 60° C., washed three times at room temperature, followed by filtering off the liquid. The resulting solid was dried to give a solid catalyst component CAT-19.

EXAMPLE 20

(21) The catalyst component was prepared in the same manner as in Example 19 except that the internal electron donor compound was sequentially changed to 3 g a10 and 1 g of 2-isopropyl-2-isopentyl-1,3-dimethoxypropane to give a solid catalyst component CAT-20.

COMPARATIVE EXAMPLE 1

(22) The catalyst component was prepared in the same manner as in Example 1, except that the internal electron donor compound was changed to 3 g of 9,9-bismethoxymethylfluorene to give a solid catalyst component REF-1.

COMPARATIVE EXAMPLE 2

(23) The catalyst component was prepared in the same manner as in Example 1, except that the internal electron donor compound was changed to 3 g of the electron donor 2-isopropyl-2-isopentyl-1,3-dimethoxypropane to give a solid catalyst component REF-2.

COMPARATIVE EXAMPLE 3

(24) The catalyst component was prepared in the same manner as in Example 1, except that the internal electron donor compound was changed to 4.5 g of the electron donor a10 to give a solid catalyst component REF-3.

COMPARATIVE EXAMPLE 4

(25) The catalyst component was prepared in the same manner as in Example 1, except that the internal electron donor compound was changed to 3 g of di-n-butyl phthalate to give a solid catalyst component REF-4.

COMPARATIVE EXAMPLE 5

(26) In a 500 ml of 5-necked flask with a stirrer fully purged with nitrogen, 150 mL of titanium tetrachloride was pre-cooled to −15° C., and 10 g of MgCl.sub.2.Math.2.5C.sub.2H.sub.5OH microspheres was added at −15° C. to prepare a suspension. After the temperature was maintained at −15° C. for 3 hours and slowly raised to 80° C., 3 g of electron donor compound a10 and 1.5 g of 9,9-dimethoxymethyl fluorene were added, and then the temperature was raised to 110° C. and maintained for 1 hour. Thereafter the solution was filtered under pressure under the liquid was filtered off. The obtained solid was washed 3 times with 125 mL of titanium tetrachloride at 125° C., washed 4 times with 150 mL of hexane at 60° C., followed by filtering off the liquid. The resulting solid was dried to give a solid catalyst component REF-5.

COMPARATIVE EXAMPLE 6

(27) 7.1 g of anhydrous magnesium chloride, 38 mL of decane and 35 mL of 2-ethylhexanol were reacted at 130° C. for 2 hours to form a homogeneous solution. 1.7 g of phthalic anhydride was added to the solution, and the mixture was stirred at 130° C. for 1 hour to completely dissolve the phthalic anhydride in the homogeneous solution. The obtained homogeneous solution was cooled to room temperature, and dropwise added to 200 mL of titanium tetrachloride kept at −20° C. in 1 hour. After the addition, the mixed solution was heated to 110° C. in 4 hours, when the temperature reached 110° C., 3 g of the electron donor compound a10 and 1.5 g of 9,9-dimethoxymethylfluorene were added, the mixture was stirred at the above temperature for 2 hours. After reacting for 2 hours, the solid portion was collected by hot filtration. The solid portion was suspended in 275 mL of titanium tetrachloride and reacted at 110° C. for 2 hours. After the reaction, the solid portion was collected by hot filtration, thoroughly washed with decane and hexane at 110° C., and then dried to give a solid catalyst component REF-6.

COMPARATIVE EXAMPLE 7

(28) In 500 ml of a 5-necked flask with a stirrer fully purged with nitrogen, 10 g of anhydrous magnesium chloride, 150 mL of toluene, 17 mL of epoxy chloropropane and 16 mL of tributyl phosphate were added at room temperature, and the temperature was raised to 50° C. with stirring and maintained for 2 hours. After the solid was completely dissolved, 2.40 g of phthalic anhydride was added and maintained for 1 hour. The solution was cooled to −25° C., 110 mL of titanium tetrachloride was dropwise added over 1 hour, and the temperature was slowly raised to 80° C., and the solid matter was gradually precipitated during the temperature rise. 3 g of the electron donor compound a10 and 1.5 g of 9,9-dimethoxymethylhydrazine were added and maintained at 80° C. for 1 hour. After filtering, the (iterate was washed twice with 200 mL of toluene, then 120 mL of toluene and 80 mL of titanium tetrachloride were added, and the temperature was further raised to 110° C., and maintained for 2 hours. The liquid was filtered under pressure and the treatment was repeated once more. The liquid was filtered off, and the obtained solid was washed once with 100 mL of dichloroethane, and then washed four times with hexane to give solid catalyst component REF-7.

