CA1092295A - Process for producing stereoregular polymers or copolymers of olefins - Google Patents
Process for producing stereoregular polymers or copolymers of olefinsInfo
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- CA1092295A CA1092295A CA287,481A CA287481A CA1092295A CA 1092295 A CA1092295 A CA 1092295A CA 287481 A CA287481 A CA 287481A CA 1092295 A CA1092295 A CA 1092295A
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- 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
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- Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
Abstract
Abstract of the Disclosure The invention is a process for producing in high yield a highly stereoregular polymer or copolymer of an olefin containing at least 3 carbon atoms. Polymerization is carried out in the presence of a catalyst composed of (A) a magnesium-containing solid titanium catalyst component and (B) an organometallic compound of a metal of Groups I to III of the periodic table;
characterized in that the solid titanium catalyst component (A) is a composi-tion formed by contacting (I) a mechanically co-pulverized product of (i) a halogen-containing magnesium organo-aromatic compound of the formula Mg(OR)nx2-n wherein R represents an aryl or aralkyl group and n is a positive number of 0 < n < 2 and (ii) an electron donor, with (II) a titanium compound in the liquid phase without mechanical pulverization.
characterized in that the solid titanium catalyst component (A) is a composi-tion formed by contacting (I) a mechanically co-pulverized product of (i) a halogen-containing magnesium organo-aromatic compound of the formula Mg(OR)nx2-n wherein R represents an aryl or aralkyl group and n is a positive number of 0 < n < 2 and (ii) an electron donor, with (II) a titanium compound in the liquid phase without mechanical pulverization.
Description
10~ ?S
Ihis invention relates to a process for producing a highly stereoregular poly~er or copolymer of an olefin containing at least 3 carbon stoms. ~pecifically, the invention relates to an improved process for producing a highly stereoregular polymer or copolymer of an olefin containing at least 3 carbon atoms in high yieldsO
More specifically, this invention relates to a process for producing a polymer or copolymer of an olefin containing at least 3 carbon atoms, which comprises poly-merizing or copolymerizing at least one olefin containing at least 3 carbon atoms, or copolymerizing the olefin with up to 10 mole% of ethylene and/or a diolefin, in the presence of a catalyst composed of (A) a magnesium-contain- - -ing solid titanium catalyst component and (B) an organo-metallic compound of a metal of Groups I to III of the periodic table; characterized in that the solid titanium catalyst component (A) is a composition formed by contact-ing (I) a mechanically co-pulverized product of (i) a halogen-containing magnesium organo-aromatic compound of the formula Mg(OR)nX~ n wherein R is an aryl group or aralkyl -group and n is a positive number of 0~ n C2 and (ii) an electron doner with (II) a titanium compound in the liquid phase without mechanical pulverizationO
Many prior suggestions are known for polymeri~-iDg or copolymerizing olefins in the presence of a catalyst composed of a magnesium-containing solid titanium catalyst component and an organometallic compound of a metal of Groups I to III of the periodic table. In many of these suggestions, a magnesium-containing solid titanium compound - , . . .
10~ZZ95 obtained by chemically depositing a titanium cor~polmd on a halogen compound of magnesium such as a magnesium dihalide, magnesium hydroxychloride, or a ma~nesium alkoxy-halide is utilized as a catalyst componen-t~ It is also known that halogen-free magnesium compounds can be converted to feasible magnesium-containing solid titanium compounds by using suitable halogenating agents or halogen-contain-ing titanium compounds during the catalyst-forming reactionG
It has been difficult however to provide a catal~st which is easy to produce, has a good reproducibility of catalytic activity and exhibits satisfactory stereoregu-larity and activity in the polymerization or copolymeriza-tion of olefins containing at least 3 carbon atoms while avoiding the formation of a very fine powdery product which causes various troubles such as the blockage of pipes at the time of transporting a slurry containing the resulting polymer or copolymer, the difficulty of separating the polymer -:.
or copolymer, or the clogging of machine components.
As one prior suggestion, Japanese Laid-Open Patent Publication NoO 16986/73 (laid open on March 3, 1973) shows that a titanium catalyst component in which either the carrier or the titanium catal~st component has a surface area of more than 3 m2/g, or which contains an amorphous .
magnesium dihalide can be utilized in the high stereo-regular polymerization of propylene, etcO when used together with an organoaluminum compound and an organic acid ester Ihis Publication neither discloses nor suggests the method of copulverizing a magnesium compound and an electron donor and contacting the pulverized product with a titanium 3 ~ ~.
., . "- . . .
compound in the liquid phase. As will be shown by Comparati~e Exanple 2 to be given hereinbelow, the effect of the present invention cannot be achieYed if the catalyst component i8 prep~red by copulverizing the magnesium compound, the electron donor and the titanium compound together in accordance with the method recommended by the above prior Publication.
Another sugge~tion is disclosed in Japanese Patent Application ~o.
42137/72 (published October 24, 1972~ and Japanese Laid-Open Patent Publica-tion No. 8395/72 (laid open on May 2, 1972; published as Japanese Patent Publication ~o. 30118/76 on Ausust 30, 1976). In these suggestions, an or-ganic acid ester, which is a preferable electron donor in the present invention, i8 not used in forming a magnesium-containing solid titanium catalyst conpon-ent. Polymerization of an olefin containing at least 3 carbon atoms such as propylene using the catalyst~ suggested in these Japanese patents cannot afford a highly stereoregular polymer. This can be seen from the fact th~t these specifications show only the polymerization of ethylenel and is more ; apparent from the results of Comparative Example 1 given hereinbelow.
Japanese Laid-Open Patent Publication No. 126590/75 (laid open on October 4, 1975) discloses that in the preparation of a magnesium~containing solid titanium catalyst component, the solid to be contacted with a titanium B
109ZZ!95 tetrahalide in the liquid or gaseous phase is prepared ~y mechanical pulverizationO ~owever~ this Publication fails to disclose the use of magnesium compounds specified in the present inventionO
As additional prior suggestions, Japanese Laid-Cpen Patent Publication NoO 108385/75 (laid open on August 26, 1975) and Japanese ~aid-Open Patent Publication ~oO
20297/75 (laid open on February 189 1976) suggest the use of a reaction product consisting essentially of a magnesium halide, a silicon compound, an organic carboxylic acid -ester and a titanium compound as a magnesium-conta; n; ng solid titanium catalyst componentO In these suggestions, it is desirable to use a copulverizing means so as to form a satisfactory solid titanium catalyst component~ A . . .
satisfactory titanium catalyst component in these suggestions is obtained by using a magnesium dihalide, and these prior Publications do not disclose magnesium compounds specified in the present inventionO It is further noted that the present invention can achieve sufficient effects without using a silicon compound which is an essential ingredient in the above suggestionsO
The present inventors worked extensively in order to provide an improved process for preparing a polymer or copolymer of an olefin containing at least 3 carbon atoms which can overcome the disadvantages associated with the conventional techniquesO As a result, they found that the . ~:
use of a mechanically co-pulverized product of (i) an .. :
organo-aromatic compound containing a halogen and aryloxy or aralkyloxy moiety which is expressed by the above-given . .
10~22~5 formula Mg(OR)n ~ n and (ii) an electron donor can afford a highly stereoregular polymer or copolymer of an olefin containing at least 3 carbon atoms in high yields while inhibiting the formation of a very fine powdery product~
It was also found that the number of catalyst-forming components can be reduced, the means for preparing the catalyst is simple~ and the catalyst has a good repro-ducibility of quality and can afford a polymer or copolymer of an olefin containing at least 3 carbon atoms with com-mercial advantage~ Furthermore, as is shown in Comparative -Example 2 to be given hereinbelow~ it is necessary that the reaction of ~I) the mechanically co-pulverized product of (i) and (ii) with ~II) the titanium compound in the liquid phase by contacting should be performed without ` 15 mechanical pulverizationO It has been found that the improvement attained by this invention will be substantially lost if this contacting is carried out under mechanically pulverizing conditions~
It is an object of this invention to provide a process for producing a highly stereoregular polymer or ; copolymer of an olefin containing at least 3 carbon atoms in high ~ields and with commercial advantages~
Ihe above and other objects and advantages of the : inventio~ will become more apparent from the following de-scription. :
~he magnesium-containing solid titanium catalyst component used in this invention is a solid titanium com-position which is obtained by contacting (I) a mechanically copulverized product of (i) a halogen-containing magnesium - 6 - :~
~:. :
~ .
~ ' .' : ~', , :.
lO9Z2~S
organo-aromatic co~npound of the formula Mg(OR)nY~_n wherein R represents ~n aryl or aralk-yl group and n is ~ pcsitive number of Ocn~2 and (ii) an electron donor~ preferably an organic acid ester and/or ether9 with (II3 a titanium compound in the liquid phase without mechanical pulveriza-tion~
The term "mechanical pulverization" or '!mechanical copulverization~, as used herein, means a mechanical - --pulverizing operation by which a vigorous mechanical pulver-izing action typified by pulverization in a ball mill, vibratory mill or impact mill is exerted in contacting the compounds for forming the catalyst component (A)o An ordinary stirring operation for ensuring good contact is not included within the definition of mechanical pulverization or mechanical copulverizationO
The halogen-containing magnesium organo-aromatic compound (i) used to form the solid titanium catalyst com ponent (A) which forms the catalyst used in this inve~tion contains halogen, magnesium and an aromatic hydrocarbon ~ . .
moiety belonging to an aryl group or aralkyl group represented by R in the above-given formulaO A solid titanium componet . .:
prepared by using a compound of the above formula in which R is an aliphatic hydrocarbon moiety gives a catalyst of inferior activity, and does not serve to achieve the improve~
ments intended by the present inventionO
Examples of preferred species of R in the halogen-containing magnesium organo-aromatic compound of the formula ~ :
Mg(0~ ~ n are a phenyl group which is optionally substi-tuted by a lower alkyl group containing 1 to 4 carbon atoms9 .,; : . , . , , : . , lOg~Z95 a lower alkoxy group containing 1 to 4 carbon atoms or a halogen atom such as chlorine, bromine or iodine, and phenyl lower (Cl-C4) alkyl groups subs-tituted by ~ lower alkyl group containing 1 to 4 carbon atoms, a lower alkoxy group containing 1 to 4 carbon atoms or a halogen atomO
Especially preferred compounds are those of the above formula in which X is chlorine and n is 1 and R is lower alkyl-~ubstituted phenyl or naphthylO
~lUS, according to one preferred embodiment of this invention, the compound of the formula Mg(OR~X2 n is one in which R is a moiety selected from the group con-sisting of phenylg naphthyl~ lower alkyl-substituted phenyl, lower alkyl-substituted naphthyl, lower alkoxy-substituted phenylg lower alkyl-substituted naphthyl, lower alkoxy-substituted phenyl, lower alkoxy-substituted naphthyl, halogen-substituted phenyl, halogen-substituted naphthyl, hydroxy-substituted phenyl, amino-substituted phenyl, phenyl lower alkyl, lower alkyl-substituted phenyl lower alkyl, lower alkoxy-substituted phenyl lower alkyl and halogen-substituted phenyl lower alkylO Specific examples ~ ~-of such compounds are shown below (in the formulae, n is - -0~ nC 2)o Arykoxy-containing magnesium compounds such as Mg(OC6H5) X2 , Mg(C6H4-CH~)nX2_n, Mg(OC6H4 C2 5)n 2-n Mg(OC6H4-C3H7)nX2_n, Mg(OC6H4-C4 ~ )nX2-n' Mg( C6H4 C8H17)nX2_n' Mg(OC6H4-C9H19)nX2 Mg~ 6 3 (CH3)2)nX2-n~ Mg(oc6H3-(cly3)(c2H5) ~ X2 M~t 6I3 (C2H5)2~nX2_n~ Mg(oc6H2-(cH3)3)nx2 9 .
