CA1089843A - PROCESS FOR POLYMERIZING .alpha.-OLEFINS AND CATALYST THEREFOR - Google Patents
PROCESS FOR POLYMERIZING .alpha.-OLEFINS AND CATALYST THEREFORInfo
- Publication number
- CA1089843A CA1089843A CA272,787A CA272787A CA1089843A CA 1089843 A CA1089843 A CA 1089843A CA 272787 A CA272787 A CA 272787A CA 1089843 A CA1089843 A CA 1089843A
- Authority
- CA
- Canada
- Prior art keywords
- carbon atoms
- compound
- titanium
- magnesium
- saturated
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S526/00—Synthetic resins or natural rubbers -- part of the class 520 series
- Y10S526/906—Comminution of transition metal containing catalyst
Abstract
ABSTRACT OF THE DISCLOSURE
A process for polymerising .alpha.-olefins with improved yields is dis-closed which uses a novel catalyst composition comprising a solid halogen-containing titanium catalyst component and an organometallic compound of a metal of Group I, II or III of the periodic table. The halogen-containing titanium catalyst component is obtained by reacting a mechanically copulverized solid product in the absence of mechanical pulverization with a titanium compound which is liquid under the reaction conditions. The mechanically copulverised solid product is derived from a magnesium compound, an organic acid ester and an active hydroger-containing compound selected from alcohols and phenols.
A process for polymerising .alpha.-olefins with improved yields is dis-closed which uses a novel catalyst composition comprising a solid halogen-containing titanium catalyst component and an organometallic compound of a metal of Group I, II or III of the periodic table. The halogen-containing titanium catalyst component is obtained by reacting a mechanically copulverized solid product in the absence of mechanical pulverization with a titanium compound which is liquid under the reaction conditions. The mechanically copulverised solid product is derived from a magnesium compound, an organic acid ester and an active hydroger-containing compound selected from alcohols and phenols.
Description
This invention relates to a process for polymerizing ~-olefins and a catalyst suitable for use in the process. More specifically, the invention relates to a process for producing highly stereoregular ~-olefin polymers or copolymers in improved yields with a superior polymer output per unit weight of a solid titanium compound used as a catalyst component, and per unit weight of halogen containing the solid titanium compound while greatly inhibiting the formation of a fine powdery polymer which is detrimental to the separation of the resulting desired polymer.
The catalyst used has a superior activity in terms of the number of grams of the polymer formed per millimole of titanium atom per hour. Furthermore, the time required for mechanical copulveriz-ation in catalyst preparation can be shortened.
The present invention provides a process for polymeriz-ing or copolymerizing ~-olefins in the presence of a catalyst composed of (A) a mechanically pulverized solid titanium-containing catalyst component and (B) an organometallic compound of a metal of Groups I to III of the periodic table, wherein said titanium-containing component is obtained by reacting a halogen-containing titanium compound which is liquid under the reactionconditions and has the formula:
Ti(OR)gx4-g wherein R represents a hydrocarbon group selected from the class consisting of alkyl groups containing 1 to 4 carbon atoms, cyclo-alkyl groups containing 6 to 12 carbon atoms and aryl groups con-taining 6 to 10 carbon atoms, X represents a halogen atom, and g is 0 ~ g ~ 4, with a mechanically copulverized solid product in the absence of mechanical pulverization, said mechanically co-; pulverized product being derived from (1) a magnesium compound of the formula:
'C
lUt3~
MgX X
wherein Xl is a halogen atom, x2 represents a member selected from the group consisting of halogen atoms and a group OR" in which R" is a group selected from alkyl groups, cycloalkyl groups and aryl groups, ~2) an organic acid ester selected from the group consisting of (i) aliphatic carboxylic acid esters containing 2 to 40 carbon atoms, ~ii) alicyclic carboxylic acid esters containing 7 to 20 carbon atoms, (iii) aromatic carboxylic acid esters containing 8 to 40 carbon atoms and (iv) lactones containing 4 to 10 carbon atoms, and (3) an active hydrogen~containing compound selected from aliphatic alcohols containing 1 to 12 carbon atoms, alicyclic alcohols containing 3 to 12 carbon atoms, aromatic alcohols containing 7 to 12 carbon atoms and phenols containing 6 to 18 carbon atoms; the molar ratio of said organic acid ester (2) to magnesium atoms in said magnesium compound (1) being from about 0.001 to 10 moles, the ratio of said active hydrogen containing compound (3) to magnesium atoms in said magnesium compound (1) being from about 0.001 to 10 moles, and the amount of said titanium compound being such that about 0.001 to 1000 titanium atoms are present per atom of magnesium in said magnesium com-pound (1).
The invention further provides a - 2a -r~
lV~ 4;3 catalyst composition suitable for use in the practice of this process.
Methods have heretofore been suggested for polymerizing or copoly-merizing - olefins in the presence of a catalyst composed of ~A) a solid titanium compound mechanically pulverized in the presence or absence of another compound, and (B) an organometallic compound of a metal of Groups I to III of the periodic table. One example of the titanium catalyst com-ponent of this type is the highly active titanium catalyst component dis-closed in Japanese Laid-Open Patent Publication No. 126590/75 (laid open on October 4, 1975) which is obtained by contacting a halogen-containing magnesium compound with an aromatic carboxylic acid ester by a mechanically pulverizing means, and reacting the resulting mixture with a titanium com-pound. This Patent Publication does not at all give a description about pulverization in the presence of the active hydrogen-containing compound (3).
Highly stereoregular ~- orefin polymers or copolymers can be prepared with superior activity using the solid titanium compound suggested in this Publication. On further investigations, it was found that a further improve-ment is desired in the output of polymer or copolymer per unit weight of halogen which is likely to be contained in the resulting polymer or copolymer, and cause rust to fabricating molds and other metallic materials at the time of, say molding, and that the formation of a fine powdery polymer detrimental to the separation of the resulting polymer cannot be ignored, and it is desired to inhibit the formation of such a fine powdery polymer. Moreover, it is desired to further shorten the time required for mechanical copulveriz-ation in catalyst preparation.
Another suggestion was made in Japanese Laid-Open Patent Publication No. 16986/73 laid open on March 3, 1973 (corresponding to west German OLS
No 2,230,728, and ~o French Patent No. 2,143,347). Example 13 of this patent discloses a solid titanium compound used as a catalyst component which was prepared by dissolving anhydrous magnesium chloride in anhydrous ethanol, evaporating the ethanol rapidly, drying the residue at 300C and 0.1 mmHg, and mechanically copulverizing the resulting product togetncr with a complex of TiC14 and ethyl benzoate. This patent fails to disclose anything about a solid titanium catalyst component which is obtained by reacting the afore-said titanium compound with a liquid titanium compound in the absence of mechanical pulverization. The amount of polymer yielded in Example 13 is as low as 1340 g/Ti millimole. The stereospecificity ~I.I. -----the boiling n-heptane extraction residue) is as low as 74.3%.
The present inventors furtheTed their investigations in order to overcome the disadvantages of the prior art methods mentioned above. These investigations led to the discovery that the use of a solid halogen-containing titanium compound obtained by reacting a mechanically copulverized solid product derived from (1) a magnesium compound, ~2) an organic acid ester, and (3) an active hydrogen-containing compound selected from the group of alcohols and phenols, with titanium compound liquid under the reaction con-ditions in the absence of mechanical pulverization can increase the output of polymer per gram of the halogen which becomes a cause of rust formation in the first-mentioned prior patent, and inhibit the undesirable formation of a fine powdery polymer in the aforementioned patent. It was also found that the low yield and the low stereoregularity of polymer in the second prior patent mentioned above can be obviated.
It was confirmed as shown in Comparative Examples 1 and 2 to be given hereinbelow that when the mechanically copulverized solid product derived from the compounds (1), (2) and ~3) is used without reaction with the specified titanium compound in the absence of mechanical pulverization, or the reaction of the solid product with the titanium compound is carried out in the presence of mechanical pulverization, the improvement contemplated by the present invention cannot be achieved.
It is an object of this invention therefore to provide a process for polymerizing olefins, which can overcome the disadvantages of the con-ventional processes for polymerizing or copolymerizing a-olefins in the lU~
presence of a catalyst composed of ~A) a mechanically pulverized solid titanium catalyst component, and (B) an organometallic compound of a metal of Groups I to III of the periodic table.
Another ~bject of this invention is to provide a catalyst composi-tion for polymerization or copolymerization of ~-olefins which is used in performing the aforesaid improved process of this invention.
The above and other objects of the invention along with its ad-vantages will become more apparent from the following description.
The solid halogen-containing titanium catalyst component used in the process of this invention is obtained by reacting a mechanically pulver-ized solid product derived from (1) a magnesium compound, ~2) an organic acid ester, and ~3) an active hydrogen-containing compound selected from alcohols and phenols, with a titanium compound liquid under the reaction conditions in the absence of mechanical pulverization.
The magnesium compound ~1) used in this invention is preferably a compound containing a halogen or both a halogen and an organic group ~includ-ing a member selected from hydrocarbon groups, alkoxy groups, aryloxy groups and acyloxy groups) which may further contain another metal such as aluminum, tin, silicon or germanium. The magnesium compound may be prepared by any method, and may also be a mixture of two or more such compounds. Examples of the magnesium compound are decomposition products of organic Mg compounds such as Grignard reagents. There can also be used complex compounds obtained by dissolving halogen-containing magnesium compounds with or without other compounds soluble in acetone and ether, such as Al~OR~X3 n ~in which R is a hydrocarbon group, X is a halogen atom, and O - n - 3) or GeC14, in the aforesaid solvent, and then evaporating the solvent. Of the exemplified compounds, magnesium dihalides and their complex compounds are preferred.
Examples of especially preferred magnesium compounds ~1) used in this in-vention are compounds of the formula MgXlX2 wherein Xl is halogen and x2 represents a member selected from halogen atoms, and the groups OR" in which R" is a group selected from the group consisting of alkyl groups, preferably alkyl groups containing 1 to 10 carbon atoms, cycloalkyl groups, preferably cycloalkyl groups containing 6 to 12 carbon atoms, and aryl groups, preferably, a phenyl group optionally substituted by an alkyl group containing 1 to 4 carbon atoms. Specific examples include MgC12, MgBr2, MgI2, MgF2, Mg(OCH3)Cl, Mg(OC2H5)Cl, Mg(O n-C4Hg)Cl, Mg(O ~ )Cl, Mg(O ~ -CH3)Cl, Mg(O- ~ )Cl, and Mg~O )Cl.
Preferably, the magnesium compo~nd (1) is as anhydrous as possible.
It is permissible however for the magnesium compound to contain moisture in an amount which does not substantially affect the performance of the catalyst.
For the convenience of use, it is advantageous to use the magnesium compound as a powder having an average particle diameter of about 1 to about 50 microns.
Since a mechanical pulverization step is essential in the preparation of the titanium catalyst component, larger particle sizes are also feasible.
Examples of the organic acid es~er (2) used in this invention are (i) aliphatic carboxylic acid esters containing 2 to 40 carbon atoms, (ii) alicyclic carboxylic acid esters containing 7 to 20 carbon atoms, (iii) aromatic carboxylic acid esters containing 8 to 40 carbon atoms, and (iv) lactones containing 4 to 10 carbon atoms. More specifically, the organic acid esters include the following.
(i) Esters formed between a member selected from saturated or unsaturated aliphatic carboxylic acids containing 1 to 18 carbon atoms, pre-ferably 1 to 4 carbon atoms, and halogen-substitution products of the above i carboxylic acids, and a mem~er selected from the group consisting of saturated or unsaturated aliphatic primary alcohols containing 1 to 18, preferably 1 to 4, carbon atoms, saturated or unsaturated cycloaliphatic alcohols con-taining 3 to 8, preferably 5 to 6, carbon atoms, phenols containing 6 to 10, preferably 6 to 8, carbon atoms) saturated or unsaturated primary alcohols lUI~
containing 1 to 4 carbon atoms and bonded to an aliphatic ring with 3 to 10 carbon atoms, and saturated or unsaturated primary alcohols containing 1 to 4 carbon atoms and bonded to an aromatic ring with 6 to 10 carbon atoms;
(ii) Esters formed between alicyclic carboxylic acids containing 6 to 12, preferably 6 to 8, carbon atoms and saturated or unsaturated primary alcohols containing 1 to 8, preferably 1 to 4, carbon atoms;
(iii) Esters formed between aromatic carboxylic acids containing 7 to 18 carbon atoms, preferably 7 to 12 carbon atoms, and a member selected from the group consisting of saturated or unsaturated aliphatic primary alcohols containing 1 to 18, preferably 1 to 4, carbon atoms, saturated or unsaturated cycloaliphatic alcohols containing 3 to 8, preferably 5 to 8, carbon atoms, phenols containing 6 to 10, preferably 6 to 8, carbon atoms, saturated or unsaturated primary alcohols containing 1 to 4 carbon atoms and bonded to an aliphatic ring with 3 to 10 carbon atoms, and saturated or unsaturated primary alcohols containing 1 to 4 carbon atoms and bonded to an aromatic ring with 6 to 10 carbon atoms; and (i~) 5- or 6~ membered cyclic lactones containing 4 to 10 carbon atoms.
Specific examples of the esters (i) are primary alkyl esters of saturated fatty acids such as methyl formate, ethyl acetate, n-amyl acetate,
The catalyst used has a superior activity in terms of the number of grams of the polymer formed per millimole of titanium atom per hour. Furthermore, the time required for mechanical copulveriz-ation in catalyst preparation can be shortened.
The present invention provides a process for polymeriz-ing or copolymerizing ~-olefins in the presence of a catalyst composed of (A) a mechanically pulverized solid titanium-containing catalyst component and (B) an organometallic compound of a metal of Groups I to III of the periodic table, wherein said titanium-containing component is obtained by reacting a halogen-containing titanium compound which is liquid under the reactionconditions and has the formula:
Ti(OR)gx4-g wherein R represents a hydrocarbon group selected from the class consisting of alkyl groups containing 1 to 4 carbon atoms, cyclo-alkyl groups containing 6 to 12 carbon atoms and aryl groups con-taining 6 to 10 carbon atoms, X represents a halogen atom, and g is 0 ~ g ~ 4, with a mechanically copulverized solid product in the absence of mechanical pulverization, said mechanically co-; pulverized product being derived from (1) a magnesium compound of the formula:
'C
lUt3~
MgX X
wherein Xl is a halogen atom, x2 represents a member selected from the group consisting of halogen atoms and a group OR" in which R" is a group selected from alkyl groups, cycloalkyl groups and aryl groups, ~2) an organic acid ester selected from the group consisting of (i) aliphatic carboxylic acid esters containing 2 to 40 carbon atoms, ~ii) alicyclic carboxylic acid esters containing 7 to 20 carbon atoms, (iii) aromatic carboxylic acid esters containing 8 to 40 carbon atoms and (iv) lactones containing 4 to 10 carbon atoms, and (3) an active hydrogen~containing compound selected from aliphatic alcohols containing 1 to 12 carbon atoms, alicyclic alcohols containing 3 to 12 carbon atoms, aromatic alcohols containing 7 to 12 carbon atoms and phenols containing 6 to 18 carbon atoms; the molar ratio of said organic acid ester (2) to magnesium atoms in said magnesium compound (1) being from about 0.001 to 10 moles, the ratio of said active hydrogen containing compound (3) to magnesium atoms in said magnesium compound (1) being from about 0.001 to 10 moles, and the amount of said titanium compound being such that about 0.001 to 1000 titanium atoms are present per atom of magnesium in said magnesium com-pound (1).
