Olefin polymerization catalyst comprising cyclotriveratrylene and derivatives thereof

Abstract

The present invention discloses a Ziegler-Natta catalyst system for olefin polymerization, comprising at least one compound represented by formula (I) as (i) an internal electron donor, (ii) an external electron donor, or (iii) the both, wherein M.sub.1, M.sub.2, M.sub.3, M.sub.4, M.sub.5, M.sub.6, M.sub.1′, M.sub.2′, M.sub.3′, M.sub.4′, M.sub.5′ and M.sub.6′ are each independently selected from the group consisting of hydrogen, hydroxy, amino, aldehyde group, carboxy, acyl, halogen atoms, —R.sub.1 and —OR.sub.2, wherein R.sub.1 and R.sub.2 are each independently a C.sub.1-C.sub.10 hydrocarbyl, which is unsubstituted or substituted by a substituent selected from the group consisting of hydroxy, amino, aldehyde group, carboxy, acyl, halogen atoms, C.sub.1-C.sub.10 alkoxy and heteroatoms; and wherein, when among M.sub.1-M.sub.6 and M.sub.1′-M.sub.6′, any two adjacent groups on the same phenyl ring are each independently selected from the group consisting of R.sub.1 and —OR.sub.2, the two adjacent groups may optionally be linked to form a ring, with a proviso that M.sub.1, M.sub.2, M.sub.3, M.sub.4, M.sub.5, M.sub.6, M.sub.1′, M.sub.2′, M.sub.3′, M.sub.4′, M.sub.5′ and M.sub.6′ are not simultaneously hydrogen. ##STR00001##

Claims

1. A Ziegler-Natta catalyst system for olefin polymerization, comprising at least one compound represented by formula (I) as (i) an internal electron donor, (ii) an external electron donor, or (iii) the both, ##STR00012## wherein M.sub.1, M.sub.2, M.sub.3, M.sub.4, M.sub.5, M.sub.6, M.sub.1′, M.sub.2′, M.sub.3′, M.sub.4′, M.sub.5′ and M.sub.6′ are each independently selected from the group consisting of hydrogen, hydroxy, amino, aldehyde group, carboxy, acyl, halogen atoms, —R.sub.1 and —OR.sub.2, where R.sub.1 and R.sub.2 are each independently a C.sub.1-C.sub.10 hydrocarbyl, which is unsubstituted or substituted by a substituent selected from the group consisting of hydroxy, amino, aldehyde group, carboxy, acyl, halogen atoms, C.sub.1-C.sub.10 alkoxy and heteroatoms; and wherein, when among M.sub.1-M.sub.6 and M.sub.1′-M.sub.6′, any two adjacent groups on the same phenyl ring are each independently selected from the group consisting of R.sub.1 and —OR.sub.2, the two adjacent groups may optionally be linked to form a ring, with a proviso that M.sub.1, M.sub.2, M.sub.3, M.sub.4, M.sub.5, M.sub.6, M.sub.1′, M.sub.2′, M.sub.3′, M.sub.4′, M.sub.5′ and M.sub.6′ are not simultaneously hydrogen.

2. The catalyst system according to claim 1, wherein the compound represented by formula (I) is selected from those represented by formula (I′): ##STR00013## wherein M.sub.1, M.sub.2, M.sub.3, M.sub.4, M.sub.5 and M.sub.6 are each independently selected from the group consisting of hydrogen, hydroxy, amino, aldehyde group, carboxy, acyl, halogen atoms, —R.sub.1 and —OR.sub.2, where R.sub.1 and R.sub.2 are each independently a C.sub.1-C.sub.10 hydrocarbyl, which is unsubstituted or substituted by a substituent selected from the group consisting of hydroxy, amino, aldehyde group, carboxy, acyl, halogen atoms, C.sub.1-C.sub.10 alkoxy and heteroatoms, with a proviso that when two adjacent groups on the same phenyl ring, i.e., M.sub.1 and M.sub.2, or M.sub.3 and M.sub.4, or M.sub.5 and M.sub.6, are each independently selected from the group consisting of —R.sub.1 and —OR.sub.2, the two adjacent groups may optionally be linked to form a ring, and further with a proviso that M.sub.1, M.sub.2, M.sub.3, M.sub.4, M.sub.5 and M.sub.6 are not simultaneously hydrogen.

3. The catalyst system according to claim 2, wherein in the formula (I′), M.sub.1, M.sub.2, M.sub.3, M.sub.4, M.sub.5 and M.sub.6 are each independently selected from the group consisting of hydroxy, amino, aldehyde group, halogen atoms, —R.sub.1 and —OR.sub.2, where R.sub.1 and R.sub.2 are each independently selected from the group consisting of unsubstituted or halogen-substituted C.sub.1-C.sub.10 hydrocarbyl groups.

4. The catalyst system according to claim 1, wherein the at least one compound represented by formula (I) is selected from the group consisting of: Compound A: M.sub.1=M.sub.2=M.sub.3=M.sub.4=M.sub.5=M.sub.6=OCH.sub.3, M.sub.1′=M.sub.2′=M.sub.3′=M.sub.4′=M.sub.5′=M.sub.6′=H; Compound B: M.sub.1=M.sub.2=M.sub.3=M.sub.4=M.sub.5=M.sub.6=OCH.sub.2CH.sub.3, M.sub.1′=M.sub.2′=M.sub.3′=M.sub.4′=M.sub.5′=M.sub.6′=H Compound C: M.sub.1=M.sub.2=M.sub.3=M.sub.4=M.sub.5=M.sub.6=OCH.sub.2CH.sub.2CH.sub.3, M.sub.1′=M.sub.2′=M.sub.3′=M.sub.4′=M.sub.5′=M.sub.6′=H; Compound D: M.sub.1=M.sub.2=M.sub.3=M.sub.4=M.sub.5=M.sub.6=OCH(CH.sub.3).sub.2, M.sub.1′=M.sub.2′=M.sub.3′=M.sub.4′=M.sub.5′=M.sub.6′=H; Compound E: M.sub.1=M.sub.2=M.sub.3=M.sub.4=M.sub.5=M.sub.6=OCH.sub.2CH.sub.2CH.sub.2CH.sub.3, M.sub.1′=M.sub.2′=M.sub.3′=M.sub.4′=M.sub.5′=M.sub.6′=H; Compound F: M.sub.1=M.sub.3=M.sub.5=OCH.sub.3, M.sub.2=M.sub.4=M.sub.6=OCH.sub.2CH.sub.3, M.sub.1′=M.sub.2′=M.sub.3′=M.sub.4′=M.sub.5′=M.sub.6′=H; Compound G: M.sub.1=M.sub.3=M.sub.5=OCH.sub.3, M.sub.2=M.sub.4=M.sub.6=OCH.sub.2CH.sub.2CH.sub.3, M.sub.1′=M.sub.2′=M.sub.3′=M.sub.4′=M.sub.5′=M.sub.6′=H; Compound H: M.sub.1=M.sub.3=M.sub.5=OCH.sub.3, M.sub.2=M.sub.4=M.sub.6=OCH.sub.2CH.sub.2CH.sub.2CH.sub.3, M.sub.1′=M.sub.2′=M.sub.3′=M.sub.4′=M.sub.5′=M.sub.6′=H; Compound I: M.sub.1=M.sub.2=M.sub.3=M.sub.4=M.sub.5=M.sub.6=OH, M.sub.1′=M.sub.2′=M.sub.3′=M.sub.4′=M.sub.5′=M.sub.6′=H; Compound J: M.sub.1=M.sub.3=M.sub.5=OCH.sub.3, M.sub.2=M.sub.4=M.sub.6=OH, M.sub.1′=M.sub.2′=M.sub.3′=M.sub.4′=M.sub.5′=M.sub.6′=H; Compound K: M.sub.1=M.sub.3=M.sub.5=OCH.sub.3, M.sub.2=M.sub.4=M.sub.6=NH.sub.2, M.sub.1′=M.sub.2′=M.sub.3′=M.sub.4′=M.sub.5′=M.sub.6′=H; Compound L: M.sub.1=M.sub.3=M.sub.5=OCH.sub.3, M.sub.2=M.sub.4=M.sub.6=Cl, M.sub.1′=M.sub.2′=M.sub.3′=M.sub.4′=M.sub.5′=M.sub.6′=H; Compound M: M.sub.1=M.sub.3=M.sub.5=OCH.sub.3, M.sub.2=M.sub.4=M.sub.6=Br, M.sub.1′=M.sub.2′=M.sub.3′=M.sub.4′=M.sub.5′=M.sub.6′=H; Compound N: M.sub.1=M.sub.3=M.sub.5=OCH.sub.3, M.sub.2=M.sub.4=M.sub.6=I, M.sub.1′=M.sub.2′=M.sub.3′=M.sub.4′=M.sub.5′=M.sub.6′=H; Compound O: M.sub.1=M.sub.3=M.sub.5=OCH.sub.3, M.sub.2=M.sub.4=M.sub.6=CHO, M.sub.1′=M.sub.2′=M.sub.3′=M.sub.4′=M.sub.5′=M.sub.6′=H; Compound P: M.sub.1=M.sub.3=M.sub.5=OCH.sub.3, M.sub.2=M.sub.4=M.sub.6=OCH.sub.2CH.sub.2CH.sub.2Br, M.sub.1′=M.sub.2′=M.sub.3′=M.sub.4′=M.sub.5′=M.sub.6′=H; Compound Q: M.sub.1=M.sub.2=M.sub.3=M.sub.4=M.sub.5=M.sub.6=OCH.sub.2CH.sub.2Cl, M.sub.1′=M.sub.2′=M.sub.3′=M.sub.4′=M.sub.5′=M.sub.6′=H; Compound R: M.sub.1=M.sub.3=M.sub.5=OH, M.sub.2=M.sub.4=M.sub.6=OCH.sub.2CH.sub.3, M.sub.1′=M.sub.2′=M.sub.3′=M.sub.4′=M.sub.5′=M.sub.6′=H; Compound S: M.sub.1=M.sub.2=M.sub.3=M.sub.4=M.sub.5=M.sub.6=OCH.sub.3, M.sub.1′=Cl, M.sub.2′=M.sub.3′=M.sub.4′=M.sub.5′=M.sub.6′=H; Compound T: M.sub.1=M.sub.2=M.sub.3=M.sub.4=M.sub.5=M.sub.6=OCH.sub.3, M.sub.1′=M.sub.3′=Cl, M.sub.2′=M.sub.4′=M.sub.5′=M.sub.6′=H; Compound U: M.sub.1=M.sub.2=M.sub.3=M.sub.4=M.sub.5=M.sub.6=OCH.sub.3, M.sub.1′=M.sub.3′=M.sub.5′=Cl, M.sub.2′=M.sub.4′=M.sub.6=H; and Compound V: M.sub.1=M.sub.2=M.sub.3=M.sub.4=M.sub.5=M.sub.6=OCH.sub.3, M.sub.1′=M.sub.3′=M.sub.6′=Cl, M.sub.2′=M.sub.4′=M.sub.5=H.