Mg 6 2 (CH3)2(C3H7))nX2_n~ Mg(0C6H2-(CH3)2(C4H9)) X2 9 M~;(OC6H4C~ )nX2_n~ Mg(Oc6H40cH3)nx2_ns Mg(C10~7)nX2-n' -- 8 -- . .
109~95 Mg(ClOH6~CrI3)nX2_ns ~g~(~loH60C 3)nX2-n Mg(OCloH6C~ )nX2_nand, Mg(OC6H40H)nX~_n; aralkoxyloxy-contain.
ing magnesium compounds such as Mg(OC~-C6n5)n ~ n~
Mg(C2n4~C6H5)nX2-n~ Mg(C3H6-(~6H5)nX2_n, Mg(OC4H~-C6iI5)nX2_n~
Mg(OC ~-C6H4-CH3)nX2_n 9 Mg(OC ~C6H4-C3 ~ )nX2_n, 3 6 6 4 3 ~ )nX2-n~ and Mg(oc3H6-c6H4-c6H5)nx2 n.
~he compound of formula Mg(OR)nX2 n used in the process of this invention may be a single compound or a mixture of two or more compoundsO ~here is no particular restriction on the method of producing a compound of formula Mg(OR)nX2 n' and any known method can be usedO
For example, it can be prepared by reacting a Grignard compound of the formula R"MgX in which R" represents an alkyl group or aryl group, and X is a halogen atom with ::
a compound containing in the molecule a moiety or bond ~ :
selected from the group consisting of a hydroxyl group, a carbonyl group, a carboxyl group, an ester bond and an ether bond, such as phenol, cresol, 2,6-dimethyl phenol, aceto-phenone, benzophenone, benzoic acid, benzaldehyde, methyl -.
benzoatel ethyl b~nzoate, benzoic acid amide, benzoic acid :~
chloride, diphenyl ether, benzyl alcohol~ ethyl toluate, phthalic anhydride, naphthol and p-methyl benzyl chlorideO
Or it can be produced by reacting the aforesaid Grignard reagent with an aliphatic alcohol to afford a compound of ~- -the formula Mg(OR"')nX2_n in which R"' represents an alkyl group containing 1 to 8 carbon atoms, X is a halogen atom~
and n is O' n< 2, and subjecting the resulting compound to an exchange reaction with an aryloxy-containing metal compound such as A~(OC6Hs)3, Ca(OC~Hs)2 or S ( 2 5 3 6 5 _ g _ lOg~Z95 an alkoxy-containing metal cor~pound containing an aromatic ring such as ~1(0C~ 0C6H5)3 or Si(C~H5)3(0C ~-C6~ ), a phenol or aro~atic alcohol such as phenol, cIesol~ 2~6-dimethyl phenol, ~-phenyl ethy] alcohol OI naphtholO
~he compound of the formula M~(OR)n ~ n can be obtained by reacting a compound of formula Mg ~ wherein X
is an defined above with the compound Mg(0R)2o In the present invention, one or more of electrol donors (ii) can be used to form (I) the mechanically co-pulverized product of (i) and (ii)o Preferably, such electron donors are those which do not contain active ~.
hydrogenO Examples are organic acid esters, ketones, ethers, acid halides N,N-disubstituted amides, tertiary amines, and ; nitriles~ 0f these, the organic acid esters and ethers are preferredO ~:
Examples of the organic acid ester as electron donor (ii) used to form the solid titanium catalyst component .
constituting the catalyst used in this invention are aliphatic acid esters (ii-a), alicyclic acid esters (ii-b), and aromatic acid esters (ii-c)~ .
Examples of the aliphatic esters (ii-a) are esters formed between carboxylic acids or halogen-substitution products selected fr~m the group consisting of saturated :
or unsaturated aliphatic carbox~lic acids containing l to 18 carbon atoms, preferably l to 8 carbon atoms, more preferably l to 4 carbon atoms, and their halogen-substitu- :
tion products, and alcohols or phenols selected from the group consisting of saturated or unsaturated aliphatic -- 10 -- ,, . . . . .. . .... ..... .. ...
primary alcohols containing 1 to 18 carbon atozns, preferasl7 1 to 8 carbon atoms, more preferab]y 1 to 4 carbon atoms, saturated or unsaturated alicyclic alcohols cont~ining 3 to 8 carbon atoms, preferably 5 to 6 carbon atoms~ phenols containing 6 to 10 carbon atom~ preferably 6 to ~ carbon atoms, and Cl-C4 saturated or unsaturated aliphatic primar~
`: alcohols bonded to the ring carbon atom of a C3-C10 aliphatic or aromatic ring; and lactones containing 3 to 10 carbon atomsO
~pecific examples of the aliphatic esters (ii-a) . :
10 include primary alkyl esters of saturated fatty acids such ~ --as methyl formate~ ethyl acetate~ n-amyl acetate~ 2-ethyl- .
` hexyl acetate 9 n-butyl formate, ethyl butyrate or ethyl : valerate; alkenyl esters of sat-urated fatty acids such as ~ vinyl acetate and allyl acetate, primary alkyl esters of :.
; 15 unsaturated fatty acids such as methyl acrylate, methyl .~
methacrylate or n-butyl crotonate; alkyl esters of halogenated `
; aliphatic monocarboxylic acids such as methyl chloroacetate or ethyl dichloroacetate; and lactones such as propiolactone, ~:~
~-butyrolactone or 6-valerolactone~
Examples of the alicyclic esters (ii-b) are esters formed between alicyclic carboxylic acids containing - ~-6 to 12 carbon atoms, preferably 6 to 8 carbon atoms, and saturated or unsaturated aliphatic primary alcohols contain-ing 1 to 8 carbon atoms, preferably 1 to 4, carbon atoms.
Specific examples include methyl cyclohexanecar.boxylate, ethyl cyclohexanecarboxylate, methyl methylcyclohexanecar-boxylate, and ethyl methylcyclohexanecarboxylateO
Examples of the aromatic esters (ii-c) are esters formed bet~een aromatic carboxylic acids containing ~- ' ' ,, , ' '' '. , ' .
109Z2g5 7 -to 18 carbon atorns~ preferably 7 to 12 carbon ato-~s, and alcohols or phenols selected ~rom the group consistin~ of saturated or unsaturated aliphatic primary alcohols contain-ing 1 to 18 carbon atoms~ preferably 1 to 8 carbon atoms~
more preferably 1 to 4 carbon atoms, saturated or unsatu-rated alicyclic alcohols containing 3 to 8 carbon atoms~
preferably 3 to 6 carbon atoms~ phenol containing 6 to 10 carbon atoms, preferably 6 to 8 carbon atoms and Cl-C4 saturated or unsaturated aliphatic primary alcohols bonded to the ring carbon atom of a C3-C10 aliphatic or aromatic ring; and aromatic lactones containing 8 to 12 carbon atomsO ~:
Specific examples of the aromatic ester (ii-c) are alkyl or alkenyl esters, preferably Cl-C8, more prefer-ably Cl-C4~ alkyl esters or C2-C8, more preferably C2-C4, alkenyl esters, of oenzoic acid, such as methyl benzoate, ethyl benzoate, n- and i-propyl benzoate, n-, i-, sec-, and tert-butyl benzoates, n- and i-amyl benzoates, n-hexyl benzoate, n-octyl benzoate, 2-ethylhexyl benzoate, vin~l -benzoate, and allyl benzoate; cycloalkyl or cycloalkenyl -esters of benzoic acid, preferably C3-C8, more preferably C5-C8, cycloalkyl or cycloalkenyl esters of benzoic acid such as cyclopentyl benzoate, cyclohexyl bonzoate or c~clo- : -hexenyl benzoate; aryl or aralkyl esters, preferably C6-C10, -more preferably C6-C8, aryl or aralkyl esters optionally ;
containing a substituent such as a halogen arom atom or a Cl-C4 lower alkyl group of benzoic acid such as phenyl ~ .
benzoate, 4-tolyl benzoate, benzyl benzoate, styryl benzoate,
Ihis invention relates to a process for producing a highly stereoregular poly~er or copolymer of an olefin containing at least 3 carbon stoms. ~pecifically, the invention relates to an improved process for producing a highly stereoregular polymer or copolymer of an olefin containing at least 3 carbon atoms in high yieldsO
More specifically, this invention relates to a process for producing a polymer or copolymer of an olefin containing at least 3 carbon atoms, which comprises poly-merizing or copolymerizing at least one olefin containing at least 3 carbon atoms, or copolymerizing the olefin with up to 10 mole% of ethylene and/or a diolefin, in the presence of a catalyst composed of (A) a magnesium-contain- - -ing solid titanium catalyst component and (B) an organo-metallic compound of a metal of Groups I to III of the periodic table; characterized in that the solid titanium catalyst component (A) is a composition formed by contact-ing (I) a mechanically co-pulverized product of (i) a halogen-containing magnesium organo-aromatic compound of the formula Mg(OR)nX~ n wherein R is an aryl group or aralkyl -group and n is a positive number of 0~ n C2 and (ii) an electron doner with (II) a titanium compound in the liquid phase without mechanical pulverizationO
Many prior suggestions are known for polymeri~-iDg or copolymerizing olefins in the presence of a catalyst composed of a magnesium-containing solid titanium catalyst component and an organometallic compound of a metal of Groups I to III of the periodic table. In many of these suggestions, a magnesium-containing solid titanium compound - , . . .
10~ZZ95 obtained by chemically depositing a titanium cor~polmd on a halogen compound of magnesium such as a magnesium dihalide, magnesium hydroxychloride, or a ma~nesium alkoxy-halide is utilized as a catalyst componen-t~ It is also known that halogen-free magnesium compounds can be converted to feasible magnesium-containing solid titanium compounds by using suitable halogenating agents or halogen-contain-ing titanium compounds during the catalyst-forming reactionG
It has been difficult however to provide a catal~st which is easy to produce, has a good reproducibility of catalytic activity and exhibits satisfactory stereoregu-larity and activity in the polymerization or copolymeriza-tion of olefins containing at least 3 carbon atoms while avoiding the formation of a very fine powdery product which causes various troubles such as the blockage of pipes at the time of transporting a slurry containing the resulting polymer or copolymer, the difficulty of separating the polymer -:.
or copolymer, or the clogging of machine components.
As one prior suggestion, Japanese Laid-Open Patent Publication NoO 16986/73 (laid open on March 3, 1973) shows that a titanium catalyst component in which either the carrier or the titanium catal~st component has a surface area of more than 3 m2/g, or which contains an amorphous .
magnesium dihalide can be utilized in the high stereo-regular polymerization of propylene, etcO when used together with an organoaluminum compound and an organic acid ester Ihis Publication neither discloses nor suggests the method of copulverizing a magnesium compound and an electron donor and contacting the pulverized product with a titanium 3 ~ ~.
., . "- . . .
compound in the liquid phase. As will be shown by Comparati~e Exanple 2 to be given hereinbelow, the effect of the present invention cannot be achieYed if the catalyst component i8 prep~red by copulverizing the magnesium compound, the electron donor and the titanium compound together in accordance with the method recommended by the above prior Publication.
Another sugge~tion is disclosed in Japanese Patent Application ~o.
42137/72 (published October 24, 1972~ and Japanese Laid-Open Patent Publica-tion No. 8395/72 (laid open on May 2, 1972; published as Japanese Patent Publication ~o. 30118/76 on Ausust 30, 1976). In these suggestions, an or-ganic acid ester, which is a preferable electron donor in the present invention, i8 not used in forming a magnesium-containing solid titanium catalyst conpon-ent. Polymerization of an olefin containing at least 3 carbon atoms such as propylene using the catalyst~ suggested in these Japanese patents cannot afford a highly stereoregular polymer. This can be seen from the fact th~t these specifications show only the polymerization of ethylenel and is more ; apparent from the results of Comparative Example 1 given hereinbelow.