The invention further provides a - 2a -r~
lV~ 4;3 catalyst composition suitable for use in the practice of this process.
Methods have heretofore been suggested for polymerizing or copoly-merizing - olefins in the presence of a catalyst composed of ~A) a solid titanium compound mechanically pulverized in the presence or absence of another compound, and (B) an organometallic compound of a metal of Groups I to III of the periodic table. One example of the titanium catalyst com-ponent of this type is the highly active titanium catalyst component dis-closed in Japanese Laid-Open Patent Publication No. 126590/75 (laid open on October 4, 1975) which is obtained by contacting a halogen-containing magnesium compound with an aromatic carboxylic acid ester by a mechanically pulverizing means, and reacting the resulting mixture with a titanium com-pound. This Patent Publication does not at all give a description about pulverization in the presence of the active hydrogen-containing compound (3).
Highly stereoregular ~- orefin polymers or copolymers can be prepared with superior activity using the solid titanium compound suggested in this Publication. On further investigations, it was found that a further improve-ment is desired in the output of polymer or copolymer per unit weight of halogen which is likely to be contained in the resulting polymer or copolymer, and cause rust to fabricating molds and other metallic materials at the time of, say molding, and that the formation of a fine powdery polymer detrimental to the separation of the resulting polymer cannot be ignored, and it is desired to inhibit the formation of such a fine powdery polymer. Moreover, it is desired to further shorten the time required for mechanical copulveriz-ation in catalyst preparation.
Another suggestion was made in Japanese Laid-Open Patent Publication No. 16986/73 laid open on March 3, 1973 (corresponding to west German OLS
No 2,230,728, and ~o French Patent No. 2,143,347). Example 13 of this patent discloses a solid titanium compound used as a catalyst component which was prepared by dissolving anhydrous magnesium chloride in anhydrous ethanol, evaporating the ethanol rapidly, drying the residue at 300C and 0.1 mmHg, and mechanically copulverizing the resulting product togetncr with a complex of TiC14 and ethyl benzoate. This patent fails to disclose anything about a solid titanium catalyst component which is obtained by reacting the afore-said titanium compound with a liquid titanium compound in the absence of mechanical pulverization. The amount of polymer yielded in Example 13 is as low as 1340 g/Ti millimole. The stereospecificity ~I.I. -----the boiling n-heptane extraction residue) is as low as 74.3%.
The present inventors furtheTed their investigations in order to overcome the disadvantages of the prior art methods mentioned above. These investigations led to the discovery that the use of a solid halogen-containing titanium compound obtained by reacting a mechanically copulverized solid product derived from (1) a magnesium compound, ~2) an organic acid ester, and (3) an active hydrogen-containing compound selected from the group of alcohols and phenols, with titanium compound liquid under the reaction con-ditions in the absence of mechanical pulverization can increase the output of polymer per gram of the halogen which becomes a cause of rust formation in the first-mentioned prior patent, and inhibit the undesirable formation of a fine powdery polymer in the aforementioned patent. It was also found that the low yield and the low stereoregularity of polymer in the second prior patent mentioned above can be obviated.
It was confirmed as shown in Comparative Examples 1 and 2 to be given hereinbelow that when the mechanically copulverized solid product derived from the compounds (1), (2) and ~3) is used without reaction with the specified titanium compound in the absence of mechanical pulverization, or the reaction of the solid product with the titanium compound is carried out in the presence of mechanical pulverization, the improvement contemplated by the present invention cannot be achieved.
It is an object of this invention therefore to provide a process for polymerizing olefins, which can overcome the disadvantages of the con-ventional processes for polymerizing or copolymerizing a-olefins in the lU~
presence of a catalyst composed of ~A) a mechanically pulverized solid titanium catalyst component, and (B) an organometallic compound of a metal of Groups I to III of the periodic table.
Another ~bject of this invention is to provide a catalyst composi-tion for polymerization or copolymerization of ~-olefins which is used in performing the aforesaid improved process of this invention.
The above and other objects of the invention along with its ad-vantages will become more apparent from the following description.
The solid halogen-containing titanium catalyst component used in the process of this invention is obtained by reacting a mechanically pulver-ized solid product derived from (1) a magnesium compound, ~2) an organic acid ester, and ~3) an active hydrogen-containing compound selected from alcohols and phenols, with a titanium compound liquid under the reaction conditions in the absence of mechanical pulverization.
The magnesium compound ~1) used in this invention is preferably a compound containing a halogen or both a halogen and an organic group ~includ-ing a member selected from hydrocarbon groups, alkoxy groups, aryloxy groups and acyloxy groups) which may further contain another metal such as aluminum, tin, silicon or germanium. The magnesium compound may be prepared by any method, and may also be a mixture of two or more such compounds. Examples of the magnesium compound are decomposition products of organic Mg compounds such as Grignard reagents. There can also be used complex compounds obtained by dissolving halogen-containing magnesium compounds with or without other compounds soluble in acetone and ether, such as Al~OR~X3 n ~in which R is a hydrocarbon group, X is a halogen atom, and O - n - 3) or GeC14, in the aforesaid solvent, and then evaporating the solvent. Of the exemplified compounds, magnesium dihalides and their complex compounds are preferred.
Examples of especially preferred magnesium compounds ~1) used in this in-vention are compounds of the formula MgXlX2 wherein Xl is halogen and x2 represents a member selected from halogen atoms, and the groups OR" in which R" is a group selected from the group consisting of alkyl groups, preferably alkyl groups containing 1 to 10 carbon atoms, cycloalkyl groups, preferably cycloalkyl groups containing 6 to 12 carbon atoms, and aryl groups, preferably, a phenyl group optionally substituted by an alkyl group containing 1 to 4 carbon atoms. Specific examples include MgC12, MgBr2, MgI2, MgF2, Mg(OCH3)Cl, Mg(OC2H5)Cl, Mg(O n-C4Hg)Cl, Mg(O ~ )Cl, Mg(O ~ -CH3)Cl, Mg(O- ~ )Cl, and Mg~O )Cl.
Preferably, the magnesium compo~nd (1) is as anhydrous as possible.
It is permissible however for the magnesium compound to contain moisture in an amount which does not substantially affect the performance of the catalyst.
For the convenience of use, it is advantageous to use the magnesium compound as a powder having an average particle diameter of about 1 to about 50 microns.
Since a mechanical pulverization step is essential in the preparation of the titanium catalyst component, larger particle sizes are also feasible.
Examples of the organic acid es~er (2) used in this invention are (i) aliphatic carboxylic acid esters containing 2 to 40 carbon atoms, (ii) alicyclic carboxylic acid esters containing 7 to 20 carbon atoms, (iii) aromatic carboxylic acid esters containing 8 to 40 carbon atoms, and (iv) lactones containing 4 to 10 carbon atoms. More specifically, the organic acid esters include the following.
(i) Esters formed between a member selected from saturated or unsaturated aliphatic carboxylic acids containing 1 to 18 carbon atoms, pre-ferably 1 to 4 carbon atoms, and halogen-substitution products of the above i carboxylic acids, and a mem~er selected from the group consisting of saturated or unsaturated aliphatic primary alcohols containing 1 to 18, preferably 1 to 4, carbon atoms, saturated or unsaturated cycloaliphatic alcohols con-taining 3 to 8, preferably 5 to 6, carbon atoms, phenols containing 6 to 10, preferably 6 to 8, carbon atoms) saturated or unsaturated primary alcohols lUI~
containing 1 to 4 carbon atoms and bonded to an aliphatic ring with 3 to 10 carbon atoms, and saturated or unsaturated primary alcohols containing 1 to 4 carbon atoms and bonded to an aromatic ring with 6 to 10 carbon atoms;
(ii) Esters formed between alicyclic carboxylic acids containing 6 to 12, preferably 6 to 8, carbon atoms and saturated or unsaturated primary alcohols containing 1 to 8, preferably 1 to 4, carbon atoms;
(iii) Esters formed between aromatic carboxylic acids containing 7 to 18 carbon atoms, preferably 7 to 12 carbon atoms, and a member selected from the group consisting of saturated or unsaturated aliphatic primary alcohols containing 1 to 18, preferably 1 to 4, carbon atoms, saturated or unsaturated cycloaliphatic alcohols containing 3 to 8, preferably 5 to 8, carbon atoms, phenols containing 6 to 10, preferably 6 to 8, carbon atoms, saturated or unsaturated primary alcohols containing 1 to 4 carbon atoms and bonded to an aliphatic ring with 3 to 10 carbon atoms, and saturated or unsaturated primary alcohols containing 1 to 4 carbon atoms and bonded to an aromatic ring with 6 to 10 carbon atoms; and (i~) 5- or 6~ membered cyclic lactones containing 4 to 10 carbon atoms.
Specific examples of the esters (i) are primary alkyl esters of saturated fatty acids such as methyl formate, ethyl acetate, n-amyl acetate,
2-ethylhexyl acetate, n-butyl formate, ethyl butyrate, and ethyl valerate;
alkenyl esters of saturated fatty acids such as ~inyl acetate or allyl acetate; primary alkyl esters of unsaturated fatty acids such as methyl acrylate, methyl methacrylate or n-butyl crotonate; and halogenated aliphatic monocarboxylic acid esters such as methyl chloroacetate or ethyl dichloro-acetate.
Specific examples of the esters (ii) are methyl cyclohexane-carboxylate, ethyl cyclohexanecarboxylate, methyl methylcyclohexanecarboxylate, and ethyl methylcyclohexanecarboxylate.
Specific examples of the esters (iii) are alkyl benzoates in which the alkyl group is a saturated or ~nsaturated hydrocarbon group usually containing 1 to 8 carbon atoms, preferably 1 to 4 carbon atoms, such as methyl benzoate, ethyl benzoate, n- or i-propyl benzoate, n-, i-, sec-or tert-butyl benzoate, n- or i-amyl benzoate, n-hexyl benzoate, n-octyl benzoate, 2-ethylhexyl benzoate, vinyl benzoate, and allyl benzoate ~prefer-ably methyl benzoate and ethyl benzoate); cycloalkyl benzoates in which the cycloalkyl group is a non-aromatic cyclic hydrocarbon group usually containing
alkenyl esters of saturated fatty acids such as ~inyl acetate or allyl acetate; primary alkyl esters of unsaturated fatty acids such as methyl acrylate, methyl methacrylate or n-butyl crotonate; and halogenated aliphatic monocarboxylic acid esters such as methyl chloroacetate or ethyl dichloro-acetate.
Specific examples of the esters (ii) are methyl cyclohexane-carboxylate, ethyl cyclohexanecarboxylate, methyl methylcyclohexanecarboxylate, and ethyl methylcyclohexanecarboxylate.
Specific examples of the esters (iii) are alkyl benzoates in which the alkyl group is a saturated or ~nsaturated hydrocarbon group usually containing 1 to 8 carbon atoms, preferably 1 to 4 carbon atoms, such as methyl benzoate, ethyl benzoate, n- or i-propyl benzoate, n-, i-, sec-or tert-butyl benzoate, n- or i-amyl benzoate, n-hexyl benzoate, n-octyl benzoate, 2-ethylhexyl benzoate, vinyl benzoate, and allyl benzoate ~prefer-ably methyl benzoate and ethyl benzoate); cycloalkyl benzoates in which the cycloalkyl group is a non-aromatic cyclic hydrocarbon group usually containing
3 to 8 carbon atoms, preferably 5 or 6 carbon atoms, such as cyclopentyl benzoate and cyclohexyl benzoate; aryl benzoates in which the aryl group is a hydrocarbon group usually containing 6 to 10 carbon atoms, preferably 6 to 8 carbon atoms in which halogen and/or an alkyl group with 1 to 4 carbon atoms may be bonded to the ring, such as phenyl benzoate, 4-tolyl benzoate, benzyl benzoate, styryl benzoate, 2-chlorophenyl benzoate, and 4-chlorobenzyl benzoate; aromatic monocarboxylic acid esters in which an electrondonating substituent, such as a member selected from halogens, alkoxy groups and alkyl groups, may be bonded to the aromatic ring; alkoxy benzoates in which the alkyl group constituting the alkoxy group is an alkyl group usually con-taining 1 to 4 carbon atoms, preferably methyl or ethyl, and the alkyl and aryl groups in the ester are the same as described hereinabove, such as methyl anisate, ethyl anisate, i-propyl anisate, i-butyl anisate, phenyl anisate, benzyl anisate, ethyl o-methoxybenzoate, methyl p-ethoxyben-zoate, ethyl p-ethoxybenzoate, n-butyl p-ethoxybenzoate, ethyl p-alloyloxy-benzoate, phenyl p-ethoxybenzoate, methyl o-ethoxybenzoate, ethyl veratrate, and ethyl asym-guaiacolcarboxylate; alkylbenzoic acid esters in which the alkyl group attached to the aromatic ring of benzoic acid is a saturated or unsaturated hydrocarbon group usually containing 1 to 8 carbon atoms, and the alkyl and aryl groups of the ester are the same as mentioned hereinabove, such as methyl p-toluate, ethyl p-toluate, i-propyl p-toluate, n- or i-amyl toluate, allyl p-toluate, phenyl p-toluate, 2-tolyl p-toluate, ethyl o-toluate, ethyl m-toluate, methyl p-ethylbenzoate, ethyl p-ethylbenzoate, sec-butyl p-ethylbenzoate, i-propyl o-ethylbenzoate, n-butyl m-ethylbenzoate, ethyl 3,5-xylenecarboxylate, and ethyl p-styrenecarboxylate; halogen-sub-llU~3~
stituted benzoic acid esters (in which the halogen is chlorine, bromine, oriodine, preferably chlorine), such as methyl chlorobenzoate, ethyl chloro-benzoate, n-butyl chlorobenzoate, and benzyl chlorobenzoate.
Examples of the lactones (iv) are y-butyrolactone, ~-valerolactone, coumarin, and phthalide.
