Catalyst composition for olefin polymerization and application of same

Abstract

The present disclosure discloses a catalyst composition for olefin polymerization, comprising the following components: a): a solid catalyst component containing magnesium, titanium, halogens, and at least one internal electron donor having a lone pair of electrons; b): an aluminum alkyl compound; and c): an external electron donor containing a first external electron donor C1, which is a malonate compound. In the present disclosure, a catalyst composition having an external electron donor that contains a malonate compound is used in olefin polymerization, in particular propene polymerization, and can significantly improve catalytic activity and hydrogen response of the catalyst and expand molecular weight distribution of polymers, which facilitates development of different polymers.

Claims

1. A catalyst composition for olefin polymerization, comprising the following components: a): a solid catalyst component containing magnesium, titanium, halogens, and at least one internal electron donor having a lone pair of electrons; b): an aluminum alkyl compound; and c): an external electron donor containing a first external electron donor C1, which is a malonate compound and a second external electron donor C2 selected from the group consisting of silane, diether, and amine compounds, wherein the internal electron donor is selected from the group of compounds containing the atom of O, N, P, or S.

2. The catalyst composition of claim 1, wherein the malonate compound has a general formula as shown in Formula (I): ##STR00006## wherein R.sub.9 is a substituted or non-substituted C.sub.1 to C.sub.20 hydrocarbyl group, and R.sub.7 and R.sub.8, identical with or different from each other, are selected from the group consisting of hydrogen, halogens, and substituted or non-substituted C.sub.1 to C.sub.20 hydrocarbyl groups.

3. The catalyst composition according to claim 2, wherein R.sub.9 is selected from the group consisting of substituted or non-substituted C.sub.1 to C.sub.10 straight-chain alkyl groups, C.sub.3 to C.sub.10 branched-chain alkyl groups, C.sub.3 to C.sub.10 cycloalkyl groups, C.sub.6 to C.sub.10 aryl groups, C.sub.7 to C.sub.10 alkaryl groups, and C.sub.7 to C.sub.10 aralkyl groups; and wherein, R.sub.7 and R.sub.8, identical with or different from each other, are selected from the group consisting of hydrogen, halogens, and substituted or non-substituted C.sub.1 to C.sub.10 alkyl groups, C.sub.1 to C.sub.10 alkylene groups, C.sub.3 to C.sub.10 cycloalkyl groups, C.sub.6 to C.sub.10 aryl groups, and C.sub.7 to C.sub.10 alkaryl or aralkyl groups.

4. The catalyst composition of claim 1, wherein the malonate compound is at least one selected from the group consisting of diethyl malonate, di-n-propyl malonate, diisopropyl malonate, di-n-butyl malonate, diisobutyl malonate, diethyl methylmalonate, di-n-propyl methylmalonate, di-iso-propyl methylmalonate, di-n-butyl methylmalonate, di-iso-butyl methylmalonate, di-tert-butyl methylmalonate, diethyl ethylmalonate, di-n-propyl ethylmalonate, di-iso-propyl ethylmalonate, di-n-butyl ethylmalonate, di-iso-butyl ethylmalonate, di-tert-butyl ethylmalonate, diethyl n-propylmalonate, di-n-propyl n-propylmalonate, di-iso-propyl n-propylmalonate, di-n-butyl n-propylmalonate, di-iso-butyl n-propylmalonate, di-tert-butyl n-propylmalonate, diethyl isopropylmalonate, di-n-propyl isopropylmalonate, di-iso-propyl isopropylmalonate, di-n-butyl isopropylmalonate, di-iso-butyl isopropylmalonate, di-tert-butyl isopropylmalonate, diethyl phenylmalonate, di-n-propyl phenylmalonate, di-iso-propyl phenylmalonate, di-n-butyl phenylmalonate, di-iso-butyl phenylmalonate, di-tert-butyl phenylmalonate, diethyl benzylmalonate, di-n-propyl benzylmalonate, di-iso-propyl benzylmalonate, di-n-butyl benzylmalonate, di-iso-butyl benzylmalonate, di-tert-butyl benzylmalonate, diethyl dimethylmalonate, diethyl diethylmalonate, diethyl methylethylmalonate, diethyl methyl-n-butylmalonate, diethyl methylisobutylmalonate, diethyl methyl-n-propylmalonate, diethyl methylisopropylmalonate, diethyl di-n-propyl-malonate, diethyl di-n-butyl-malonate, diethyl di-iso-propyl-malonate, diethyl di-iso-butyl-malonate, and diethyl di-allyl-malonate.

5. The catalyst composition of claim 1, wherein the internal electron donor in solid catalyst component a) is selected from the group consisting of ether, ester, phenolic ether, phenolic ester, and ketone compounds.

6. The catalyst composition of claim 5, wherein the internal electron donor in solid catalyst component a) is selected from the group consisting of diol ester compounds, succinate compounds, phthalate compounds, and diether compounds.