(29) Polymerization Condition 1

(30) The solid catalysts prepared in Examples 1-20 and Comparative Examples 1-6 were used as components for the olefin polymerization catalyst to carry out polymerization evaluation under the following conditions:

(31) To a 5 L of stainless steel reactor fully purged with nitrogen were added 4 mL of 0.5 mol/L triethylaluminum solution in hexane, 1 mL of 0.1 mol/L methylcyclohexyldimethoxysilane (CMMS) solution in hexane and 5 mg of prepared catalyst, then 10 mL of hexane was added to rinse the feed line, and 2 L of hydrogen (standard state) and 2.5 L of refined propylene were added. The reaction was controlled to prepolymerize at 20° C. for 5 minutes, the temperature was raised to 70° C., and the polymerization was carried out at this temperature for 1 hour. After completion of the reaction, the reaction vessel was cooled and the stirring was stopped to discharge the reaction product, and then a polymer was obtained after drying. The polymerization results were shown in Table 3.

(32) TABLE-US-00003 TABLE 3 Internal electron donor compound Molecular Catalyst a/b Activity weight distribution No. No. a b (mol/mol) KgPP/gCat Isotacticity % M.sub.w/M.sub.n example 1 CAT-1 a1 b1 1.54 89 97.7 5.6 example 2 CAT-2 a2 b1 1.32 76 97.6 5.7 example 3 CAT-3 a3 b1 1.40 77 97.6 5.8 example 4 CAT-4 a4 b1 1.07 86 97.4 6.0 example 5 CAT-5 a5 b1 0.96 80 97.8 5.9 example 6 CAT-6 a6 b1 0.87 81 97.4 5.8 example 7 CAT-7 a7 b1 0.77 79 97.3 6.0 example 8 CAT-8 a8 b1 1.64 76 98.0 6.1 example 9 CAT-9 a9 b1 1.60 94 98.1 6.5 example 10 CAT-10 a10 b1 1.36 106 98.9 7.1 example 11 CAT-11 a11 b1 1.18 93 98.2 6.2 example 12 CAT-12 a12 b1 1.18 99 98.0 6.2 example 13 CAT-13 a13 b1 1.18 101 98.0 6.1 example 14 CAT-14 a14 b1 1.33 96 98.3 6.5 example 15 CAT-15 a15 b1 1.44 93 98.1 6.5 example 16 CAT-16 a16 b1 1.11 105 98.3 6.9 example 17 CAT-17 a10 b1 1.02 115 98.8 7.2 example 18 CAT-18 a10 b2 1.73 108 99.0 8.4 example 19 CAT-19 a10 b1 1.02 138 99.2 7.5 example 20 CAT-20 a10 b2 1.73 129 98.9 8.2 comparative REF-1 — b1 — 65 98.8 4.5 example 1 comparative REF-2 — b2 — 60 98.2 4.8 example 2 comparative REF-3 a10 — — 49 98.0 8.9 example 3 comparative REF-4 — c — 45 98.4 5.4 example 4 comparative REF-5 a10 b1 1.36 88 98.2 7.1 example 5 comparative REF-6 a10 b1 1.36 75 98.4 7.6 example 6 comparative REF-7 a10 b1 1.36 74 98.3 7.3 example 7 Note: b1 is 9,9-dimethoxymethylfluorene b2 is 2-isopropyl-2-isopentyl-1,3-dimethoxypropane c is di-n-butyl phthalate “—” means empty

(33) It can be seen from the data in Table 3 that Examples 1-16 respectively used 16 kinds of different ortho-phenylenedicarboxylate compounds to combine with 9,9-dimethoxymethylfluorene in different molar ratios as internal electron donor compound. The prepared catalysts had high activity of 72-106 KgPP/gCat under the conditions, the obtained polymers had isotacticity higher than 97.4%, and the molecular weight distribution was between 5.3 and 7.1 that was wider than that of the diether catalyst.

(34) When the same ethoxy magnesium carrier was used, the activity of the catalyst obtained by use of the compound of ortho-phenylenedicarboxylate and the diether (72-106 KgPP/gCat of Examples 1-16) was much higher than that of the catalysts obtained by single use of 9,9-dimethoxymethylfluorene (65 KgPP/gCat of Comparative Example 1), 2-isopropyl-2-isopentyl-1,3-dimethoxypropane (60 KgPP/gCat of Comparative Example 2), 1,2-benzenediol-4-tert-butyl-1,2-dibenzoate (49 KgPP/gCat of Comparative Example 3) or di-n-butyl phthalate (45 KgPP/gCat of Comparative Example 4) as an internal electron donor.

(35) The catalyst prepared by using the ethoxy magnesium carrier after high pressure treatment (Example 19 activity 138 KgPP/gCat and Example 20 activity 129 KgPP/gCat), has an activity higher than those prepared by using the internal electron donor (Example 17 activity 115 KgPP/gCat and Example 18 activity 108 KgPP/gCat) with the same type and ratio without high pressure treatment (above atmospheric pressure).

(36) The catalyst activity prepared using the ethoxy magnesium carrier (76-138 KgPP/gCat of Examples 1-20) in total was higher than the catalyst prepared by using the magnesium chloride alcoholate carrier (88 KgPP/gCat of Comparative Example 5) and the catalyst prepared by the dissolution precipitation method (75 KgPP/gCat of Comparative Example 6 and 74 KgPP/gCat of Comparative Example 7). It is indicated that the ethoxy magnesium carrier is more advantageous than the magnesium chloride alcoholate carrier and the activated carrier obtained after dissolution and precipitation to exert the catalytic activity of the complex system of ortho-phenylenedicarboxylate compound and the diether compound.