Of these, the benzoic acid, alkylbenzoic acid, and alkoxybenzoic acid esters are preferred. Alkyl esters with 1 to 4 carbon atoms, especially methyl or ethyl esters, of benzoic acid, o- or p-toluic acid, and p-anisic acid are especially preferred.
These esters are usually employed as such, but may be fed to the reaction system in such a form which will form an ester during the formation of the mechanically pulverized solid product derived from the compounds ~l), (2) and (3). For example, when an alkoxy-magnesium compound is used as the magnesium compound, the organic acid ester may be supplied in the form of a carboxylic acid halide.
The active hydrogen-containing compound (3) used in this invention includes, for example, aliphatic alcohols containing 1 to 12 carbon atoms, preferably 3 to 12 carbon atoms, more preferably 6 to 12 carbon atoms;
alicyclic alcohols containing 3 to 12 carbon atoms, preferably 6 to 12 carbon atoms, aromatic alcohols containing 7 to 12 carbon atoms, and phenols containing 6 to 18 carbon atoms.
Specific examples of these compounds include alcohols such as methanol, ethanolJ n- or iso-propanol, n-, iso-, sec- or tert-butanol, n-pentanol, 2-methyl butanol, hexanol, 2-ethylhexanol, ethyleneglycol mono-methyle~her, mono-n-butylether or monophenylether, cyclopentyl alcohol, cyclohexanol~ 2,6-dimethylhexanol, menthol, benzyl alcohol, phenethyl alcohol, and cumyl alcohol; and phenols such as phenol, cresol, xylenol, butyl phenol, octyl phenol, nonyl phenol, dibutyl phenol, naphthol, and cumyl phenol. Of the alcohols, alcohols containing at least 3 carbon atoms, such as n-butanol and aromatic alcohols are preferred, and monohydric t~
alkylphenols are the preferred phenols.
The organic acid ester (2) and the active hydrogen-containing com-pound (3) may be used in the form of a complex with the magnesium compound (1) .
Suitable titanium compounds used to prepare the solid titanium compound (A) in this invention are tetravalent titanium compounds of the following formula Ti~OR)gx4-g wherein R is a hydrocarbon group selected from the group consisting of alkyl groups, preferably containing 1 to 4 carbon atoms, cycloalkyl groups, pre-ferably containing 6 to 12 carbon atoms, and aryl groups, preferably contain-ing 6 to 10 carbon atoms; X is halogen; and 0 - g <- 4. Examples of such titanium compounds are titanium tetrahalides such as TiC14, TiBr4 and TiI4;
alkoxytitanium trihalides such as Ti(OCH3)C13, Ti(OC2H5)C13, Ti(O n-C4Hg)C13, Ti(OC2H5)Br3, Ti(O iso-C4Hg)Br3 and Ti(O cyclo-C6H12)C13; aryloxy titanium trihalides such as Ti(OC6H5)C13, Ti(O- ~ )C13; alkoxytitanium dihalides such as Ti(OCH3)2C12, Ti(OC2H5)2C12, Ti(O n-C4Hg)2Cl2, ( 2 5 2 2 trialkoxytitanium monohalides such as Ti(OCH3)3Cl, Ti(OC2H5)3Cl, Ti(O n-C4Hg)3Cl, and Ti(OC2H5)3Br; and tetraalkoxy titaniums such as Ti~OCH3)4, Ti(OC2H5)4, and Ti(O n-C4Hg)4. Of these, the titanium tetrahalides are pre-ferred, and titanium tetrachloride is most preferred.
The magnesium compound (1) and the titanium compound are used pre-ferably as halides. When they are used in other forms, it is necessary to include halogen in the final solid titanium catalyst component by using a suitable halogenating agent.
The solid halogen-containing titanium catalyst component (A) used in this invention is prepared by reacting the mechanically pulverized solid product derived from the compounds (1), (2) and (3), with the titanium com-pound liquid under the reaction conditions in the absence of mechanical pulveri~ation. In the copulverization process, the compounds ~1), (2) and (3) may be pulverized together. Or it is possible to copulverize any two compounds, then add the remaining compound, and further pulverize them together. The order of addition, and the method of addition (for example, whether to add a particular compound at a time or portionwise) can be properly chosen.
The copulverization may be carried out in the copresence of an in-organic or organic filler such as LiCl, CaCO3, CaCL2, SrC12, BaC12, Na2SO4, Na2C03. TiO2, NaB407, Ca3(P04)2, CaS04~ BaC03~ A12~S4)3~ B203~ A1203~ SiO
polyethylene, polypropylene or polystrene.
The mechanical copulverization is carried out using a ball mill, a vibratory mill, or impact mill or the like preferably in the substantial absence of oxygen or water.
The "mechanical copulverization", as used in this application, denotes pulverization which imparts a violent pulverizing effect to a material, and excludes such means as mere mechanical stirring.
The ratio between the magnesium compound ~1) and the organic acid ester (2) in copulverization is such that the latter is used in an amount of about 0.01 to about 10 moles, preferably about 0.01 to about 5 moles, especially preferably about 0.01 to about 1 mole, per atom of magnesium in the former. The amount of the active hydrogen-containing compound ~3), when it contains at least 3 carbon atoms, is about 0.001 to about 10 moles, preferably about 0.01 to about 1 mole, especially preferably about 0.01 to about 0.5 mole, per atom of magnesium in the magnesium compound (1). When it contains 2 or less carbon atoms, the amount is preferably about 0.001 to about 10 moles, more preferably about 0.01 to about S moles, especially pre-ferably about 0.01 to about 3 moles.
The pulverization conditions should preferably be chosen according to the types of the materials or the pulverizing apparatus used. Generally, 30 the pulverization time is about 1 hour to 10 days. The pulverization can be carried out at room temperature, and it is not especially necessary to cool or heat the pulverization system. Usually, however, temperatures of about 0 to 100C can be employed.
Where the organic acid ester or the active hydrogen-containing compound is solid, especially strong pulverization is desired. For example, when pulverization is to be performed in a vibratory ball mill, the strength of pulverization is desirably such that 20 to 40 g of materials to be treated are placed in an inner cylinder (100 mm in inside diameter) of an 800 ml.
stainless steel ~SUS 32) vibratory ball mill which ~s~nmodates therein 2.8 kg of stainless steel (SUS 32) balls each with a diameter of 15 mm, and pulverized at an impact acceleration of 7G for at least 3 hours, preferably -at least 6 hours, especially preferably at least 24 hours.
The mechanically copulverized solid product so produced from the compounds (l), (2~ and (3) is then reacted in the absence of mechanical pulverization with a titanium compound which is liquid under the reaction conditions.
The term "in the absence of mechanical pulverization", as used in the present application, means that the violent mechanical copulverizing action used at the time of forming the solid product from the compounds (1), (2) and ~3) is absent, but such an operation as mere stirring is permissible.
It is preferred that the above reaction be performed while suspend-ing the mechanically copulverized solid product in a normally liquid titanium compound such as titanium tetrachloride, or a solution of it in an inert solvent such as hexane, heptane or kerosene, or a solution of a normally solid titanium compound in the inert solvent. This procedure undergoes little effects of traces of impurities generated in the copulverizing step, and makes it possible to vary the proportions of the raw materials within a broad range.
The amount of the titanium compound varies according to the amounts of the organic acid ester (2) and the active hydrogen-containing compound (3), but is desirably such that about 0.001 to about 1000, preferably at least about 0.05, titanium atoms are used per atom of magnesium.
There is no special restriction on the temperature at which the solid copulverization product is reacted with the titanium compound in the liquid phase. Usually, it is convenient to perform the reaction at about 20 to about 200C for at least 0.5 hour. Preferably, the solid halogen-contain-ing titanium compound is isolated after the reaction, and washed well with an inert solvent before it is used for polymerization.
A typical example of the composition of the solid halogen-containing titanium catalyst component which is suitable for polymerization catalyst, although varying according to the conditions for catalyst preparation, is:
2.0-5% by weight of titanium, 16.0-25.0% by weight of magnesium, 55.0-65.0%
by weight of halogen, and 5.0-15.0% by weight of the organic acid ester.
The composition does not substantially change by washing with hexane at room temperature.
Usually, the resulting solid halogen-containing titanium compound has a surface area of at least 10 m2/g, preferably at least 50 m2/g, especially preferably at least 100 m2/g.
The organometallic compound (B) of a metal of Groups I to III of the periodic table to be used in conjunction with the titanium catalyst com-ponent ~A) is a compound ha~ing a hydrocarbon group directly bonded to a metal.
Examples of the organometallic compound (B) are alkylaluminum compounds, alkylaluminum alkoxides, alkylaluminum hydrides, alkylaluminum halides, dialkyl zincs, and dialkyl magnesiums. Of these, the organoaluminum compounds are especially suitable. Examples of the organoaluminum compounds are tri-alkyl or trialkenyl aluminums such as Al(C2H5)3, Al(CH3)3, Al(C3H7), Al(C4Hg), or Al(C12H25)3; alkylaluminum compounds in which a number of aluminum atoms are connected through an oxygen or nitrogen atom, such as (C2H5)2AlOAl~C2H5)2, (C4~9)2AlOAl(C4Hg), or (C2H5)2AlNAl(C2H5)2; dialkylaluminum hydrides such as (C2H5)2AlH or (C4Hg)2AlH; dialkylaluminum halides such as (C2H5)2AlCl, -~v~
(C2H5)2AlI, or (C4Hg)2AlCl; and dialkylaluminum alkoxides or phenoxides such as (C2H5)2Al(OC2H5) or ~C2H5)2Al(OC6H5). The trialkylaluminums are most pre-ferred.
Examples of the olefins used for polymerization are ethylene, propylene, 1-butene, and 4-methyl-1-pentene. The olefins can be homopoly-merized, random-copolymerized and block-copolymerized. In copolymerization, a poly-unsaturated compound such as a conjugated or nonconjugated diene can be used as a comonomer. Examples of the dienes are 5-ethylidene-2-norbornene, 1,7-octadiene, vinyl cyclohexene, 1,4-hexadiene, and dicyclopentadiene.
Highly stereoregular polymers can be obtained in high yields es-pecially when the process of this invention is applied to the polymerization of a-olefins having at least 3 carbon atoms, the copolymerization of these olefins with the dienes, and the copolymerization of the a-olefins having at least 3 carbon atoms with a minor amount of ethylene.
The polymerization can be carried out either in the liquid or gas-eous phase. When it is carried out in the liquid phase, an inert organic solvent such as hexane, heptane or kerosene can be used as a reaction medium, or the olefin itself can be used as the reaction medium. In the liquid-phase polymerization, it is preferred that the concentration of the solid halogen-containing titanium c~talyst component ~A) be adjusted to about 0.001 to about O.S millimoles calculated as titanium atom, and the concentration of the organometallic compound (B) to about 0.1 to about 50 millimoles, both per liter of liquid phase.
A molecular weight regulator such as hydrogen may be used during the polymerization. It is also possible to perform the polymerization in the copresence of an ether, ethylene glycol derivative such as ethylene glycol monomethylether, a ketone, an amine, a sulfur-containing compound, a nitrile, or an ester in order to control the stereoregularity of the polymer. An organic acid ester, especially an aromatic carboxylic acid ester, is preferred as such a controlling agent. The species of the aromatic carboxylic acid esters which are exemplified hereinabove with regard to the preparation of the solid halogen-containing titanium compound can be chosen for this purpose.
Especially suitable species are benzoic acid esters and ring-substituted ben-zoic acid esters, such as toluates, anisates, phthalate diesters, terephthalate diesters, hydroxybenzoates, and aminobenzoates. The lower alkyl toluates, such as methyl p-toluate or ethyl p-toluate are most preferred.
Such a controlling agent may be used in the form of an adduct with the organometallic compound (B). The effective amount of the controller is usually about 0.001 to about 10 moles, preferably about 0.01 to about 2 moles, especially preferably about 0.1 to about 1 mole, per mole of the organometallic compound (B).
The polymerization temperature for olefins is about 20 to about 200 C, preferably about 50 to about 180C. The polymerization pressure is from atmospheric pressure to about 50 kg/cm2, preferably about 2 to about 20 kg/cm .
The polymerization can be carried out by any of batchwise, semi-continuous and continuous methods. It is also possible to perform the poly-merization in two or more stages under different reaction conditions.
The following examples illustrate the present invention more specifically.
Example 1 and Comparative Examples 1 and 2 Preparation of the catalyst component (A) Commercially available magnesium chloride (20g), 6.30 g of ethyl benzoate and 14.49 g of ethanol were placed in an 800 ml. stainless steel ; ~SUS-32) ball mill cylinder having an inside diameter of 100 mm and accommo-dating therein 2.8 kg of stainless steel (S~S-32) balls with a diameter of 15 mm under an a$omosphere-of nitrogen and contacted with one another at an impact acceleration of 7G. Ten grams of the resulting solid product was suspended in 100 ml of titanium tetrachloride, and the suspension was stirred at 110 C for 2 hours. It was again suspended in 100 ml of TiC14, and reacted .
at 110C for 2 hours. The solid component was collected by filtration, and washed with refined hexane until free titanium tetrachloride was no longer detected in the wash liquid. The washed product was dried to afford a titanium-containing solid catalyst component containing 3.0% by weight of titanium and 58.5% by weight of chlorine.
Polymerization A 2-liter autoclave was purged with propylene, and charged with 750 ml of hexane thoroughly deprived of oxygen and water, 0.744 g (3.75 millimoles) of triisobutyl aluminum, 0.188 g (1.25 millimoles of methyl p-toluate, and 0.0359 g (0.0225 millimole calculated as titanium atom)of the solid catalyst component (A) prepared by the procedure of the preceding section. The autoclave was sealed, and 0.3 NQ of hydrogen was introduced.
The temperature was raised. When the temperature of the polymerization system reached 60C, propylene was introduced, and its polymerization was started at a total pressure of 8 kg/cm2. After polymerizing at 60 for 4 hours, the introduction of propylene was stopped. The inside of the autoclave was cooled to room temperature, and the resulting solid was collected by filtra-tion, and dried to afford 209.5 g of polypropylene as a white powder, which had a boiling n-heptane extraction residue of 96.1%, an apparent density of 0.36 g/ml, and a melt index (MI) of 1.70. On the other hand, concentration of the liquid phase afforded 5.8 g of a solvent-soluble polymer. A very fine polymer having a particle size of less than 105 microns was formed in an amount of 8% by weight.
For comparison, the following two runs were performed.
In the preparation of the catalyst component (A) of Example 1, anhydrous magnesium chloride was dissolved in ethanol, and then the ethanol was evaporated rapidly. The residue was dried under reduced pressure. The resulting product and a complex of ethyl benzoate and titanium tetrachloride were copulverized in the same way as in Example 1 to afford a solid product.
30 Without treating the product with titanium tetrachloride, it was directly used 1~8~4;~
in the polymerization of propylene under the same conditions as in Example 1.