5. A solid catalyst component for olefin polymerization, comprising magnesium, titanium, halogen and an internal electron donor compound, wherein the internal electron donor compound comprises at least one compound of the formula (I) as defined in claim 1.

6. The solid catalyst component according to claim 5, comprising at least one titanium compound and the at least one compound represented by formula (I), supported on a magnesium halide.

7. The solid catalyst component according to claim 5, wherein a molar ratio of the at least one compound represented by formula (I) to magnesium ranges from 0.0005:1 to 0.1:1, or from 0.001:1 to 0.1:1, or from 0.002:1 to 0.05:1.

8. The solid catalyst component according to claim 6, wherein the at least one titanium compound is selected from the group consisting of titanium trichloride and those having general formula Ti(OR).sub.nX′.sub.4-n, where R is a C.sub.1-C.sub.8 hydrocarbyl, X′ is a halogen atom, and 0≤n≤4; or the at least one titanium compound is selected from the group consisting of titanium trichloride, titanium tetrachloride, titanium tetrabromide, tetraethoxy titanium, triethoxy titanium chloride, diethoxy titanium dichloride, tetrabutoxy titanium and ethoxy titanium trichloride.

9. The solid catalyst component according to claim 5, comprising a reaction product of: 1) a magnesium halide-alcohol adduct; 2) a titanium compound; 3) an internal electron donor compound; and 4) optionally, an organic aluminum compound, wherein the internal electron donor compound comprises the at least one compound represented by formula (I).

10. The solid catalyst component according to claim 9, having at least one feature of the followings: the organic aluminum compound is of general formula AlR.sup.1.sub.aX.sup.1.sub.bH.sub.c, where R.sup.1 is a C.sub.1-C.sub.14 hydrocarbyl; X.sup.1 is a halogen atom; a, b and c are each a number of from 0 to 3; and a+b+c=3; the content of the at least one compound represented by formula (I) is at least 0.0005 moles, or at least 0.001 moles, or from 0.001 to 0.1 moles, relative to one mole of magnesium; the magnesium halide-alcohol adduct is of general formula MgX.sub.2.m(ROH), where X is Cl, Br or I; R is a C.sub.1-C.sub.6 alkyl; and m ranges from 0.5 to 4.0, or from 2.5 to 4.0; the titanium compound is of general formula Ti(OR.sup.2).sub.nX.sup.2.sub.4-n, where R.sup.2 is a C.sub.1-C.sub.8 hydrocarbyl; X.sup.2 is Cl, Br or I; and 0≤n≤4; or the titanium compound is selected from the group consisting of TiCl.sub.4, Ti(OC.sub.2H.sub.5)Cl.sub.3, Ti(OCH.sub.3)Cl.sub.3, Ti(OC.sub.4H.sub.9)Cl.sub.3, Ti(OC.sub.4H.sub.9).sub.4 and mixtures thereof; and in a reaction for forming the solid catalyst component, relative to one mole of magnesium, the amount of the titanium compound used ranges from 0.1 to 100 moles, or from 1 to 50 moles, and the amount of the organic aluminum compound used ranges from 0 to 5 moles.

11. The solid catalyst component according to claim 5, comprising a reaction product of: 1) an alkoxy magnesium compound; 2) a titanium compound; and 3) an internal electron donor compound; wherein the internal electron donor compound comprises the at least one compound represented by formula (I).

12. The solid catalyst component according to claim 11, having at least one feature of the followings: the content of the at least one compound represented by formula (I) is at least 0.0005 moles, or at least 0.001 moles, or in a range of from 0.001 to 0.1 moles, relative to one mole of magnesium; the alkoxy magnesium compound is of general formula Mg(OR.sub.3).sub.a(OR.sub.4).sub.2-a, where R.sub.3 and R.sub.4 are each independently selected from the group consisting of C.sub.1-C.sub.10 hydrocarbyl groups, which are unsubstituted or substituted by a substituent selected from the group consisting of hydroxy, amino, aldehyde group, carboxy, acyl, halogen atoms, alkoxy and heteroatoms, and 0≤a≤2; the titanium compound is of general formula Ti(OR).sub.nX.sub.4-n, where R is a C.sub.1-C.sub.8 hydrocarbyl; X is a halogen atom; and 0≤n≤4; or the titanium compound is selected from the group consisting of TiCl.sub.4, Ti(OC.sub.2H.sub.5)Cl.sub.3, Ti(OCH.sub.3)Cl.sub.3, Ti(OC.sub.4H.sub.9)Cl.sub.3, Ti(OC.sub.4H.sub.9).sub.4 and mixtures thereof; in a reaction for forming the solid catalyst component, relative to one mole of magnesium, the amount of the titanium compound used ranges from 0.1 to 100 moles, or from 1 to 50 moles; the solid catalyst component is prepared by a process comprising: dispersing the alkoxy magnesium compound in an inert solvent to afford a suspension; contacting the suspension with the titanium compound and the at least one compound represented by formula (I) to obtain a contacted product; and further reacting the contacted product with the titanium compound to afford the solid catalyst component, alternatively, the solid catalyst component is prepared by a process comprising: dispersing the alkoxy magnesium compound in an inert solvent to afford a suspension; contacting the suspension with the titanium compound to obtain a contacted product; and further reacting the contacted product with the titanium compound and the at least one compound represented by formula (I) to afford the solid catalyst component.

13. The solid catalyst component according to claim 5, comprising a reaction product of: 1) a finely-divided support having a particle size of from 0.01 to 10 microns; 2) a magnesium halide; 3) a titanium halide; and 4) an internal electron donating compound, which comprises an internal electron donor a and an internal electron donor b, wherein the internal electron donor a is the at least one compound represented by formula (I), and the internal electron donor b is at least one selected from the group consisting of alkyl esters of C.sub.2-C.sub.10 saturated aliphatic carboxylic acids, alkyl esters of C.sub.7-C.sub.10 aromatic carboxylic acids, C.sub.2-C.sub.10 aliphatic ethers, C.sub.3-C.sub.10 cyclic ethers, and C.sub.3-C.sub.10 saturated aliphatic ketones; and wherein a molar ratio of the titanium halide to the internal electron donor a ranges from 5:1 to 2000:1, and a molar ratio of the titanium halide to the internal electron donor b ranges from 1:1 to 1:600.

14. The solid catalyst component according to claim 13, having at least one feature of the followings: the internal electron donor b is at least one selected from the group consisting of methyl formate, ethyl acetate, butyl acetate, diethyl ether, dihexyl ether, tetrahydrofuran, acetone and methyl isobutyl ketone; the magnesium halide is at least one selected from the group consisting of MgCl.sub.2, MgBr.sub.2 and MgI.sub.2; the titanium halide is at least one selected from the group consisting of titanium tetrachloride and titanium trichloride; the finely-divided support is at least one selected from the group consisting of alumina, activated carbon, clays, silica, titania, polystyrenes and calcium carbonate; and the solid catalyst component is prepared by a process comprising: mixing the magnesium halide, the titanium halide, the internal electron donor a and the internal electron donor b and allowing the resultant mixture to react at 0 to 90° C. for 0.5 to 5 hours to afford a mother liquor; at 0 to 90° C., mixing the mother liquor with the finely-divided support and stirring the resultant mixture for 0.5 to 3 hours to afford a finely-divided support-admixed mother liquor; and spray-drying the finely-divided support-admixed mother liquor to obtain the solid catalyst component, wherein a content of the finely-divided support in the finely-divided support-admixed mother liquor ranges from 3 to 50 wt. %, or from 10 to 30 wt. %.

15. The solid catalyst component according to claim 5, comprising a reaction product of: 1) a magnesium-containing liquid-state component, which is at least one selected from the following components: i) an alkyl magnesium or a solution thereof in a liquid hydrocarbon, the alkyl magnesium being of general formula MgR.sub.1R.sub.2, where R.sub.1 and R.sub.2 are each independently selected from the group consisting of C.sub.1-C.sub.10 hydrocarbyl groups, which are unsubstituted or substituted by a substituent selected from the group consisting of hydroxy, amino, aldehyde group, carboxy, halogen atoms, alkoxy and heteroatoms; ii) a product obtained by dissolving, in a solvent system comprising an organophosphorus compound, an organic epoxy compound and an optional alcohol compound R.sub.5OH, a magnesium dihalide or a derivative deriving from a magnesium dihalide by replacing one halogen atom in the molecular formula of the magnesium dihalide with group R.sub.3 or OR.sub.4; and iii) a product obtained by dispersing, in an alcohol compound R.sub.5OH, a magnesium dihalide or a derivative deriving from a magnesium dihalide by replacing one halogen atom in the molecular formula of the magnesium dihalide with group R.sub.3 or OR.sub.4; where R.sub.3, R.sub.4 and R.sub.5 are each independently selected from the group consisting of C.sub.1-C.sub.10 hydrocarbyl groups, which are unsubstituted or substituted by a substituent selected from the group consisting of hydroxy, amino, aldehyde group, carboxy, halogen atoms, alkoxy and heteroatoms; 2) a titanium compound; 3) an internal electron donor compound; and 4) optionally, an auxiliary precipitant, which is selected from the group consisting of organic anhydride compounds and/or organic silicon compounds, wherein the internal electron donor compound comprises the at least one compound represented by formula (I).