Japanese Laid-Open Patent Publication No. 126590/75 (laid open on October 4, 1975) discloses that in the preparation of a magnesium~containing solid titanium catalyst component, the solid to be contacted with a titanium B
109ZZ!95 tetrahalide in the liquid or gaseous phase is prepared ~y mechanical pulverizationO ~owever~ this Publication fails to disclose the use of magnesium compounds specified in the present inventionO
As additional prior suggestions, Japanese Laid-Cpen Patent Publication NoO 108385/75 (laid open on August 26, 1975) and Japanese ~aid-Open Patent Publication ~oO
20297/75 (laid open on February 189 1976) suggest the use of a reaction product consisting essentially of a magnesium halide, a silicon compound, an organic carboxylic acid -ester and a titanium compound as a magnesium-conta; n; ng solid titanium catalyst componentO In these suggestions, it is desirable to use a copulverizing means so as to form a satisfactory solid titanium catalyst component~ A . . .
satisfactory titanium catalyst component in these suggestions is obtained by using a magnesium dihalide, and these prior Publications do not disclose magnesium compounds specified in the present inventionO It is further noted that the present invention can achieve sufficient effects without using a silicon compound which is an essential ingredient in the above suggestionsO
The present inventors worked extensively in order to provide an improved process for preparing a polymer or copolymer of an olefin containing at least 3 carbon atoms which can overcome the disadvantages associated with the conventional techniquesO As a result, they found that the . ~:
use of a mechanically co-pulverized product of (i) an .. :
organo-aromatic compound containing a halogen and aryloxy or aralkyloxy moiety which is expressed by the above-given . .
10~22~5 formula Mg(OR)n ~ n and (ii) an electron donor can afford a highly stereoregular polymer or copolymer of an olefin containing at least 3 carbon atoms in high yields while inhibiting the formation of a very fine powdery product~
It was also found that the number of catalyst-forming components can be reduced, the means for preparing the catalyst is simple~ and the catalyst has a good repro-ducibility of quality and can afford a polymer or copolymer of an olefin containing at least 3 carbon atoms with com-mercial advantage~ Furthermore, as is shown in Comparative -Example 2 to be given hereinbelow~ it is necessary that the reaction of ~I) the mechanically co-pulverized product of (i) and (ii) with ~II) the titanium compound in the liquid phase by contacting should be performed without ` 15 mechanical pulverizationO It has been found that the improvement attained by this invention will be substantially lost if this contacting is carried out under mechanically pulverizing conditions~
It is an object of this invention to provide a process for producing a highly stereoregular polymer or ; copolymer of an olefin containing at least 3 carbon atoms in high ~ields and with commercial advantages~
Ihe above and other objects and advantages of the : inventio~ will become more apparent from the following de-scription. :
~he magnesium-containing solid titanium catalyst component used in this invention is a solid titanium com-position which is obtained by contacting (I) a mechanically copulverized product of (i) a halogen-containing magnesium - 6 - :~
~:. :
~ .
~ ' .' : ~', , :.
lO9Z2~S
organo-aromatic co~npound of the formula Mg(OR)nY~_n wherein R represents ~n aryl or aralk-yl group and n is ~ pcsitive number of Ocn~2 and (ii) an electron donor~ preferably an organic acid ester and/or ether9 with (II3 a titanium compound in the liquid phase without mechanical pulveriza-tion~
The term "mechanical pulverization" or '!mechanical copulverization~, as used herein, means a mechanical - --pulverizing operation by which a vigorous mechanical pulver-izing action typified by pulverization in a ball mill, vibratory mill or impact mill is exerted in contacting the compounds for forming the catalyst component (A)o An ordinary stirring operation for ensuring good contact is not included within the definition of mechanical pulverization or mechanical copulverizationO
The halogen-containing magnesium organo-aromatic compound (i) used to form the solid titanium catalyst com ponent (A) which forms the catalyst used in this inve~tion contains halogen, magnesium and an aromatic hydrocarbon ~ . .
moiety belonging to an aryl group or aralkyl group represented by R in the above-given formulaO A solid titanium componet . .:
prepared by using a compound of the above formula in which R is an aliphatic hydrocarbon moiety gives a catalyst of inferior activity, and does not serve to achieve the improve~
ments intended by the present inventionO
Examples of preferred species of R in the halogen-containing magnesium organo-aromatic compound of the formula ~ :
Mg(0~ ~ n are a phenyl group which is optionally substi-tuted by a lower alkyl group containing 1 to 4 carbon atoms9 .,; : . , . , , : . , lOg~Z95 a lower alkoxy group containing 1 to 4 carbon atoms or a halogen atom such as chlorine, bromine or iodine, and phenyl lower (Cl-C4) alkyl groups subs-tituted by ~ lower alkyl group containing 1 to 4 carbon atoms, a lower alkoxy group containing 1 to 4 carbon atoms or a halogen atomO
Especially preferred compounds are those of the above formula in which X is chlorine and n is 1 and R is lower alkyl-~ubstituted phenyl or naphthylO
~lUS, according to one preferred embodiment of this invention, the compound of the formula Mg(OR~X2 n is one in which R is a moiety selected from the group con-sisting of phenylg naphthyl~ lower alkyl-substituted phenyl, lower alkyl-substituted naphthyl, lower alkoxy-substituted phenylg lower alkyl-substituted naphthyl, lower alkoxy-substituted phenyl, lower alkoxy-substituted naphthyl, halogen-substituted phenyl, halogen-substituted naphthyl, hydroxy-substituted phenyl, amino-substituted phenyl, phenyl lower alkyl, lower alkyl-substituted phenyl lower alkyl, lower alkoxy-substituted phenyl lower alkyl and halogen-substituted phenyl lower alkylO Specific examples ~ ~-of such compounds are shown below (in the formulae, n is - -0~ nC 2)o Arykoxy-containing magnesium compounds such as Mg(OC6H5) X2 , Mg(C6H4-CH~)nX2_n, Mg(OC6H4 C2 5)n 2-n Mg(OC6H4-C3H7)nX2_n, Mg(OC6H4-C4 ~ )nX2-n' Mg( C6H4 C8H17)nX2_n' Mg(OC6H4-C9H19)nX2 Mg~ 6 3 (CH3)2)nX2-n~ Mg(oc6H3-(cly3)(c2H5) ~ X2 M~t 6I3 (C2H5)2~nX2_n~ Mg(oc6H2-(cH3)3)nx2 9 .
Mg 6 2 (CH3)2(C3H7))nX2_n~ Mg(0C6H2-(CH3)2(C4H9)) X2 9 M~;(OC6H4C~ )nX2_n~ Mg(Oc6H40cH3)nx2_ns Mg(C10~7)nX2-n' -- 8 -- . .
109~95 Mg(ClOH6~CrI3)nX2_ns ~g~(~loH60C 3)nX2-n Mg(OCloH6C~ )nX2_nand, Mg(OC6H40H)nX~_n; aralkoxyloxy-contain.
ing magnesium compounds such as Mg(OC~-C6n5)n ~ n~
Mg(C2n4~C6H5)nX2-n~ Mg(C3H6-(~6H5)nX2_n, Mg(OC4H~-C6iI5)nX2_n~
Mg(OC ~-C6H4-CH3)nX2_n 9 Mg(OC ~C6H4-C3 ~ )nX2_n, 3 6 6 4 3 ~ )nX2-n~ and Mg(oc3H6-c6H4-c6H5)nx2 n.
~he compound of formula Mg(OR)nX2 n used in the process of this invention may be a single compound or a mixture of two or more compoundsO ~here is no particular restriction on the method of producing a compound of formula Mg(OR)nX2 n' and any known method can be usedO
For example, it can be prepared by reacting a Grignard compound of the formula R"MgX in which R" represents an alkyl group or aryl group, and X is a halogen atom with ::
a compound containing in the molecule a moiety or bond ~ :
selected from the group consisting of a hydroxyl group, a carbonyl group, a carboxyl group, an ester bond and an ether bond, such as phenol, cresol, 2,6-dimethyl phenol, aceto-phenone, benzophenone, benzoic acid, benzaldehyde, methyl -.
benzoatel ethyl b~nzoate, benzoic acid amide, benzoic acid :~
chloride, diphenyl ether, benzyl alcohol~ ethyl toluate, phthalic anhydride, naphthol and p-methyl benzyl chlorideO
Or it can be produced by reacting the aforesaid Grignard reagent with an aliphatic alcohol to afford a compound of ~- -the formula Mg(OR"')nX2_n in which R"' represents an alkyl group containing 1 to 8 carbon atoms, X is a halogen atom~
and n is O' n< 2, and subjecting the resulting compound to an exchange reaction with an aryloxy-containing metal compound such as A~(OC6Hs)3, Ca(OC~Hs)2 or S ( 2 5 3 6 5 _ g _ lOg~Z95 an alkoxy-containing metal cor~pound containing an aromatic ring such as ~1(0C~ 0C6H5)3 or Si(C~H5)3(0C ~-C6~ ), a phenol or aro~atic alcohol such as phenol, cIesol~ 2~6-dimethyl phenol, ~-phenyl ethy] alcohol OI naphtholO
~he compound of the formula M~(OR)n ~ n can be obtained by reacting a compound of formula Mg ~ wherein X
is an defined above with the compound Mg(0R)2o In the present invention, one or more of electrol donors (ii) can be used to form (I) the mechanically co-pulverized product of (i) and (ii)o Preferably, such electron donors are those which do not contain active ~.
hydrogenO Examples are organic acid esters, ketones, ethers, acid halides N,N-disubstituted amides, tertiary amines, and ; nitriles~ 0f these, the organic acid esters and ethers are preferredO ~:
Examples of the organic acid ester as electron donor (ii) used to form the solid titanium catalyst component .
constituting the catalyst used in this invention are aliphatic acid esters (ii-a), alicyclic acid esters (ii-b), and aromatic acid esters (ii-c)~ .
Examples of the aliphatic esters (ii-a) are esters formed between carboxylic acids or halogen-substitution products selected fr~m the group consisting of saturated :
or unsaturated aliphatic carbox~lic acids containing l to 18 carbon atoms, preferably l to 8 carbon atoms, more preferably l to 4 carbon atoms, and their halogen-substitu- :
tion products, and alcohols or phenols selected from the group consisting of saturated or unsaturated aliphatic -- 10 -- ,, . . . . .. . .... ..... .. ...
primary alcohols containing 1 to 18 carbon atozns, preferasl7 1 to 8 carbon atoms, more preferab]y 1 to 4 carbon atoms, saturated or unsaturated alicyclic alcohols cont~ining 3 to 8 carbon atoms, preferably 5 to 6 carbon atoms~ phenols containing 6 to 10 carbon atom~ preferably 6 to ~ carbon atoms, and Cl-C4 saturated or unsaturated aliphatic primar~
`: alcohols bonded to the ring carbon atom of a C3-C10 aliphatic or aromatic ring; and lactones containing 3 to 10 carbon atomsO
~pecific examples of the aliphatic esters (ii-a) . :
10 include primary alkyl esters of saturated fatty acids such ~ --as methyl formate~ ethyl acetate~ n-amyl acetate~ 2-ethyl- .
` hexyl acetate 9 n-butyl formate, ethyl butyrate or ethyl : valerate; alkenyl esters of sat-urated fatty acids such as ~ vinyl acetate and allyl acetate, primary alkyl esters of :.
; 15 unsaturated fatty acids such as methyl acrylate, methyl .~
methacrylate or n-butyl crotonate; alkyl esters of halogenated `
; aliphatic monocarboxylic acids such as methyl chloroacetate or ethyl dichloroacetate; and lactones such as propiolactone, ~:~
~-butyrolactone or 6-valerolactone~
Examples of the alicyclic esters (ii-b) are esters formed between alicyclic carboxylic acids containing - ~-6 to 12 carbon atoms, preferably 6 to 8 carbon atoms, and saturated or unsaturated aliphatic primary alcohols contain-ing 1 to 8 carbon atoms, preferably 1 to 4, carbon atoms.