(Comparative Example 1) Propylene was polymerized under the same conditions as in Example 1 except using a catalyst component (A) which was prepared by placing 20 g of the copulverized solid product and 1.9 g of titanium tetrachloride in an 800 ml pot including 100 balls with a diameter of 15 mm, and rotating the pot at 67 rpm for 100 hou~s ~Comparative Example 2~.
The results of Example 1 and Comparative Examples 1 and 2 are shown in Table 1.
Table 1 ~ield of Activity t-I.I.
poly- (boiling Melt propylene Yield of poly- n-heptane index (g/millimole propylene (g/milli- extraction of Ti) mole of Ti.atm.hr) residue) Example 1 9600 300 93.9 1.7 Comparative 2100 53 87.1 1.2 10 Example 1 Example 2 1500 47 85.2 1.3 Example 2 A titanium catalyst component containing 2.30% by weight of titanium and 61.95% by weight of chlorine was prepared by the same procedure as in Example 1 except that 7.76 g of n-butanol was used instead of the ethanol, and the reaction of the copulverized product with titanium tetrachloride was performed at 100C.
The same polymerization as in Example 1 was performed using the resulting catalyst component (A), thereby to afford 341.4 g of polypropylene as a white powder which had a boiling n-heptane extraction residue of 95.1%, an apparent density of 0.33 g~ml and a melt index of 0.8. On the other hand, concentration of the liquid phase afforded 9.6 g of a solvent-soluble polymer.
A fine powdery polymer having a particle size of less than 105 1~8~43 microns was formed in an amount of 8% by weight.
Example 3 A catalyst component (A) containing 3.35% by weight of titanium and 53.70% by weight of chlorine was prepared in the same way as in Example 2 except that the amount of the n-butanol was changed to 31.06.
The same polymerization as in Example 1 was performed except that this catalyst component (A) was used, and the polymerization pressure was changed to 10 kg/cm . Thus, 200.8 g of a white powdery polymer was obtained.
The polymer had a boiling n-heptane extraction residue of 96.5%, an apparent density of 0.37 g/ml and a melt index of 0.5. Concentration of the liquid phase afforded 4.2 g of a solvent-soluble polymer. A fine powdery polymer having a particle diameter of less than 105 microns was formed in an amount of 13% by weight.
Example 4 Preparation of catalyst component (A) Commercially available anhydrous magnesium chloride (20 g), 5.74 g of ethyl o-toluate and 2.27 g of o-cresol were placed in the same ball mill cylinder as set forth in Example 1 under an atomsphere of nitrogen, and contacted with one another at an impact acceleration of 7G for 24 hours.
Ten grams of the resulting solid product was suspended in 100 ml of titanium tetrachloride, and the mixture was stirred at 80C for 2 hours. The solid component was collected by filtration, and washed with refined hexane until free titanium tetrachloride was no longer detected in the wash liquid. The product was then dried to afford a titanium-containing solid catalyst com-ponent (A) containing 4.2% by weight of titanium and 60.0% by weight of chlorine.
Polymerization ~ 2-liter autoclave was purged with propylene, and then charged with 750 ml of hexane thoroughly deprived of oxygen and water, 0.428 g ~3.75 millimoles) of triethyl aluminum, 0.205 g (1.25 millimoles) of ethyl lU~3~3 p-toluate, and 0.026 g (0.0225 millimole calculated as titanium atom) of the solid catalyst component (A) obtained by the procedure of the previous section.
The autoclave was sealed, and 0.5 NQ of hydrogen was introduced. The tem-perature was raised, and when the temperature of the polymerization system reached 60C, propylene was introduced and its polymerization was started at a total pressure of 8 kg/cm2. After polymerization at 60C for 4 hours, the introduction of propylene was stopped, and the inside of the autoclave was cooled to room temperature. The resulting solid was collected by filtration, and dried to afford 380.4 g of polypropylene as a white powder which had a boiling n-heptan extraction residue of 95.3%, an apparent density of 0.31g/ml, and a melt index of 3.55. On the other hand~ concentration of the liquid phase afforded 12.1 g of a solvent-soluble polymer.
A fine powdery polymer having a particle size diameter of less than 105 microns was formed in an amount of 12.6% by weight. The yield of the polymer (g/Clg) was 25,000.
Example 5 Preparation of the catalyst component (A) Anhydrous magnesium chloride (20 g) was suspended in 200 ml of kerosene containing 7.5 ml of ethyl benzoate, and with stirring, they were reacted at 150C for 2 hours. The solid component was collected by filtration, washed thoroughly with hexane, and dried to afford 26.7 g of a white powdery solid which was considered to be a complex having an average composition:
MgC12 0.22 ~ -COOEt.
The resulting powdery solid (26 g) and 2.~5 g of cumyl alcohol were placed in the same ball mill cylinder as set forth in Example 1, and contacted with one another at an impact acceleration of 7G for 24 hours.
The resulting solid product was suspended in 150 ml of titanium tetrachloride, and stirred at ~0C for 2 hours. The solid component was collected by filtration, and washed with refined hexane until free titanium tetrachloride was no longer detected in the wash liquid. The resulting titanium-containing 39~43 catalyst component contained 3.2% by weight of titanium and 58.0% by weight of chlorine.
Polymerization Propylene was polymerized under the same conditions as in Example 4 using 0.034 g of the resulting solid catalyst component (A), 0.428 g of triethyl aluminum and 0.743 g of triisobutyl aluminum. As a result, 263 g of polypropylene as a white powder and 9.8 g of a solvent soluble polymer were obtained. The powdery polypropylene obtained has a boiling n-heptane extraction residue of 95.6%, an apparent density of 0.30 g/ml and a melt index of 3.86.
A fine powdery polymer having a particle diameter of less than 105 microns was formed in an amount of 12.1% by weight. The yield of the polymer (g/Cl g) was 14,000.
Comparative Example 3 A titanium catalyst component ~A) containing 3.8% by weight of titanium and 59.0% by weight of chlorine was prepared in the same way as in Example 4 except that o-cresol was not used.
Propylene was polymerized under the same conditions as in Example 4 using 0.028 g of the resulting titanium catalyst component (A). As a result, 138.5 g of a powdery solid polymer and 5.6 g of a solvent-soluble polymer were obtained. The powdery solid polymer had a boiling n-heptane extraction residue of 94.9%, and apparent density of 0.32 g/ml and a melt index of 5.08.
A fine powdery polymer having a particle diameter of less than 105 microns was formed in an amount of 25.0% by weight. The yield of the polymer ~g/Cl g) was 8,600.
Examples 6 to 8 A solid titanium catalyst component (A) was prepared in the same way as in Example 4 except that each of the active hydrogen-containing com-pounds shown in Table 2 was used in the amounts indicated instead of the o-30 cresol.
Propylene was polymerized in the same way as in Example 4 using the resulting titanium catalyst component (A) in an amount of 0.032 g ~Example 6), 0.030 g (Example 7), and 0.028 g ~Example ~), respectively.
The results are shown in Table 2.
Examples 9 to 14 Propylene was polymerized under the same conditions as in Example 4 using the same solid catalyst component (A) used in Example 4 and each of the organic acid esters indicated in Table 3 in the amounts indicated.
The results are also shown in Table 3.
39~4;~
_ h u~ O _ _ O ~ 3 ~ . . .
E3 ~ ~rl O .~ rC O ~ ~ t~ 0 ~: O ~ 3 _ h ~o $ ~ O
~o.~ O o O
P~ , _ ~ _ X ~_ O ~ ~ o . ~ t`
~t ~ ~ ~ ~: . o a~
~C ~rl ~ .
h ~ 4 E3 _ _ Q~ ~
O h ~,~ ~ ~ 0 t~
p~ ~ ~: E3 t4~ ~
~0 ~ t,o O O O
~ _ ~o a~
.r~ h ~: ~ 3 Il~ u~ 0 X h ~ ~ o o~O ~C~ O~
h O ~ '--O ~ ~ ~ ~ ~ o ~`I
O O O ~ 0 0~
~ ~:o~
. ~ h ~ ~ 0 ~0 ~3'1-~1~ ~ ~) _ au ~ ~ ~ ~
~ ~0~. O O O
C 0 _ ~ _~
o~ ~tl~
~ ~ ~ ~4 a ~s z ~ ~ ~ c ~ x t~ o . l ~ ~ ~.5 I
s ~ ~ <~c x ~ ~ ~ 0
stituted benzoic acid esters (in which the halogen is chlorine, bromine, oriodine, preferably chlorine), such as methyl chlorobenzoate, ethyl chloro-benzoate, n-butyl chlorobenzoate, and benzyl chlorobenzoate.
Examples of the lactones (iv) are y-butyrolactone, ~-valerolactone, coumarin, and phthalide.
Of these, the benzoic acid, alkylbenzoic acid, and alkoxybenzoic acid esters are preferred. Alkyl esters with 1 to 4 carbon atoms, especially methyl or ethyl esters, of benzoic acid, o- or p-toluic acid, and p-anisic acid are especially preferred.
These esters are usually employed as such, but may be fed to the reaction system in such a form which will form an ester during the formation of the mechanically pulverized solid product derived from the compounds ~l), (2) and (3). For example, when an alkoxy-magnesium compound is used as the magnesium compound, the organic acid ester may be supplied in the form of a carboxylic acid halide.
The active hydrogen-containing compound (3) used in this invention includes, for example, aliphatic alcohols containing 1 to 12 carbon atoms, preferably 3 to 12 carbon atoms, more preferably 6 to 12 carbon atoms;
alicyclic alcohols containing 3 to 12 carbon atoms, preferably 6 to 12 carbon atoms, aromatic alcohols containing 7 to 12 carbon atoms, and phenols containing 6 to 18 carbon atoms.
Specific examples of these compounds include alcohols such as methanol, ethanolJ n- or iso-propanol, n-, iso-, sec- or tert-butanol, n-pentanol, 2-methyl butanol, hexanol, 2-ethylhexanol, ethyleneglycol mono-methyle~her, mono-n-butylether or monophenylether, cyclopentyl alcohol, cyclohexanol~ 2,6-dimethylhexanol, menthol, benzyl alcohol, phenethyl alcohol, and cumyl alcohol; and phenols such as phenol, cresol, xylenol, butyl phenol, octyl phenol, nonyl phenol, dibutyl phenol, naphthol, and cumyl phenol. Of the alcohols, alcohols containing at least 3 carbon atoms, such as n-butanol and aromatic alcohols are preferred, and monohydric t~
alkylphenols are the preferred phenols.
The organic acid ester (2) and the active hydrogen-containing com-pound (3) may be used in the form of a complex with the magnesium compound (1) .
Suitable titanium compounds used to prepare the solid titanium compound (A) in this invention are tetravalent titanium compounds of the following formula Ti~OR)gx4-g wherein R is a hydrocarbon group selected from the group consisting of alkyl groups, preferably containing 1 to 4 carbon atoms, cycloalkyl groups, pre-ferably containing 6 to 12 carbon atoms, and aryl groups, preferably contain-ing 6 to 10 carbon atoms; X is halogen; and 0 - g <- 4. Examples of such titanium compounds are titanium tetrahalides such as TiC14, TiBr4 and TiI4;
alkoxytitanium trihalides such as Ti(OCH3)C13, Ti(OC2H5)C13, Ti(O n-C4Hg)C13, Ti(OC2H5)Br3, Ti(O iso-C4Hg)Br3 and Ti(O cyclo-C6H12)C13; aryloxy titanium trihalides such as Ti(OC6H5)C13, Ti(O- ~ )C13; alkoxytitanium dihalides such as Ti(OCH3)2C12, Ti(OC2H5)2C12, Ti(O n-C4Hg)2Cl2, ( 2 5 2 2 trialkoxytitanium monohalides such as Ti(OCH3)3Cl, Ti(OC2H5)3Cl, Ti(O n-C4Hg)3Cl, and Ti(OC2H5)3Br; and tetraalkoxy titaniums such as Ti~OCH3)4, Ti(OC2H5)4, and Ti(O n-C4Hg)4. Of these, the titanium tetrahalides are pre-ferred, and titanium tetrachloride is most preferred.
The magnesium compound (1) and the titanium compound are used pre-ferably as halides. When they are used in other forms, it is necessary to include halogen in the final solid titanium catalyst component by using a suitable halogenating agent.
The solid halogen-containing titanium catalyst component (A) used in this invention is prepared by reacting the mechanically pulverized solid product derived from the compounds (1), (2) and (3), with the titanium com-pound liquid under the reaction conditions in the absence of mechanical pulveri~ation. In the copulverization process, the compounds ~1), (2) and (3) may be pulverized together. Or it is possible to copulverize any two compounds, then add the remaining compound, and further pulverize them together. The order of addition, and the method of addition (for example, whether to add a particular compound at a time or portionwise) can be properly chosen.
The copulverization may be carried out in the copresence of an in-organic or organic filler such as LiCl, CaCO3, CaCL2, SrC12, BaC12, Na2SO4, Na2C03. TiO2, NaB407, Ca3(P04)2, CaS04~ BaC03~ A12~S4)3~ B203~ A1203~ SiO
polyethylene, polypropylene or polystrene.
The mechanical copulverization is carried out using a ball mill, a vibratory mill, or impact mill or the like preferably in the substantial absence of oxygen or water.
The "mechanical copulverization", as used in this application, denotes pulverization which imparts a violent pulverizing effect to a material, and excludes such means as mere mechanical stirring.
The ratio between the magnesium compound ~1) and the organic acid ester (2) in copulverization is such that the latter is used in an amount of about 0.01 to about 10 moles, preferably about 0.01 to about 5 moles, especially preferably about 0.01 to about 1 mole, per atom of magnesium in the former. The amount of the active hydrogen-containing compound ~3), when it contains at least 3 carbon atoms, is about 0.001 to about 10 moles, preferably about 0.01 to about 1 mole, especially preferably about 0.01 to about 0.5 mole, per atom of magnesium in the magnesium compound (1). When it contains 2 or less carbon atoms, the amount is preferably about 0.001 to about 10 moles, more preferably about 0.01 to about S moles, especially pre-ferably about 0.01 to about 3 moles.
The pulverization conditions should preferably be chosen according to the types of the materials or the pulverizing apparatus used. Generally, 30 the pulverization time is about 1 hour to 10 days. The pulverization can be carried out at room temperature, and it is not especially necessary to cool or heat the pulverization system. Usually, however, temperatures of about 0 to 100C can be employed.
Where the organic acid ester or the active hydrogen-containing compound is solid, especially strong pulverization is desired. For example, when pulverization is to be performed in a vibratory ball mill, the strength of pulverization is desirably such that 20 to 40 g of materials to be treated are placed in an inner cylinder (100 mm in inside diameter) of an 800 ml.
stainless steel ~SUS 32) vibratory ball mill which ~s~nmodates therein 2.8 kg of stainless steel (SUS 32) balls each with a diameter of 15 mm, and pulverized at an impact acceleration of 7G for at least 3 hours, preferably -at least 6 hours, especially preferably at least 24 hours.