16. The solid catalyst component according to claim 15, having at least one feature of the followings: the alkyl magnesium is at least one selected from the group consisting of dimethyl magnesium, diethyl magnesium, n-butyl ethyl magnesium, di-n-butyl magnesium, and butyl octyl magnesium; the magnesium dihalide or derivative deriving from a magnesium dihalide by replacing one halogen atom in the molecular formula of the magnesium dihalide with group R.sub.3 or OR.sub.4 is at least one selected from the group consisting of MgCl.sub.2, MgBr.sub.2, MgI.sub.2, MgCl(OCH.sub.2CH.sub.3), MgCl(OBu), CH.sub.3MgCl and CH.sub.3CH.sub.2MgCl; the organophosphorus compound is selected from the group consisting of hydrocarbyl esters and halogenated hydrocarbyl esters of ortho-phosphoric acid, and hydrocarbyl esters and halogenated hydrocarbyl esters of phosphorous acid, or the organophosphorus compound is at least one selected from the group consisting of triethyl phosphate, tributyl phosphate, tri-isooctyl phosphate, triphenyl phosphate, triethyl phosphite, tributyl phosphite and di-n-butyl phosphite; the organic epoxy compound is at least one selected from the group consisting of aliphatic epoxy compounds and diepoxy compounds, halogenated aliphatic epoxy compounds and diepoxy compounds, glycidyl ethers, and inner ethers, having from 2 to 18 carbon atoms, or is at least one selected from the group consisting of epoxy ethane, epoxy propane, epoxy butane, vinyl epoxy ethane, epoxy chloropropane, glycidyl methacrylate, glycidyl ethyl ether and glycidyl butyl ether; the alcohol compound is at least one selected from the group consisting of methanol, ethanol, propanol, isopropanol, butanol, isobutanol, tert-butanol, hexanol, cyclohexanol, octanol, isooctanol, decanol, benzyl alcohol and phenylethanol; the titanium compound is of general formula Ti(OR.sub.6).sub.nX.sub.4-n, where R.sub.6 is a C.sub.1-C.sub.8 hydrocarbyl, X is a halogen atom, and 0≤n≤3; or the titanium compound is at least one selected from the group consisting of TiCl.sub.4, TiBr.sub.4, TiI.sub.4, Ti(OC.sub.2H.sub.5)Cl.sub.3, Ti(OCH.sub.3)Cl.sub.3, Ti(OC.sub.4H.sub.9)Cl.sub.3, Ti(OC.sub.2H.sub.5)Br.sub.3, Ti(OC.sub.2H.sub.5).sub.2Cl.sub.2, Ti(OCH.sub.3).sub.2Cl.sub.2, Ti(OCH.sub.3).sub.2I.sub.2, Ti(OC.sub.2H.sub.5).sub.3Cl, Ti(OCH.sub.3).sub.3Cl and Ti(OC.sub.2H.sub.5).sub.3I; the organic anhydride compounds are represented by formula (II): R.sup.1CO—O—CO—R.sup.2 (II), where R.sup.1 and R.sup.2 are each independently selected from the group consisting of hydrogen and C.sub.1-C.sub.10 hydrocarbyl groups, and R.sup.1 and R.sup.2 may optionally be linked to form a ring; the organic silicon compounds are of general formula R.sup.3.sub.xR.sup.4.sub.ySi(OR.sup.5).sub.z, where R.sup.3 and R.sup.4 are each independently selected from the group consisting of C.sub.1-C.sub.10 hydrocarbyl groups and halogen atoms; R.sup.5 is a C.sub.1-C.sub.10 hydrocarbyl; each x, y and z is a positive integer, 0≤x≤2, 0≤y≤2, 0≤z≤4, and x+y+z=4; in a reaction for forming the solid catalyst component, relative to one mole of magnesium, the amount of the titanium compound used ranges from 0.5 to 120 moles, or from 1 to 50 moles; and the amount of the at least one compound represented by formula (I) used ranges from 0.0005 to 1 mole, or from 0.001 to 1 mole, or from 0.001 to 0.05 moles.

17. A catalyst system for olefin polymerization, comprising a reaction product of: 1) the solid catalyst component according to claim 5; 2) a cocatalyst; and 3) an optional external electron donor compound.

18. The catalyst system according to claim 17, wherein the cocatalyst is at least one organic aluminum compound represented by general formula AlR.sup.1.sub.dX.sup.1.sub.3-d, where R.sup.1 is hydrogen or a C.sub.1-C.sub.20 hydrocarbyl, X.sup.1 is a halogen atom, and 0≤d≤3, and a molar ratio of aluminum in the cocatalyst to titanium in the solid catalyst component ranges from 5:1 to 500:1, or from 20:1 to 200:1.

19. A catalyst system for olefin polymerization, comprising a reaction product of: 1) a solid catalyst component comprising magnesium, titanium, halogen and an optional internal electron donor compound; 2) a cocatalyst; and 3) an external electron donor compound, which comprises at least one compound of the formula (I) as defined in claim 1.

20. The catalyst system according to claim 19, wherein the solid catalyst component comprises at least one titanium compound having at least one Ti-halogen bond, supported on a magnesium halide.

21. The catalyst system according to claim 20, wherein the at least one titanium compound is selected from the group consisting of titanium trihalides and compounds represented by general formula Ti(OR.sup.2).sub.nX.sup.2.sub.4-n, where R.sup.2 is a C.sub.1-C.sub.8 hydrocarbyl; X.sup.2 is Cl, Br or I; and 0≤n≤4; or the at least one titanium compound is selected from the group consisting of TiCl.sub.3, TiCl.sub.4, TiBr.sub.4, Ti(OC.sub.2H.sub.5)Cl.sub.3, Ti(OC.sub.2H.sub.5).sub.2Cl.sub.2 and Ti(OC.sub.2H.sub.5).sub.3Cl.

22. The catalyst system according to claim 19, having at least one feature of the followings: the cocatalyst is at least one organic aluminum compound represented by general formula AlR.sup.1.sub.dX.sup.1.sub.3-d, where R.sup.1 is hydrogen or a C.sub.1-C.sub.20 hydrocarbyl, X.sup.1 is a halogen atom, and 0≤d≤3, and a molar ratio of aluminum in the cocatalyst to titanium in the solid catalyst component ranges from 5:1 to 500:1, or from 20:1 to 200:1; a molar ratio of the external electron donor compound to titanium in the solid catalyst component ranges from 0.05:1 to 50:1.

23. The catalyst system according to claim 19, wherein the solid catalyst component comprises a reaction product of: a magnesium halide-alcohol adduct, a titanium compound, an optional internal electron donor compound and an optional second organic aluminum compound, the second organic aluminum compound being of general formula AlR.sup.3.sub.aX.sup.3.sub.bH.sub.c, where R.sup.3 is a C.sub.1-C.sub.14 hydrocarbyl; X.sup.3 is a halogen atom; each a, b and c is a number of from 0 to 3, and a+b+c=3.

24. The catalyst system according to claim 23, having at least one feature of the followings: the magnesium halide-alcohol adduct is of general formula MgX.sub.2.m(ROH), where X is Cl, Br or I; R is a C.sub.1-C.sub.6 alkyl; and m is from 0.5 to 4.0, or from 2.5 to 4.0; the titanium compound is of general formula Ti(OR.sup.2).sub.nX.sup.2.sub.4-n, where R.sup.2 is a C.sub.1-C.sub.8 hydrocarbyl; X.sup.2 is Cl, Br or I; and 0≤n≤4; or the titanium compound is selected from the group consisting of TiCl.sub.4, Ti(OC.sub.2H.sub.5)Cl.sub.3, Ti(OCH.sub.3)Cl.sub.3, Ti(OC.sub.4H.sub.9)Cl.sub.3, Ti(OC.sub.4H.sub.9).sub.4 and mixtures thereof; the second organic aluminum compound is selected from the group consisting of Al(CH.sub.2CH.sub.3).sub.3, Al(i-Bu).sub.3, Al(n-C.sub.6H.sub.13).sub.3 and mixtures thereof; in a reaction for forming the solid catalyst component, relative to one mole of magnesium, the amount of the titanium compound used ranges from 1 to 50 moles; the amount of the internal electron donor compound used ranges from 0 to 1 mole; and the amount of the second organic aluminum compound used ranges from 0 to 100 moles.

25. The catalyst system according to claim 19, wherein the solid catalyst component comprises a reaction product of: an alkoxy magnesium compound, a titanium compound and an optional internal electron donor compound.

26. The catalyst system according to claim 25, having at least one feature of the followings: the alkoxy magnesium compound is of general formula Mg(OR.sub.3).sub.a(OR.sub.4).sub.2-a, where R.sub.3 and R.sub.4 are each independently a C.sub.1-C.sub.10 alkyl, which is unsubstituted or substituted by a substituent selected from the group consisting of hydroxy, amino, aldehyde group, carboxy, acyl, halogen atoms, alkoxy and heteroatoms, and 0≤a≤2; the titanium compound is of general formula Ti(OR.sup.2).sub.nX.sup.2.sub.4-n, where R.sup.2 is a C.sub.1-C.sub.8 hydrocarbyl; X.sup.2 is Cl, Br or I; and 0≤n≤4; or the titanium compound is selected from the group consisting of TiCl.sub.4, Ti(OC.sub.2H.sub.5)Cl.sub.3, Ti(OCH.sub.3)Cl.sub.3, Ti(OC.sub.4H.sub.9)Cl.sub.3, Ti(OC.sub.4H.sub.9).sub.4 and mixtures thereof; in a reaction for forming the solid catalyst component, relative to one mole of magnesium, the amount of the titanium compound used ranges from 0.1 to 15 moles; and the amount of the internal electron donor compound used ranges from 0 to 0.1 moles.

27. The catalyst system according to claim 19, wherein the solid catalyst component comprises a reaction product of: a finely-divided support, a magnesium halide, a titanium halide, an internal electron donor b and an optional internal electron donor a, wherein the internal electron donor b is at least one selected from the group consisting of alkyl esters of C.sub.2-C.sub.10 saturated aliphatic carboxylic acids, alkyl esters of C.sub.7-C.sub.10 aromatic carboxylic acids, C.sub.2-C.sub.10 aliphatic ethers, C.sub.3-C.sub.10 cyclic ethers and C.sub.3-C.sub.10 saturated aliphatic ketones, and wherein the optional internal electron donor a is at least one compound represented by the formula (I).

28. The catalyst system according to claim 27, having at least one feature of the followings: the finely-divided support is selected from the group consisting of alumina, activated carbon, clays, silica, titania, polystyrenes, calcium carbonate and mixtures thereof, and the finely-divided support has a particle size of from 0.01 to 10 μm; the magnesium halide is selected from the group consisting of MgCl.sub.2, MgBr.sub.2, MgI.sub.2 and mixtures thereof; the titanium halide is TiCl.sub.3 and/or TiCl.sub.4; the solid catalyst component is prepared by a process comprising: combining the magnesium halide, the titanium halide, the internal electron donor b and the optional internal electron donor a to obtain a mother liquor; admixing the finely-divided support with the mother liquor to obtain a slurry; and spray-drying the slurry to afford the solid catalyst component, wherein a content of the finely-divided support in the slurry ranges from 3 to 50 wt %, or from 5 to 30 wt %; a molar ratio of the titanium halide to the magnesium halide ranges from 1:20 to 1:2; a molar ratio of the titanium halide to the internal electron donor b ranges from 1:1 to 1:600.

29. The catalyst system according to claim 19, wherein the solid catalyst component comprises a reaction product of: a magnesium-containing liquid-state component, a titanium compound, an optional internal electron donor compound and an optional auxiliary precipitant, wherein the auxiliary precipitant is selected from the group consisting of organic anhydride compounds and organic silicon compounds.