(37) Polymerization Condition 2

(38) The polymerization evaluation was carried out by using a solid catalyst as a component of the olefin polymerization catalyst under the following conditions:

(39) To a 5 L stainless steel reactor sufficiently purged with nitrogen were added a solution of 0.5 mol/L of triethylaluminum in hexane (the amount of triethylaluminum is shown in Al/Ti in Table 4) and prepared 3-5 mg of catalyst were added. Then, 10 mL of hexane was added to rinse the feed line, and 2 L of hydrogen (standard state) and 2.5 L of refined propylene were added thereto. The reaction was controlled to prepolymerize at 20° C. for 5 minutes and the temperature was raised to 70° C. At this temperature, the polymerization reaction was carried out for corresponding time (see Table 4). After completion of the reaction, the reaction vessel was cooled and the stirring was stopped to discharge the reaction product, and then a polymer was obtained after drying. The results obtained were shown in Table 4.

EXAMPLES 21-26

(40) Polymerization was carried out using Catalyst CAT-19 according to the conditions described in Polymerization Conditions 2 and Table 4, and the polymerization results were shown in Table 4.

EXAMPLES 27-32

(41) Polymerization was carried out using Catalyst CAT-20 according to the conditions described in Polymerization Conditions 2 and Table 4, and the polymerization results were shown in Table 4.

COMPARATIVE EXAMPLES 10-14

(42) The polymerization was carried out using the catalyst REF-1-REF-7 according to the conditions described in the polymerization conditions 2 and Table 4, respectively, and the polymerization results were shown in Table 4.

(43) TABLE-US-00004 TABLE 4 Polymer Polymerization Polymerization molecular ash Al/Ti time activity weight distribution content No. Catalyst No. (mol/mol) (min) (KgPP/gCat) Isotacticity % M.sub.w/M.sub.n (ppm) example CAT-19 500 60 201 98.4 6.9 249 21 example CAT-19 500 90 249 98.3 6.8 210 22 example CAT-19 500 120 272 98.1 6.8 163 23 example CAT-19 200 60 210 98.2 6.9 60 24 example CAT-19 100 60 225 98.0 7.0 28 25 example CAT-19 90 120 287 98.1 6.9 18 26 example CAT-20 500 60 182 98.5 7.5 233 26 example CAT-20 500 90 210 98.3 7.4 197 27 example CAT-20 500 120 251 98.2 7.5 159 28 example CAT-20 200 60 190 98.0 7.6 82 29 example CAT-20 100 60 208 98.1 7.6 33 30 example CAT-20 90 120 260 98.0 7.5 20 32 comparative REF-1 500 60 104 98.3 4.8 158 example 8 comparative REF-2 500 60 90 97.8 4.9 140 example 9 comparative REF-3 500 60 79 96.2 8.0 200 example 10 comparative REF-4 500 60 70 97.0 5.6 194 example 11 comparative REF-5 500 60 132 98.0 7.0 229 example 12 comparative REF-6 500 60 110 98.2 7.1 230 example 13 comparative REF-7 500 60 105 98.3 6.8 190 example 14

(44) It can be seen from the data in Table 4 that the catalysts CAT-19 and CAT-20 prepared by using the ethoxy magnesium carrier and compounding the ortho-phenylene diester compound and the diether compound could have ultrahigh activity with no use of the external electron donor compound during polymerization, which is much higher than that of the non-complexed catalysts under the same polymerization conditions (Comparative Examples 8-11) and the catalysts prepared by using the magnesium chloride alcoholate carrier or the dissolution precipitation method (Comparative Examples 12-14), and still maintain a high isotacticity of 97.9% or more. When the polymerization time is extended from 60 minutes to 90 minutes and 120 minutes, the catalyst can maintain ultra high activity without attenuation. The polypropylene obtained by using low Al/Ti has a lower ash content that can be reduced to a minimum of 18 ppm.

(45) Although the present invention has been described in detail with reference to the preferred embodiments of the present invention, it will be apparent to those skilled in the art to make modifications or improvements. Therefore, such modifications or improvements made without departing from the spirit of the invention are intended to be within the scope of the invention.

INDUSTRIAL APPLICABILITY

(46) The present invention provides an alkoxy magnesium supported olefin polymerization catalyst component, comprising the reaction products of the following components: at least one alkoxy magnesium compound of Mg(OR1′)N(OR2′)2-N, at least one titanium compound of general formula Ti(OR)nX4-n, at least one ortho-phenylene diester electron donor compound a, and at least one diether electron donor compound b, wherein the molar ratio of a to b is 0.05 to 20. The catalyst component has an ultrahigh polymerization activity when used for olefin polymerization, and does not require the use of an external electron donor, but can also obtain a polymer with a high isotacticity, and the resulting polymer has a relatively wide molecular weight distribution and a relatively low ash content. The invention has industrial applicability.