7. The catalyst composition of claim 6, wherein the diol ester compounds have a general formula as shown in Formula (II): ##STR00007## wherein, R.sub.1 and R.sub.2, identical with or different from each other, are selected from the group consisting of substituted or non-substituted C.sub.1 to C.sub.20 alkyl groups, C.sub.3 to C.sub.20 cycloalkyl groups, C.sub.6 to C.sub.20 aryl groups, C.sub.7 to C.sub.20 alkaryl groups, and C.sub.7 to C.sub.20 aralkyl groups; wherein, R.sub.3 and R.sub.4, identical with or different from each other, are selected from the group consisting of hydrogen, halogens, and substituted or non-substituted C.sub.1 to C.sub.10 straight-chain alkyl groups, C.sub.3 to C.sub.10 branched-chain alkyl groups, C.sub.3 to C.sub.10 cycloalkyl groups, C.sub.6 to C.sub.10 aryl groups, and C.sub.7 to C.sub.10 alkaryl or aralkyl groups; and wherein, R.sub.5 and R.sub.6, identical with or different from each other, are selected from the group consisting of halogens, and substituted or non-substituted C.sub.1 to C.sub.10 straight-chain alkyl groups, C.sub.3 to C.sub.10 branched-chain alkyl groups, C.sub.3 to C.sub.10 cycloalkyl groups, C.sub.6 to C.sub.10 aryl groups, and C.sub.7 to C.sub.10 alkaryl or aralkyl groups.

8. The catalyst composition of claim 6, wherein the diol ester compounds are at least one selected from the group consisting of 2,4-pentanediol dibenzoate, 2,4-pentanediol di-p-methyl-benzoate, 2,4-pentanediol di-m-methyl-benzoate, 2,4-pentanediol di-o-methyl-benzoate, 2,4-pentanediol di-p-ethyl-benzoate, 2,4-pentanediol di-p-n-propyl-benzoate, 2,4-pentanediol di-p-iso-propyl-benzoate, 2,4-pentanediol di-p-iso-butyl-benzoate, 2,4-pentanediol di-p-n-butyl-benzoate, 2,4-pentanediol di-p-tert-butyl-benzoate, 3-methyl-2,4-pentanediol dibenzoate, 3-ethyl-2,4-pentanediol dibenzoate, 3-n-propyl-2,4-pentanediol dibenzoate, 3-ethyl-2,4-pentanediol di-p-methyl-benzoate, 3-ethyl-2,4-pentanediol di-p-ethyl-benzoate, 3-ethyl-2,4-pentanediol di-p-n-propyl-benzoate, 3-ethyl-2,4-pentanediol di-p-iso-propyl-benzoate, 3-ethyl-2,4-pentanediol di-p-iso-butyl-benzoate, 3-ethyl-2,4-pentanediol di-p-n-butyl-benzoate, 3-ethyl-2,4-pentanediol di-p-tert-butyl-benzoate, 3-n-butyl-2,4-pentanediol dibenzoate, 3,3-di-methyl-2,4-pentanediol dibenzoate, 3-chloro-2,4-pentanediol dibenzoate, 3-bromo-2,4-pentanediol dibenzoate, 3,5-heptanediol dibenzoate, 3,5-heptanediol di-p-methyl-benzoate, 3,5-heptanediol di-p-ethyl-benzoate, 3,5-heptanediol di-p-n-propyl-benzoate, 3,5-heptanediol di-p-iso-propyl-benzoate, 3,5-heptanediol di-p-iso-butyl-benzoate, 3,5-heptanediol di-p-n-butyl-benzoate, 3,5-heptanediol di-p-tert-butyl-benzoate, 4-methyl-3,5-heptanediol dibenzoate, 4,4-dimethyl-3,5-heptanediol dibenzoate, 4-ethyl-3,5-heptanediol dibenzoate, 4-ethyl-3,5-heptanediol di-p-methyl-benzoate, 4-ethyl-3,5-heptanediol di-p-ethyl-benzoate, 4-ethyl-3,5-heptanediol di-p-propyl-benzoate, 4-ethyl-3,5-heptanediol di-p-butyl-benzoate, 4-ethyl-3,5-heptanediol di-p-tert-butyl-benzoate, 4-n-propyl-3,5-heptanediol dibenzoate, 4-n-butyl-3,5-heptanediol dibenzoate, 4-chloro-3,5-heptanediol dibenzoate, and 4-bromo-3,5-heptanediol dibenzoate.

9. The catalyst composition of claim 6, wherein the phthalate compounds have a general formula as shown in Formula (III): ##STR00008## wherein R.sub.21 is selected from the group consisting of C.sub.1 to C.sub.10 straight-chain alkyl groups, C.sub.3 to C.sub.15 branched-chain alkyl groups, C.sub.3 to C.sub.15 cycloalkyl groups, C.sub.6 to C.sub.20 aryl groups, C.sub.7 to C.sub.20 alkaryl groups, and C.sub.7 to C.sub.20 aralkyl groups; and wherein R.sub.22 to R.sub.25, identical with or different from one another, are selected from the group consisting of hydrogen, halogens, and substituted or non-substituted C.sub.1 to C.sub.10 straight-chain alkyl groups, C.sub.3 to C.sub.15 branched-chain alkyl groups, C.sub.3 to C.sub.15 cycloalkyl groups, C.sub.6 to C.sub.20 aryl groups, C.sub.7 to C.sub.20 alkaryl groups, and C.sub.7 to C.sub.20 aralkyl groups.