30. The catalyst system according to claim 29, having at least one feature of the followings: the magnesium-containing liquid-state component is at least one selected from the group consisting of: Component A: an alkyl magnesium compound of general formula MgR.sub.3R.sub.4; Component B: a reaction product of a magnesium compound, an organophosphorus compound, an organic epoxy compound and an optional alcohol compound of general formula R.sub.7OH; Component C: a reaction product of a magnesium compound and an alcohol compound of general formula R.sub.7OH, wherein the magnesium compound is of general formula MgX.sup.3.sub.mR.sup.3.sub.2-m, where X.sup.3 is halogen, R.sup.3 is —R.sub.5 or —OR.sub.6, m=1 or 2; R.sub.3, R.sub.4, R.sub.5, R.sub.6 and R.sub.7 are each independently a hydrocarbyl, which is unsubstituted or substituted by a substituent selected from the group consisting of hydroxy, amino, aldehyde group, carboxy, halogen atoms, alkoxy and heteroatoms; the organophosphorus compound is selected from the group consisting of hydrocarbyl esters and halogenated hydrocarbyl esters of ortho-phosphoric acid, and hydrocarbyl esters and halogenated hydrocarbyl esters of phosphorous acid, or the organophosphorus compound is at least one selected from the group consisting of triethyl phosphate, tributyl phosphate, tri-isooctyl phosphate, triphenyl phosphate, triethyl phosphite, tributyl phosphite and di-n-butyl phosphite; the organic epoxy compound is at least one selected from the group consisting of aliphatic epoxy compounds and diepoxy compounds, halogenated aliphatic epoxy compounds and diepoxy compounds, glycidyl ethers, and inner ethers, having from 2 to 18 carbon atoms, or is at least one selected from the group consisting of epoxy ethane, epoxy propane, epoxy butane, vinyl epoxy ethane, epoxy chloropropane, glycidyl methacrylate, glycidyl ethyl ether and glycidyl butyl ether; the alcohol compound of the general formula R.sub.7OH is at least one selected from the group consisting of methanol, ethanol, propanol, isopropanol, butanol, isobutanol, tert-butanol, hexanol, cyclohexanol, octanol, isooctanol, decanol, benzyl alcohol and phenylethanol; the titanium compound is of general formula Ti(OR.sup.2).sub.nX.sup.2.sub.4-n, where R.sup.2 is a C.sub.1-C.sub.8 hydrocarbyl; X.sup.2 is Cl, Br or I; and 0≤n≤4; or the titanium compound is selected from the group consisting of TiCl.sub.4, Ti(OC.sub.2H.sub.5)Cl.sub.3, Ti(OCH.sub.3)Cl.sub.3, Ti(OC.sub.4H.sub.9)Cl.sub.3 and mixtures thereof; the organic anhydride compound is at least one selected from those represented by formula (II): R.sup.1CO—O—CO—R.sub.2 (II), wherein R.sup.4 and R.sup.5 are each independently selected from the group consisting of hydrogen, C.sub.1-C.sub.10 alkyl, C.sub.2-C.sub.10 alkenyl, C.sub.2-C.sub.10 alkynyl, C.sub.3-C.sub.8 cycloalkyl and C.sub.6-C.sub.10 aromatic hydrocarbyl, and R.sup.4 and R.sup.5 may optionally be linked to form a ring; the organic silicon compound is of general formula R.sup.6.sub.xR.sup.7.sub.ySi(OR.sup.8).sub.z, where R.sup.6 and R.sup.7 are each independently a C.sub.1-C.sub.10 hydrocarbyl or halogen, R.sup.8 is a C.sub.1-C.sub.10 hydrocarbyl, each x, y and z is an integer, 0≤x≤2, 0≤y≤2, 0≤z≤4, and x+y+z=4; in a reaction for forming the solid catalyst component, relative to one mole of magnesium, the amount of the titanium compound used ranges from 0.5 to 120 moles, or from 1 to 50 moles; the amount of the internal electron donor compound used ranges from 0 to 0.1 moles, or from 0 to 0.05 moles; and the amount of the auxiliary precipitant used ranges from 0 to 1 mole, or from 0 to 0.7 moles.

31. An olefin polymerization process comprising: contacting an olefin monomer and an optional comonomer with the catalyst system according to claim 1 under polymerization conditions to form a polyolefin product and recovering the polyolefin product.

32. An olefin polymerization process comprising: contacting an olefin monomer and an optional comonomer with the catalyst system according to claim 17 under polymerization conditions to form a polyolefin product and recovering the polyolefin product.

33. An olefin polymerization process comprising: contacting an olefin monomer and an optional comonomer with the catalyst system according to claim 19 under polymerization conditions to form a polyolefin product and recovering the polyolefin product.

Description

EXAMPLES

(1) The following examples are provided to further illustrate the present disclosure and by no means intend to limit the scope thereof.

(2) In the following examples and comparative examples, unless specified otherwise, temperature values refer to degree Celsius, and pressure values refer to gauge pressure.

Testing Methods

(3) 1. Relative percentage by weight of titanium element in solid catalyst component: measured by spectrophotometry. The other compositional data of solid catalyst component: measured by liquid .sup.1H-NMR.

(4) 2. Melt index (MI) of polymer: measured according to ASTM D1238-99, at 190° C. and 2.16 kg (or 21.6 Kg) load.

(5) 3. Content of copolymerized units for polymer powder: measured by liquid .sup.13C-NMR.

(6) 4. Content by weight of hexane extractables for polymer powder: m grams of dried powder is placed in a Soxhlet's extractor and then extracted with hexane for 4 hours. The extracted powder is fully dried to afford n grams of powder. Then, the percentage by mass of the hexane extractables is: (m−n)/m*100%.

(7) 5. Melting enthalpy for polymer powder: a sample is subjected to a three-stage measurement on a Perkin Elmer DSC8500 differential scanning calorimeter under a measuring atmosphere of nitrogen gas as follows:

(8) first stage: the sample is heated from 0 degree to 160 degree at a ramping rate of 10K/min and maintained at 160 degree for 5 min to eliminate heat history;

(9) second stage: the sample is cooled from 160 degree to 0 degree at a cooling rate of 10K/min; and

(10) third stage: the sample is heated from 0 degree to 160 degree at a ramping rate of 10K/min.

(11) The melting enthalpy of the temperature-rising profile in the third stage is taken as the measured result.

(12) Both melting enthalpy and bulk density of a sample are determined by crystallinity. For polymer powders obtained under the identical copolymerization conditions (for example, identical comonomer type/concentration, reaction temperature/pressure/time, hydrogen gas-ethylene ratio and the like), polymer powders having a lower melting enthalpy will have a lower bulk density.

(13) Preparation Examples 1-4 are to illustrate processes for preparing cyclotriveratrylene and derivatives thereof.

Preparation Example 1

(14) Under ice bath condition, 1,2-dimethoxybenzene (1.0 g) was added dropwise into a mixture of a formaldehyde aqueous solution (4 mL, 38%), chloroform (0.1 mL) and concentrated hydrochloric acid (6 mL) and reaction was allowed to proceed. After 30 minutes, the solution became a paste, and the reaction mixture was continuously stirred at room temperature for 4 hours. The reaction mixture was filtrated to collect solids, and the solids were washed with chilled water and then thoroughly dried to afford 0.5 g of Compound A.

(15) ##STR00008##

Preparation Example 2

(16) Under ice bath condition, 3-methoxy-4-bromine-benzyl alcohol (3.6 g) was dissolved in 30 mL of methanol. Under ice bath and stirring conditions, 15 mL of 65% perchloric acid was added dropwise into the above solution. Under nitrogen atmosphere, the reaction solution was stirred in ice bath for 18 h. 30 mL of water was slowly added into the reaction solution, and dichloromethane was then used to extract organic phase. The organic phase was carefully washed with a sodium hydroxide aqueous solution, followed by washing with deionized water. After having been dried, the organic phase was thoroughly evaporated under reduced pressure, and then purified through column chromatography to afford 0.8 g of Compound M.

(17) ##STR00009##

Preparation Example 3

(18) 1,2-Diethoxybenzene (3.3 g) and triformol (0.63 g) were dissolved in dry dichloromethane (30 mL), and the resultant solution was stirred in an ice bath. Boron trifloride-diethyl ether (4.25 g) was slowly added dropwise to the above solution. Upon the completion of the addition, the ice-water bath was removed. The reaction solution was stirred at normal atmospheric temperature for 3 h, and the reaction was monitored by TLC (thin-layer chromatography) until the reaction was completed. The reaction was stopped, and the reaction solution was washed with water trice. An organic phase was separated by using a separating funnel, and then the organic solvent was thoroughly evaporated under reduced pressure to afford an oil. The oil was dissolved in a minor amount of acetone at first, and then a large amount of methanol was added thereto. The resultant mixture was placed in a refrigerator to precipitate white solids. The white solids were vacuum filtrated and then thoroughly dried to afford 1.5 g of Compound B.

(19) ##STR00010##

Preparation Example 4

(20) Under ice bath condition and nitrogen atmosphere, 3-methoxy-4-ethoxy-benzyl alcohol (3 g) was dissolved in 30 mL of methanol. Under ice bath and stirring conditions, 15 mL of 65% perchloric acid was added dropwise to the above solution, and then the reaction solution was continuously stirred in ice bath for 18 h. 30 mL of water was slowly added to the reaction solution, and then the organic phase was extracted with dichloromethane. The organic phase was washed with a sodium hydroxide aqueous solution and then with deionized water. After having been dried, the organic phase was thoroughly evaporated under reduced pressure, and then purified through column chromatography to afford 1.0 g of Compound F.

(21) ##STR00011##

(22) Examples 1-5 are to illustrate use of cyclotriveratrylene and derivatives thereof as an internal electron donor in catalysts for ethylene polymerization.

Example 1

(1) Preparation of Solid Catalyst Component A

(23) To a reactor, in which air had been fully replaced with high pure N.sub.2, were successively charged with 6.0 g of spherical support MgCl.sub.2.2.6C.sub.2H.sub.5OH and 120 mL of toluene, and the reaction mixture was cooled with stirring to −10° C. To the reaction mixture was added dropwise 50 mL of triethyl aluminum solution in hexane (1.0 M) and then 0.15 g of Compound A, and the mixture was warmed to 50° C. and maintained at that temperature for 3 hours. The stirring in the reactor was stopped, the reaction mixture was let stand, and solid particles precipitated quickly. A supernatant was sucked out, and precipitants were washed sequentially with toluene and hexane several times. 120 mL of hexane was added to the reactor containing the solid particles, and the reaction mixture was cooled with stirring to 0° C. 6 mL of titanium tetrachloride was slowly added dropwise to the above reaction mixture, thereafter the temperature was enhanced to 60° C. and maintained for 2 hours. The stirring in the reactor was stopped, the reaction mixture was let stand, and solid particles precipitated quickly. A supernatant was sucked out, and precipitants were washed with hexane twice, then transferred by means of hexane to a fritted glass filter, and dried with a high pure nitrogen flow, to afford solid spherical catalyst component a having good flowability, of which composition is shown in Table 1 below.

(2) Homopolymerization

(i) Polymerization at Low Hydrogen Gas-Ethylene Ratio

(24) To a 2 L stainless steel reactor, in which air had been fully replaced with high pure N.sub.2, were charged 1 L of hexane and 1.0 mL of 1 M triethyl aluminum solution, followed by the addition of the solid catalyst component (containing 0.6 mg of titanium) prepared by the above-described process. The reactor was heated with stirring to 75° C., hydrogen gas was introduced to bring the pressure inside the reactor to 0.28 MPa (gauge), and then ethylene was introduced to bring the total pressure inside the reactor to 1.03 MPa (gauge). The polymerization was allowed to continue at 85° C. for 2 hours, with ethylene being continuously introduced into the reactor to maintain the total pressure at 1.03 MPa (gauge). Polymerization results are shown in Table 2 below.