Specific examples include methyl cyclohexanecar.boxylate, ethyl cyclohexanecarboxylate, methyl methylcyclohexanecar-boxylate, and ethyl methylcyclohexanecarboxylateO
Examples of the aromatic esters (ii-c) are esters formed bet~een aromatic carboxylic acids containing ~- ' ' ,, , ' '' '. , ' .
109Z2g5 7 -to 18 carbon atorns~ preferably 7 to 12 carbon ato-~s, and alcohols or phenols selected ~rom the group consistin~ of saturated or unsaturated aliphatic primary alcohols contain-ing 1 to 18 carbon atoms~ preferably 1 to 8 carbon atoms~
more preferably 1 to 4 carbon atoms, saturated or unsatu-rated alicyclic alcohols containing 3 to 8 carbon atoms~
preferably 3 to 6 carbon atoms~ phenol containing 6 to 10 carbon atoms, preferably 6 to 8 carbon atoms and Cl-C4 saturated or unsaturated aliphatic primary alcohols bonded to the ring carbon atom of a C3-C10 aliphatic or aromatic ring; and aromatic lactones containing 8 to 12 carbon atomsO ~:
Specific examples of the aromatic ester (ii-c) are alkyl or alkenyl esters, preferably Cl-C8, more prefer-ably Cl-C4~ alkyl esters or C2-C8, more preferably C2-C4, alkenyl esters, of oenzoic acid, such as methyl benzoate, ethyl benzoate, n- and i-propyl benzoate, n-, i-, sec-, and tert-butyl benzoates, n- and i-amyl benzoates, n-hexyl benzoate, n-octyl benzoate, 2-ethylhexyl benzoate, vin~l -benzoate, and allyl benzoate; cycloalkyl or cycloalkenyl -esters of benzoic acid, preferably C3-C8, more preferably C5-C8, cycloalkyl or cycloalkenyl esters of benzoic acid such as cyclopentyl benzoate, cyclohexyl bonzoate or c~clo- : -hexenyl benzoate; aryl or aralkyl esters, preferably C6-C10, -more preferably C6-C8, aryl or aralkyl esters optionally ;
containing a substituent such as a halogen arom atom or a Cl-C4 lower alkyl group of benzoic acid such as phenyl ~ .
benzoate, 4-tolyl benzoate, benzyl benzoate, styryl benzoate,
2-chlorophenyl benzoate or 4-chlorobenzyl benzoate; and : :-aromatic monocarboxylic acid esters in which an electron .. . . .
.. . .
109~295 donating substituent such as a hydroxyl, alkoxy, alkyl or amino group is bonded to the aromatic ring~ ~amples of the aromatic monocarboxylic acid esters containing the electron donatin~ substituent include esters of hydroxybenzoic acid7 preferably Cl-C8, more preferably Cl-C4, alkyl esters, pre-ferably C2-C8, more preferably C2-C4, alkenyl esters, pre-ferably C3-C8, more preferably C5-C8 cycloalkyl OI' cyclo-alkenyl esters, and preferably C6-C10~ more preferably C8- :-C10 aryl or aralkyl estres, of hydroxybenzoic acid, typified -by methyl salicylate, ethyl s~licylate, i-butyl salicylate, i-amyl salicylate, allyl salicylate, methyl p-hydroxybenzoate, n-propyl p-hydroxybenzoate, sec-butyl p-hydroxybenzoate, 2-ethylhexyl p-hydroxybenzoate, cyclohexyl p-hydroxybenzoate~
phenyl salicylate, 2-tolyl salicylate, benzyl salicylate, phenyl p-hydroxybenzoate, 3-tolyl p-hydroxybenzoate, benzyl p-hydroxybenzoate and ethyl a-resorcylate; esters of alkoxy benzoic acids9 preferably esters of lower alkoxy benzoic acids containing 1 to 4 carbon atoms, preferably containing a Cl-C2 alkoxy group, and preferablg Cl-C8, more preferably Cl-C4, alkyl esters, or preferably C6-C10, more preferably C8-C10, aryl or aralkyl esters of lower alkoxy benzoic acids, such as methyl anisate, ethyl anisate, i-propyl anisate, i-butyl anisate, phenyl anisate, benzyl anisate, ethyl o-emethoxybenzoate, methyl p-ethoxybenzoate, ethyl p-ethoxybenzoate, n-butyl p-ethoxybenzoate, ethyl p-allyl-oxybenzoate, phenyl p-ethoxybenzoate, methyl o-ethoxybenzoate, ethyl veratrate and ethyl asym-guacolcarboxylate; esters of ::
alkyl or alkenyl benzoic acids, preferably alkyl or alkenyl ~ I.
benzoatic acids containing preferably Cl-C8, more preferably -.
"
109ZZ~5 Cl-C4~ alkyl group or C2-C81 more preferab]y C2-~47 alkenyl group9 and preferably Cl--~8~ more preferably Cl-C47 alkyl esters and preferably C6-C10, more preferably C8-~10~ aryl or aralkyl esters of alkyl or alkenyl benzoic acid, such as methyl p-toluateq ethyl p-tolua-te, i-propyl p-toluate, n-and i-amyl toluates, 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-ethyl-benzoate, i-propyl o-ethylbenzoate, n-butyl m-ethylbenzoate, ethyl 3,5-xylenecarboxylate, and ethyl p-styrenecarboxylate;
and aminobenzoic acid esters, preferably Cl-C4 alkyl esters of aminobenzoic acid, such as methyl p-aminobenzoate and ethyl p-aminobenzoateO Other examples of the aromatic esters (ii-c) include naphthoic acid esters, preferably ~ ~ .
Cl-C4 alkyl esters thereof, such as methyl naphthoate, ethyl naphthoate, propyl naphthoate or butyl naphthoate, and aromatic lactones such as coumarine and phthalideO -0f the aromatic esters (ii-c) exemplified above, esters of benzoic ac.id, alkyl or alkenyl benzoic acids, and alkoxy benzoic acids are preferredO Especially preferred ..
species are Cl-C4 alkyl esters, for example, methyl or ethyl ~ -esters, of benzoic acid, o- or p-toluic acid, and p-anisic -~
acid. ,-Examples of the ethers as electron donor (ii).used ..
to form the solid titanium catalyst component constituting .
the catalyst used in this invention are alkyl ethers contain- .
ing 1 to 20 carbon atoms, preferably 6 to 20 carbon atoms, such as methyl ether, ethyl ether, isopropyl ether, butyl ether, isoamyl ether, octyl ether and anisole;cyclic ethers :
- 14 - ~s.:
containing 2 to 10 carbon atoms such as tetr~h~Jdrofuran ar~
tetrahydropyran; and aromati~ ethers containing 7 to 18 carbon atoms such as diphenyl etherO :
Preferred titanium compounds (II) used to form the solid titanium catalyst component of the catalyst used in this invention are tetravalent titanium compound of the formula Ti(OR')gX4_g wherein R' is an alkyl group containing l to 8 carbon atoms, X is a halogen atom such as chlorine, bromine or iodine, and g is a number of O to 40 Specific examples of these titanium compounds are ~.titanium tetrahalides such as TiC14,TiBr4 or IiI4;alkoxy-titanium trihalides such as Ii(OCH3)Cl3, Ii(OC2H5)C13, Ti(O n-C4H~)C13, Ti(OC2H5)Br3 or Ti(O iso-C4H~)Br3; alkoxy-titanium dihalides such as Ti(OCH3)2C12, Ti(OC2H5)2C12, Ti(O n-C4 ~ )2Cl and Ti(OC2H5)2Br2; trialkoxytitanium mono-halides such as Ti(OCH3)3Cl, Ti(OC2H5)3Cl, Ti(O n-C4 ~ )3Cl and Ti(OC2H5)3Br; and tetraalkoxytitaniumssuch as Ti(OCH3)4, Ii(OC2H5)4 and Ii(O n-C4H9)40 Of these, t~e titanium tetrahalides are especially preferredO mitanium tetrachloride :-is most preferredO
~he magnesium-containing solid titanium catalyst ~i component (A) used in the process of this invention can be formed by contacting (I) the mechanically co-pulverized -:
product of (i) the halogen-containing magne~ium organo-aromatic compound of the formula Mg(OR)n ~ n and (ii) the electron donor with (II) the titanium compound in the . . . . . .
109zz95 liquid phase without mechanic31 pulveriza-tion~
Mechanical copulverization for producing the reac tion product of (i) and (ii) may be carried out in the presence of pulverizing aids or inert solvents or dilue-~ts such as hexane9 heptane or keroseneO Moreover~ a part of the titanium compound (II) may be present inthe copu]veri-zation systemO
In copulverization, the electron donor needs not to be added in the free state, and may be in the form of an adduct or complex with the organo-aromatic magnesium compound (i) or the titanium compound (II)o ~he amount of the electron donor is preferably about 00005 to about 10 moles, more preferably about OoOl to about 1 mole~ per mole of the organo-aromatic magnesium compound (i)o Various pulverizing devices such as a rotary ball mill, a vibratory ball mill or an impact ball mill can be used for the copulverizationO In the case of a rotary ball ;-~
mill, the suitable degree of copulverization is such that if 100 stainless steel (SUS 32) balls each with a diame-ter ~-.
of 15 mm are accomodated in a stainless steel (SUS 32) ball --mill cylinder having an inner capacity of 800 ml and an inside diameter of 100 mm, and 20 to 40 g of the materials to be copulverized are charged into it, the materials are : :
copulverized at 1~ rpm for a period of preferably at least ~ :
24 hours, more preferably at least 4~ hoursO ~he tempera-ture for the pulverization treatment is preferably from room temperature to about 100~
~he copulverized product of the organo-aromatic magnesium compound and the electron donor is then reacted .
in the absence of mechanical pul~erizatio~ with a titani~l~
compound in the liquid phase~ for ex~mple a liquid titanium compound or a titanium compound dissol~ed in an inert sol~Jent~
~his reaction can also be performed in two or more st~ges~
An electron donor may be present during the reaction of the copulverized product with the titanium compondO Alternative-ly~ the reaction can also be performed while suspending the copulverized product in the liquid-phase titanium compound.
