CA1221956A - Catalyst component for polymerization of olefins - Google Patents
Catalyst component for polymerization of olefinsInfo
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- CA1221956A CA1221956A CA000462037A CA462037A CA1221956A CA 1221956 A CA1221956 A CA 1221956A CA 000462037 A CA000462037 A CA 000462037A CA 462037 A CA462037 A CA 462037A CA 1221956 A CA1221956 A CA 1221956A
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- Prior art keywords
- catalyst component
- compound
- component
- polymerization
- catalyst
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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
Abstract
ABSTRACT OF THE DISCLOSURE
A titanium-containing catalyst component for polymerization of olefins which is prepared by reacting a magnesium hydrocarbyl oxide with a silicon compound having a hydrogen-silicon bond, contacting the reaction product with an electron donor compound, contacting the resulting contact product with an organoaluminum compound and further with a titanium compound.
A titanium-containing catalyst component for polymerization of olefins which is prepared by reacting a magnesium hydrocarbyl oxide with a silicon compound having a hydrogen-silicon bond, contacting the reaction product with an electron donor compound, contacting the resulting contact product with an organoaluminum compound and further with a titanium compound.
Description
f 1 Description of the Invention:
2 Field of Technolog~
3 The present invention relates to a catalyst component for
4 polymerization of olefins. More particularly, the invention relates to (a) a catalyst component which provides olefin polymers having a 6 high stereoregularity and a high bulk density in high yields, (b) an 7 olefin polymerization catalyst system comprising the titanium 8 halide-containing catalyst component and an organo metal cocatalyst, g and (c) the process of polymerizing olefins in the presence of the catalyst system.
11 Background Technology 12 Heretofore, it has been known that a contact product of a 13 halogen-free magnesium compound and a titanium compound is useful as a 14 catalyst component for the polymerization of olefins. However, it is low in catalytic performance, and attempts have been made for 16 improvement. Such attempts include a process in which Mg(OR)2 is 17 contacted with titanium tetrahalide in the presence of a halogenated 18 silane represented by SiXpR4 p (X = halogen, R = hydrocarbyl 19 radical) or in the presence of said halogenated silane and an electron donor compound (Japanese Patent Laid-open No. 98076/1977), a process 21 in which a magnesium compound having the Mg-0-R linkage is contacted 22 with a halogenating agent such as a silicon compound represented by 23 the formula XmSiRn (X and R being as defined above) in the 24 presence of an electron donor compound (Japanese Patent Laid-open No.
~3094/l978), a process in which the solid reaction product of a 26 halogenated aluminum, an organic compound having the Si-0 bond, and 27 magnesium alcoholate is contacted with a tetravalent titanium compound 28 having at least one halogen atom (Japanese Patent Laid-open No.
29 78287/1978), a process in which the reaction product of a magnesium compound, titanium compound, and silicon compound is contacted with at 31 least one kind of halogenated aluminum compound (Japanese Patent 32 Laid-open No. 155205/1981).
33 The catalyst components obtained according to the 34 above-mentioned processes, however, are poor in catalytic activity and stereoregularity and provide polymers having a low bulk density. In 36 addition to the above-mentioned catalyst components, there is known ~%~
1 one which is obtained by contacting a magnesium compound, an electron 2 donor compound, a silicon compound having the Si-H bond, and a 3 titanium ha1ide compound all together tJapanese Patent Laid-open No.
4 92009/1982). According to this process, the magnesium compound is essentially a magnesium halide and the silicon compound and titanium 6 halide are used simultaneously for contacting. Therefore, the 7 resulting product is not necessarily satisfactory.
8 Summary of the Invention 9 In order to produce from a halogen-free magnesium compound a catalyst component which can be made into a catalyst which exhibits 11 high stereoregularity and high catalytic activity and provides olefin 12 polymers having a high bulk density, the present inventors carried out 13 extensive researches, which led to the findings that the object can be 14 achieved with a solid substance obtained by reacting a magnesium hydrocarbyl oxide with a silicon compound having at least one 16 hydrogen-silicon bond, contacting the reaction product with an 17 electron donor compound, contacting the resulting contact product with 18 an organoaluminum compound and finally contacting with a titanium 19 compound. The present invention has been completed based on these findin9S-21 The essence of this invention resides in a catalyst component 22 for polymerization of olefins which is prepared by reacting a 23 magnesium hydrocarbyl oxide with a silicon compound having at least 24 one hydrogen-silicon bond, contacting the reaction product with an electron donor compound, and contacting the resulting contact product 26 with an organoaluminum compound and further with a titanium compound.