10. The catalyst composition of claim 6, wherein the phthalate compounds are at least one selected from the group consisting of dimethyl phthalate, diethyl phthalate, di-n-propyl phthalate, di-iso-propyl phthalate, di-n-butyl phthalate, di-iso-butyl phthalate, di-n-pentyl phthalate, di-iso-pentyl phthalate, di-n-hexyl phthalate, di-iso-hexyl phthalate, di-n-octyl phthalate, di-iso-octyl phthalate, dibenzyl phthalate, dimethyl tetramethylphthalate, diethyl tetramethylphthalate, di-n-propyl tetramethylphthalate, di-iso-propyl tetramethylphthalate, di-n-butyl tetramethylphthalate, di-iso-butyl tetramethylphthalate, di-n-pentyl tetramethylphthalate, di-iso-pentyl tetramethylphthalate, di-n-hexyl tetramethylphthalate, di-iso-hexyl tetramethylphthalate, di-n-octyl tetramethylphthalate, di-iso-octyl tetramethylphthalate, dibenzyl tetramethylphthalate, dimethyl tetrabromophthalate, diethyl tetrabromophthalate, di-n-propyl tetrabromophthalate, di-iso-propyl tetrabromophthalate, di-n-butyl tetrabromophthalate, di-iso-butyl tetrabromophthalate, di-n-pentyl tetrabromophthalate, di-iso-pentyl tetrabromophthalate, di-n-hexyl tetrabromophthalate, di-iso-hexyl tetrabromophthalate, di-n-octyl tetrabromophthalate, di-iso-octyl tetrabromophthalate, and dibenzyl tetrabromophthalate.

11. The catalyst composition of claim 6, wherein the diether compounds have a general formula as shown in Formula (IV): ##STR00009## wherein R.sub.31 and R.sub.32, identical with or different from each another, are selected from the group consisting of substituted or non-substituted C.sub.1 to C.sub.10 straight-chain alkyl groups, C.sub.3 to C.sub.15 branched-chain alkyl groups, C.sub.3 to C.sub.15 cycloalkyl groups, C.sub.6 to C.sub.20 aryl groups, C.sub.7 to C.sub.20 alkaryl groups, and C.sub.7 to C.sub.20 aralkyl groups R.sub.31 and R.sub.32 optionally being bounded to or not to form a ring.