Ihe amount of the titanium compound is preferably at least about 0O01 mole, more preferably about 0O1 mole to about 50 moles, per mole of the magnesium compoundO Desirably, the reaction is carried out generally at a temperature of from room temperature to about 200C for about 6 minutes to about 5 hoursO After the reaction, it is preferred to hot-filter the reaction mixgure at a high temperature of, say, about 60 to 150C to isolate the product, and to wash -~
it well with an inert solvent such as hexane, heptane or kerosene prior to use in polymerizationO
~he resulting titanium catalyst component suitable for a polymeri~ation c.talyst has a halogen/titanium molar -ratio of more than about 4, preferably at least about ~
more preferably at least about 8, a magnesium/titanium molar ratio of at least about 3, preferably about 5 to about 50, an electron donor/titanium molar ratio of about 002 to about 6, preferably about 0O4 to about 3, more preferably about 0.8 to about 2, and a specific surface area of at least about 3 m2/g, preferably at least about 40 m2/g, more preferably at least about 100 m2/g The catalyst used in the process of this invention lO~ZZ9S
is composed of the magnesiu~-containing solid titaniu~
catalyst component (A) and the organometallic com-pound of a metal of Groups I to III of the periodic table (B)o ~he compound (B) is a compound having a h~Jdrocarbon group directly bonded to the metalO Preferably~ themetal compounds (B) are organoaluminum compoundsO
~ xamples of the organometal compound (B) are or~anoaluminum compounds selected from alkylaluminum com-pounds~ alkenylaluminum compounds, alkyl aluminum alkoxides, alkyl aluminum hydrides and alkyl aluminum halides; dialkyl zincs; dialkyl magnesiums;aIkyl magnesium halides; and alkyl lithiums~ The alkyl group may be Cl-C13 alkyl groupsO :
The alkenyl groups may be C2-C13 alkenyl groupsO ~he alkoxy groups may be Cl-C13 alkoxy groupsO ~pecific examples of the organometallic compounds (B) include trialkyl or tri-alkenyl aluminums such as Al(C2H5)3, Al(CH3)3, Al(C3H7)~, 4 ~ 3 (C12H25)3; alkyl aluminums in which a plurality of aluminum atoms are bonded through an oxygen or nitrogen atom, such as ~;
( 2H5)2~10Al(C2H5)2, (C4H~)2AlOAl(C4H~)2or (C2H5)2Al-N-Al(C2H5)2; dialkylaluminum hydrides such as ~6H5 ~ :
(C2 ~ )2AlH or (C4 ~ )2AlH; dialkylaluminum halides such as (C2H5)2AlCl, (C2H5)2AlI or (C4H~)2AlCl; and dialkylauminum alkoxides or phenoxides such as (C2H5)2Al(OC2H5) or (C2H5)2Al(OC6H5). The trialkyl aluminums are most preferredO
In the process of this invention, at least one :~
o~efin containing at least ~ carbon atoms is polymerized or copolymerized, or it is copolymerized with up to 10 mole% of ,. . .
lO9ZZ9S
ethylene and/or a diolefin~ in the pr~sence of a c~talysc com~osed of (A) the magnesium-containing solid ~itaniu~
catalyst component and (B) the organometallic compound of the metal of Groups I to III of theperiodic tableO E~amples of the olefins containing at least ~ carbon atoms are propylene, l-butene and 4-methyl-1-penteneO Examples of the olefin are conaugated dienes such as butadiene and cyclopentadiene~ and nonconjugated dienes such as 1,4-hexadiene, dicyclopentadiene and ethylidenenorborneneO
The polymerization can be carried out in the liquid phase or vapor phaseO When it is carried out in the liquid phase 9 an inert solvent such as hexane 7 heptane or kerosene may be used as a reaction mediumO ~he olefin itself may also be used as a reaction mediumO
In the case of the liquid-phase polymerization, : :
it is preferred to maintain the amount of the solid titanium catalyst component (A) at OoOOl to 0O5 millimole calculated .
as titanium atom per liter of li~uid phase, and the amount of the orga~ometallic compound (B) at 001 to 50 millimoles calculated as metal atom per liter of liquid phaseO
When the polymerization is carried out in the gaseous phase, the solid titanium catalyst component (A) is -~
used in an amount of preferably OoOOl to loO millimole/liter :~
of gaseous phase, more preferably OoOl to 0O5 millimole/
liter of gaseous phase, calculated as titanium atomD ~he organometallic compound (B) is used preferebly in an amount of 0.01 to 50 millimoles/liter of gaseou~s phase calculated as titanium atomO
me polymerization in accordance with the process 10~3ZZg5 of this invention may be carried out in the presence of a molecular weight controller such 3S hydrogenO ~or adjust-ment of stereoregularity, the reaction m~y also be perform~d in the copresence of, for example~ an ether, an ethylene ~-glycol derivative~ an ester such as an organic carboxylic :-acid ester, an oxygen-containing donor such as an organic :: -acid, an amina9 a sulfur-containing organic compound, or a nitrileO Utilization of oxygen-containing aromatic compounds, especially aromati.c carboxylic acid esters, is preferred~
~uch aromatic carboxylic acid esters can be selected from those usable in the preparation of the magnesium- ~:
containing solid titanium catalyst component (A), preferably from benzoic acid esters and benzoic acid esters ring sub- ~
stituted by an electron-donating substituentO Examples of -these esters are benzoic acid esters unsubstituted or sub- :
stituted by a substituent selected from alkyl groups contain~
ing 1 to 4 carbon atoms, alkoxy groups containing 1 to 4 : :
carbon atoms, a hydroxyl group and an amino group, which are selected from Cl-C18 saturated or unsaturated aliphatic primary alcohol esters, C3-C8 saturated or unsaturated -alicyclic alcohol esters, and C6-C10 phenol estersO ~hey :
include benzoic acid esters, toluic acid esters 9 anisic -acid esters, phthalic acid diesters, terephthalic acid di- ~
esters, hydroxybenzoic acid esters, and aminobenzoic acid - -esters. Preferred esters are Cl-C4 alkyl esters of p-toluic :
~cid such as methyl p-toluate and ethyl p-toluateO ... -These aromatic carboxylic acid esters may be used in the form of an addition reaction product with the -i -- -organomet211ic compound (B)o . . ' , ' , ' .' . ,' ,. ., . ,~,, ., , ,, , ,,~ , :
1~9229S
Ihe amount of the compound for adjustme~t of stefeo-regularity is about 0~001 to 10 moles, preferably about OoO1 to 2 moles, more preferably about Ool to 1 mole, per mole of organometallic compound(B)0 ~he polymerization temperature is preferably about 2Q to 200C~ more preferably about 50 to 180Co ~he poly-merization pressure is preferably normal atmospheric pressure to about 50 kg/cm2, more preferably about 2 to 20 kg/cm20 The polymerization can be carried out by a batch-10 wise method, a semi-continuous method, or a continuous --methodO It is also possible to perform it in two or more ~-stages under different conditionsO
~he following examples illustrate the present invention in more detailO
Exam~le 1 Preparation of a titanium-containing catalyst component:-A round-bottomed flask was charged with 003 mole of commercially available magnesium methoxide under an . :
20 atmosphere of nitrogen. Phenol (006 mole) was diluted in .
200 ml of hexane, and the solution was fed into the flaskO
With stirring, the mixture was heatedO ~he distillate was removed from the reaction mixture to afford Mg(OC6H5)2o A stainless steel (SUS 32) ball mill cylinder ~-having an inner capacity of 800 ml and an inside diameter of 100 mm containing 100 stainless steel (SU~ 32) balls each with a diameter of 15 mm was charged with Ool mole of Mg(OC6H5)2 and Ool mole of MgC12o ~hese materials were contacted at 125 rpm for 72 hours to afford a compound ,: . . . . . . .
.
lO9Z2~5 having the average co~position Mg(OG6~ )Clo The resulting Mg~OC6H5)Cl (002 mole) and 0~033 mole of ethyl benzoate were contac-ted under the ball mill-ing conditions described aboveO ~he resulting solid product was suspended in 200 ml of titanium tetrachloride~ and reacted with stirring at 80C for 2 hoursO After the reac-tion, the solid portion was collected by filtration, and sufficiently washed with hexane to afford a titanium-contain-ing solid catalyst component which contained 204% by weight of titanium, 5600% by weight of chlorine, and 1200% by weight of ethyl benzoateO
Polymerization~
A 2-liter autoclave was charged with 750 ml of hexane sufficiently deprived of oxygen and moisture, and 375 millimoles of triethyl aluminum and 1025 millimoles of ethyl p-toluate were added under ~n atmosphere of propylene at 300CD ~hen, the titanium-containing solid catalyst component was introduced into the autoclave in an amount of 0O0225 millimoles calculated as titanium atom Hydrogen (400 ml) was introduced, and the polymerization system was .
heated to 60C, and the total pressure was increa~ed to 7 kg/cm2 by propyleneO Propylene was polymerized under these ~-. -.
conditions for 4 hoursO After the polymerication, the ~:
solid portion w~s collected by filtration to afford 244O7 g of polypropylene as a white powder having a boiling n-heptane extraction residue of ~50 2%~ a bulk density of 0036 and a melt index of 500 Concentrating the liquid-phase portion yielded 1104 g of a solvent-soluble polymerO :
~ 22 ~
. . . , : , ., . .. , ., . ~'.. ' ' ~ - lO9Z2~S
~xP~m~es 2 to 7 Eropylene was polymerized in the same way as in Example 1 using a titanium-containing catalyst component which w~s prepared under the same conditions as in E~ample 1 except that the phenol was changed to each of the com- -paunds shown in ~able lo ~he results are shown in qable lo - 23 - ~ -.
lO9Z295 I' I .. .. _ r~O~
m ~ ~ o o o o o o __ .. .. .. _ __ g ~ o C~ ~ ~ ~ O
.. _ ~ r~
~5 ~ O h N ~ ,~ o o ~
a ,, U2 p~_ , _ _ ~ ~ g~^
q~ ~ ~ ~ o~
r I r-l ~ h rl o o .~ ~,~ tn .
u~ m ~ ~ h ~; _ .. _ .. _ '.
h ~ ~ : -D O O O ~) O ~J
~ ~ " - ` , ' ~11 J' ,_ _ ~ ~ ~ O ~ ,~ ,.. - .
~ ~ hN O ~ ~ O ~ O
tl ~0 ~ ~ ~
V ~ ~ 0 0 g æ
~ ~ ~ ~ U~ ~ 0 C~
v'~ v '~~ ~
. .. _ ............ . . , 0~
h o O P: O
0,51 ~?o ~ v-v?
~v~ v ~ ~'.',.
._ _ . ''.: ~''` ' \~ . . - .,.. .. - _ ~ .. 1 ` ~ :
- 24- `:
: :' lO9Z~9S
Exam~les8 to 12 _ .
A titanium-containing catalyst cornponent was prepared in the same way as in Example 1 except that Mg(0 ~ )Cl synthesized in Example 2 was used, and the ethyl benzoate was changed to each of the esters indicated in Table 20 Using the resulting catalyst component, propylene was polymerized in the same way as in Example 1 ~he results are shown in ~able 2 . ' .
~. ' '~ ' ~ .
'-`" lOg2295 ,~ ~ I o o o o o o _ .~ ~ ~
0 ~ ~, ~ ;, o ~1 _ , _ ___ __ h ~ o h ~ ~ ,9 ~N Ir~ ~ N 1--l ~-1 P ~ ~ ~D (~ ~
O ~ O O - :-CH U~ pl _ .. _ _ O I ~
~n ~ o ~ ~ ~ , ,, 4 ~
~ ~ 0~ ~ ~ ~ ~ ~ ~ ~
tQ ~14 h-rl ~a~ rl p~
h _ 0~ 'd ~D O N C~
~-~1~ N ~ N~
~ 1 bO ~ N'\ N~ ~D
_ O o ` N N N N N
4 :. -a)'l ~ ~
g ~ ~ ~ ~ ~D O ~ ~ , o ~
o ~
rl-r~ ~ ~
~ ~ ~ ~ ~0 C5~
O O 0 3: ~ N N ~ N
v ~ , ' '- ' - ', _ . . -' I I~ 0~ o ~ o ~ , ~-~ ~ o N
,"' ,- .
__ . ~ __ _ . _ :,.' "' . .
~ .
. , .
. . : ' ' ' ' ': ., :
lO9ZZ~
----~
~ ~ ~ K ~ K ~ K`. K`~ ¦
O _ .. _ _ . _ N ~ o c o 1,~,1~ a~
~ ~K~ ~o o ~ II~ , __ , ~0`- N\ i ~I
V~ _ ~" _ , , ~
o ~o V }: ~9 ~ ~ o ~ ~ , .
~$ ~ ~ ~ ~o oo V ~ O ~ K~ `U ~
, ' "--~', ' .
~ O ~ h h ~ K~ o I# ,~ ~ -r~ P~0~ P~ r ~oh~O
~ N ,D N ~ ,~, N Ot) ,~3,0 ~ ~) : ~ ~
o ~ 0 c) m~ 0~
,, ,, : '~ ' -- 27 -- .
~ ' .