27 Raw Materials for Catalyst Component 28 The raw materials used for preparing the catalyst component 29 of this invention are described below.
(A) Magnesium Alkoxide 31 The magnesium hydrocarbyl oxide used in this invention is 32 represented by the formula Mg(OR)(OR'), wherein R and R' are alkyl, 33 alkenyl, cycloalkyl, aryl, or aralkyl groups having l to 20 carbon 34 atoms, preferably l to lO carbon atoms, and R and R' may be the same or different.
36 These compounds include, for e~ample, Mg(OCH3)2, Mg(C2H5)2, Mg 37 (OCH3)(0C2H5), Mg(Oi-C3H7)2~ Mg(OC3H7)2~ 9( 4 9 2 38 Mg(Oi-C4Hg)2, Mg(OC4Hg)(O-iC4H9) 9 Mg(OC4~9)(Osec-C~Hg), ~2Z~
1 Mg(oc6Hl3)2~ Mg(CgHl7)2~ M9(C6Hll)2' Mg( 6 5)2 2 Mg(oc6H4cH3)2~ and M9(0CH2C6H5)2 3 These magnesium hydrocarbyl oxides should preferably be dried 4 before use, and more preferably be dried with heating under reduced pressure. These magnesium hydrocarbyl oxides may be obtained 6 commercially or may be synthesized according to the known methods.
7 These magnesium hydrocarbyl oxides may be contacted ~ith an 8 inorganic or organic inert solid substance prior to use.
9 Suitable inorganic solid substances include metal compounds in the form of sulfate, hydroxide, carbonate, phosphate, or silicate.
11 Examples of such compounds include Mg(OH)2, BaC03, and Ca3(P04)2.
12 Suitable organic solid substances include low-molecular 13 aromatic hydrocarbons such as durene, anthracene, napthalene, and 14 diphenyl. They also include high-molecular compounds such as polyethylene, polypropylene, polyvinyl toluene, polystyrene, 16 polymethyl methacrylate, polyamide, polyester, and polyvinyl chloride.
17 (B) Silicon Compound 18 The silicon compound used in this invention may be any 1g compound having the hydrogen-silicon bond. It is represented by the formula HmRnSiXr, wherein R is (l) a hydrocarbon group, (2) R'0-21 (R' is a nydrocarbon group), (3) R R N- (R and R are 22 hydrocarbcln groups), or (4) R4Coo- (R4 is a hydrogen atom or 23 hydrocarbon group); X is a halogen atom, and m is l to 3, 0 ' r ~ 4, 24 and m + n + r = 4. When n is greater than l, R may be the same or different.
26 The hydrocarbon groups represented by R, Rl, R2, R3, 27 and R4 include alkyl, alkenyl, cycloalkyl, aryl, and aralkyl groups 28 of carbon number l to 16. The alkyl group includes, for example, 29 methyl, ethyl, propyl, n-butyl, isobutyl 9 n-hexyl, n-octyl, 2-ethylhexyl, and n-decyl. The alkenyl group includes, for example, 31 vinyl, allyl, isopropenyl, propenyl, and butenyl. The cycloalkyl 32 group includes, for example, cyclopentyl and cyclohexyl. The aryl 33 group includes, for example, phenyl, tolyl, and xylyl. The aralkyl 34 group includes, for example, benzyl, phenetyl, and phenylpropyl.
Preferable among them are lower alkyl groups such as methyl, 36 ethyl, propyl, isopropyl, n-butyl, isobutyl, and t-butyl, and aryl 37 groups such as phenyl and tolyl.