(ii) Polymerization at High Hydrogen Gas-Ethylene Ratio

(25) To a 2 L stainless steel reactor, in which air had been fully replaced with high pure N.sub.2, were charged 1 L of hexane and 1.0 mL of 1 M triethyl aluminum solution, followed by the addition of the solid catalyst component (containing 0.6 mg of titanium) prepared by the above-described process. The reactor was heated with stirring to 75° C., hydrogen gas was introduced to bring the pressure inside the reactor to 0.68 MPa, and then ethylene was introduced to bring the total pressure inside the reactor to 1.03 MPa. The polymerization was allowed to continue at 85° C. for 2 hours, with ethylene being continuously introduced into the reactor to maintain the total pressure at 1.03 MPa. Polymerization results are shown in Table 2 below.

Comparative Example 1-1

(1) Preparation of Solid Catalyst Component D1-1

(26) To a reactor, in which air had been fully replaced with high pure N.sub.2, were successively charged with 6.0 g of spherical support MgCl.sub.2.2.6C.sub.2H.sub.5OH and 120 mL of toluene, and the reaction mixture was cooled with stirring to −10° C. To the reaction mixture was added dropwise 50 mL of triethyl aluminum solution in hexane (1.0 M), and the mixture was warmed to 50° C. and maintained at that temperature for 3 hours. The stirring in the reactor was stopped, the reaction mixture was let stand, and solid particles precipitated quickly. A supernatant was sucked out, and precipitants were washed sequentially with toluene and hexane several times. 120 mL of hexane was added to the reactor containing the solid particles, and the reaction mixture was cooled with stirring to 0° C. 6 mL of titanium tetrachloride was slowly added dropwise to the above reaction mixture, thereafter the temperature was enhanced to 60° C. and maintained for 2 hours. The stirring in the reactor was stopped, the reaction mixture was let stand, and solid particles precipitated quickly. A supernatant was sucked out, and precipitants were washed with hexane twice, then transferred by means of hexane to a fritted glass filter, and dried with a high pure nitrogen flow, to afford solid spherical catalyst component D1-1 having good flowability, of which composition is shown in Table 1 below.

(2) Homopolymerization

(27) The polymerization procedure is the same as described in Example 1, except that the solid catalyst component D1-1 prepared in Comparative Example 1-1 was used. Polymerization results are shown in Table 2 below.

Comparative Example 1-2

(1) Preparation of Solid Catalyst Component D1-2

(28) To a reactor, in which air had been fully replaced with high pure N.sub.2, were successively charged with 6.0 g of spherical support MgCl.sub.2.2.6C.sub.2H.sub.5OH and 120 mL of toluene, and the reaction mixture was cooled with stirring to −10° C. To the reaction mixture was added dropwise 50 mL of triethyl aluminum solution in hexane (1.0 M) and then 1.5 mL of ethyl benzoate, and the mixture was warmed to 50° C. and maintained at that temperature for 3 hours. The stirring in the reactor was stopped, the reaction mixture was let stand, and solid particles precipitated quickly. A supernatant was sucked out, and precipitants were washed sequentially with toluene and hexane several times. 120 mL of hexane was added to the reactor containing the solid particles, and the reaction mixture was cooled with stirring to 0° C. 6 mL of titanium tetrachloride was slowly added dropwise to the above reaction mixture, thereafter the temperature was enhanced to 60° C. and maintained for 2 hours. The stirring in the reactor was stopped, the reaction mixture was let stand, and solid particles precipitated quickly. A supernatant was sucked out, and precipitants were washed with hexane twice, then transferred by means of hexane to a fritted glass filter, and dried with a high pure nitrogen flow, to afford solid spherical catalyst component D1-2 having good flowability, of which composition is shown in Table 1 below.

(2) Homopolymerization

(29) The polymerization procedure is the same as described in Example 1, except that the solid catalyst component D1-2 prepared in Comparative Example 1-2 was used. Polymerization results are shown in Table 2 below.

(30) TABLE-US-00001 TABLE 2 Polymerization results 0.28 MPa H.sub.2/ 0.68 MPa H.sub.2/ 0.75 MPa ethylene 0.35 MPa ethylene Melt index Melt index Catalyst Activity (21.6 Kg) Activity (2.16 Kg) Ex. 1 31900 194 13000 409 Comp. Ex. 1-1 23400 107 6100 90 Comp. Ex. 1-2 30000 120 6200 282

(31) As shown in Table 2, when a cyclotriveratrylene derivative is introduced into the solid catalyst component a (Example 1), catalyst activity under polymerization condition of high hydrogen gas-ethylene ratio is significantly higher than that for the comparative examples, and the melt index for the polymer powder is also significantly higher than that for the comparative examples.

(32) Furthermore, as shown in Table 2, when the cyclotriveratrylene derivative is introduced, as an internal electron donor, into the solid catalyst component, catalyst activity and melt index for polymer powder under polymerization condition of low hydrogen gas-ethylene ratio are also enhanced.

Example 2

(1) Preparation of Solid Catalyst Component B

(33) To a reactor, in which air had been fully replaced with high pure N.sub.2, were successively charged with 4.0 g of magnesium dichloride, 50 mL of toluene, 3.0 mL of epoxy chloropropane, 9 mL of tri-n-butyl phosphate, 4.4 mL of ethanol and 0.2 g of Compound A. The reaction mixture was heated with stirring to 70° C. and maintained at that temperature for 2 hours. The reaction mixture was cooled to −10° C., and then 70 mL of titanium tetrachloride was slowly added dropwise, followed by the dropwise-addition of 5 mL of tetraethoxy silicane. Next, the temperature was gradually enhanced to 85° C. and maintain for 1 hour. The stirring in the reactor was stopped, the reaction mixture was let stand, and solid particles precipitated quickly. A supernatant was sucked out, and precipitants were washed sequentially with toluene and hexane several times, then transferred by means of hexane to a fritted glass filter, and dried with a high pure nitrogen flow, to afford solid spherical catalyst component b having good flowability, of which composition is shown in Table 1 below.

(2) Homopolymerization

(i) Polymerization at Low Hydrogen Gas-Ethylene Ratio

(34) To a 2 L stainless steel reactor, in which air had been fully replaced with high pure N.sub.2, were charged 1 L of hexane and 1.0 mL of 1 M triethyl aluminum solution, followed by the addition of the solid catalyst component (containing 0.6 mg of titanium) prepared by the above-described process. The reactor was heated with stirring to 70° C., hydrogen gas was introduced to bring the pressure inside the reactor to 0.28 MPa (gauge), and then ethylene was introduced to bring the total pressure inside the reactor to 0.73 MPa (gauge). The polymerization was allowed to continue at 80° C. for 2 hours, with ethylene being continuously introduced into the reactor to maintain the total pressure at 0.73 MPa (gauge). Polymerization results are shown in Table 3 below.

(ii) Polymerization at High Hydrogen Gas-Ethylene Ratio

(35) To a 2 L stainless steel reactor, in which air had been fully replaced with high pure N.sub.2, were charged 1 L of hexane and 1.0 mL of 1M triethyl aluminum solution, followed by the addition of the solid catalyst component (containing 0.6 mg of titanium) prepared by the above-described process. The reactor was heated with stirring to 70° C., hydrogen gas was introduced to bring the pressure inside the reactor to 0.60 MPa (gauge), and then ethylene was introduced to bring the total pressure inside the reactor to 1.00 MPa (gauge). The polymerization was allowed to continue at 90° C. for 2 hours, with ethylene being continuously introduced into the reactor to maintain the total pressure at 1.00 MPa (gauge). Polymerization results are shown in Table 3 below.

(3) Ethylene-Butene Copolymerization

(36) To a 2 L stainless steel reactor, in which air had been fully replaced with high pure N.sub.2, were charged 1 L of hexane and 1.0 mL of 1 M triethyl aluminum solution, followed by the addition of the solid catalyst component (containing 0.6 mg of titanium) prepared by the above-described process. The reactor was heated with stirring to 70° C., hydrogen gas was introduced to bring the pressure inside the reactor to 0.28 MPa (gauge), and then ethylene/butene mixed gases (having a molar ratio of 0.75:0.25) was introduced to bring the total pressure inside the reactor to 0.73 MPa (gauge). The polymerization was allowed to continue at 80° C. for 0.5 hours, with the ethylene/butene mixed gases being continuously introduced into the reactor to maintain the total pressure at 0.73 MPa (gauge). Polymerization results are shown in Table 4 below.

(4) Ethylene-Hexene Copolymerization

(37) To a 2 L stainless steel reactor, in which air had been fully replaced with high pure N.sub.2, were charged 1 L of hexane and 1.0 mL of 1 M triethyl aluminum solution, followed by the addition of the solid catalyst component (containing 0.6 mg of titanium) prepared by the above-described process. The reactor was heated with stirring to 70° C., 20 mL of hexene was added thereinto, hydrogen gas was introduced to bring the pressure inside the reactor to 0.28 MPa (gauge), and then ethylene was introduced to bring the total pressure inside the reactor to 0.73 MPa (gauge). The polymerization was allowed to continue at 80° C. for 0.5 hours, with the ethylene being continuously introduced into the reactor to maintain the total pressure at 0.73 MPa (gauge). Polymerization results are shown in Table 5 below.

Comparative Example 2

(1) Preparation of Solid Catalyst Component D2

(38) To a reactor, in which air had been fully replaced with high pure N.sub.2, were successively charged 4.0 g of magnesium dichloride, 50 mL of toluene, 3.0 mL of epoxy chloropropane, 9 mL of tri-n-butyl phosphate, and 4.4 mL of ethanol. The reaction mixture was heated with stirring to 70° C. and maintained at that temperature for 2 hours. The reaction mixture was cooled to −10° C., and then 70 mL of titanium tetrachloride was slowly added dropwise, followed by the dropwise-addition of 5 mL of tetraethoxy silicane. Next, the temperature was gradually enhanced to 85° C. and maintain for 1 hour. The stirring in the reactor was stopped, the reaction mixture was let stand, and solid particles precipitated quickly. A supernatant was sucked out, and precipitants were washed sequentially with toluene and hexane several times, then transferred by means of hexane to a fritted glass filter, and dried with a high pure nitrogen flow, to afford solid catalyst component D2 having good flowability, of which composition is shown in Table 1 below.

(2) Homopolymerization

(39) The polymerization procedure is the same as described in Example 2, except that the solid catalyst component D2 prepared in Comparative Example 2 was used. Polymerization results are shown in Table 3 below.

(3) Ethylene-Butene Copolymerization

(40) The polymerization procedure is the same as described in Example 2, except that the solid catalyst component D2 prepared in Comparative Example 2 was used. Polymerization results are shown in Table 4 below.

(4) Ethylene-Hexene Copolymerization

(41) The polymerization procedure is the same as described in Example 2, except that the solid catalyst component D2 prepared in Comparative Example 2 was used. Polymerization results are shown in Table 5 below.