--" 109ZZ95 Comparative Ex~ e 1 Preparation o~ catalyst co~nponent:-A reactor equipped with a reflux condenser was charged with 200 ml of a commercially available ~rignard - -reagent (a tetrahydrofuran solution of C2H5MgCl in a con-centration of ~ moles/liter) under a nitrogen atmosphere, and o-cresol was added gradually to form a o-cresoxy-con-taining magnesium compoundO During the reaction, the reaction mixture was maintained at a constant temperature by ice coolingO ~he te-~rahydrofuran was removed by decan-tation, and the residue left after the removal of tetrahydro- :
furan was dried under reduced pressureO
The resulting product was suspended in 300 ml of TiC14, and wi-th stirring, reacted at 80C for 2 hoursO
After the reaction, the reaction mixture was hot-filtered ~- .
by a glass filtex, fully washed with refined hexane, and .-dried under reduced pressure to form a magnesium-contain- .
ing solid titanium catalyst componentO . .
Polymerization of propylene:- ~
A 2-liter autoclave was charged with 750 ml of : -hexane which had been fully deprived of oxygen and moisture and at 40C in an atmosphere of propylene~ 5O0 millimoles of triethyl aluminum and 0005 millimole, calculated as --titanium atom, of the magnesium-containing solid titanium catalyst component obtained above were introduced into the - .
autoclaveO ~he reaction system was heated to 60C, and ~ :
the total pressure of propylene was raised to 800 kg/cm20 ~ubsequently, 350 ml of hydrogen was introduced7 and propylene was polymerized for 4 hoursO After the polymeri-. , '~
- 28 - -:
zation9 ~11 the polymer was precipit,~lted by addirlg met~nol 'o afford 126 g of rubbery polypropylene having a boiling n-heptane extraction residue of 4702%o The specific pol~mer-iz,ation activity of the catalyst was 79 g-PP/~i-mmolOhroatmo Co~arative Exam~le 2 _ . , Mg(OC6Hs)Cl (Oo 2 mole) set forth in Example 1, 00033 mole of ethyl benzoate and 6076 g of titanium tetra-chloride were contacted under the ball milling conditions set forth in ~xample lo ~he resulting solid was washed with fresh hexane, and dried to afford a titanium-containing solid catalyst comporent which contained 308% by weight of titanium and 5200% by weight of chlorineO Propylene was polymerized under the same conditions aS in Example 1 using -~.
the resulting solid catalyst component to afford 6309g of a powdery polymer which had a boiling n-heptane extraction residue of 9101%, a melt index of 103 dg/min. and a bulk density of 0021 g/ccO
Concentrating the solvent lalyer yielded 306 g of a solvent-soluble polymerO
:, " ' . .
.. . .
109~295 donating substituent such as a hydroxyl, alkoxy, alkyl or amino group is bonded to the aromatic ring~ ~amples of the aromatic monocarboxylic acid esters containing the electron donatin~ substituent include esters of hydroxybenzoic acid7 preferably Cl-C8, more preferably Cl-C4, alkyl esters, pre-ferably C2-C8, more preferably C2-C4, alkenyl esters, pre-ferably C3-C8, more preferably C5-C8 cycloalkyl OI' cyclo-alkenyl esters, and preferably C6-C10~ more preferably C8- :-C10 aryl or aralkyl estres, of hydroxybenzoic acid, typified -by methyl salicylate, ethyl s~licylate, i-butyl salicylate, i-amyl salicylate, allyl salicylate, methyl p-hydroxybenzoate, n-propyl p-hydroxybenzoate, sec-butyl p-hydroxybenzoate, 2-ethylhexyl p-hydroxybenzoate, cyclohexyl p-hydroxybenzoate~
phenyl salicylate, 2-tolyl salicylate, benzyl salicylate, phenyl p-hydroxybenzoate, 3-tolyl p-hydroxybenzoate, benzyl p-hydroxybenzoate and ethyl a-resorcylate; esters of alkoxy benzoic acids9 preferably esters of lower alkoxy benzoic acids containing 1 to 4 carbon atoms, preferably containing a Cl-C2 alkoxy group, and preferablg Cl-C8, more preferably Cl-C4, alkyl esters, or preferably C6-C10, more preferably C8-C10, aryl or aralkyl esters of lower alkoxy benzoic acids, such as methyl anisate, ethyl anisate, i-propyl anisate, i-butyl anisate, phenyl anisate, benzyl anisate, ethyl o-emethoxybenzoate, methyl p-ethoxybenzoate, ethyl p-ethoxybenzoate, n-butyl p-ethoxybenzoate, ethyl p-allyl-oxybenzoate, phenyl p-ethoxybenzoate, methyl o-ethoxybenzoate, ethyl veratrate and ethyl asym-guacolcarboxylate; esters of ::
alkyl or alkenyl benzoic acids, preferably alkyl or alkenyl ~ I.
benzoatic acids containing preferably Cl-C8, more preferably -.
"
109ZZ~5 Cl-C4~ alkyl group or C2-C81 more preferab]y C2-~47 alkenyl group9 and preferably Cl--~8~ more preferably Cl-C47 alkyl esters and preferably C6-C10, more preferably C8-~10~ aryl or aralkyl esters of alkyl or alkenyl benzoic acid, such as methyl p-toluateq ethyl p-tolua-te, i-propyl p-toluate, n-and i-amyl toluates, 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-ethyl-benzoate, i-propyl o-ethylbenzoate, n-butyl m-ethylbenzoate, ethyl 3,5-xylenecarboxylate, and ethyl p-styrenecarboxylate;
and aminobenzoic acid esters, preferably Cl-C4 alkyl esters of aminobenzoic acid, such as methyl p-aminobenzoate and ethyl p-aminobenzoateO Other examples of the aromatic esters (ii-c) include naphthoic acid esters, preferably ~ ~ .
Cl-C4 alkyl esters thereof, such as methyl naphthoate, ethyl naphthoate, propyl naphthoate or butyl naphthoate, and aromatic lactones such as coumarine and phthalideO -0f the aromatic esters (ii-c) exemplified above, esters of benzoic ac.id, alkyl or alkenyl benzoic acids, and alkoxy benzoic acids are preferredO Especially preferred ..
species are Cl-C4 alkyl esters, for example, methyl or ethyl ~ -esters, of benzoic acid, o- or p-toluic acid, and p-anisic -~
acid. ,-Examples of the ethers as electron donor (ii).used ..
to form the solid titanium catalyst component constituting .
the catalyst used in this invention are alkyl ethers contain- .
ing 1 to 20 carbon atoms, preferably 6 to 20 carbon atoms, such as methyl ether, ethyl ether, isopropyl ether, butyl ether, isoamyl ether, octyl ether and anisole;cyclic ethers :
- 14 - ~s.:
containing 2 to 10 carbon atoms such as tetr~h~Jdrofuran ar~
tetrahydropyran; and aromati~ ethers containing 7 to 18 carbon atoms such as diphenyl etherO :
Preferred titanium compounds (II) used to form the solid titanium catalyst component of the catalyst used in this invention are tetravalent titanium compound of the formula Ti(OR')gX4_g wherein R' is an alkyl group containing l to 8 carbon atoms, X is a halogen atom such as chlorine, bromine or iodine, and g is a number of O to 40 Specific examples of these titanium compounds are ~.titanium tetrahalides such as TiC14,TiBr4 or IiI4;alkoxy-titanium trihalides such as Ii(OCH3)Cl3, Ii(OC2H5)C13, Ti(O n-C4H~)C13, Ti(OC2H5)Br3 or Ti(O iso-C4H~)Br3; alkoxy-titanium dihalides such as Ti(OCH3)2C12, Ti(OC2H5)2C12, Ti(O n-C4 ~ )2Cl and Ti(OC2H5)2Br2; trialkoxytitanium mono-halides such as Ti(OCH3)3Cl, Ti(OC2H5)3Cl, Ti(O n-C4 ~ )3Cl and Ti(OC2H5)3Br; and tetraalkoxytitaniumssuch as Ti(OCH3)4, Ii(OC2H5)4 and Ii(O n-C4H9)40 Of these, t~e titanium tetrahalides are especially preferredO mitanium tetrachloride :-is most preferredO
~he magnesium-containing solid titanium catalyst ~i component (A) used in the process of this invention can be formed by contacting (I) the mechanically co-pulverized -:
product of (i) the halogen-containing magne~ium organo-aromatic compound of the formula Mg(OR)n ~ n and (ii) the electron donor with (II) the titanium compound in the . . . . . .
109zz95 liquid phase without mechanic31 pulveriza-tion~
Mechanical copulverization for producing the reac tion product of (i) and (ii) may be carried out in the presence of pulverizing aids or inert solvents or dilue-~ts such as hexane9 heptane or keroseneO Moreover~ a part of the titanium compound (II) may be present inthe copu]veri-zation systemO
In copulverization, the electron donor needs not to be added in the free state, and may be in the form of an adduct or complex with the organo-aromatic magnesium compound (i) or the titanium compound (II)o ~he amount of the electron donor is preferably about 00005 to about 10 moles, more preferably about OoOl to about 1 mole~ per mole of the organo-aromatic magnesium compound (i)o Various pulverizing devices such as a rotary ball mill, a vibratory ball mill or an impact ball mill can be used for the copulverizationO In the case of a rotary ball ;-~
mill, the suitable degree of copulverization is such that if 100 stainless steel (SUS 32) balls each with a diame-ter ~-.
of 15 mm are accomodated in a stainless steel (SUS 32) ball --mill cylinder having an inner capacity of 800 ml and an inside diameter of 100 mm, and 20 to 40 g of the materials to be copulverized are charged into it, the materials are : :
copulverized at 1~ rpm for a period of preferably at least ~ :
24 hours, more preferably at least 4~ hoursO ~he tempera-ture for the pulverization treatment is preferably from room temperature to about 100~
~he copulverized product of the organo-aromatic magnesium compound and the electron donor is then reacted .
in the absence of mechanical pul~erizatio~ with a titani~l~
compound in the liquid phase~ for ex~mple a liquid titanium compound or a titanium compound dissol~ed in an inert sol~Jent~
~his reaction can also be performed in two or more st~ges~
An electron donor may be present during the reaction of the copulverized product with the titanium compondO Alternative-ly~ the reaction can also be performed while suspending the copulverized product in the liquid-phase titanium compound.