9~
1 X denotes halogen atoms such as chlorine, bromine, and 2 iodine. The preferred halogen is chlorine.
3 The si1icon compounds are exemplified by HSiC13, H2SiC12, 4 H3SiCl, HCH3SiC12, HC2H5SiC12, H(t C4Hg)SiC12~ HC6 5 C 2' H(CH3)2SiCl, H(i-C3H7)2SiCl, H2C2H5SiCl, H2(n-C4Hg)SiCl, 6 H2(C6H4CH3)SiCl, HSi(CH3)3, HSiCH3(0CH32, HSiCH3(0C2H5)2, ( 3)3, (C2H5)2SiH2, HSi(CH3)2(0C2H5), HSi(CH3)2[N(CH3)2], 3( 2 5)2~ HSiC2~l5(0C2H5)2~ HSiCH3[N(CH3)2]2' C6H5SiH
9 HSi(C2H5)3~ HSi(OC2Hs)3~ HSi(CH3)2[N(C2H5)2]~ [ ( 3 2 3 6 5 3 H2' C6H5(CH3)2siH~ (n-C3H7)3SiH~ HSiCl(C6H ) 11 H2Si(C6H5)2, HSi(C6H5)2CH3, (n-C5H11o)3si , ( 6 5 3 12 (n-C5Hll)3SiH. Another example of the compounds not covered by 13 the above formula include (ClCh2CH20)2-CH3SiH, HSi(OCH2CH2Cl)3, [ (CH3)2Si]20, [H(CH3)2Si]2~H, (CH3)35iOSi(CH3) H
[H(CH3)2si]2C6H4~ [H(cH3)2sio]2si(cH3)2~ [(CH3)3sio]2sjHcH3, 16 [(CH3)3SiO]3SiH, and [Si(CH3)(H)0]5.
17 Preferable among these halogenated silicon compounds are 18 those which are represented by the formula in which R is a 19 hydrocarbon, n is O to 2, and r is 1 to 3. They are HSiC13, H2SiC12, H3SiCl, HCH3SiC12, HC2H5SiC12, H(t C4Hg)S 2' 6 5 2 21 H(CH32SiCl, H(i-C3H7)2SiCl, H2C2H5SiCl, H2(n-C4Hg)SiCl, 22 H2(C6H4C~3)SiCl, and HSiCl(C6H5)2. Most preferable among them are 23 HSiC13, HCH3SiC12, and H(CH3)2SiCl. Especially preferred among the 24 silicon c~mpounds is HSiC13.
(C) Electron Donor Compound 26 The electron donor compound used in this invention includes 27 carboxylic acids, carboxylic anhydrides, carboxylic esters, carboxylic 28 acid halides, alcohols, ethers, ketones, amines, amides, nitriles, 29 aldehydes, alcoholates, phosphoamides, thioethers, thioesters, and carbonic esters, and phosphorus, arsenic, and antimony compounas in 31 which these atoms are bonded to an organic group through a carbon or 32 oxygen. Preferable among them are carboxylic esters, carboxylic 33 anhydrides, carboxylic acid halides, alcohol, and ethers.
34 Examples of carboxylic esters include butyl formate, ethyl acetate, butyl acetate, ethyl acrylate, ethyl butyrate, isobutyl 36 isobutyrate, methyl methacrylate, diethyl maleate, diethyl tartrate, 37 ethyl cyclohexanecarbonate, ethyl benzoate, ethyl p-methoxybenzoate, 38 methyl p-methylbenzoate, ethyl p-tert-butylbenzoate, dibutyl ~2~
1 phthalate, dia11yl phthalate, and ethyl alpha-naphthoate. They are 2 not limitative. Preferable among them are alkyl esters of aromatic 3 carboxylic acid, particularly Cl 8 alkyl esters of benzoic acid or 4 nucleus-substituted benzoic acid such as p-methylbenzoic acid and p-methoxy benzoic acid.
6 Examples of the carboxylic anhydride include aliphatic 7 monocarboxylic anhydrides such as acetic anhydride, propionic 8 anhydride, butyric anhydride, valeric anhydride, and caproic 9 anhydride; aliphatic olefinmonocarboxylic anhydride such as acrylic anhydride, crotonic anhydride, and methacrylic anhydride; alicyclic 11 carboxylic anhydrides such as cyclohexanemonocarboxylic anhydride, 12 cyclohexenemonocarboxylic anhydride, cis-1,2-cyclohexanedicarboxylic 13 anhydride, and cis-4-cyclohexene-1,2-dicarboxylic anhydride; aromatic 14 monocarboxylic anhydrides such as benzoic anhydride, p-toluylic anhydride, p-ethylbenzoic anhydride, and p-methoxybenzoic anhydride;
16 and aromatic dicarboxylic anhydrides such as phthalic anhydride.