(42) TABLE-US-00002 TABLE 3 Homopolymerization results 0.28 MPa H.sub.2/ 0.60 MPa H.sub.2/ 0.45 MPa ethylene 0.40 MPa ethylene Melt index Melt index Catalyst Activity (2.16 Kg) Activity (2.16 Kg) Ex. 2 35000 1.1 22000 51 Comp. 30000 0.5 15000 30 Ex. 2

(43) As shown in Table 3, when a cyclotriveratrylene derivative is introduced into the solid catalyst component b (Example 2), catalyst activity under polymerization condition of high hydrogen gas-ethylene ratio is significantly higher than that for the comparative example, and the melt index of the polymer powder is also significantly higher than that for the comparative example.

(44) Also, as shown in Table 3, when the cyclotriveratrylene derivative is introduced, as an internal electron donor, into the solid catalyst component, catalyst activity and melt index of polymer powder under polymerization condition of low hydrogen gas-ethylene ratio may also be enhanced.

(45) TABLE-US-00003 TABLE 4 Ethylene-butene copolymerization results (powder) Melting Content of enthalpy copolymerized units Example 2 139 J/g 3.0 mol % Comparative 146 J/g 4.2 mol % Example 2

(46) As shown in Table 4, when the cyclotriveratrylene derivative is introduced into the solid catalyst component b of Example 2, in ethylene/butene copolymerization, the resultant polymerization product can have a lower melting enthalpy (i.e., lower density) at a lower content of copolymerized units. This suggests that the copolymerized units in the polymerization product of Example 2 are more uniformly distributed.

(47) TABLE-US-00004 TABLE 5 Ethylene-hexene copolymerization results (powder) Melting Content of Hexane enthalpy copolymerized units extractables Ex. 2 176 J/g 0.75 mol % 3.9 wt % Comp. Ex. 2 179 J/g 0.68 mol % 4.1 wt %

(48) As shown in Table 5, when the cyclotriveratrylene derivative is introduced into the solid catalyst component b of Example 2, in ethylene/hexene copolymerization, the resultant polymerization product has a lower melting enthalpy (i.e., lower density). Furthermore, even though the polymerization product of Example 2 has a higher content of copolymerized units, it has less hexane extractables. This suggests that the copolymerized units in the polymerization product of Example 2 are more uniformly distributed.

Example 3

(1) Preparation of Solid Catalyst Component C

(49) To a reactor, in which air had been fully replaced with high pure N.sub.2, were successively charged 4.0 g of magnesium dichloride, 50 mL of toluene, 3.0 mL of epoxy chloropropane, 9 mL of tri-n-butyl phosphate, and 4.4 mL of ethanol. The reaction mixture was heated with stirring to 70° C. and maintained at that temperature for 2 hours. The reaction mixture was cooled to −10° C., and then 65 mL of titanium tetrachloride was slowly added dropwise, followed by the dropwise-addition of 4 mL of tetraethoxy silicane. Next, the temperature was gradually enhanced to 85° C. and maintain for 1 hour. 0.2 g of Compound B was added to the reactor, and the reactor was maintained at 85° C. for 1 hour. The stirring in the reactor was stopped, the reaction mixture was let stand, and solid particles precipitated quickly. A supernatant was sucked out, and precipitants were washed sequentially with toluene and hexane several times, then transferred by means of hexane to a fritted glass filter, and dried with a high pure nitrogen flow, to afford solid catalyst component c having good flowability, of which composition is shown in Table 1 below.

(2) Homopolymerization

(i) Polymerization at Low Hydrogen Gas-Ethylene Ratio

(50) To a 2 L stainless steel reactor, in which air had been fully replaced with high pure N.sub.2, were charged 1 L of hexane and 1.0 mL of 1 M triethyl aluminum solution, followed by the addition of the solid catalyst component (containing 0.6 mg of titanium) prepared by the above-described process. The reactor was heated with stirring to 70° C., hydrogen gas was introduced to bring the pressure inside the reactor to 0.28 MPa (gauge), and then ethylene was introduced to bring the total pressure inside the reactor to 0.73 MPa (gauge). The polymerization was allowed to continue at 80° C. for 2 hours, with ethylene being continuously introduced into the reactor to maintain the total pressure at 0.73 MPa (gauge). Polymerization results are shown in Table 6 below.

(ii) Polymerization at High Hydrogen Gas-Ethylene Ratio

(51) To a 2 L stainless steel reactor, in which air had been fully replaced with high pure N.sub.2, were charged 1 L of hexane and 1.0 mL of 1 M triethyl aluminum solution, followed by the addition of the solid catalyst component (containing 0.6 mg of titanium) prepared by the above-described process. The reactor was heated with stirring to 70° C., hydrogen gas was introduced to bring the pressure inside the reactor to 0.58 MPa (gauge), and then ethylene was introduced to bring the total pressure inside the reactor to 0.73 MPa (gauge). The polymerization was allowed to continue at 80° C. for 2 hours, with ethylene being continuously introduced into the reactor to maintain the total pressure at 0.73 MPa (gauge). Polymerization results are shown in Table 6 below.

Comparative Example 3

(1) Preparation of Solid Catalyst Component D3

(52) To a reactor, in which air had been fully replaced with high pure N.sub.2, were successively charged 4.0 g of magnesium dichloride, 50 mL of toluene, 3.0 mL of epoxy chloropropane, 9 mL of tri-n-butyl phosphate, and 4.4 mL of ethanol. The reaction mixture was heated with stirring to 70° C. and maintained at that temperature for 2 hours. The reaction mixture was cooled to −10° C., and then 65 mL of titanium tetrachloride was slowly added dropwise, followed by the dropwise-addition of 4 mL of tetraethoxy silicane. Next, the temperature was gradually enhanced to 85° C. and maintain for 1 hour. The stirring in the reactor was stopped, the reaction mixture was let stand, and solid particles precipitated quickly. A supernatant was sucked out, and precipitants were washed sequentially with toluene and hexane several times, then transferred by means of hexane to a fritted glass filter, and dried with a high pure nitrogen flow, to afford solid catalyst component D3 having good flowability, of which composition is shown in Table 1 below.

(2) Homopolymerization

(53) The polymerization procedure is the same as described in Example 3, except that the solid catalyst component D3 prepared in Comparative Example 3 was used. Polymerization results are shown in

(54) Table 6 below.

(55) TABLE-US-00005 TABLE 6 Homopolymerization results 0.28 MPa H.sub.2/ 0.58 MPa H.sub.2/ 0.45 MPa ethylene 0.15 MPa ethylene Melt index Melt index Catalyst Activity (2.16 Kg) Activity (2.16 Kg) Example 3 30800 1.2 4800 209 Comparative 30900 1.2 3600 189 Example 3

(56) As shown in Table 6, when a cyclotriveratrylene derivative is introduced into the solid catalyst component c of Example 3, both catalyst activity and melt index of polymer powder under polymerization condition of high hydrogen gas-ethylene ratio are significantly higher than those for the comparative example.

Example 4a

(1) Preparation of Solid Catalyst Component D1

(57) To a reactor, in which air had been fully replaced with high pure N.sub.2, were successively charged 4.0 g of magnesium dichloride, 80 mL of toluene, 3.5 mL of epoxy chloropropane, and 13 mL of tri-n-butyl phosphate. The reaction mixture was heated with stirring to 60° C. and maintained at that temperature for 2 hours. 1.4 g of phthalic anhydride was added to the reactor, and the reactor was maintained at 60° C. for 1 hour. The reaction mixture was cooled to −30° C., and then 60 mL of titanium tetrachloride was slowly added dropwise. Next, the temperature was gradually enhanced to 85° C. and maintain for 1 hour. 0.15 g of Compound A was added to the reactor, and the reactor was maintained at 85° C. for 1 hour. The stirring in the reactor was stopped, the reaction mixture was let stand, and solid particles precipitated quickly. A supernatant was sucked out, and precipitants were washed sequentially with toluene and hexane several times, then transferred by means of hexane to a fritted glass filter, and dried with a high pure nitrogen flow, to afford solid catalyst component d1 having good flowability, of which composition is shown in Table 1 below.

(2) Homopolymerization

(58) The polymerization procedure is the same as described in Example 1, except that the solid catalyst component d1 prepared in Example 4a was used. Polymerization results are shown in Table 7 below.

Example 4b

(1) Preparation of Solid Catalyst Component D2

(59) To a reactor, in which air had been fully replaced with high pure N.sub.2, were successively charged 4.0 g of magnesium dichloride, 80 mL of toluene, 3.5 mL of epoxy chloropropane, and 13 mL of tri-n-butyl phosphate. The reaction mixture was heated with stirring to 60° C. and maintained at that temperature for 2 hours. 1.4 g of phthalic anhydride was added to the reactor, and the reactor was maintained at 60° C. for 1 hour. The reaction mixture was cooled to −30° C., and then 60 mL of titanium tetrachloride was slowly added dropwise. Next, the temperature was gradually enhanced to 85° C. and maintain for 1 hour. 0.1 g of Compound B was added to the reactor, and the reactor was maintained at 85° C. for 1 hour. The stirring in the reactor was stopped, the reaction mixture was let stand, and solid particles precipitated quickly. A supernatant was sucked out, and precipitants were washed sequentially with toluene and hexane several times, then transferred by means of hexane to a fritted glass filter, and dried with a high pure nitrogen flow, to afford solid catalyst component d2 having good flowability, of which composition is shown in Table 1 below.

(2) Homopolymerization

(60) The polymerization procedure is the same as described in Example 1, except that the solid catalyst component d2 prepared in Example 4b was used. Polymerization results are shown in Table 7 below.

(3) Copolymerization

(61) To a 2 L stainless steel reactor, in which air had been fully replaced with high pure N.sub.2, were charged 1 L of hexane and 1.0 mL of 1 M triethyl aluminum solution, followed by the addition of the solid catalyst component (containing 0.6 mg of titanium) prepared by the above-described process. The reactor was heated with stirring to 75° C., 20 ml of hexene was added thereinto, hydrogen gas was introduced to bring the pressure inside the reactor to 0.28 MPa (gauge), and then ethylene was introduced to bring the total pressure inside the reactor to 1.03 MPa (gauge). The polymerization was allowed to continue at 85° C. for 0.5 hours, with the ethylene being continuously introduced into the reactor to maintain the total pressure at 1.03 MPa (gauge). Polymerization results are shown in Table 8 below.

Comparative Example 4

(1) Preparation of Solid Catalyst Component D4

(62) To a reactor, in which air had been fully replaced with high pure N.sub.2, were successively charged 4.0 g of magnesium dichloride, 80 mL of toluene, 3.5 mL of epoxy chloropropane, and 13 mL of tri-n-butyl phosphate. The reaction mixture was heated with stirring to 60° C. and maintained at that temperature for 2 hours. 1.4 g of phthalic anhydride was added to the reactor, and the reactor was maintained at 60° C. for 1 hour. The reaction mixture was cooled to −30° C., and then 60 mL of titanium tetrachloride was slowly added dropwise. Next, the temperature was gradually enhanced to 85° C. and maintain for 1 hour. The stirring in the reactor was stopped, the reaction mixture was let stand, and solid particles precipitated quickly. A supernatant was sucked out, and precipitants were washed sequentially with toluene and hexane several times, then transferred by means of hexane to a fritted glass filter, and dried with a high pure nitrogen flow, to afford solid catalyst component D4 having good flowability, of which composition is shown in Table 1 below.