12. The catalyst composition of claim 6, wherein the diether compounds are at least one selected from the group consisting of 2,2-dimethyl-1,3-dimethoxypropane, 2,2-diethyl-1,3-dimethoxypropane, 2,2-dipropyl-1,3-dimethoxypropane, 2,2-diisopropyl-1,3-dimethoxypropane, 2,2-dibutyl-1,3-dimethoxypropane, 2,2-diisobutyl-1,3-dimethoxypropane, 2,2-dipentyl-1,3-dimethoxypropane, 2,2-di-isopentyl-1,3-dimethoxypropane, 2-methyl-2-ethyl-1,3-dimethoxypropane, 2-methyl-2-propyl-1,3-dimethoxypropane, 2-methyl-2-isopropyl-1,3-dimethoxypropane, 2-methyl-2-butyl-1,3-dimethoxypropane, 2-methyl-2-isobutyl-1,3-dimethoxypropane, 2-methyl-2-pentyl-1,3-dimethoxypropane, 2-methyl-2-isopentyl-1,3-dimethoxypropane, 2-ethyl-2-propyl-1,3-dimethoxypropane, 2-ethyl-2-isopropyl-1,3-dimethoxypropane, 2-ethyl-2-butyl-1,3-dimethoxypropane, 2-ethyl-2-isobutyl-1,3-dimethoxypropane, 2-ethyl-2-pentyl-1,3-dimethoxypropane, 2-ethyl-2-isopentyl-1,3-dimethoxypropane, 2-propyl-2-isopropyl-1,3-dimethoxypropane, 2-propyl-2-butyl-1,3-dimethoxypropane, 2-propyl-2-isobutyl-1,3-dimethoxypropane, 2-propyl-2-pentyl-1,3-dimethoxypropane, 2-propyl-2-isopentyl-1,3-dimethoxypropane, 2-isopropyl-2-isobutyl-1,3-dimethoxypropane, 2-isopropyl-2-pentyl-1,3-dimethoxypropane, 2-isopropyl-2-isopentyl-1,3-dimethoxypropane, 2-butyl-2-isobutyl-1,3-dimethoxypropane, 2-butyl-2-pentyl-1,3-dimethoxypropane, 2-butyl-2-isopentyl-1,3-dimethoxypropane, 2-isobutyl-2-pentyl-1,3-dimethoxypropane, 2-isobutyl-2-isopentyl-1,3-dimethoxypropane, 2-isobutyl-2-phenyl-1,3-dimethoxypropane, 2-isopentyl-2-phenyl-1,3-dimethoxypropane, 2-(2-methylbutyl)-2-benzyl-1,3-dimethoxypropane, 2-(2-ethylbutyl)-2-phenyl-1,3-dimethoxypropane, 2-(2-ethylhexyl)-2-phenyl-1,3-dimethoxypropane, 2-methyl-2-phenyl-1,3-dimethoxypropane, 2-ethyl-2-phenyl-1,3-dimethoxypropane, 2-isobutyl-2-benzyl-1,3-dimethoxypropane, 2-isopentyl-2-benzyl-1,3-dimethoxypropane, 2-(2-methylbutyl)-2-benzyl-1,3-dimethoxypropane, 2-(2-ethylbutyl)-2-benzyl-1,3-dimethoxypropane, 2-(2-ethylhexyl)-2-benzyl-1,3-dimethoxypropane, 2-propyl-2-benzyl-1,3-dimethoxypropane, 2-isopropyl-2-benzyl-1,3-dimethoxypropane, 2-isobutyl-2-(2-ethylbutyl)-1,3-dimethoxypropane, 2-isopentyl-2-(2-ethylbutyl)-1,3-dimethoxypropane, 2-(2-methylbutyl)-2-(2-ethylbutyl)-1,3-dimethoxypropane, 2-(2-ethylhexyl)-2-(2-ethylbutyl)-1,3-dimethoxypropane, 2-methyl-2-(2-ethylbutyl)-1,3-dimethoxypropane, 2-ethyl-2-(2-ethylbutyl)-1,3-dimethoxypropane, 2-isobutyl-2-(2-methylbutyl)-1,3-dimethoxypropane, 2-isopentyl-2-(2-methylbutyl)-1,3-dimethoxypropane, 2-(2-ethylbutyl)-2-(2-methylbutyl)-1,3-dimethoxypropane, 2-(2-ethylhexyl)-2-(2-methylbutyl)-1,3-dimethoxypropane, 2-isobutyl-2-(2-methylbutyl)-1,3-dimethoxypropane, 2-isobutyl-2-(2-ethylhexyl)-1,3-dimethoxypropane, 2-isopentyl-2-(2-ethylhexyl)-1,3-dimethoxypropane, 2,2-bis(2-methylbutyl)-1,3-dimethoxypropane, 2-isopropyl-2-isopentyl-1,3-dimethoxypropane, 2,2-bis(2-ethylhexyl)-1,3-dimethoxypropane, and 9,9-bis(methoxymethyl)fluorene.

13. The catalyst composition of claim 1, wherein the silane compounds have a general formula of R.sup.41.sub.m″R.sup.42.sub.n″Si(OR.sup.43).sub.4-m″-n″, wherein, R.sup.41 and R.sup.42, identical with or different from each other, can be independently selected from the group consisting of halogens, hydrogen, C.sub.1 to C.sub.20 alkyl groups, C.sub.3 to C.sub.20 cycloalkyl groups, C.sub.6 to C.sub.20 aryl groups, and C.sub.1 to C.sub.20 halogenated alkyl groups, wherein, R.sup.43 is selected from the group consisting of C.sub.1 to C.sub.20 alkyl groups, C.sub.3 to C.sub.20 cycloalkyl groups, C.sub.6 to C.sub.20 aryl groups, and C.sub.1 to C.sub.20 halogenated alkyl groups, and wherein m″ and n″ are integers in the range from 0 to 3, respectively, and m″+n″<4.

14. The catalyst composition of claim 1, wherein the diether compounds have a general formula as shown in Formula (IV): ##STR00010## wherein R.sub.31 and R.sub.32, identical with or different from each another, are selected from the group consisting of substituted or non-substituted C.sub.1 to C.sub.10 straight-chain alkyl groups, C.sub.3 to C.sub.15 branched-chain alkyl groups, C.sub.3 to C.sub.15 cycloalkyl groups, C.sub.6 to C.sub.20 aryl groups, C.sub.7 to C.sub.20 alkaryl groups, and C.sub.7 to C.sub.20 aralkyl groups R.sub.31 and R.sub.32 optionally being bounded to or not to form a ring.

15. The catalyst composition of claim 1, wherein the second external electron donor C2 is at least one selected from the group consisting of cyclohexylmethyldimethoxysilane, diphenyldimethoxysilane, phenyltriethoxysilane, diisopropyldimethoxysilane, dipropyldimethoxysilane, dicyclopentyldimethoxysilane, diphenyldimethylsilane, tetraalkoxysilane, butyltrimethoxysilane, 2-isopropyl-2-isopentyl-1,3-dimethoxypropane, 9,9-bis(methoxymethyl)fluorene, 2,2-dibutyl-1,3-dimethoxypropane, 2,2-diisobutyl-1,3-dimethoxypropane, and 2-isobutyl-2-isopentyl-1,3-dimethoxypropane.