17 Examples of the carboxylic acid halides include aliphatic 18 monocarboxylic acid halides (acid chlorides such as acetyl chloride, 19 propionyl chloride, n-butyl chloride; and acid bromides such as acetyl bromide and n-butyl bromide; and acid iodides such as acetyl iodide 21 and n-butyl iodide), aliphatic monoolefincarboxylic acid halides (acid 22 chlorides such as acryl chloride, crotonyl chloride, and methacryl 23 chloride; acid bromides such as acryl bromide and methacryl bromide;
24 and acid iodides such as acryl iodide and methacryl iodide), alicyclic carboxylic acid halides (cyclohexane-carboxylic acid chloride, 26 cis-4-methylcyclohexanecarboxylic acid chloride, 27 l-cyclohexenecarboxylic acid chloride, cyclohexanecarboxylic acid 28 bromide, and cis-4-methylhexenecarboxylic acid bromide), aromatic 29 monocarboxylic acid halides (acid chlorides such as benzoyl chloride, p-toluic acid chloride, p-ethylbenzoic acid chloride, and 31 p-methoxybenzoic acid chloride; acid bromides such as benzoyl bromide;
32 and acid iodides such as benzoyl iodide), and aromatic dicarboxylic 33 acid halides such as phthalic acid dichloride.
34 The alcohols are represented by the formula ROH, wherein R is an alkyl, alkenyl, cycloalkyl, aryl, or aralkyl group of carbon number 36 l to l2. Examples of the alcohols include methanol, ethanol, 37 propanol, isopropanol, butanol, isobutanol, pentanol, hexanol, 38 octanol, 2-ethylhexanol, cyclohexanol, benzyl alcohol, allyl alcohol, phenol, cresol, xylenol, ethylphenol, isopropylphenol, 2 p-t-butylphenol, n octylphenol, and naphthol.
3 The ethers are represented by the formula ROR', wherein R and 4 R' are alkyl9 alkenyl, cycloalkyl, aryl, or aralkyl groups of carbon number l to 12, and R and R' may be the same or different. Examples 6 of the ethers include diethyl ether, diisopropyl ether, dibutyl ether, 7 diisobutyl ether, diisoamyl ether, di-2-ethylhexyl ether, diallyl 8 ether, ethyl allyl ether, butyl allyl ether, diphenyl ether, anisole, 9 and ethyl phenyl ether.
(D) Organoaluminum Compound 11 The organoaluminum compound (component D) used in this 12 invention is one which is represented by the formula RnAlX3 n' 13 wherein R is an alkyl group or aryl group, X is a halogen atom, alkoxy 14 group, or hydrogen atom, n is an arbitrary number in the range of l ' n ' 3. Preferred ones are alkyl aluminum compounds and a mixture 16 thereof or complex thereof having l to 18 carbon atoms, preferably 2 17 to 6 carbon atoms, such as trialkyl aluminum, dialkyl aluminum 18 rnonohalide, monoalkyl aluminum dihalide, alkyl aluminum sesquihalide, 19 dialkyl aluminum monoalkoxide, and dialkyl aluminum monohydride.
Examples of such compounds include trialkyl aluminum such as trimethyl 21 aluminum, triethyl aluminum, tripropyl aluminum, triisobutyl aluminum, 22 and trihexyl aluminum; dialkyl aluminum monohalide such as dimethyl 23 aluminum chloride, diethyl aluminum iodide, and diisobutyl aluminum 24 chloride; monoalkyl aluminum dihalide such as methyl aluminum dichloride, ethyl aluminum dichloride, methyl aluminum dibromide, 26 ethyl aluminum dibromide, ethyl aluminum diiodide, and isobutyl 27 aluminum dichloride; alkyl aluminum sesquihalide such as ethyl 28 aluminum sesquichloride; dialkyl aluminum monoalkoxide such as 29 dimethyl aluminum methoxide, diethyl aluminum ethoxide, diethyl aluminum phenoxide, dipropyl aluminum ethoxide, diisobutyl aluminum 31 ethoxide, and diisobutyl aluminum phenoxide; and dialkyl aluminum 32 hydride such as dimethyl aluminum hydride, diethyl aluminum hydride, 33 dipropyl aluminum hydride, and diisobutyl aluminum hydride.
34 Particularly preferable among them are triethyl aluminum, diethyaluminum chloride, ethylaluminum sesquichloride, and 36 ethylaluminum dichloride.
1 (E) Titanium Compound 2 The titanium compound used in this invention includes 3 divalent, trivalent, and tetravalent titanium compounds. They are 4 exemplified by titanium tetrachloride, titanium tetrabromide, trichloroethoxytitanium, dichlorodibutoxytitanium, 6 dichlorodiphenoxytitanium, chlorotiethoxytitanium, 7 chlorotributoxytitanium, tetrabutoxytitanium, and titanium 8 trichloride. Preferable among them are tetravalent titanium halides 9 such as titanium tetrachloride, trichloroethoxytitanium, dichlorobutoxytitanium, and dichlorodiphenoxytitanium, and most 11 preferable is titanium tetrachloride.