The mechanically copulverized solid product so produced from the compounds (l), (2~ and (3) is then reacted in the absence of mechanical pulverization with a titanium compound which is liquid under the reaction conditions.
The term "in the absence of mechanical pulverization", as used in the present application, means that the violent mechanical copulverizing action used at the time of forming the solid product from the compounds (1), (2) and ~3) is absent, but such an operation as mere stirring is permissible.
It is preferred that the above reaction be performed while suspend-ing the mechanically copulverized solid product in a normally liquid titanium compound such as titanium tetrachloride, or a solution of it in an inert solvent such as hexane, heptane or kerosene, or a solution of a normally solid titanium compound in the inert solvent. This procedure undergoes little effects of traces of impurities generated in the copulverizing step, and makes it possible to vary the proportions of the raw materials within a broad range.
The amount of the titanium compound varies according to the amounts of the organic acid ester (2) and the active hydrogen-containing compound (3), but is desirably such that about 0.001 to about 1000, preferably at least about 0.05, titanium atoms are used per atom of magnesium.
There is no special restriction on the temperature at which the solid copulverization product is reacted with the titanium compound in the liquid phase. Usually, it is convenient to perform the reaction at about 20 to about 200C for at least 0.5 hour. Preferably, the solid halogen-contain-ing titanium compound is isolated after the reaction, and washed well with an inert solvent before it is used for polymerization.
A typical example of the composition of the solid halogen-containing titanium catalyst component which is suitable for polymerization catalyst, although varying according to the conditions for catalyst preparation, is:
2.0-5% by weight of titanium, 16.0-25.0% by weight of magnesium, 55.0-65.0%
by weight of halogen, and 5.0-15.0% by weight of the organic acid ester.
The composition does not substantially change by washing with hexane at room temperature.
Usually, the resulting solid halogen-containing titanium compound has a surface area of at least 10 m2/g, preferably at least 50 m2/g, especially preferably at least 100 m2/g.
The organometallic compound (B) of a metal of Groups I to III of the periodic table to be used in conjunction with the titanium catalyst com-ponent ~A) is a compound ha~ing a hydrocarbon group directly bonded to a metal.
Examples of the organometallic compound (B) are alkylaluminum compounds, alkylaluminum alkoxides, alkylaluminum hydrides, alkylaluminum halides, dialkyl zincs, and dialkyl magnesiums. Of these, the organoaluminum compounds are especially suitable. Examples of the organoaluminum compounds are tri-alkyl or trialkenyl aluminums such as Al(C2H5)3, Al(CH3)3, Al(C3H7), Al(C4Hg), or Al(C12H25)3; alkylaluminum compounds in which a number of aluminum atoms are connected through an oxygen or nitrogen atom, such as (C2H5)2AlOAl~C2H5)2, (C4~9)2AlOAl(C4Hg), or (C2H5)2AlNAl(C2H5)2; dialkylaluminum hydrides such as (C2H5)2AlH or (C4Hg)2AlH; dialkylaluminum halides such as (C2H5)2AlCl, -~v~
(C2H5)2AlI, or (C4Hg)2AlCl; and dialkylaluminum alkoxides or phenoxides such as (C2H5)2Al(OC2H5) or ~C2H5)2Al(OC6H5). The trialkylaluminums are most pre-ferred.
Examples of the olefins used for polymerization are ethylene, propylene, 1-butene, and 4-methyl-1-pentene. The olefins can be homopoly-merized, random-copolymerized and block-copolymerized. In copolymerization, a poly-unsaturated compound such as a conjugated or nonconjugated diene can be used as a comonomer. Examples of the dienes are 5-ethylidene-2-norbornene, 1,7-octadiene, vinyl cyclohexene, 1,4-hexadiene, and dicyclopentadiene.
Highly stereoregular polymers can be obtained in high yields es-pecially when the process of this invention is applied to the polymerization of a-olefins having at least 3 carbon atoms, the copolymerization of these olefins with the dienes, and the copolymerization of the a-olefins having at least 3 carbon atoms with a minor amount of ethylene.
The polymerization can be carried out either in the liquid or gas-eous phase. When it is carried out in the liquid phase, an inert organic solvent such as hexane, heptane or kerosene can be used as a reaction medium, or the olefin itself can be used as the reaction medium. In the liquid-phase polymerization, it is preferred that the concentration of the solid halogen-containing titanium c~talyst component ~A) be adjusted to about 0.001 to about O.S millimoles calculated as titanium atom, and the concentration of the organometallic compound (B) to about 0.1 to about 50 millimoles, both per liter of liquid phase.
A molecular weight regulator such as hydrogen may be used during the polymerization. It is also possible to perform the polymerization in the copresence of an ether, ethylene glycol derivative such as ethylene glycol monomethylether, a ketone, an amine, a sulfur-containing compound, a nitrile, or an ester in order to control the stereoregularity of the polymer. An organic acid ester, especially an aromatic carboxylic acid ester, is preferred as such a controlling agent. The species of the aromatic carboxylic acid esters which are exemplified hereinabove with regard to the preparation of the solid halogen-containing titanium compound can be chosen for this purpose.
Especially suitable species are benzoic acid esters and ring-substituted ben-zoic acid esters, such as toluates, anisates, phthalate diesters, terephthalate diesters, hydroxybenzoates, and aminobenzoates. The lower alkyl toluates, such as methyl p-toluate or ethyl p-toluate are most preferred.
Such a controlling agent may be used in the form of an adduct with the organometallic compound (B). The effective amount of the controller is usually about 0.001 to about 10 moles, preferably about 0.01 to about 2 moles, especially preferably about 0.1 to about 1 mole, per mole of the organometallic compound (B).
The polymerization temperature for olefins is about 20 to about 200 C, preferably about 50 to about 180C. The polymerization pressure is from atmospheric pressure to about 50 kg/cm2, preferably about 2 to about 20 kg/cm .
The polymerization can be carried out by any of batchwise, semi-continuous and continuous methods. It is also possible to perform the poly-merization in two or more stages under different reaction conditions.
The following examples illustrate the present invention more specifically.
Example 1 and Comparative Examples 1 and 2 Preparation of the catalyst component (A) Commercially available magnesium chloride (20g), 6.30 g of ethyl benzoate and 14.49 g of ethanol were placed in an 800 ml. stainless steel ; ~SUS-32) ball mill cylinder having an inside diameter of 100 mm and accommo-dating therein 2.8 kg of stainless steel (S~S-32) balls with a diameter of 15 mm under an a$omosphere-of nitrogen and contacted with one another at an impact acceleration of 7G. Ten grams of the resulting solid product was suspended in 100 ml of titanium tetrachloride, and the suspension was stirred at 110 C for 2 hours. It was again suspended in 100 ml of TiC14, and reacted .
at 110C for 2 hours. The solid component was collected by filtration, and washed with refined hexane until free titanium tetrachloride was no longer detected in the wash liquid. The washed product was dried to afford a titanium-containing solid catalyst component containing 3.0% by weight of titanium and 58.5% by weight of chlorine.
Polymerization A 2-liter autoclave was purged with propylene, and charged with 750 ml of hexane thoroughly deprived of oxygen and water, 0.744 g (3.75 millimoles) of triisobutyl aluminum, 0.188 g (1.25 millimoles of methyl p-toluate, and 0.0359 g (0.0225 millimole calculated as titanium atom)of the solid catalyst component (A) prepared by the procedure of the preceding section. The autoclave was sealed, and 0.3 NQ of hydrogen was introduced.
The temperature was raised. When the temperature of the polymerization system reached 60C, propylene was introduced, and its polymerization was started at a total pressure of 8 kg/cm2. After polymerizing at 60 for 4 hours, the introduction of propylene was stopped. The inside of the autoclave was cooled to room temperature, and the resulting solid was collected by filtra-tion, and dried to afford 209.5 g of polypropylene as a white powder, which had a boiling n-heptane extraction residue of 96.1%, an apparent density of 0.36 g/ml, and a melt index (MI) of 1.70. On the other hand, concentration of the liquid phase afforded 5.8 g of a solvent-soluble polymer. A very fine polymer having a particle size of less than 105 microns was formed in an amount of 8% by weight.
For comparison, the following two runs were performed.
In the preparation of the catalyst component (A) of Example 1, anhydrous magnesium chloride was dissolved in ethanol, and then the ethanol was evaporated rapidly. The residue was dried under reduced pressure. The resulting product and a complex of ethyl benzoate and titanium tetrachloride were copulverized in the same way as in Example 1 to afford a solid product.
30 Without treating the product with titanium tetrachloride, it was directly used 1~8~4;~
in the polymerization of propylene under the same conditions as in Example 1.
(Comparative Example 1) Propylene was polymerized under the same conditions as in Example 1 except using a catalyst component (A) which was prepared by placing 20 g of the copulverized solid product and 1.9 g of titanium tetrachloride in an 800 ml pot including 100 balls with a diameter of 15 mm, and rotating the pot at 67 rpm for 100 hou~s ~Comparative Example 2~.
The results of Example 1 and Comparative Examples 1 and 2 are shown in Table 1.
Table 1 ~ield of Activity t-I.I.
poly- (boiling Melt propylene Yield of poly- n-heptane index (g/millimole propylene (g/milli- extraction of Ti) mole of Ti.atm.hr) residue) Example 1 9600 300 93.9 1.7 Comparative 2100 53 87.1 1.2 10 Example 1 Example 2 1500 47 85.2 1.3 Example 2 A titanium catalyst component containing 2.30% by weight of titanium and 61.95% by weight of chlorine was prepared by the same procedure as in Example 1 except that 7.76 g of n-butanol was used instead of the ethanol, and the reaction of the copulverized product with titanium tetrachloride was performed at 100C.
The same polymerization as in Example 1 was performed using the resulting catalyst component (A), thereby to afford 341.4 g of polypropylene as a white powder which had a boiling n-heptane extraction residue of 95.1%, an apparent density of 0.33 g~ml and a melt index of 0.8. On the other hand, concentration of the liquid phase afforded 9.6 g of a solvent-soluble polymer.
A fine powdery polymer having a particle size of less than 105 1~8~43 microns was formed in an amount of 8% by weight.
Example 3 A catalyst component (A) containing 3.35% by weight of titanium and 53.70% by weight of chlorine was prepared in the same way as in Example 2 except that the amount of the n-butanol was changed to 31.06.
The same polymerization as in Example 1 was performed except that this catalyst component (A) was used, and the polymerization pressure was changed to 10 kg/cm . Thus, 200.8 g of a white powdery polymer was obtained.
The polymer had a boiling n-heptane extraction residue of 96.5%, an apparent density of 0.37 g/ml and a melt index of 0.5. Concentration of the liquid phase afforded 4.2 g of a solvent-soluble polymer. A fine powdery polymer having a particle diameter of less than 105 microns was formed in an amount of 13% by weight.
Example 4 Preparation of catalyst component (A) Commercially available anhydrous magnesium chloride (20 g), 5.74 g of ethyl o-toluate and 2.27 g of o-cresol were placed in the same ball mill cylinder as set forth in Example 1 under an atomsphere of nitrogen, and contacted with one another at an impact acceleration of 7G for 24 hours.
Ten grams of the resulting solid product was suspended in 100 ml of titanium tetrachloride, and the mixture was stirred at 80C for 2 hours. The solid component was collected by filtration, and washed with refined hexane until free titanium tetrachloride was no longer detected in the wash liquid. The product was then dried to afford a titanium-containing solid catalyst com-ponent (A) containing 4.2% by weight of titanium and 60.0% by weight of chlorine.
Polymerization ~ 2-liter autoclave was purged with propylene, and then charged with 750 ml of hexane thoroughly deprived of oxygen and water, 0.428 g ~3.75 millimoles) of triethyl aluminum, 0.205 g (1.25 millimoles) of ethyl lU~3~3 p-toluate, and 0.026 g (0.0225 millimole calculated as titanium atom) of the solid catalyst component (A) obtained by the procedure of the previous section.
The autoclave was sealed, and 0.5 NQ of hydrogen was introduced. The tem-perature was raised, and when the temperature of the polymerization system reached 60C, propylene was introduced and its polymerization was started at a total pressure of 8 kg/cm2. After polymerization at 60C for 4 hours, the introduction of propylene was stopped, and the inside of the autoclave was cooled to room temperature. The resulting solid was collected by filtration, and dried to afford 380.4 g of polypropylene as a white powder which had a boiling n-heptan extraction residue of 95.3%, an apparent density of 0.31g/ml, and a melt index of 3.55. On the other hand~ concentration of the liquid phase afforded 12.1 g of a solvent-soluble polymer.
A fine powdery polymer having a particle size diameter of less than 105 microns was formed in an amount of 12.6% by weight. The yield of the polymer (g/Clg) was 25,000.
Example 5 Preparation of the catalyst component (A) Anhydrous magnesium chloride (20 g) was suspended in 200 ml of kerosene containing 7.5 ml of ethyl benzoate, and with stirring, they were reacted at 150C for 2 hours. The solid component was collected by filtration, washed thoroughly with hexane, and dried to afford 26.7 g of a white powdery solid which was considered to be a complex having an average composition:
MgC12 0.22 ~ -COOEt.
The resulting powdery solid (26 g) and 2.~5 g of cumyl alcohol were placed in the same ball mill cylinder as set forth in Example 1, and contacted with one another at an impact acceleration of 7G for 24 hours.
The resulting solid product was suspended in 150 ml of titanium tetrachloride, and stirred at ~0C for 2 hours. The solid component was collected by filtration, and washed with refined hexane until free titanium tetrachloride was no longer detected in the wash liquid. The resulting titanium-containing 39~43 catalyst component contained 3.2% by weight of titanium and 58.0% by weight of chlorine.
Polymerization Propylene was polymerized under the same conditions as in Example 4 using 0.034 g of the resulting solid catalyst component (A), 0.428 g of triethyl aluminum and 0.743 g of triisobutyl aluminum. As a result, 263 g of polypropylene as a white powder and 9.8 g of a solvent soluble polymer were obtained. The powdery polypropylene obtained has a boiling n-heptane extraction residue of 95.6%, an apparent density of 0.30 g/ml and a melt index of 3.86.
A fine powdery polymer having a particle diameter of less than 105 microns was formed in an amount of 12.1% by weight. The yield of the polymer (g/Cl g) was 14,000.
Comparative Example 3 A titanium catalyst component ~A) containing 3.8% by weight of titanium and 59.0% by weight of chlorine was prepared in the same way as in Example 4 except that o-cresol was not used.