Ihe amount of the titanium compound is preferably at least about 0O01 mole, more preferably about 0O1 mole to about 50 moles, per mole of the magnesium compoundO Desirably, the reaction is carried out generally at a temperature of from room temperature to about 200C for about 6 minutes to about 5 hoursO After the reaction, it is preferred to hot-filter the reaction mixgure at a high temperature of, say, about 60 to 150C to isolate the product, and to wash -~
it well with an inert solvent such as hexane, heptane or kerosene prior to use in polymerizationO
~he resulting titanium catalyst component suitable for a polymeri~ation c.talyst has a halogen/titanium molar -ratio of more than about 4, preferably at least about ~
more preferably at least about 8, a magnesium/titanium molar ratio of at least about 3, preferably about 5 to about 50, an electron donor/titanium molar ratio of about 002 to about 6, preferably about 0O4 to about 3, more preferably about 0.8 to about 2, and a specific surface area of at least about 3 m2/g, preferably at least about 40 m2/g, more preferably at least about 100 m2/g The catalyst used in the process of this invention lO~ZZ9S
is composed of the magnesiu~-containing solid titaniu~
catalyst component (A) and the organometallic com-pound of a metal of Groups I to III of the periodic table (B)o ~he compound (B) is a compound having a h~Jdrocarbon group directly bonded to the metalO Preferably~ themetal compounds (B) are organoaluminum compoundsO
~ xamples of the organometal compound (B) are or~anoaluminum compounds selected from alkylaluminum com-pounds~ alkenylaluminum compounds, alkyl aluminum alkoxides, alkyl aluminum hydrides and alkyl aluminum halides; dialkyl zincs; dialkyl magnesiums;aIkyl magnesium halides; and alkyl lithiums~ The alkyl group may be Cl-C13 alkyl groupsO :
The alkenyl groups may be C2-C13 alkenyl groupsO ~he alkoxy groups may be Cl-C13 alkoxy groupsO ~pecific examples of the organometallic compounds (B) include trialkyl or tri-alkenyl aluminums such as Al(C2H5)3, Al(CH3)3, Al(C3H7)~, 4 ~ 3 (C12H25)3; alkyl aluminums in which a plurality of aluminum atoms are bonded through an oxygen or nitrogen atom, such as ~;
( 2H5)2~10Al(C2H5)2, (C4H~)2AlOAl(C4H~)2or (C2H5)2Al-N-Al(C2H5)2; dialkylaluminum hydrides such as ~6H5 ~ :
(C2 ~ )2AlH or (C4 ~ )2AlH; dialkylaluminum halides such as (C2H5)2AlCl, (C2H5)2AlI or (C4H~)2AlCl; and dialkylauminum alkoxides or phenoxides such as (C2H5)2Al(OC2H5) or (C2H5)2Al(OC6H5). The trialkyl aluminums are most preferredO
In the process of this invention, at least one :~
o~efin containing at least ~ carbon atoms is polymerized or copolymerized, or it is copolymerized with up to 10 mole% of ,. . .
lO9ZZ9S
ethylene and/or a diolefin~ in the pr~sence of a c~talysc com~osed of (A) the magnesium-containing solid ~itaniu~
catalyst component and (B) the organometallic compound of the metal of Groups I to III of theperiodic tableO E~amples of the olefins containing at least ~ carbon atoms are propylene, l-butene and 4-methyl-1-penteneO Examples of the olefin are conaugated dienes such as butadiene and cyclopentadiene~ and nonconjugated dienes such as 1,4-hexadiene, dicyclopentadiene and ethylidenenorborneneO
The polymerization can be carried out in the liquid phase or vapor phaseO When it is carried out in the liquid phase 9 an inert solvent such as hexane 7 heptane or kerosene may be used as a reaction mediumO ~he olefin itself may also be used as a reaction mediumO
In the case of the liquid-phase polymerization, : :
it is preferred to maintain the amount of the solid titanium catalyst component (A) at OoOOl to 0O5 millimole calculated .
as titanium atom per liter of li~uid phase, and the amount of the orga~ometallic compound (B) at 001 to 50 millimoles calculated as metal atom per liter of liquid phaseO
When the polymerization is carried out in the gaseous phase, the solid titanium catalyst component (A) is -~
used in an amount of preferably OoOOl to loO millimole/liter :~
of gaseous phase, more preferably OoOl to 0O5 millimole/
liter of gaseous phase, calculated as titanium atomD ~he organometallic compound (B) is used preferebly in an amount of 0.01 to 50 millimoles/liter of gaseou~s phase calculated as titanium atomO
me polymerization in accordance with the process 10~3ZZg5 of this invention may be carried out in the presence of a molecular weight controller such 3S hydrogenO ~or adjust-ment of stereoregularity, the reaction m~y also be perform~d in the copresence of, for example~ an ether, an ethylene ~-glycol derivative~ an ester such as an organic carboxylic :-acid ester, an oxygen-containing donor such as an organic :: -acid, an amina9 a sulfur-containing organic compound, or a nitrileO Utilization of oxygen-containing aromatic compounds, especially aromati.c carboxylic acid esters, is preferred~
~uch aromatic carboxylic acid esters can be selected from those usable in the preparation of the magnesium- ~:
containing solid titanium catalyst component (A), preferably from benzoic acid esters and benzoic acid esters ring sub- ~
stituted by an electron-donating substituentO Examples of -these esters are benzoic acid esters unsubstituted or sub- :
stituted by a substituent selected from alkyl groups contain~
ing 1 to 4 carbon atoms, alkoxy groups containing 1 to 4 : :
carbon atoms, a hydroxyl group and an amino group, which are selected from Cl-C18 saturated or unsaturated aliphatic primary alcohol esters, C3-C8 saturated or unsaturated -alicyclic alcohol esters, and C6-C10 phenol estersO ~hey :
include benzoic acid esters, toluic acid esters 9 anisic -acid esters, phthalic acid diesters, terephthalic acid di- ~
esters, hydroxybenzoic acid esters, and aminobenzoic acid - -esters. Preferred esters are Cl-C4 alkyl esters of p-toluic :
~cid such as methyl p-toluate and ethyl p-toluateO ... -These aromatic carboxylic acid esters may be used in the form of an addition reaction product with the -i -- -organomet211ic compound (B)o . . ' , ' , ' .' . ,' ,. ., . ,~,, ., , ,, , ,,~ , :
1~9229S
Ihe amount of the compound for adjustme~t of stefeo-regularity is about 0~001 to 10 moles, preferably about OoO1 to 2 moles, more preferably about Ool to 1 mole, per mole of organometallic compound(B)0 ~he polymerization temperature is preferably about 2Q to 200C~ more preferably about 50 to 180Co ~he poly-merization pressure is preferably normal atmospheric pressure to about 50 kg/cm2, more preferably about 2 to 20 kg/cm20 The polymerization can be carried out by a batch-10 wise method, a semi-continuous method, or a continuous --methodO It is also possible to perform it in two or more ~-stages under different conditionsO
~he following examples illustrate the present invention in more detailO
Exam~le 1 Preparation of a titanium-containing catalyst component:-A round-bottomed flask was charged with 003 mole of commercially available magnesium methoxide under an . :
20 atmosphere of nitrogen. Phenol (006 mole) was diluted in .
200 ml of hexane, and the solution was fed into the flaskO
With stirring, the mixture was heatedO ~he distillate was removed from the reaction mixture to afford Mg(OC6H5)2o A stainless steel (SUS 32) ball mill cylinder ~-having an inner capacity of 800 ml and an inside diameter of 100 mm containing 100 stainless steel (SU~ 32) balls each with a diameter of 15 mm was charged with Ool mole of Mg(OC6H5)2 and Ool mole of MgC12o ~hese materials were contacted at 125 rpm for 72 hours to afford a compound ,: . . . . . . .
.
lO9Z2~5 having the average co~position Mg(OG6~ )Clo The resulting Mg~OC6H5)Cl (002 mole) and 0~033 mole of ethyl benzoate were contac-ted under the ball mill-ing conditions described aboveO ~he resulting solid product was suspended in 200 ml of titanium tetrachloride~ and reacted with stirring at 80C for 2 hoursO After the reac-tion, the solid portion was collected by filtration, and sufficiently washed with hexane to afford a titanium-contain-ing solid catalyst component which contained 204% by weight of titanium, 5600% by weight of chlorine, and 1200% by weight of ethyl benzoateO
Polymerization~
A 2-liter autoclave was charged with 750 ml of hexane sufficiently deprived of oxygen and moisture, and 375 millimoles of triethyl aluminum and 1025 millimoles of ethyl p-toluate were added under ~n atmosphere of propylene at 300CD ~hen, the titanium-containing solid catalyst component was introduced into the autoclave in an amount of 0O0225 millimoles calculated as titanium atom Hydrogen (400 ml) was introduced, and the polymerization system was .
heated to 60C, and the total pressure was increa~ed to 7 kg/cm2 by propyleneO Propylene was polymerized under these ~-. -.
conditions for 4 hoursO After the polymerication, the ~:
solid portion w~s collected by filtration to afford 244O7 g of polypropylene as a white powder having a boiling n-heptane extraction residue of ~50 2%~ a bulk density of 0036 and a melt index of 500 Concentrating the liquid-phase portion yielded 1104 g of a solvent-soluble polymerO :
~ 22 ~
. . . , : , ., . .. , ., . ~'.. ' ' ~ - lO9Z2~S
~xP~m~es 2 to 7 Eropylene was polymerized in the same way as in Example 1 using a titanium-containing catalyst component which w~s prepared under the same conditions as in E~ample 1 except that the phenol was changed to each of the com- -paunds shown in ~able lo ~he results are shown in qable lo - 23 - ~ -.
lO9Z295 I' I .. .. _ r~O~
m ~ ~ o o o o o o __ .. .. .. _ __ g ~ o C~ ~ ~ ~ O
.. _ ~ r~
~5 ~ O h N ~ ,~ o o ~
a ,, U2 p~_ , _ _ ~ ~ g~^
q~ ~ ~ ~ o~
r I r-l ~ h rl o o .~ ~,~ tn .
u~ m ~ ~ h ~; _ .. _ .. _ '.
h ~ ~ : -D O O O ~) O ~J
~ ~ " - ` , ' ~11 J' ,_ _ ~ ~ ~ O ~ ,~ ,.. - .
~ ~ hN O ~ ~ O ~ O
tl ~0 ~ ~ ~
V ~ ~ 0 0 g æ
~ ~ ~ ~ U~ ~ 0 C~
v'~ v '~~ ~
. .. _ ............ . . , 0~
h o O P: O
0,51 ~?o ~ v-v?
~v~ v ~ ~'.',.
._ _ . ''.: ~''` ' \~ . . - .,.. .. - _ ~ .. 1 ` ~ :
- 24- `:
: :' lO9Z~9S
Exam~les8 to 12 _ .
A titanium-containing catalyst cornponent was prepared in the same way as in Example 1 except that Mg(0 ~ )Cl synthesized in Example 2 was used, and the ethyl benzoate was changed to each of the esters indicated in Table 20 Using the resulting catalyst component, propylene was polymerized in the same way as in Example 1 ~he results are shown in ~able 2 . ' .
~. ' '~ ' ~ .
'-`" lOg2295 ,~ ~ I o o o o o o _ .~ ~ ~
0 ~ ~, ~ ;, o ~1 _ , _ ___ __ h ~ o h ~ ~ ,9 ~N Ir~ ~ N 1--l ~-1 P ~ ~ ~D (~ ~
O ~ O O - :-CH U~ pl _ .. _ _ O I ~
~n ~ o ~ ~ ~ , ,, 4 ~
~ ~ 0~ ~ ~ ~ ~ ~ ~ ~
tQ ~14 h-rl ~a~ rl p~
h _ 0~ 'd ~D O N C~
~-~1~ N ~ N~
~ 1 bO ~ N'\ N~ ~D
_ O o ` N N N N N
4 :. -a)'l ~ ~
g ~ ~ ~ ~ ~D O ~ ~ , o ~
o ~
rl-r~ ~ ~
~ ~ ~ ~ ~0 C5~
O O 0 3: ~ N N ~ N
v ~ , ' '- ' - ', _ . . -' I I~ 0~ o ~ o ~ , ~-~ ~ o N
,"' ,- .
__ . ~ __ _ . _ :,.' "' . .
~ .
. , .
. . : ' ' ' ' ': ., :
lO9ZZ~
----~
~ ~ ~ K ~ K ~ K`. K`~ ¦
O _ .. _ _ . _ N ~ o c o 1,~,1~ a~
~ ~K~ ~o o ~ II~ , __ , ~0`- N\ i ~I
V~ _ ~" _ , , ~
o ~o V }: ~9 ~ ~ o ~ ~ , .
~$ ~ ~ ~ ~o oo V ~ O ~ K~ `U ~
, ' "--~', ' .
~ O ~ h h ~ K~ o I# ,~ ~ -r~ P~0~ P~ r ~oh~O
~ N ,D N ~ ,~, N Ot) ,~3,0 ~ ~) : ~ ~
o ~ 0 c) m~ 0~
,, ,, : '~ ' -- 27 -- .
~ ' .