16. The catalyst composition of claim 1, wherein the molar ratio of the first external electron donor to the second external electron donor is (1-100):100-1).

17. The catalyst composition of claim 1, wherein the molar ratio of component a) to component b) based on the molar ratio of titanium to aluminum is 1:(5-1000.

18. A pre-polymerization catalyst system, comprising a pre-polymer obtained by pre-polymerizing an olefin in the presence of the catalyst composition of claim 1, wherein the pre-polymerization multiple is 0.1 to 1000 gram of olefin polymer per gram of solid catalyst component a).

19. A method of olefin polymerization, comprising polymerizing an olefin in the presence of the catalyst composition of claim 1 or the pre-polymerization catalyst system of claim 18, wherein the olefin has a general formula of CH.sub.2═CHR, with R being hydrogen or a C.sub.1 to C.sub.12 hydrocarbyl or aryl group.

Description

DETAILED DESCRIPTION OF THE EMBODIMENTS

(1) In order to make the present disclosure more understandable, examples will be referred to in the following for explanation of the present disclosure. These examples are merely used to explain, rather than to limit the scope of the present disclosure. Specific experimental methods not indicated in the following examples are usually performed according to respective conventional experimental methods.

(2) Test Methods:

(3) 1. Melt indexes (MI) of polymers are tested in accordance with test standard GB/T 3682-2000.

(4) 2. Molecular weight distributions (MWD) (MWD=Mw/Mn) of polymers are tested by the gel permeation chromatography method with PL-GPC220 in trichlorobenzene as a solvent at 150° C. (standard sample: polystyrene; flow rate: 1.0 mL/min; column: 3×Plgel 10 um M1×ED-B 300×7.5 nm).

(5) 3. Isotactic indexes of polymers are tested by the heptane extraction method (6 hours of heptane extraction is performed at a boiling state), wherein 2 g of a dry polymer sample is arranged in an extractor for 6 hours of heptane extraction at a boiling state, and the residue is dried to constant weight to obtain polymers. The weight (g) of the resulting polymers is divided by 2 to obtain the isotactic index thereof.

Examples 1 to 8 and Comparative Examples 1 to 2

(6) Preparation of Solid Catalyst Component a)

(7) In a reactor where air was sufficiently displaced by high purity nitrogen, 6.0 g of magnesium chloride, 119 mL of toluene, 5 mL of epichlorohydrin, and 15.6 mL of tributyl phosphate (TBP) were successively added. The resulting mixture was heated up to 50° C. under stirring and kept at this temperature for 2.5 hours, during which period the solid added was adequately dissolved. 1.7 g of phthalic anhydride was added and kept for 1 hour. The resulting solution was cooled down to below −25° C., followed by addition of 70 mL of TiCl.sub.4 within one hour. The temperature was gradually raised to 80° C., during which a solid precipitated. 6 mmol of the internal electron donor as shown in Table 1 was added and the temperature was kept for one hour. After filtration, 80 mL of toluene was added for twice of washing to obtain a solid precipitate.

(8) Subsequently, 60 mL of toluene and 40 mL of TiCl.sub.4 were added and the temperature was raised up to 100° C. for 2 hours of treatment. The filtrate was removed, which preceded further addition of 60 mL of toluene and 40 mL of TiCl.sub.4. The temperature was raised up to 100° C. for 2 hours of treatment, and filtrate was removed. 60 mL of toluene was added for three times of washing at a boiling state. After that, 60 mL of hexane was added for twice of washing at a boiling state, followed by addition of 60 mL of hexane for twice of washing at room temperature. Thus, solid catalyst component a) was obtained.

(9) Experiment of Propene Polymerization

(10) Solid catalyst component a) was used for propene polymerization in the following procedures. In a 5 L stainless steel reactor, after air was sufficiently displaced by gaseous propene, 2.5 mmol of AlEt.sub.3 and 0.1 mmol of the external electron donor as shown in Table 1 were added, followed by addition of 8 mg to 10 mg of solid catalyst component a), 1.2 NL of hydrogen, and 2.3 L of liquid propene. The resulting mixture was heated up to 70° C. and kept at this temperature for 1 hour. Afterwards, the temperature was lowered and the pressure was released to obtain the PP powder material used in Examples 1 to 8 and Comparative Examples 1 to 2. The data are shown in Table 1.

(11) In propene polymerization, when 7.2 NL rather than 1.2 NL of hydrogen was added, the polymerization data would read Table 2.