Propylene was polymerized under the same conditions as in Example 4 using 0.028 g of the resulting titanium catalyst component (A). As a result, 138.5 g of a powdery solid polymer and 5.6 g of a solvent-soluble polymer were obtained. The powdery solid polymer had a boiling n-heptane extraction residue of 94.9%, and apparent density of 0.32 g/ml and a melt index of 5.08.
A fine powdery polymer having a particle diameter of less than 105 microns was formed in an amount of 25.0% by weight. The yield of the polymer ~g/Cl g) was 8,600.
Examples 6 to 8 A solid titanium catalyst component (A) was prepared in the same way as in Example 4 except that each of the active hydrogen-containing com-pounds shown in Table 2 was used in the amounts indicated instead of the o-30 cresol.
Propylene was polymerized in the same way as in Example 4 using the resulting titanium catalyst component (A) in an amount of 0.032 g ~Example 6), 0.030 g (Example 7), and 0.028 g ~Example ~), respectively.
The results are shown in Table 2.
Examples 9 to 14 Propylene was polymerized under the same conditions as in Example 4 using the same solid catalyst component (A) used in Example 4 and each of the organic acid esters indicated in Table 3 in the amounts indicated.
The results are also shown in Table 3.
39~4;~
_ h u~ O _ _ O ~ 3 ~ . . .
E3 ~ ~rl O .~ rC O ~ ~ t~ 0 ~: O ~ 3 _ h ~o $ ~ O
~o.~ O o O
P~ , _ ~ _ X ~_ O ~ ~ o . ~ t`
~t ~ ~ ~ ~: . o a~
~C ~rl ~ .
h ~ 4 E3 _ _ Q~ ~
O h ~,~ ~ ~ 0 t~
p~ ~ ~: E3 t4~ ~
~0 ~ t,o O O O
~ _ ~o a~
.r~ h ~: ~ 3 Il~ u~ 0 X h ~ ~ o o~O ~C~ O~
h O ~ '--O ~ ~ ~ ~ ~ o ~`I
O O O ~ 0 0~
~ ~:o~
. ~ h ~ ~ 0 ~0 ~3'1-~1~ ~ ~) _ au ~ ~ ~ ~
~ ~0~. O O O
C 0 _ ~ _~
o~ ~tl~
~ ~ ~ ~4 a ~s z ~ ~ ~ c ~ x t~ o . l ~ ~ ~.5 I
s ~ ~ <~c x ~ ~ ~ 0
4;~
_ ~ o ~ ~, ~, o. U~
O ~ 3 ~ n ~ _~ _ ._ _~
F O O ~ 0 3 A _ ~C~ O 00 0000 Co O
o eo r~ ~ I`~D ~`D
~_ N N N N N ~
~ ~ o r_Ln ~U~ ~~D u~
~ )~ ~Dt~l ~~Iot~Il) :.
O E ~ t~ ~ d' ~ Nl~
t~
.~ ~ ~
t~ o O N O 0~ O
~1~ ~ ~ O O O O O O
~0 __ V~ I C~
_I cd'3 $-~ d-~ L~L~ L~ ~
:~ h ~ ~ .. . . . .
v~ ~ Otl~3 L"L~ n ~ ~ In o X ,~ a~ ~ o ~ o~ '~ CJ> ' h O ~_ ~ ~ ~ Du~ o~ NC~ ~ ~O
~ .~ 0 ~ ~ 0 ~ 1l~ `D _ E-~
~o ~ ~D ~ U~ ~ `D u~
~ . ~ . . .
o 3 r~ ~ ~) O `D ~D O O ~0 O O O t~ t~ 1~ . N
_ .
Lq oO o~~o oo u~
'-' ~! ~4 N 0 N N N N
~ _ _ .
~ a>
~ ~O
~D ~ ~ ~ ~ ~ G~ ~ ~ _l ~> P~ ~ ~p~ Q~P~ ~ O
.~ E~ ~ ~ ~ ~ ~ ~ O O ~ ~ ~0 ~ _1 ~d :~ ~ ,~ O ~ ~ ~ ~ ~ ~ G> ~ S
~4 ~ ~ ~ ~~ ~ ~ rC~
~ ~ I ~ I J 5 ~ ~3 ~D ~ I ~D
O ` 11~ ~:4 ~ P. U~ ,C) jl~ ~d D 11~ .D O
x ~ o~ - L~ ~ ~ ~
1~8~
Example 15 Preparation of the catalyst component (A) A catalyst component ~A) containing 4.3% by weight of titanium and 57.0% by weight of chlorine was prepared under the same conditions as in Example 4 except that a compound of the following formula Cl-Mg-0- ~
prepared in a conventional manner was used instead of the anhydrous magnesium chloride, and 2.85 g of cumyl alcohol was used instead of 2.27 g of o-cresol.
Polymerization Propylene was polymerized under the same conditions as in Example 4 except that 0.025 g of the catalyst component (A) obtained by the procedure set forth in the previous section was used. As a result, 208.5 g of poly-propylene as a white powder and 10.8 g of a solvent-soluble polymer were obtained. The powdery polymer had an extraction residue of 94.2%, an apparent density of 0.29 g/ml, and a melt index of 4.86.
The yield of the polymer ~g/Cl g) was 15,000 and the amount of a very fine powdery polymer having a particle diameter of less than 105 microns was 5.0% by weight.
~0 Example 16 Preparation of the catalyst component (A~
Commercially available anhydrous magnesium chloride (20 g), 12.4 g of a complex having an average composition TiC14-(ethyl p-toluate), and 2.85 g of cumyl alcohol were copulverized under the conditions set forth in ~xample 4, and treated with titanium tetrachloride. The resulting solid catalyst component ~A) contained 4.5% by weight of titanium and 58.0% by weight of chlorine.
Polymerization Propylene was polymerized under the same conditions as in Example 4 using 0.024 g of the titanium catalyst component (A) obtained by the procedure ... . . . .
. . .
set forth in the previous section. As a result, 300.6 g of a white powdery solid polymer and 13.1 g of a solvent-soluble polymer were obtained. The powdery solid had an extraction residue of 94.9%, an apparent density of 0.30 g/ml, and a melt index of 4.21.
The yield of the polymer (g/Cl g) was 23,000 and the amount of a very fine polymer having a particle diameter of less than 105 microns was 10.1% by weight.
Example 17 Anhydrous magnesium chloride ~10 g), 2.87 g of ethyl o-toluate, and 1.43 g of cumyl alcohol were pulverized in a vibratory mill under the same conditions as in Example 4. Ten grams of the resulting solid product was suspended in titanium tetrachloride, and stirred at 80C for 2 hours.
The solid component was collected by filtration, and washed with refined hexane until free titanium tetrachloride was no longer detected in the wash liquid, The washed product was dried to afford a titanium-containing catalyst component (A) containing 2.2% by weight of titanium and 31.0% by weight of chlorine.
Propylene was polymerized under the same conditions as in Example 4 using 0.049 g of the solid titanium catalyst component ~A) obtained by the procedure set forth above. As a result, 224.6 g of a powdery solid and 12.6 g of a solvent-soluble polymer were obtained. The powdery solid had an ~ extraction residue of 93.9%, an apparent density of 0.26 g/ml, and a melt ; index of 8.83.
The yield of the polymer (g/Cl g) was 8,800 and the amount of a very finepDl~polymer having a particle diameter of less than 105 microns was 9.5% by weight.
_ ~ o ~ ~, ~, o. U~
O ~ 3 ~ n ~ _~ _ ._ _~
F O O ~ 0 3 A _ ~C~ O 00 0000 Co O
o eo r~ ~ I`~D ~`D
~_ N N N N N ~
~ ~ o r_Ln ~U~ ~~D u~
~ )~ ~Dt~l ~~Iot~Il) :.
O E ~ t~ ~ d' ~ Nl~
t~
.~ ~ ~
t~ o O N O 0~ O
~1~ ~ ~ O O O O O O
~0 __ V~ I C~
_I cd'3 $-~ d-~ L~L~ L~ ~
:~ h ~ ~ .. . . . .
v~ ~ Otl~3 L"L~ n ~ ~ In o X ,~ a~ ~ o ~ o~ '~ CJ> ' h O ~_ ~ ~ ~ Du~ o~ NC~ ~ ~O
~ .~ 0 ~ ~ 0 ~ 1l~ `D _ E-~
~o ~ ~D ~ U~ ~ `D u~
~ . ~ . . .
o 3 r~ ~ ~) O `D ~D O O ~0 O O O t~ t~ 1~ . N
_ .
Lq oO o~~o oo u~
'-' ~! ~4 N 0 N N N N
~ _ _ .
~ a>
~ ~O
~D ~ ~ ~ ~ ~ G~ ~ ~ _l ~> P~ ~ ~p~ Q~P~ ~ O
.~ E~ ~ ~ ~ ~ ~ ~ O O ~ ~ ~0 ~ _1 ~d :~ ~ ,~ O ~ ~ ~ ~ ~ ~ G> ~ S
~4 ~ ~ ~ ~~ ~ ~ rC~
~ ~ I ~ I J 5 ~ ~3 ~D ~ I ~D
O ` 11~ ~:4 ~ P. U~ ,C) jl~ ~d D 11~ .D O
x ~ o~ - L~ ~ ~ ~
1~8~
Example 15 Preparation of the catalyst component (A) A catalyst component ~A) containing 4.3% by weight of titanium and 57.0% by weight of chlorine was prepared under the same conditions as in Example 4 except that a compound of the following formula Cl-Mg-0- ~
prepared in a conventional manner was used instead of the anhydrous magnesium chloride, and 2.85 g of cumyl alcohol was used instead of 2.27 g of o-cresol.
Polymerization Propylene was polymerized under the same conditions as in Example 4 except that 0.025 g of the catalyst component (A) obtained by the procedure set forth in the previous section was used. As a result, 208.5 g of poly-propylene as a white powder and 10.8 g of a solvent-soluble polymer were obtained. The powdery polymer had an extraction residue of 94.2%, an apparent density of 0.29 g/ml, and a melt index of 4.86.
The yield of the polymer ~g/Cl g) was 15,000 and the amount of a very fine powdery polymer having a particle diameter of less than 105 microns was 5.0% by weight.
~0 Example 16 Preparation of the catalyst component (A~
Commercially available anhydrous magnesium chloride (20 g), 12.4 g of a complex having an average composition TiC14-(ethyl p-toluate), and 2.85 g of cumyl alcohol were copulverized under the conditions set forth in ~xample 4, and treated with titanium tetrachloride. The resulting solid catalyst component ~A) contained 4.5% by weight of titanium and 58.0% by weight of chlorine.
Polymerization Propylene was polymerized under the same conditions as in Example 4 using 0.024 g of the titanium catalyst component (A) obtained by the procedure ... . . . .
. . .
set forth in the previous section. As a result, 300.6 g of a white powdery solid polymer and 13.1 g of a solvent-soluble polymer were obtained. The powdery solid had an extraction residue of 94.9%, an apparent density of 0.30 g/ml, and a melt index of 4.21.
The yield of the polymer (g/Cl g) was 23,000 and the amount of a very fine polymer having a particle diameter of less than 105 microns was 10.1% by weight.
Example 17 Anhydrous magnesium chloride ~10 g), 2.87 g of ethyl o-toluate, and 1.43 g of cumyl alcohol were pulverized in a vibratory mill under the same conditions as in Example 4. Ten grams of the resulting solid product was suspended in titanium tetrachloride, and stirred at 80C for 2 hours.
The solid component was collected by filtration, and washed with refined hexane until free titanium tetrachloride was no longer detected in the wash liquid, The washed product was dried to afford a titanium-containing catalyst component (A) containing 2.2% by weight of titanium and 31.0% by weight of chlorine.
Propylene was polymerized under the same conditions as in Example 4 using 0.049 g of the solid titanium catalyst component ~A) obtained by the procedure set forth above. As a result, 224.6 g of a powdery solid and 12.6 g of a solvent-soluble polymer were obtained. The powdery solid had an ~ extraction residue of 93.9%, an apparent density of 0.26 g/ml, and a melt ; index of 8.83.
The yield of the polymer (g/Cl g) was 8,800 and the amount of a very finepDl~polymer having a particle diameter of less than 105 microns was 9.5% by weight.
Claims (7)
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. A process for polymerizing or copolymerizing .alpha.-olefins in the presence of a catalyst composed of (A) a mechanically pulverized solid titanium-containing catalyst component and (B) an organometallic compound of a metal of Groups I to III of the periodic table, wherein said titanium-containing component is obtained by reacting halogen-containing titanium compound which is liquid under the reaction conditions and has the formula:
Ti(OR)gX4-g wherein R represents a hydrocarbon group selected from the class consisting of alkyl groups containing 1 to 4 carbon atoms, cyclo-alkyl groups containing 6 to 12 carbon atoms and aryl groups con-taining 6 to 10 carbon atoms, X represents a halogen atom, and g is 0 ? g ? 4, with a mechanically copulverized solid product in the absence of mechanical pulverization, said mechanically co-pulverized product being derived from (1) a magnesium compound of the formula:
MgX1X2 wherein X1 is a halogen atom, X2 represents a member selected from the group consisting of halogen atoms and a group OR" in which R" is a group selected from alkyl groups, cycloalkyl groups and aryl groups, (2) an organic acid ester selected from the group consisting of (i) aliphatic carboxylic aced esters con-taining 2 to 40 carbon atoms, (ii) alicyclic carboxylic acid esters containing 7 to 20 carbon atoms, (iii) aromatic carbox-ylic acid esters containing 8 to 40 carbon atoms and (iv) lactones containing 4 to 10 carbon atoms, and (3) an active hydrogen-containing compound selected from aliphatic alcohols containing 1 to 12 carbon atoms, alicyclic alcohols containing 3 to 12 carbon atoms, aromatic alcohols containing 7 to 12 carbon atoms, and phenols containing 6 to 18 carbon atoms; the molar ratio of said organic acid ester (2) to magnesium atoms in said magnesium compound (1) being from about 0.001 to 10 moles, the ratio of said active hydrogen containing compound (3) to magnesium atoms in said magnesium compound (1) being from about 0.001 to 10 moles, and the amount of said titanium com-pound being such that about 0.001 to 1000 titanium atoms are present per atom of magnesium in said magnesium compound (1).