(2) Homopolymerization

(63) The polymerization procedure is the same as described in Example 1, except that the solid catalyst component D4 prepared in Comparative Example 4 was used. Polymerization results are shown in Table 7 below.

(3) Copolymerization

(64) The polymerization procedure is the same as described in Example 4b, except that the solid catalyst component D4 prepared in Comparative Example 4 was used. Polymerization results are shown in Table 8 below.

(65) TABLE-US-00006 TABLE 7 Homopolymerization results 0.28 MPa H.sub.2/ 0.68 MPa H.sub.2/ 0.75 MPa ethylene 0.35 MPa ethylene Melt index Melt index Catalyst Activity (21.6 Kg) Activity (2.16 Kg) Example 4a 33000 13.6 5400 70 Example 4b — — 6200 55 Comparative 32000 14.6 3900 52 Example 4

(66) As shown in Table 7, when a cyclotriveratrylene derivative is introduced into the solid catalyst component d1/d2 of Example 4a/4b, both catalyst activity and melt index of polymer powder under polymerization condition of high hydrogen gas-ethylene ratio are higher than those for the comparative example.

(67) TABLE-US-00007 TABLE 8 Ethylene-hexene copolymerization results (powder) Melting enthalpy Example 4b 181 J/g Comparative 184 J/g Example 4

(68) As shown in Table 8, when a cyclotriveratrylene derivative is introduced into the solid catalyst component d2 of Example 4b, in ethylene/hexene copolymerization, the resultant polymerization product has a lower melting enthalpy (i.e., lower density) than that for Comparative Example 4.

Example 5

(1) Preparation of Solid Catalyst Component E

(69) To a reactor, in which air had been fully replaced with high pure N.sub.2, were successively charged 2.0 g of magnesium dichloride, 80 mL of toluene, 2 mL of epoxy chloropropane, and 6 mL of tri-n-butyl phosphate. The reaction mixture was heated with stirring to 60° C. and maintained at that temperature for 2 hours. The reaction mixture was cooled to −30° C., and then 30 mL of titanium tetrachloride was slowly added dropwise. Next, the temperature was gradually enhanced to 85° C. and maintain for 1 hour. 0.1 g of Compound A was added to the reactor, and the reactor was maintained at 85° C. for 1 hour. The stirring in the reactor was stopped, the reaction mixture was let stand, and solid particles precipitated quickly. A supernatant was sucked out, and precipitants were washed sequentially with toluene and hexane several times, then transferred by means of hexane to a fritted glass filter, and dried with a high pure nitrogen flow, to afford solid catalyst component e having good flowability, of which composition is shown in Table 1 below.

(2) Homopolymerization

(70) The polymerization procedure is the same as described in Example 1, except that the solid catalyst component e prepared in Example 5 was used. Polymerization results are shown in Table 9 below.

(3) Ethylene-Butene Copolymerization

(71) The polymerization procedure is the same as described in Example 2, except that the solid catalyst component e prepared in Example 5 was used. Polymerization results are shown in Table 10 below.

Comparative Example 5

(1) Preparation of Solid Catalyst Component D5

(72) To a reactor, in which air had been fully replaced with high pure N.sub.2, were successively charged 2.0 g of magnesium dichloride, 80 mL of toluene, 2 mL of epoxy chloropropane, and 6 mL of tri-n-butyl phosphate. The reaction mixture was heated with stirring to 60° C. and maintained at that temperature for 2 hours. The reaction mixture was cooled to −30° C., and then 30 mL of titanium tetrachloride was slowly added dropwise. Next, the temperature was gradually enhanced to 85° C. and maintain for 1 hour. The stirring in the reactor was stopped, the reaction mixture was let stand, and solid particles precipitated quickly. A supernatant was sucked out, and precipitants were washed sequentially with toluene and hexane several times, then transferred by means of hexane to a fritted glass filter, and dried with a high pure nitrogen flow, to afford solid catalyst component D5 having good flowability, of which composition is shown in Table 1 below.

(2) Homopolymerization

(73) The polymerization procedure is the same as described in Example 1, except that the solid catalyst component D5 prepared in Comparative Example 5 was used. Polymerization results are shown in Table 9 below.

(3) Ethylene-Butene Copolymerization

(74) The polymerization procedure is the same as described in Example 2, except that the solid catalyst component D5 prepared in Comparative Example 5 was used. Polymerization results are shown in Table 10 below.

(75) TABLE-US-00008 TABLE 9 Homopolymerization results 0.28 MPa H.sub.2/ 0.68 MPa H.sub.2/0 0.75 MPa ethylene .35 MPa ethylene Melt index Melt index Catalyst Activity (21.6 Kg) Activity (2.16 Kg) Example 5 28100 24.2 8400 111 Comparative 27400 35.1 7800 53 Example 5

(76) As shown in Table 9, when a cyclotriveratrylene derivative is introduced into the solid catalyst component e of Example 5, catalyst activity under polymerization condition of high hydrogen gas-ethylene ratio is higher than that for the comparative example, and the melt index of the polymer powder is significantly higher than that for the comparative example.

(77) TABLE-US-00009 TABLE 10 Ethylene-butene copolymerization results (powder) Melting Hexane enthalpy extractables Example 5 127 J/g 26.4 mol % Comparative 139 J/g 35.4 mol % Example 5

(78) As shown in Table 10, when a cyclotriveratrylene derivative is introduced into the solid catalyst component e of Example 5, in ethylene//butene copolymerization, not only can the resultant polymerization product have a lower melting enthalpy (i.e., lower density), but also it has less hexane extractables. This suggests that the copolymerized units in the polymerization product of Example 5 are more uniformly distributed.

(79) Examples 6-8 are to illustrate use of cyclotriveratrylene and derivatives thereof as an external electron donor in ethylene polymerization catalysts.

Example 6

(1) Preparation of Solid Catalyst Component F

(80) The preparation procedure of the solid catalyst component is the same as described in Comparative Example 4.

(2) Ethylene-Butene Copolymerization

(81) To a 2 L stainless steel reactor, in which air had been fully replaced with high pure N.sub.2, were charged 1 L of hexane and 1.0 mL of 1 M triethyl aluminum solution, followed by the addition of 25 mg of the solid catalyst component prepared by the above-described process and 40 mg of Compound A. The reactor was heated with stirring to 70° C., hydrogen gas was introduced to bring the pressure inside the reactor to 0.28 MPa (gauge), and then ethylene/butene mixed gases (having a molar ratio of 0.935:0.065) was introduced to bring the total pressure inside the reactor to 0.73 MPa (gauge). The polymerization was allowed to continue at 80° C. for 0.5 hours, with the ethylene/butene mixed gases being continuously introduced into the reactor to maintain the total pressure at 0.73 MPa (gauge). Polymerization results are shown in Table 11 below.

Comparative Example 6

(1) Preparation of Solid Catalyst Component F

(82) The preparation procedure of the solid catalyst component is the same as described in Comparative Example 4.

(2) Ethylene-Butene Copolymerization

(83) The polymerization procedure is the same as described in Example 6, except that the Compound A was omitted. Polymerization results are shown in Table 11 below.

(84) TABLE-US-00010 TABLE 11 Ethylene-butene copolymerization results (powder) Melting Content of enthalpy copolymerized units Example 6 166 J/g 1.0 mol % Comparative 170 J/g 1.1 mol % Example 6

(85) As shown in Table 11, when a cyclotriveratrylene derivative is introduced as an external electron donor into the polymerization system of Example 6, in ethylene/butene copolymerization, the resultant polymerization product can have a lower melting enthalpy (i.e., lower density) even at a lower content of copolymerized units. This suggests that the copolymerized units in the polymerization product of Example 6 are more uniformly distributed.

Example 7

(1) Preparation of Solid Catalyst Component G

(86) The preparation procedure of the solid catalyst component is the same as described in Comparative Example 2.

(2) Ethylene-Butene Copolymerization

(87) To a 2 L stainless steel reactor, in which air had been fully replaced with high pure N.sub.2, were charged 1 L of hexane and 1.0 mL of 1 M triethyl aluminum solution, followed by the addition of 24 mg of the solid catalyst component prepared by the above-described process and 42 mg of Compound A. The reactor was heated with stirring to 70° C., hydrogen gas was introduced to bring the pressure inside the reactor to 0.28 MPa (gauge), and then ethylene/butene mixed gases (having a molar ratio of 0.75:0.25) was introduced to bring the total pressure inside the reactor to 0.73 MPa (gauge). The polymerization was allowed to continue at 80° C. for 0.5 hours, with the ethylene/butene mixed gases being continuously introduced into the reactor to maintain the total pressure at 0.73 MPa (gauge). Polymerization results are shown in Table 12 below.

Comparative Example 7

(1) Preparation of Solid Catalyst Component G

(88) The preparation procedure of the solid catalyst component is the same as described in Comparative Example 2.

(2) Ethylene-Butene Copolymerization

(89) The polymerization procedure is the same as described in Example 7, except that 42 mg of ethyl benzoate was used to replace for the 42 mg of Compound A. Polymerization results are shown in Table 12 below.

(90) TABLE-US-00011 TABLE 12 Ethylene-butene copolymerization results (powder) Melting Content of enthalpy copolymerized units Example 7 153 J/g 1.9 mol % Comparative 165 J/g 1.4 mol % Example 7

(91) As shown in Table 12, compared to the ethyl benzoate used in Comparative Example 7, when a cyclotriveratrylene derivative is introduced as an external electron donor into the polymerization system of Example 7, the resultant polymerization product can have a lower melting enthalpy (i.e., lower density).

Example 8

(1) Preparation of Solid Catalyst Component H

(92) To a reactor, in which air had been fully replaced with high pure N.sub.2, were successively charged 4.0 g of magnesium dichloride, 50 mL of toluene, 3.3 mL of epoxy chloropropane, 8 mL of tri-n-butyl phosphate, and 4.4 mL of ethanol. The reaction mixture was heated with stirring to 68° C. and maintained at that temperature for 2 hours. The reaction mixture was cooled to −10° C., and then 65 mL of titanium tetrachloride was slowly added dropwise, followed by the dropwise-addition of 6 mL of tetraethoxy silicane. Next, the temperature was gradually enhanced to 85° C. and maintain for 2 hours. The stirring in the reactor was stopped, the reaction mixture was let stand, and solid particles precipitated quickly. A supernatant was sucked out, and precipitants were washed sequentially with toluene and hexane several times, then transferred by means of hexane to a fritted glass filter, and dried with a high pure nitrogen flow, to afford solid catalyst component h having good flowability, of which composition is shown in Table 1 below.