(12) TABLE-US-00001 TABLE 1 Result of propene polymerization External Polymerization Internal electron activity Isotactic Example electron donor donor (kgPP/gcat) index % Example 1 2,4-pentanediol 1C 56.0 98.3 dibenzonate Example 2 3-methyl-2,4- 2C 58.4 98.5 pentanediol dibenzonate Example 3 3,5-heptanediol 3C 56.8 98.4 di-p-methyl benzoate Example 4 2,4-pentanediol 4C 62.3 98.7 di-p-tert-butyl benzoate Example 5 3,5-heptanediol 5C 52.0 96.0 dibenzoate Example 6 3,5-heptanediol 6C 53.1 97.9 dibenzoate Comparative 3,5-heptanediol CHMMS 50.6 98.0 Example 1 dibenzoate Example 7 2,3-diisopropyl 5C 39.5 95.0 succinate Example 8 2,3-diisopropyl 6C 40.7 98.3 succinate Comparative 2,3-diisopropyl CHMMS 39.8 98.1 Example 2 succinate In Table 1: 1C refers to diethyl malonate and cyclohexylmethyldimethoxysilane (CHMMS) in a molar ratio of 1:5; 2C refers to diethyl benzylmalonate and cyclohexylmethyldimethoxysilane in a molar ratio of 3:2; 3C refers to diethyl diethylmalonate and dicyclopentyldimethoxysilane (DCPDMS) in a molar ratio of 20:3; 4C refers to diethyl methylmalonate and dicyclopentyldimethoxysilane in a molar ratio of 4:1; 5C refers to diethyl malonate; and 6C refers to diethyl malonate and cyclohexylmethyldimethoxysilane in a molar ratio of 1:8.

(13) TABLE-US-00002 TABLE 2 Melt index/(g/10 min) Catalyst 1.2 NL of hydrogen 7.2 NL of hydrogen Example 1 1.9 28.6 Example 2 2.7 32.9 Example 5 3.0 47.7 Example 6 2.9 47.0 Comparative 1.6 28.0 Example 1 Example 7 1.8 35.6 Example 8 1.6 35.0 Comparative 1.0 19.0 Example 2

(14) Tables 1 and 2 indicate that compared with the prior art (e.g. Comparative Examples 1 and 2), the catalyst composition of the present disclosure containing a malonate compound (as shown in Formula I) in the external electron donor can significantly improve melt indexes of polymers when being used in olefin polymerization (e.g. Examples 1 to 8), especially propene polymerization in the presence of a high hydrogen concentration. It means that hydrogen response of the catalyst composition is significantly improved. Particularly, compared with the prior art, when a composite system formulated by a malonate compound (as shown in Formula I) and other external electron donors is used, the polymers obtained will keep high isotacticity and the catalyst composition a high catalytic activity, while the melt indexes of the polymers are improved (i.e., hydrogen response of the catalyst composition is improved).

Examples 9 to 13 and Comparative Example 3

(15) Preparation of Solid Catalyst Component a)

(16) Under protection of nitrogen, 4.8 g of anhydrous magnesium chloride, 19.5 g of isooctanol, and 19.5 g of decane as a solvent were added into a 500 mL reactor arranged with a stirrer. The resulting mixture was heated up to 130° C., followed by 1.5 hours of reaction until the magnesium chloride was completely dissolved. 1.1 g of phthalic anhydride was added and the temperature of 130° C. was further kept for 1 hour of reaction to obtain an alcoholate, which was cooled down to room temperature.

(17) Under the protection of nitrogen, the above alcoholate was dropwise added into 120 mL of a TiCl.sub.4 solution pre-cooled to −22° C. The temperature was slowly raised to 100° C., which preceded addition of 10 mmol of the phthalate compound as shown in Formula (III) in Table 3. The temperature was then raised to 110° C. and kept for 2 hours. After hot filtration, 120 mL of TiCl.sub.4 was added and heated up to 110° C. for one hour of reaction. Filtration was performed, and solid particles obtained were washed with anhydrous hexane for four times. Solid catalyst component a) was obtained after being dried.

(18) Experiment of Propene Polymerization

(19) Solid catalyst component a) obtained above was used for propene polymerization in the following procedures. In a 5 L stainless steel reactor, after air was sufficiently displaced by gaseous propene, 2.5 mmol of AlEt.sub.3 and 0.1 mmol of the external electron donor as shown in Table 3 were added, followed by addition of 8 mg to 10 mg of solid catalyst component a), 1.2 NL of hydrogen, and 2.3 L of liquid propene. The resulting mixture was heated up to 70° C. and kept at this temperature for one hour. Afterwards, the temperature was lowered and the pressure was released to obtain the PP powder material used in Examples 9 to 13 and Comparative Example 3. The data are shown in Table 3.

(20) In propene polymerization, when 7.2 NL rather than 1.2 NL of hydrogen was added, the polymerization data would read Table 4.

(21) TABLE-US-00003 TABLE 3 Result of propene polymerization Poly- Internal External merization electron electron activity Isotactic Example donor (III) donor (kgPP/gcat) index % WMD Example 9 di-n-butyl 7C 41.9 98.2 6.9 phthalate Example 10 di-iso-octyl 8C 42.7 98.4 7.1 phthalate Example 11 di-iso-butyl 9C 39.4 98.5 7.0 phthalate Example 12 di-iso-butyl 10C  43.6 94.9 7.2 phthalate Example 13 di-iso-butyl 11C  43.2 98.6 6.9 phthalate Comparative di-iso-butyl DCPDMS 41.3 98.5 4.5 Example 3 phthalate In Table 3: 7C refers to dicyclopentyldimethoxysilane and diethyl methylmalonate in a molar ratio of 1:5; 8C refers to cyclohexylmethyldimethoxysilane and diethyl malonate in a molar ratio of 1:2; 9C refers to 9,9-bis(methoxymethyl)fluorene and diethyl dipropylmalonate in a molar ratio of 6:1; 10C refers to diethyl di-n-butylmalonate; and 11C refers to dicyclopentyldimethoxysilane and diethyl di-n-butylmalonate in a molar ratio of 4:1.