Ti(OR)gX4-g wherein R represents a hydrocarbon group selected from the class consisting of alkyl groups containing 1 to 4 carbon atoms, cyclo-alkyl groups containing 6 to 12 carbon atoms and aryl groups con-taining 6 to 10 carbon atoms, X represents a halogen atom, and g is 0 ? g ? 4, with a mechanically copulverized solid product in the absence of mechanical pulverization, said mechanically co-pulverized product being derived from (1) a magnesium compound of the formula:
MgX1X2 wherein X1 is a halogen atom, X2 represents a member selected from the group consisting of halogen atoms and a group OR" in which R" is a group selected from alkyl groups, cycloalkyl groups and aryl groups, (2) an organic acid ester selected from the group consisting of (i) aliphatic carboxylic aced esters con-taining 2 to 40 carbon atoms, (ii) alicyclic carboxylic acid esters containing 7 to 20 carbon atoms, (iii) aromatic carbox-ylic acid esters containing 8 to 40 carbon atoms and (iv) lactones containing 4 to 10 carbon atoms, and (3) an active hydrogen-containing compound selected from aliphatic alcohols containing 1 to 12 carbon atoms, alicyclic alcohols containing 3 to 12 carbon atoms, aromatic alcohols containing 7 to 12 carbon atoms, and phenols containing 6 to 18 carbon atoms; the molar ratio of said organic acid ester (2) to magnesium atoms in said magnesium compound (1) being from about 0.001 to 10 moles, the ratio of said active hydrogen containing compound (3) to magnesium atoms in said magnesium compound (1) being from about 0.001 to 10 moles, and the amount of said titanium com-pound being such that about 0.001 to 1000 titanium atoms are present per atom of magnesium in said magnesium compound (1).
2. The process of claim 1 wherein in the formula of the magnesium compound X2 represents a group OR" in which R"
represents a member selected from alkyl groups containing 1 to 10 carbon atoms, cycloalkyl groups containing 6 to 12 carbon atoms and a phenyl group optionally substituted by an alkyl group containing 1 to 4 carbon atoms.
represents a member selected from alkyl groups containing 1 to 10 carbon atoms, cycloalkyl groups containing 6 to 12 carbon atoms and a phenyl group optionally substituted by an alkyl group containing 1 to 4 carbon atoms.
3. The process of claim 1 wherein the organic acid ester is (i) an ester formed between a member selected from saturated and unsaturated aliphatic carboxylic acids containing 1 to 18 carbon atoms and halogen-substituted products of saturated and unsaturated aliphatic carboxylic acids containing 1 to 18 carbon atoms and a member selected from saturated and unsaturated aliphatic primary alcohols containing 1 to 18 carbon atoms, saturated and unsaturated cycloaliphatic alcohols containing 3 to 8 carbon atoms, phenols containing 6 to 10 carbon atoms, saturated and unsaturated primary alcohols containing 1 to 4 carbon atoms which are bonded to an aliphatic ring with 3 to 10 carbon atoms and saturated and unsaturated primary alcohols con-taining 1 to 4 carbon atoms which are bonded to an aromatic ring with 6 to 10 carbon atoms; (ii) an ester formed between an alicyclic carboxylic acid containing 6 to 12 carbon atoms and a saturated and unsaturated aliphatic primary alcohol containing 1 to 8 carbon atoms; (iii) an ester formed between an aromatic carboxylic acid containing 7 to 18 carbon atoms and a member sel-ected from saturated and unsaturated aliphatic primary alcohol containing 1 to 18 carbon atoms, saturated and unsaturated cyclo-aliphatic alcohols containing 3 to 8 carbon atoms, phenols con-taining 6 to 10 carbon atoms, saturated and unsaturated primary alcohols containing 1 to 4 carbon atoms which are bonded to an aliphatic ring with 3 to 10 carbon atoms, and saturated and un-saturated primary alcohols containing 1 to 4 carbon atoms which are bonded to an aromatic ring with 6 to 10 carbon atoms; or (iv) a 5- or 6-membered cyclic lactone containing 4 to 10 carbon atoms.
4. The process of claim 1 wherein the organometallic com-pound (B) is an organoaluminum compound.
5. The process of claim 1 wherein the amount of the titanium-containing catalyst component (A) used is about 0.001 to about 0.5 millimole calculated as titanium atom per liter of the liquid phase in the reaction zone.
6. The process of claim 1 wherein the amount of the organo-metallic compound (B) used is about 0.1 to about 50 millimoles calculated as a metallic atom per liter of the liquid phase in the reaction zone.
7. A catalyst composition for the polymerization or co-polymerization of .alpha.-olefins, which comprises (A) a mechanically pulverized solid titanium-containing catalyst component obtained by reacting a halogen-containing titanium compound which is liquid under the reaction conditions and has the formula:
Ti(OR)gX4-g wherein R represents a hydrocarbon group selected from the class consisting of alkyl groups containing 1 to 4 carbon atoms, cyclo-alkyl groups containing 6 to 12 carbon atoms and aryl groups con-taining 6 to 10 carbon atoms, X represents a halogen atom, and g is 0 ? g ? 4, with a mechanically copulverized solid product in the absence of mechanical pulverization, said mechanically co-pulverized product being derived from (1) a magnesium compound of the formula:
MgX1X2 wherein X1 is a halogen atom, X2 represents a member selected from the group consisting of halogen atoms and a group OR" in which R" is a group selected from alkyl groups, cycloalkyl groups and aryl groups, (2) an organic acid ester selected from the group consisting of (i) aliphatic carboxylic acid esters con-taining 2 to 40 carbon atoms, (ii) alicyclic carboxylic acid esters containing 7 to 20 carbon atoms, (iii) aromatic carboxylic acid esters containing 8 to 40 carbon atoms and (iv) lactones containing 4 to 10 carbon atoms, and (3) an active hydrogen-containing compound selected from aliphatic alcohols containing 1 to 12 carbon atoms, alicyclic alcohols containing 3 to 12 car-bon atoms, aromatic alcohols containing 7 to 12 carbon atoms, and phenols containing 6 to 18 carbon atoms; the molar ratio of said organic acid ester (2) to magnesium atoms in said magnesium com-pound (1) being from about 0.001 to 10 moles, the ratio of said active hydrogen containing compound (3) to magnesium atoms in said magnesium compound (1) being from about 0.001 to 10 moles, and the amount of said titanium compound being such that about 0.001 to 1000 titanium atoms are present per atom of magnesium in said magnesium compound (1), and (B) an organometallic compound of a metal of Groups I to III of the periodic table.
Ti(OR)gX4-g wherein R represents a hydrocarbon group selected from the class consisting of alkyl groups containing 1 to 4 carbon atoms, cyclo-alkyl groups containing 6 to 12 carbon atoms and aryl groups con-taining 6 to 10 carbon atoms, X represents a halogen atom, and g is 0 ? g ? 4, with a mechanically copulverized solid product in the absence of mechanical pulverization, said mechanically co-pulverized product being derived from (1) a magnesium compound of the formula:
MgX1X2 wherein X1 is a halogen atom, X2 represents a member selected from the group consisting of halogen atoms and a group OR" in which R" is a group selected from alkyl groups, cycloalkyl groups and aryl groups, (2) an organic acid ester selected from the group consisting of (i) aliphatic carboxylic acid esters con-taining 2 to 40 carbon atoms, (ii) alicyclic carboxylic acid esters containing 7 to 20 carbon atoms, (iii) aromatic carboxylic acid esters containing 8 to 40 carbon atoms and (iv) lactones containing 4 to 10 carbon atoms, and (3) an active hydrogen-containing compound selected from aliphatic alcohols containing 1 to 12 carbon atoms, alicyclic alcohols containing 3 to 12 car-bon atoms, aromatic alcohols containing 7 to 12 carbon atoms, and phenols containing 6 to 18 carbon atoms; the molar ratio of said organic acid ester (2) to magnesium atoms in said magnesium com-pound (1) being from about 0.001 to 10 moles, the ratio of said active hydrogen containing compound (3) to magnesium atoms in said magnesium compound (1) being from about 0.001 to 10 moles, and the amount of said titanium compound being such that about 0.001 to 1000 titanium atoms are present per atom of magnesium in said magnesium compound (1), and (B) an organometallic compound of a metal of Groups I to III of the periodic table.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2117976A JPS52104593A (en) | 1976-03-01 | 1976-03-01 | Polymerization of olefins |
| JP21179/76 | 1976-03-01 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1089843A true CA1089843A (en) | 1980-11-18 |
Family
ID=12047700
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA272,787A Expired CA1089843A (en) | 1976-03-01 | 1977-02-28 | PROCESS FOR POLYMERIZING .alpha.-OLEFINS AND CATALYST THEREFOR |
Country Status (17)
| Country | Link |
|---|---|
| US (1) | US4143223A (en) |
| JP (1) | JPS52104593A (en) |
| AT (1) | AT354081B (en) |
| AU (1) | AU503354B2 (en) |
| BE (1) | BE851882A (en) |
| BR (1) | BR7701249A (en) |
| CA (1) | CA1089843A (en) |
| DE (1) | DE2708588C2 (en) |
| ES (1) | ES456371A1 (en) |
| FR (1) | FR2342995A1 (en) |
| GB (1) | GB1540323A (en) |
| IT (1) | IT1074315B (en) |
| NL (1) | NL164046C (en) |
| NO (1) | NO151368C (en) |
| PT (1) | PT66256B (en) |
| SE (1) | SE437376B (en) |
| ZA (1) | ZA771181B (en) |
Families Citing this family (90)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5948003B2 (en) * | 1976-06-02 | 1984-11-22 | 三井化学株式会社 | Method for producing polyolefins |
| IT1068112B (en) * | 1976-08-09 | 1985-03-21 | Montedison Spa | COMPONENTS OF CATALYSTS FOR THE POLYMERIZATION OF ALPHA OLEFINS AND CATALYSTS FROM THEM OBTAINED |
| JPS5339991A (en) * | 1976-09-27 | 1978-04-12 | Mitsui Petrochem Ind Ltd | Production of titanium catalyst component |
| JPS6025441B2 (en) * | 1976-09-30 | 1985-06-18 | 三井化学株式会社 | Solid catalyst components and catalysts for olefin polymerization |
| GB1569228A (en) * | 1976-12-13 | 1980-06-11 | Mitsubishi Chem Ind | Process for the polymerisation of olefins and catalyst therefor |
| JPS591407B2 (en) * | 1977-03-04 | 1984-01-12 | 三井化学株式会社 | Method for producing titanium catalyst component |
| JPS53124592A (en) * | 1977-04-07 | 1978-10-31 | Nippon Oil Co Ltd | Preparation of polyolefin |
| IT1114822B (en) * | 1977-07-04 | 1986-01-27 | Montedison Spa | COMPONENTS OF CATALYSTS FOR THE POLYMERIZATION OF ALPHA-OLEFINS |
| JPS5817521B2 (en) * | 1978-02-01 | 1983-04-07 | 三井東圧化学株式会社 | Olefin polymerization method |
| JPS54112982A (en) * | 1978-02-02 | 1979-09-04 | Sumitomo Chem Co Ltd | Polymerization of olefins |
| US4258167A (en) * | 1978-02-13 | 1981-03-24 | Nissan Chemical Industries, Ltd. | Process for producing powdery isotactic polyolefin |
| US4390677A (en) * | 1978-03-31 | 1983-06-28 | Karol Frederick J | Article molded from ethylene hydrocarbon copolymer |
| US4302566A (en) * | 1978-03-31 | 1981-11-24 | Union Carbide Corporation | Preparation of ethylene copolymers in fluid bed reactor |
| IT1113129B (en) * | 1978-04-12 | 1986-01-20 | Montedison Spa | CATALYSTS AND COMPONENTS OF CATALYSTS FOR THE POLYMERIZATION OF OLEFINS |
| JPS54158489A (en) * | 1978-06-05 | 1979-12-14 | Mitsubishi Petrochem Co Ltd | Polymerization of olefin |
| DE2830039A1 (en) * | 1978-07-07 | 1980-01-17 | Hoechst Ag | METHOD FOR PRODUCING A MIXED CATALYST |
| JPS5534238A (en) * | 1978-08-31 | 1980-03-10 | Chisso Corp | Preparation of alpha-olefin polymer |
| IT1099416B (en) * | 1978-10-23 | 1985-09-18 | Montedison Spa | COMPONENTS AND CATALYSTS FOR THE POLYMERIZATION OF OLEFINS |
| US4243552A (en) * | 1978-12-11 | 1981-01-06 | Phillips Petroleum Company | Polymerization catalyst and process |
| US4303771A (en) * | 1978-12-14 | 1981-12-01 | Union Carbide Corporation | Process for the preparation of high density ethylene polymers in fluid bed reactor |
| JPS55115416A (en) * | 1979-02-27 | 1980-09-05 | Nippon Oil Co Ltd | Manufacture of copolymer |
| ZA801724B (en) * | 1979-04-01 | 1981-03-25 | Stamicarbon | Catalytic titanium compound,process for the manufacture thereof,and process for the polymerization of lakenes-1 with application of such a titanium component |
| NL7902534A (en) * | 1979-04-01 | 1980-10-03 | Stamicarbon | PROCESS FOR POLYMERIZING OLEFINS-1. |
| JPS55133408A (en) * | 1979-04-05 | 1980-10-17 | Sumitomo Chem Co Ltd | Polymerization of olefin |
| US4366298A (en) * | 1979-07-05 | 1982-12-28 | Wacker-Chemie Gmbh | Process and heavy metal catalyst for the polymerization of α-olefins, particularly polyethylene |
| JPS5630407A (en) * | 1979-08-22 | 1981-03-27 | Sumitomo Chem Co Ltd | Preparation of highly stereoregular alpha-olefin polymer |
| DE2934689A1 (en) * | 1979-08-28 | 1981-03-12 | Hercules Inc., 19899 Wilmington, Del. | Olefin polymerisation catalyst support - obtd. from a di:alkyl magnesium, alkyl aluminium halide, electron donor and hydrocarbon solvent |
| JPS5950246B2 (en) * | 1979-10-16 | 1984-12-07 | 三井化学株式会社 | Production method of olefin copolymer for molding |
| JPS5856523B2 (en) * | 1979-12-18 | 1983-12-15 | 有限会社 東洋ストウフア−・ケミカル | Method for producing catalyst component for α-olefin polymerization |
| US4267294A (en) * | 1979-12-18 | 1981-05-12 | Hercules Incorporated | 1-Olefin polymerization catalyst |