(2) Ethylene-Hexene Copolymerization

(93) To a 2 L stainless steel reactor, in which air had been fully replaced with high pure N.sub.2, were charged 1 L of hexane and 1.0 mL of 1 M triethyl aluminum solution, followed by the addition of 11 mg of the solid catalyst component prepared by the above-described process and 11 mg of Compound A. The reactor was heated with stirring to 70° C., 20 ml of hexene was added thereinto, hydrogen gas was introduced to bring the pressure inside the reactor to 0.28 MPa (gauge), and then ethylene was introduced to bring the total pressure inside the reactor to 0.73 MPa (gauge). The polymerization was allowed to continue at 80° C. for 0.5 hours, with the ethylene being continuously introduced into the reactor to maintain the total pressure at 0.73 MPa (gauge). Polymerization results are shown in Table 13 below.

Comparative Example 8

(1) Preparation of Solid Catalyst Component H

(94) The preparation procedure of the solid catalyst component is the same as described in Example 8.

(2) Ethylene-Hexene Copolymerization

(95) The polymerization procedure is the same as described in Example 8, except that the Compound A was omitted. Polymerization results are shown in Table 13 below.

(96) TABLE-US-00012 TABLE 13 Ethylene-hexene copolymerization results (powder) Melting Hexane enthalpy extractables Example 8 186 J/g 1.1 wt % Comparative 186 J/g 2.4 wt % Example 8

(97) As shown in Table 13, when a cyclotriveratrylene derivative is introduced as an external electron donor into the polymerization system of Example 8, in ethylene/hexene copolymerization, although the resultant polymer powder has a melting enthalpy that is not lower than that of Comparative Example 8, its hexane extractables are relatively reduced. Such a property is in favor of stable production in industry.

(98) Examples 9-10 are to illustrate use of cyclotriveratrylene and derivatives thereof as an internal electron donor in catalysts for propylene polymerization.

Example 9

(1) Preparation of Solid Catalyst Component I

(99) To a 300 ml glass reactor equipped with a stirrer, in which reactor air had been fully replaced with high pure N.sub.2, were successively charged 50 ml of titanium tetrachloride and 40 ml of hexane, and the contents were cooled with stirring to −20° C. To the above solution was added 9 g of spherical magnesium dichloride-alcohol adduct (MgCl.sub.2.2.6C.sub.2H.sub.5OH, prepared from magnesium dichloride and ethanol according to process described in CN1330086A). The reaction mixture was slowly heated stagewise with stirring, with 0.25 mmol of Compound A, 5 mmol of di-isobutyl phthalate (DIBP) and 20 ml of toluene being added thereto during the heating, and then the temperature was enhanced to 110° C. and maintained at that temperature for 0.5 hours. The stirring in the reactor was stopped, the reaction mixture was let stand, and solid phase precipitated quickly. A supernatant was sucked out, and the solid phase left in the glass reactor was treated with 80 mL of titanium tetrachloride twice, washed with hexane five times, and dried under vacuum, to afford spherical solid catalyst component i, of which composition is shown in Table 1 below.

(2) Propylene Polymerization

(100) A 5 L autoclave was purged with nitrogen gas flow, and then under nitrogen atmosphere, 0.25 mmol of triethylaluminum, 0.01 mmol of cyclohexyl methyl dimethoxy silane (CHMMS), 10 ml of anhydrous hexane and 10 mg of the spherical catalyst component i were introduced thereto. The autoclave was closed, and then 1.2 NL (standard volume) of hydrogen gas and 2.3 L of liquid propylene were introduced to the autoclave. The temperature inside the autoclave was brought to 70° C., and the polymerization was allowed to continue for 1.0 hours. Polymerization results are shown in Table 14 below.

Comparative Example 9

(1) Preparation of Solid Catalyst Component D9

(101) The spherical solid catalyst component D9 was prepared by the procedure as described for Example 9, except that the Compound A was omitted. The composition of the solid catalyst component is shown in Table 1 below.

(2) Propylene Polymerization

(102) The polymerization procedure is the same as described in Example 9, except that the solid catalyst component D9 prepared in Comparative Example 9 was used. Polymerization results are shown in Table 14 below.

(103) TABLE-US-00013 TABLE 14 Propylene polymerization results Activity MI II No. (KgPP/gcat .Math. h) (g/10 min) (wt %) Example 9 53.7 4.7 97.3 Comparative 40.3 4.8 97.1 Example 9

(104) As shown in Table 14, when a cyclotriveratrylene derivative is introduced into the solid catalyst component i of Example 9, the polymerization activity of the catalyst is significantly enhanced, and the isotacticity of the polymer powder can meet the requirements of applications.

Example 10

(1) Preparation of Solid Catalyst Component J

(105) To a 300 ml glass reactor equipped with a stirrer, in which reactor air had been fully replaced with high pure N.sub.2, were successively charged 50 ml of titanium tetrachloride and 40 ml of hexane, and the contents were cooled with stirring to −20° C. To the above solution was added 9 g of spherical magnesium dichloride-alcohol adduct (MgCl.sub.2.2.6C.sub.2H.sub.5OH, prepared from magnesium dichloride and ethanol according to process described in CN1330086A). The reaction mixture was slowly heated stagewise with stirring, with 0.25 mmol of Compound A, 5 mmol of di-n-butyl phthalate (DNBP) and 20 ml of toluene being added thereto during the heating, and then the temperature was enhanced to 110° C. and maintained at that temperature for 0.5 hours. The stirring in the reactor was stopped, the reaction mixture was let stand, and solid phase precipitated quickly. A supernatant was sucked out, and the solid phase left in the reactor was treated with 80 mL of titanium tetrachloride twice, washed with hexane five times, and dried under vacuum, to afford spherical solid catalyst component j, of which composition is shown in Table 1 below.

(2) Propylene Polymerization

(106) The polymerization procedure is the same as described in Example 9, except that the solid catalyst component j prepared in Example 10 was used. Polymerization results are shown in Table 15 below.

Comparative Example 10

(1) Preparation of Solid Catalyst Component D10

(107) The spherical solid catalyst component D10 was prepared by the procedure as described for Example 10, except that the Compound A was omitted. The composition of the solid catalyst component is shown in Table 1 below.

(2) Propylene Polymerization

(108) The polymerization procedure is the same as described in Example 9, except that the solid catalyst component D10 prepared in Comparative Example 10 was used. Polymerization results are shown in Table 15 below.

(109) TABLE-US-00014 TABLE 15 Propylene polymerization results Activity MI II No. (KgPP/gcat .Math. h) (g/10 min) (wt %) Example 10 52.6 4.6 98.2 Comparative 39.8 4.5 98.3 Example 10

(110) As shown in Table 15, when a cyclotriveratrylene derivative is introduced into the solid catalyst component j of Example 10, the polymerization activity of the catalyst is significantly enhanced, and the isotacticity of the polymer powder can meet the requirements of applications.

(111) Example 11 is to illustrate use of the cyclotriveratrylene and derivatives thereof as an external electron donor in propylene polymerization catalyst.

Example 11

(112) In this example, propylene polymerization was performed by using NDQ catalyst, which is available from Aoda Catalyst Company, SINOPEC, wherein Compound A was used as an external electron donor.

Propylene Polymerization Procedure

(113) A 5 L autoclave was purged with nitrogen gas flow, and then under nitrogen atmosphere, 0.25 mmol of triethylaluminum, 0.01 mmol of external electron donor (Compound A), 10 ml of anhydrous hexane and 10 mg of the NDQ catalyst were introduced thereto. The autoclave was closed, and then 1.2 NL (standard volume) of hydrogen gas and 2.3 L of liquid propylene were introduced to the autoclave. The temperature inside the autoclave was brought to 70° C., and the polymerization was allowed to continue for 1.0 hours. Polymerization results are shown in Table 16 below.

Comparative Example 11

(114) In this comparative example, propylene polymerization was performed by using NDQ catalyst, which is available from Aoda Catalyst Company, SINOPEC, wherein no Compound A was used as an external electron donor.

Propylene Polymerization Procedure

(115) A 5 L autoclave was purged with nitrogen gas flow, and then under nitrogen atmosphere, 0.25 mmol of triethylaluminum, 10 ml of anhydrous hexane and 10 mg of the NDQ catalyst were introduced thereto. The autoclave was closed, and then 1.2 NL (standard volume) of hydrogen gas and 2.3 L of liquid propylene were introduced to the autoclave. The temperature inside the autoclave was brought to 70° C., and the polymerization was allowed to continue for 1.0 hours. Polymerization results are shown in Table 16 below.

(116) TABLE-US-00015 TABLE 16 Propylene Polymerization results External electron Activity Isotacticity Example No. donor (kgPP/gCat) (wt %) Example 11 Compound A 53 97.9 Comparative — 60 95.1 Example 11

(117) It can be seen from Table 16 that the catalyst system provided by the present disclosure may be used for propylene polymerization, and compared to Comparative Example 11, in which no Compound A is added, Example 11 obtains a polymer having an enhanced isotacticity.

(118) TABLE-US-00016 TABLE 1 Composition of solid catalyst components Cyclotriveratrylene Solid and derivatives catalyst Ti thereof No. component (wt %) (wt %) Example 1 a 5.3 2.0 Comparative Example 1-1 D1-1 7.4 — Comparative Example 1-2 D1-2 3.8 — Example 2 b 6.0 1.8 Comparative Example 2 D2 6.3 — Example 3 c 6.2 1.5 Comparative Example 3 D3 6.5 — Example 4a d1 3.2 1.2 Example 4b d2 3.0 1.0 Comparative Example 4 D4 2.8 — Example 5 e 3.0 2.0 Comparative Example 5 D5 2.6 — Example 8 h 6.5 — Example 9 i 2.5 0.5 Comparative Example 9 D9 2.4 — Example 10 j 2.6 0.8 Comparative Example 10 D10 2.8 — Example 11 NDQ 2.4 —

(119) While the illustrative embodiments of the disclosure have been described with particularity, it will be understood that various other modifications will be apparent to and can be readily made by those skilled in the art without departing from the spirit and scope of the disclosure. Accordingly, it is not intended that the scope of the claims appended hereto be limited to the examples and descriptions set forth herein, but rather that the claims be construed as encompassing all the features of patentable novelty which reside herein, including all features which would be treated as equivalents thereof by those skilled in the art to which this disclosure pertains. The present disclosure has been described hereinabove by reference to many embodiments and specific examples. In view of the above detailed descriptions, many variations are apparent to those skilled in the art. All such variations are within the scope of the whole intention of the appended claims.

(120) In the disclosure, whenever a composition, an element or a group of elements is preceded with the transitional phrase “comprising”, it is understood that we also contemplate the same composition, element or group of elements with transitional phrases “consisting essentially of”, “consisting of”, “selected from the group of consisting of”, or “is” preceding the recitation of the composition, element, or elements and vice versa.