(22) Table 3 shows, compared with the comparative example, the catalyst composition of the present disclosure containing a malonate compound as shown in Formula (I) as an external electron donor can render the molecular weight distribution of polymers obtained wider while retaining high polymerization activity, which is rather beneficial for development of different grades of resins.

(23) TABLE-US-00004 TABLE 4 Melt index/(g/10 min) Catalyst 1.2 NL of hydrogen 7.2 NL of hydrogen Example 10 6.6 38.9 Example 12 6.3 40.6 Example 13 7.0 40.7 Comparative 4.0 23.2 Example 3

(24) Table 4 teaches that, compared with the comparative example, the catalyst composition containing a malonate compound as shown in Formula (I) in the external electron donor can improve melt indexes of the polymers obtained and significantly increase hydrogen response of the catalyst composition.

Examples 14 to 18 and Comparative Example 4

(25) Preparation of Solid Catalyst Component a)

(26) In a 250 mL first reactor arranged with a reflux condenser, a mechanical stirrer, and a thermometer, after air was sufficiently displaced by nitrogen, 36.5 mL of anhydrous ethanol and 21.3 g of anhydrous magnesium chloride were added. The resulting mixture was heated under stirring until the anhydrous magnesium chloride was completely dissolved, which preceded addition of 75 mL of while oil and 75 mL of silicone oil. The temperature was retained for a certain time at 120° C. In a 500 mL second reactor arranged with a high-speed blender, 112.5 mL of while oil and the same volume of silicone oil were pre-added and pre-heated up to 120° C. The mixture in the first reactor was quickly pushed into the second reactor. The resulting mixture was kept at 120° C. and stirred for 3 min at a speed of 3,500 rmp, and then completely transferred into a third reactor that was pre-added with 1,600 mL of hexane and pre-cooled to −25° C. under stirring. The final temperature should not exceed 0° C. Suction filtration, washing with hexane, and vacuum drying were successively performed to obtain 41 g of spherical particles, i.e., an alcoholate of magnesium chloride. The particles were sieved and a 100 mesh to 400 mesh carrier was taken to be analyzed and tested. The carrier was proved to be comprised of MgCl.sub.2.2.38C.sub.2H.sub.5OH.

(27) 7 g of the above spherical carrier, i.e., MgCl.sub.2.2.38C.sub.2H.sub.5OH was taken and slowly added into a reactor that contained 150 mL of TiCl.sub.4 pre-cooled to −20° C. The temperature was gradually raised to 40° C., followed by addition of 5 mmol of a diether compound as shown in Formula (IV). The temperature continued to be raised to 130° C. and kept at this temperature for two hours, which preceded suction filtration. 120 mL of TiCl.sub.4 was further added. Afterwards, the temperature was slowly raised to 130° C. and kept for 2 hours. 60 mL of hexane was used for a plurality of times of washing until there was no chloridion in the filtrate. The filter cake was vacuum dried to obtain the solid catalyst component.

(28) Experiment of Propene Polymerization

(29) Solid catalyst component a) obtained above was used for propene polymerization in the following procedures. In a 5 L stainless steel reactor, after air was sufficiently displaced by gaseous propene, 2.5 mmol of AlEt.sub.3 and 0.1 mmol of the external electron donor as shown in Table 5 were added, followed by addition of 8 mg to 10 mg of solid catalyst component a), 1.2 NL of hydrogen, and 2.3 L of liquid propene. The resulting mixture was heated up to 70° C. and kept at this temperature for 1 hour. Afterwards, the temperature was lowered and the pressure was released to obtain the PP powder material used in Examples 14 to 18 and Comparative Example 4. The data are shown in Table 5.

(30) TABLE-US-00005 TABLE 5 Result of propene polymerization Composite Polymerization Internal external activity Isotactic Example electron donor electron donor (kgPP/gcat) index % WMD Example 14 2,2-diisobutyl-1,3- 12C 50.1 98.5 6.8 dimethoxypropane Example 15 9,9-bis(methoxymethyl) 13C 60.8 98.8 7.6 fluorene Example 16 2-isopropyl-2-isopentyl- 14C 50.8 98.2 7.3 1,3-dimethoxypropane Example 17 2-isopropyl-2-isopentyl- 15C 51.1 96.9 7.4 1,3-dimethoxypropane Example 18 2-isopropyl-2-isopentyl- 16C 51.8 98.5 7.3 1,3-dimethoxypropane Comparative 2-isopropyl-2-isopentyl- CHMMS 50.7 98.5 5.0 Example 4 1,3-dimethoxypropane In Table 5: 12C refers to cyclohexylmethyldimethoxysilane and diethyl malonate in a molar ratio of 1:8; 13C refers to 2-isopropyl-2-isopentyl-1,3-dimethoxypropane and diethyl malonate in a molar ratio of 3:1; 14C refers to dicyclopentyldimethoxysilane and diethyl methylmalonate in a molar ratio of 1:2; 15C refers to diisopropyl malonate; and 16C refers to dicyclopentyldimethoxysilane and diisopropyl malonate in a molar ratio of 20:1.