| IT1141295B (en) * | 1980-04-22 | 1986-10-01 | Montedison Spa | COMPONENTS AND CATALYSTS FOR THE POLYMERIZATION OF ALPHAOLS |
| US4312782A (en) * | 1980-05-12 | 1982-01-26 | Stauffer Chemical Company | Titanium halide catalyst for polymerization |
| US4422957A (en) * | 1980-05-02 | 1983-12-27 | Phillips Petroleum Company | Methods of producing polyolefins using supported high efficiency polyolefin catalyst components |
| US4347158A (en) * | 1980-05-02 | 1982-08-31 | Dart Industries, Inc. | Supported high efficiency polyolefin catalyst component and methods of making and using the same |
| US4425257A (en) | 1980-05-02 | 1984-01-10 | Phillips Petroleum Company | Supported high efficiency polyolefin catalyst component and methods of making and using the same |
| US4347160A (en) * | 1980-06-27 | 1982-08-31 | Stauffer Chemical Company | Titanium halide catalyst system |
| US4325836A (en) * | 1980-07-18 | 1982-04-20 | Stauffer Chemical Company | Novel titanium halide containing catalyst |
| IT1209255B (en) * | 1980-08-13 | 1989-07-16 | Montedison Spa | CATALYSTS FOR THE POLYMERIZATION OF OLEFINE. |
| US6777508B1 (en) | 1980-08-13 | 2004-08-17 | Basell Poliolefine Italia S.P.A. | Catalysts for the polymerization of olefins |
| CA1159198A (en) * | 1980-09-29 | 1983-12-20 | Akinobu Shiga | PROCESS FOR PRODUCING HIGHLY STEREOREGULA .alpha.-OLEFIN POLYMERS |
| US4394291A (en) * | 1981-03-04 | 1983-07-19 | Phillips Petroleum Company | Polyolefin polymerization process and catalyst |
| US4347162A (en) * | 1981-03-06 | 1982-08-31 | Euteco Impianti S.P.A. | Catalyst for the polymerization of alpha-olefins |
| US4400303A (en) * | 1981-03-09 | 1983-08-23 | Phillips Petroleum Company | Catalyst for olefin polymerization |
| JPS57205406A (en) * | 1981-06-11 | 1982-12-16 | Toyo Sutoufuaa Chem:Kk | Catalytic component for alpha-olefin polymerization and homopolymerization or copolymerization of alpha-olefin |
| JPS57205407A (en) * | 1981-06-11 | 1982-12-16 | Toyo Sutoufuaa Chem:Kk | Catalytic component for alpha-olefin polymerization and homopolymerization or copolymerization of alpha-olefin |
| JPS57205408A (en) * | 1981-06-11 | 1982-12-16 | Toyo Sutoufuaa Chem:Kk | Catalytic component for alpha-olefin polymerization and homopolymerization or copolymerization of alpha-olefin |
| JPS57205409A (en) * | 1981-06-11 | 1982-12-16 | Toyo Sutoufuaa Chem:Kk | Catalytic component for alpha-olefin polymerization and homopolymerization or copolymerization of alpha-olefin |
| US4425258A (en) | 1981-06-24 | 1984-01-10 | Denki Kagaku Kogyo Kabushiki Kaisha | Catalysts for polymerization of olefins |
| AT377625B (en) * | 1981-06-29 | 1985-04-10 | Georges A Cournoyer | DEVICE FOR TEACHING MUSIC SCREENS AND INTERVALS |
| JPS5827704A (en) * | 1981-08-12 | 1983-02-18 | Sumitomo Chem Co Ltd | Preparation of polyolefin |
| US4680350A (en) * | 1981-09-10 | 1987-07-14 | Stauffer Chemical Company | Purified catalyst support |
| DE3274246D1 (en) * | 1981-12-17 | 1987-01-02 | Ici Plc | Catalyst composition, production and use |
| IT1151627B (en) * | 1982-06-10 | 1986-12-24 | Anic Spa | PROCEDURE FOR THE PREPARATION OF ETHYLENE COPOLYMERS WITH LOW DENSITY VALUE |
| US4450242A (en) * | 1982-08-09 | 1984-05-22 | Stauffer Chemical Company | Catalyst for polymerizing olefins |
| US4555496A (en) * | 1982-08-20 | 1985-11-26 | Phillips Petroleum Company | Supported polyolefin catalyst components and methods of making and using the same |
| US4419269A (en) * | 1982-12-06 | 1983-12-06 | The Dow Chemical Company | Transition metal containing catalyst |
| US4532312A (en) * | 1982-12-15 | 1985-07-30 | Phillips Petroleum Company | Polyolefin polymerization process and catalyst |
| EP0113960A1 (en) * | 1982-12-15 | 1984-07-25 | Imperial Chemical Industries Plc | Production and use of magnesium halide composition |
| US4675303A (en) * | 1983-06-27 | 1987-06-23 | Chevron Research Company | Mixed metal alkyl catalyst for olefin polymerization |
| US4857612A (en) * | 1983-06-27 | 1989-08-15 | Chevron Research Company | Process for the polymerization of alpha olefins |
| US4567154A (en) * | 1983-06-27 | 1986-01-28 | Chevron Research Company | Mixed metal alkyl catalyst for olefin polymerization |
| JPS6031504A (en) * | 1983-07-29 | 1985-02-18 | Nippon Oil Co Ltd | Production of polyolefin |
| US4503159A (en) * | 1983-08-19 | 1985-03-05 | Phillips Petroleum Company | Polyolefin polymerization process and catalyst |
| US4492768A (en) * | 1983-08-19 | 1985-01-08 | Phillips Petroleum Company | Polyolefin polymerization process and catalyst |
| US4520121A (en) * | 1983-10-28 | 1985-05-28 | Inkrott Kenneth E | Magnesium halide hydrates and polymerization catalysts prepared therefrom |
| JPS6084542U (en) * | 1983-11-16 | 1985-06-11 | 株式会社吉野工業所 | container |
| US4866022A (en) * | 1984-03-23 | 1989-09-12 | Amoco Corporation | Olefin polymerization catalyst |
| US4988656A (en) * | 1984-03-23 | 1991-01-29 | Amoco Corporation | Olefin polymerization catalyst |
| US4544716A (en) * | 1984-06-22 | 1985-10-01 | Phillips Petroleum Company | Polyolefin polymerization process and catalyst |
| US4567153A (en) * | 1984-08-13 | 1986-01-28 | Exxon Research & Engineering Co. | Polymerization catalyst comprising copulverized solid magnesium compound and solid halide of scandium |
| JPH0231042Y2 (en) * | 1985-02-13 | 1990-08-22 | ||
| JPH0228815Y2 (en) * | 1985-04-04 | 1990-08-02 | ||
| JPH0355368Y2 (en) * | 1985-05-31 | 1991-12-10 | ||
| US4680351A (en) * | 1985-09-06 | 1987-07-14 | Phillips Petroleum Company | Supported polyolefin catalyst components and methods of making and using same |
| US4829038A (en) * | 1986-06-17 | 1989-05-09 | Amoco Corporation | Alpha-olefin polymerization catalyst system including an advantageous modifier component |
| US4948770A (en) * | 1987-06-29 | 1990-08-14 | Shell Oil Company | Method for crystallizing magnesium chloride and method for using in a catalyst composition |
| DE3823934C2 (en) * | 1987-07-31 | 2002-01-03 | Petroleo Brasileiro Sa | Process for producing an ethylene polymerization catalyst and ethylene polymerization process |
| US5354820A (en) * | 1987-12-07 | 1994-10-11 | Idemitsu Petrochemical Company Limited | Process for the preparation of olefin polymer |
| USH860H (en) | 1989-01-26 | 1990-12-04 | Shell Oil Company | Method for polymerizing alpha olefins |
| US5206315A (en) * | 1989-04-10 | 1993-04-27 | Phillips Petroleum Company | Process for polymerizing 1-olefins and catalyst therefor |
| KR100341040B1 (en) | 1994-08-18 | 2002-11-23 | 칫소가부시키가이샤 | High Rigidity Propylene-Ethylene Block Copolymer Composition and Its Manufacturing Method |
| JP3355864B2 (en) * | 1995-04-24 | 2002-12-09 | チッソ株式会社 | Continuous production of high-rigidity propylene / ethylene block copolymer |
| JP4666426B2 (en) * | 2000-09-29 | 2011-04-06 | 東邦チタニウム株式会社 | Solid catalyst components and catalysts for olefin polymerization |
| WO2001090200A1 (en) * | 2000-05-24 | 2001-11-29 | Toho Titanium Co., Ltd. | Solid catalyst component for olefin polymerization and catalyst |
| US20030069372A1 (en) * | 2001-10-09 | 2003-04-10 | Formosa Plastics Corporation, U.S.A. | Olefin polymerization catalyst and process for preparing polyolefins with said catalyst |
| US7151073B2 (en) * | 2004-01-16 | 2006-12-19 | Exxonmobil Chemical Patents Inc. | Mesoporous catalyst support, a catalyst system, and method of making and using same for olefin polymerization |
| EP2168988A4 (en) * | 2007-07-13 | 2011-01-26 | Mitsui Chemicals Inc | Super high molecular weight polyolefin fine particle, method for producing the same and molded body of the same |
| US9562119B2 (en) * | 2010-05-25 | 2017-02-07 | W. R. Grace & Co.-Conn. | Ethylene polymerization catalysts |
| US11162050B2 (en) | 2016-12-27 | 2021-11-02 | Mitsui Chemicals, Inc. | Lubricating oil composition, viscosity modifier for lubricating oil, and additive composition for lubricating oil |
| US11873462B2 (en) | 2019-08-29 | 2024-01-16 | Mitsui Chemicals, Inc. | Lubricating oil composition |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA920299A (en) * | 1968-08-01 | 1973-01-30 | Mitsui Petrochemical Industries | Process for the polymerization and/or copolymerization of olefins with use of ziegler-type catalytsts supported on carrier |
| NL160286C (en) | 1971-06-25 | |||
| GB1492618A (en) * | 1974-02-01 | 1977-11-23 | Mitsui Petrochemical Ind | Process for preparing highly stereoregular polyolefins and catalyst used therefor |
| US4076924A (en) * | 1974-09-03 | 1978-02-28 | Mitsui Petrochemical Industries Ltd. | Process for polymerization or copolymerizing olefins containing at least 3 carbon atoms |
| JPS565404B2 (en) * | 1975-02-14 | 1981-02-04 | ||
| US4069169A (en) * | 1975-11-24 | 1978-01-17 | Mitsui Petrochemical Industries Ltd. | Process for preparation of catalyst component supported on high performance carrier |
-
1976
- 1976-03-01 JP JP2117976A patent/JPS52104593A/en active Granted
-
1977
- 1977-02-28 ES ES456371A patent/ES456371A1/en not_active Expired
- 1977-02-28 BE BE175305A patent/BE851882A/en not_active IP Right Cessation
- 1977-02-28 CA CA272,787A patent/CA1089843A/en not_active Expired
- 1977-02-28 ZA ZA00771181A patent/ZA771181B/en unknown
- 1977-02-28 FR FR7705801A patent/FR2342995A1/en active Granted
- 1977-02-28 NO NO770681A patent/NO151368C/en unknown
- 1977-02-28 AT AT132277A patent/AT354081B/en not_active IP Right Cessation
- 1977-02-28 DE DE2708588A patent/DE2708588C2/en not_active Expired
- 1977-02-28 IT IT20761/77A patent/IT1074315B/en active
- 1977-02-28 AU AU22762/77A patent/AU503354B2/en not_active Expired
- 1977-02-28 GB GB8344/77A patent/GB1540323A/en not_active Expired
- 1977-03-01 NL NL7702174.A patent/NL164046C/en not_active IP Right Cessation
- 1977-03-01 BR BR7701249A patent/BR7701249A/en unknown
- 1977-03-01 SE SE7702271A patent/SE437376B/en not_active IP Right Cessation
- 1977-03-01 US US05/773,266 patent/US4143223A/en not_active Expired - Lifetime
- 1977-03-01 PT PT66256A patent/PT66256B/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| ES456371A1 (en) | 1978-02-16 |
| BE851882A (en) | 1977-08-29 |
| ATA132277A (en) | 1979-05-15 |
| NO151368C (en) | 1985-03-27 |
| PT66256A (en) | 1977-04-01 |
| JPS52104593A (en) | 1977-09-02 |
| NL164046C (en) | 1980-11-17 |
| GB1540323A (en) | 1979-02-07 |
| NO151368B (en) | 1984-12-17 |
| US4143223A (en) | 1979-03-06 |
| FR2342995A1 (en) | 1977-09-30 |
| DE2708588A1 (en) | 1977-09-08 |
| JPS5645404B2 (en) | 1981-10-26 |
| BR7701249A (en) | 1977-10-18 |
| NL164046B (en) | 1980-06-16 |
| IT1074315B (en) | 1985-04-20 |
| SE7702271L (en) | 1977-09-02 |
| FR2342995B1 (en) | 1978-10-20 |
| NL7702174A (en) | 1977-09-05 |
| AU2276277A (en) | 1978-09-07 |
| AU503354B2 (en) | 1979-08-30 |
| DE2708588C2 (en) | 1982-07-01 |
| ZA771181B (en) | 1978-01-25 |
| NO770681L (en) | 1977-09-02 |
| PT66256B (en) | 1978-08-07 |
| AT354081B (en) | 1979-12-27 |
| SE437376B (en) | 1985-02-25 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CA1089843A (en) | PROCESS FOR POLYMERIZING .alpha.-OLEFINS AND CATALYST THEREFOR | |
| US4232139A (en) | Process for producing polymers or copolymers of olefins containing at least 3 carbon atoms | |
| US4250285A (en) | Process for polymerizing olefins and catalysts therefor | |
| US4069169A (en) | Process for preparation of catalyst component supported on high performance carrier | |
| CA1085996A (en) | PROCESS FOR PREPARING .alpha.-OLEFIN POLYMERS OR COPOLYMERS | |
| US5583188A (en) | Process for producing an olefin polymer or copolymer and catalyst composition therefor | |
| CA1082846A (en) | Process for producing polymers or copolymers of olefins with at least three carbon atoms | |
| CA1187865A (en) | Process for producing olefin polymers or copolymers and catalyst components used therefor | |
| CA2011188C (en) | Process for polymerizing olefins and catalyst for polymerizing olefins | |
| US4742139A (en) | Process for producing olefin polymers or copolymers | |
| CA1119155A (en) | Process for preparing olefin polymers or copolymers, and catalyst for use in said process | |
| JPH0735410B2 (en) | Catalyst for stereoregular polymerization of olefins | |
| JPS58448B2 (en) | Method for manufacturing polyolefin | |
| JPH0655780B2 (en) | Olefin polymerization catalyst component | |
| JPH072775B2 (en) | Method for producing catalyst component for olefin polymerization | |
| US4221894A (en) | Process for polymerizing α-olefins containing at least 3 carbon atoms and catalyst therefor | |
| CA1115447A (en) | Process for preparing olefin polymers or copolymers | |
| EP0086645B1 (en) | Catalyst composition and process for polymerizing olefins | |
| EP0015099B1 (en) | Catalyst and process for producing olefin polymers or copolymers | |
| CA1158633A (en) | Titanium halide catalyst for polymerization | |
| EP0145368B1 (en) | Process for producing propylene block copolymers | |
| EP0376145B1 (en) | Method for producing a stereoregular polyolefin | |
| CA1289545C (en) | Catalyst component for polymerization of olefin | |
| JPH072777B2 (en) | Olefin polymerization catalyst component | |
| US3764591A (en) | Process for polymerization of {60 olefin |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| MKEX | Expiry |