--" 109ZZ95 Comparative Ex~ e 1 Preparation o~ catalyst co~nponent:-A reactor equipped with a reflux condenser was charged with 200 ml of a commercially available ~rignard - -reagent (a tetrahydrofuran solution of C2H5MgCl in a con-centration of ~ moles/liter) under a nitrogen atmosphere, and o-cresol was added gradually to form a o-cresoxy-con-taining magnesium compoundO During the reaction, the reaction mixture was maintained at a constant temperature by ice coolingO ~he te-~rahydrofuran was removed by decan-tation, and the residue left after the removal of tetrahydro- :
furan was dried under reduced pressureO
The resulting product was suspended in 300 ml of TiC14, and wi-th stirring, reacted at 80C for 2 hoursO
After the reaction, the reaction mixture was hot-filtered ~- .
by a glass filtex, fully washed with refined hexane, and .-dried under reduced pressure to form a magnesium-contain- .
ing solid titanium catalyst componentO . .
Polymerization of propylene:- ~
A 2-liter autoclave was charged with 750 ml of : -hexane which had been fully deprived of oxygen and moisture and at 40C in an atmosphere of propylene~ 5O0 millimoles of triethyl aluminum and 0005 millimole, calculated as --titanium atom, of the magnesium-containing solid titanium catalyst component obtained above were introduced into the - .
autoclaveO ~he reaction system was heated to 60C, and ~ :
the total pressure of propylene was raised to 800 kg/cm20 ~ubsequently, 350 ml of hydrogen was introduced7 and propylene was polymerized for 4 hoursO After the polymeri-. , '~
- 28 - -:
zation9 ~11 the polymer was precipit,~lted by addirlg met~nol 'o afford 126 g of rubbery polypropylene having a boiling n-heptane extraction residue of 4702%o The specific pol~mer-iz,ation activity of the catalyst was 79 g-PP/~i-mmolOhroatmo Co~arative Exam~le 2 _ . , Mg(OC6Hs)Cl (Oo 2 mole) set forth in Example 1, 00033 mole of ethyl benzoate and 6076 g of titanium tetra-chloride were contacted under the ball milling conditions set forth in ~xample lo ~he resulting solid was washed with fresh hexane, and dried to afford a titanium-containing solid catalyst comporent which contained 308% by weight of titanium and 5200% by weight of chlorineO Propylene was polymerized under the same conditions aS in Example 1 using -~.
the resulting solid catalyst component to afford 6309g of a powdery polymer which had a boiling n-heptane extraction residue of 9101%, a melt index of 103 dg/min. and a bulk density of 0021 g/ccO
Concentrating the solvent lalyer yielded 306 g of a solvent-soluble polymerO
:, " ' . .
Claims (12)
1. A process for producing a polymer or copolymer of an olefin containing at least 3 carbon atoms which comprises polymerizing or copolymerizing at least one olefin contain-ing at least 3 carbon atoms, or copolymerizing the olefin with up to 10 mole% of ethylene and/or a diolefin, in the presence of a catalyst composed of (A) a magnesium-contain-ing solid titanium catalyst component and (B) an organo-metallic compound of a metal of Groups I to III of the periodic table; characterized in that the solid titanium catalyst component (A) is a composition formed by contact-ing (I) a mechanically co-pulverized product of (i) a halogen-containing magnesium organo-aromatic compound of the formula Mg(OR)nx2-n wherein R represents an aryl or aralkyl group and n is a positive number of 0<n<2 and (ii) an electron donor, with (II) a titanium compound in the liquid phase without mechanical pulverization.
2. The process of claim 1 wherein R in the formula of the halogen-containing magnesium organo-aromatic compound (i) is a moiety selected from the group consisting of phenyl, naphthyl, lower alkyl-substituted phenyl, lower alkyl-sub-stituted naphthyl, lower alkoxy-substituted phenyl, lower alkoxy-substituted naphthyl, halogen-substituted phenyl, halogen-substituted naphthyl, hydroxy-substituted phenyl, amino-substituted phenyl, phenyl lower alkyl, lower alkyl-substituted phenyl lower alkyl, lower alkoxy-substituted phenyl lower alkyl and halogen-substituted phenyl lower alkyl.
3. The process of claim 1 wherein the electron donor (ii) is an organic acid ester selected from the group consist-ing of (a) esters formed between carboxylic acids or halogen-substituted derivatives selected from saturated or unsatu-rated aliphatic carboxylic acids containing 1 to 18 carbon atoms and halogen-substituted derivatives thereof and alcohols or phenols selected from saturated or unsaturated aliphatic primary alcohols containing 1 to 18 carbon atoms, saturated or unsaturated alicyclic alcohols containing 3 to 8 carbon atoms, phenols containing 6 to 10 carbon atoms and C1-C4 saturated or unsaturated aliphatic primary alcohols bonded to the ring carbon atom of a C3-C10 aliphatic or aromatic ring, and (b) lactones containing 3 to 10 carbon atoms.
4. The process of claim 1 wherein the electron donor (ii) is an ester formed between an alicyclic carboxylic acid containing 6 to 12 carbon atoms and a saturated or un-saturated aliphatic primary alcohol containing 1 to 8 carbon atoms.
5. The process of claim 1 wherein the electron donor (ii) is a member selected from the group consisting of (a) esters formed between aromatic carboxylic acids containing 7 to 18 carbon atoms and alcohols or phenols selected from saturated or unsaturated aliphatic primary alcohols contain-ing 1 to 18 carbon atoms, saturated or unsaturated alicyclic alcohols containing 3 to 8 carbon atoms, phenol containing 6 to 10 carbon atoms and C1-C4 saturated or unsaturated aliphatic primary alcohols bonded to the ring carbon atoms of a C3-C10 aliphatic or aromatic ring. and (b) aromatic lactones containing 8 to 12 carbon atoms.
6. The process of claim 1 wherein the electron donor (ii) is a member selected from the group consisting of alkyl ethers containing 1 to 20 carbon atoms, cyclic ethers contain-ing 2 to 10 carbon atoms and aromatic ethers containing 7 to 18 carbon atoms.
7. The process of claim 1 wherein the titanium com-pound (II) is a tetravalent titanium compound of the formula Ti(OR')gx4-g wherein R' is an alkyl group containing 1 to 8 carbon atoms, X is a halogen atom and g is 0 to 40
8. The process of claim 1 wherein the organometallic compound (B) is an organoaluminum compound.
9. The process of claim 8 wherein the organoaluminum compound is selected from the group consisting of alkyl aluminum compounds, alkenyl aluminum compounds, alkyl aluminum alkoxides, alkyl aluminum hydrides and alkyl aluminum halides.
10. The process of claim 1 wherein the polymerization or copolymerization is carried out in the presence of a catalyst formed by adding an organic acid ester in addition to the components (A) and (B).
11. The process of claim 10, wherein said organic acid ester is a member selected from the group consisting of esters formed between benzoic acid unsubstituted or sub-stituted by a substituent selected from the group consist-ing of alkyl groups containing 1 to 4 carbon atoms, alkoxyl groups containing 1 to 4 carbon atoms, a hydroxyl group and an amino group, and a member selected from the group consist-ing of C1-C18 saturated or unsaturated aliphatic primary alcohols, C3-C8 saturated or unsaturated alicyclic alcohols and C6-C10 phenols.
12. The process of claim 1 wherein the polymerization or copolymerization is carried out at a temperature of 20 to 200°C under atmospheric pressure to about 50 kg/cm2.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP11463076A JPS5339991A (en) | 1976-09-27 | 1976-09-27 | Production of titanium catalyst component |
| JP114,630/76 | 1976-09-27 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1092295A true CA1092295A (en) | 1980-12-23 |
Family
ID=14642639
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA287,481A Expired CA1092295A (en) | 1976-09-27 | 1977-09-26 | Process for producing stereoregular polymers or copolymers of olefins |
Country Status (10)
| Country | Link |
|---|---|
| JP (1) | JPS5339991A (en) |
| AT (1) | AT350261B (en) |
| AU (1) | AU508008B2 (en) |
| BE (1) | BE859089A (en) |
| CA (1) | CA1092295A (en) |
| DE (1) | DE2743415C2 (en) |
| FR (1) | FR2365591A1 (en) |
| GB (1) | GB1552728A (en) |
| IT (1) | IT1087395B (en) |
| NL (1) | NL179482C (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6025441B2 (en) * | 1976-09-30 | 1985-06-18 | 三井化学株式会社 | Solid catalyst components and catalysts for olefin polymerization |
| JPS58206608A (en) * | 1982-05-25 | 1983-12-01 | Sumitomo Chem Co Ltd | Production of olefin polymer |
| JPS59122505A (en) * | 1982-12-28 | 1984-07-16 | Toa Nenryo Kogyo Kk | Catalyst component for polymerization of olefin |
| JPS6036508A (en) * | 1983-08-09 | 1985-02-25 | Ube Ind Ltd | Polymerization of alpha-olefin |
| CA1275106A (en) * | 1986-04-18 | 1990-10-09 | Vijay Chandrakant Mehta | Hydrocarbyloxy magnesium halides |
| JPH0427826A (en) * | 1990-05-23 | 1992-01-30 | Hino Motors Ltd | Oil level gage of engine |
| DE4217173A1 (en) * | 1992-05-23 | 1993-11-25 | Daimler Benz Ag | Airbag restraint system for vehicle passenger - uses cover for airbag storage space which is made as glove compartment |
| CN101193876B (en) * | 2005-05-07 | 2011-05-11 | 财团法人首尔大学校产学协力财团 | Process for preparing ligands of PPARdelta and the intermediate compounds for preparing the same |
| CN116023552A (en) * | 2021-10-27 | 2023-04-28 | 中国石油化工股份有限公司 | Catalyst and catalyst system for olefin polymerization |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1275641A (en) * | 1969-01-06 | 1972-05-24 | Solvay | Catalysts for the polymerisation and copolymerisation of olefins |
| NL160286C (en) * | 1971-06-25 | |||
| JPS5250037B2 (en) * | 1974-03-06 | 1977-12-21 | ||
| JPS52100596A (en) * | 1976-02-19 | 1977-08-23 | Mitsui Petrochem Ind Ltd | Production of olefin |
| JPS52104593A (en) * | 1976-03-01 | 1977-09-02 | Mitsui Petrochem Ind Ltd | Polymerization of olefins |
| JPS5948003B2 (en) * | 1976-06-02 | 1984-11-22 | 三井化学株式会社 | Method for producing polyolefins |
-
1976
- 1976-09-27 JP JP11463076A patent/JPS5339991A/en active Granted
-
1977
- 1977-09-22 AT AT680777A patent/AT350261B/en not_active IP Right Cessation
- 1977-09-23 AU AU29077/77A patent/AU508008B2/en not_active Expired
- 1977-09-26 GB GB3998877A patent/GB1552728A/en not_active Expired
- 1977-09-26 FR FR7728929A patent/FR2365591A1/en active Granted
- 1977-09-26 IT IT2793277A patent/IT1087395B/en active
- 1977-09-26 CA CA287,481A patent/CA1092295A/en not_active Expired
- 1977-09-27 BE BE181231A patent/BE859089A/en not_active IP Right Cessation
- 1977-09-27 DE DE19772743415 patent/DE2743415C2/en not_active Expired
- 1977-09-27 NL NL7710526A patent/NL179482C/en not_active IP Right Cessation
Also Published As
| Publication number | Publication date |
|---|---|
| FR2365591B1 (en) | 1980-02-08 |
| BE859089A (en) | 1978-03-28 |
| GB1552728A (en) | 1979-09-19 |
| AU2907777A (en) | 1979-03-29 |
| FR2365591A1 (en) | 1978-04-21 |
| JPS5339991A (en) | 1978-04-12 |
| ATA680777A (en) | 1978-10-15 |
| DE2743415C2 (en) | 1986-10-30 |
| AT350261B (en) | 1979-05-25 |
| NL7710526A (en) | 1978-03-29 |
| DE2743415A1 (en) | 1978-03-30 |
| AU508008B2 (en) | 1980-03-06 |
| NL179482B (en) | 1986-04-16 |
| IT1087395B (en) | 1985-06-04 |
| JPS6112921B2 (en) | 1986-04-10 |
| NL179482C (en) | 1986-09-16 |
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