(31) It can be seen from Table 5, compared with the comparative example, the catalyst composition of the present disclosure which contains a malonate compound as shown in Formula (I) in the external electron donor can render the molecular weight distribution of the polymers wider while retaining high activity of the catalyst and high isotacticity of the polymers.

(32) High-Temperature Self-Extinguishment

Examples 26 to 28

(33) Preparation of Solid Catalyst Component a)

(34) In a reactor where air was sufficiently displaced with high-purity nitrogen, 6.0 g of magnesium chloride, 119 mL of toluene, 5 mL of epichlorohydrin, and 15.6 mL of tributyl phosphate (TBP) were successively added. The resulting mixture was heated to 50° C. under stirring and was kept at this temperature for 2.5 hours until the solid was dissolved adequately. 1.7 g of phthalic anhydride was added and the system was kept for one hour. The resulting solution was cooled down to below −25° C., and 70 mL of TiCl.sub.4 was dropwise added within one hour. The temperature was then gradually raised to 80° C., during which a solid gradually precipitated. 6 mmol of the internal electron donor as shown in Table 6 was added, and the temperature was kept for one hour. After filtration, 80 mL of toluene was added for twice of washing to obtain a solid precipitate.

(35) 60 mL of toluene and 40 mL of TiCl.sub.4 were added. The resulting mixture was heated up to 100° C. and treated for two hours. After removing the filtrate, 60 mL of toluene and 40 mL of TiCl.sub.4 were further added. The resulting mixture was again heated up to 100° C. and treated for two hours. The filtrate was removed, and 60 mL of toluene was added for three times of washing at a boiling state, which preceded addition of 60 mL of hexane for twice of washing at a boiling state. After that, 60 mL of hexane was added for twice of washing at room temperature to obtain the solid catalyst component.

(36) Experiment of Propene Polymerization

(37) In a dry 500 mL 3-mouth flask, after air was sufficiently displaced respectively by nitrogen and gaseous propene, 200 mL of decane was added and heated up to the temperature as required in Table 6. A certain amount of AlEt.sub.3 and the external electron donor as shown in Table 6 were added at a micro-positive pressure of the propene, so as to guarantee that Al/Si=20 (mol), and Al/Ti=100 (mol). Catalyst component a) as prepared above was added at this temperature for two hours of reaction, until the reaction was terminated with ethanol. The polymers were then washed with ethanol and vacuum dried. The data are shown in Table 6, in which, DEM, DIPM, and DEM-2Bu refer to diethyl malonate, diisopropyl malonate, and diethyl di-n-butylmalonate, respectively.

(38) TABLE-US-00006 TABLE 6 Internal External electron donor Example electron donor (molar ratio) AC*.sub.100 AC.sub.67 AC*.sub.100/AC.sub.67 Example 26 3,5-heptanediol DEM 120.7 607.4 0.20 dibenzoate DEM/CHMMS = 0.5 153.2 600.0 0.25 CHMMS 187.4 589.0 0.32 Example 27 diisobutyl DIPM 64.3 350.6 0.18 phthalate DIPM/CHMMS = 1.5 79.1 342.1 0.23 CHMMS 101.1 336.1 0.30 Example 28 9,9-bis(methoxy DEM-2Bu 135.1 725.6 0.19 methyl)fluorene DEM-2Bu/DCPDMS = 1 174.1 736.4 0.24 DCPDMS 232.4 749.7 0.31 Note: AC*.sub.100 refers to normalization at 100° C. That is, actual activity at 100° C. × 1.93 (solubility difference of propene) = normalization at 100° C.

(39) Table 6 indicates that when the catalyst composition of the present disclosure that contains a malonate compound as shown in Formula (I) in the external electron donor is used in olefin polymerization at a high temperature (e.g. 100° C.), in particular propene polymerization, it presents lower activity, i.e., a better high-temperature self-extinguishment, than when mere silane was used, so that occurrence of implosion at high temperature polymerization can be better prevented.

(40) It should be noted that the above examples are only used to explain, rather than to limit the present disclosure in any manner. Although the present disclosure has been discussed with reference to preferable examples, it should be understood that the terms and expressions adopted are for describing and explaining instead of limiting the present disclosure. The present disclosure can be modified within the scope of the claims, or can be amended without departing from the scope or spirits of the present disclosure. Although the present disclosure is described with specific methods, materials, and examples, the scope of the present disclosure herein disclosed should not be limited by the particularly disclosed examples as described above, but can be extended to other methods and uses having the same functions.