12 Preparation of Catalyst Component 13 The catalyst component of this invention is prepared by 14 reacting a magnesium hydrocarbyl oxide (component A) with a silicon compound (component B), contacting the reaction product with an 16 electron donor compound containing at least one H-Si bond (component 17 C), and contacting the resulting contact product with an 18 organoaluminum compound (component D) and further with a titanium 19 compound (component E). The process is described below.
(1) Reaction of Magnesium Alkoxide with Silicon Compound 21 The reaction of a magnesium hydrocarbyl oxide (component A) 22 with a silicon compound containing at least one H-Si bond (component 23 B) is accomplished by contacting the two components with each other.
24 The contacting can be accomplished by mixing/stirring or mechanically copulverizing the two compounds in the presence or absence of a 26 hydrocarbon. Preferably, the two components should be mixed and 27 stirred in a hydrocarbon.
28 The preferred hydrocarbon is a saturated aliphatic, saturated 29 alicyclic, or aromatic hydrocarbon of carbon number 6 to 12 such as hexane, heptane, octane, cyclohexane, benzene, toluene, and xylene.
31 One mol of component A is contacted with 0.5 to 10 mol, 32 preferably 1 to 50 mol of component B. Usually, the contacting is 33 performed at O to 200C for 0.5 to 100 hours. More than one kind 34 each of component A and component B may be used.
The hydrocarbon may be used in any amount; but it should 36 preferably be less than 100 ml for 1 9 of component A.
37 The quantity of silicon atom in the reaction product, which 38 is insoluble in an inert solvent, particularly n-hexane or n-heptane, 1 at 65C, is more than 8 wt %.
2 The contact product of component A and component B is 3 separated from the reaction system, and is used for the subsequent 4 contacting. If necessary, it may be washed with an inert hydrocarbon such as one which is used in the contacting of component A and 6 component B, prior to the subsequent contacting~ This washing may be 7 carried out with heating.
8 (2) Contacting with Electron Donor Compound 9 The contacting of the reaction product obtained in the above step (l) with an electron donor compound (component C) may be 11 accomplished by mixing and stirring them together in the presence or 12 absence of an inert hydrocarbon, or by mechanically copulverizing 13 them. The inert hydrocarbon includes hexane, heptane, octane, 14 cyclohexane, benzene, toluene, and xylene.
The contacting by mechanical copulverization should be 16 carried out at O to 100C for O.l to lOO hours. The contacting by 17 mere stirring should be carried out at O to 150C for 0.5 to lO
18 hourS-19 Component C is used in an amount of O.Ol to lO gram mol, particularly 0.05 to l gram mol, for l gram atom of magnesium in the 21 reaction product of magnesium alkoxide and silicon compound.
22 (3) Contacting with Organoaluminum Compound 23 Ihe contact product (contact product l) obtained in the above 24 step (2) is subsequently contacted with an organoaluminum compound (component D). Before being contacted with component D, the contact 26 product l may be washed with a proper cleaning agent such as the 27 above-mentioned inert hydrocarbon. The contact product l and 28 component D may be contacted with each other as such; but it is 29 preferable that they are mixed and stirred in a hydrocarbon. The hydrocarbon includes hexane, heptane, octane, cyclohexane, benzene, 31 toluene, and xylene.
32 Component D is used in an amount of O.l to 20 mol, preferably 33 0.5 to 5 mol, for l mol of component C in the contact product l.
34 The contacting in a hydrocarbon should be carried out at O to 100C for O.l to l5 hours, and preferably at lO to 70C for 0.5 to 36 5 hours.
37 More than one kind of component D may be used simultaneously;
38 and the contacting with component D may be carried out more than once.
1 (4) Contactin~ with Titanium Compound 2 The contact product (contact product 2) obtained in the above 3 step (3) is then contacted with a titanium compound (component E).
4 Prior to contacting with component E, the contact product 2 may be washed with a proper cleaning agent such as the above-mentioned inert 6 hydrocarbon.
7 The contact product 2 and component E may be contacted with 8 each other as such; but it is preferable that they are mixed and 9 stirred in a hydrocarbon. The hydrocarbon includes hexane, heptane, octane, cyclohexane, benzene, toluene, and xylene.
11 Component E is used in an amount more than 0.1 gram moT, 12 preferably 1 to S0 gram mol, for 1 gram atom of magnesium in the 13 contact product 2.
14 The contacting should be carried out at 0 to 200C for 0.5 to 20 hours, and preferably at 60 to 150C for 1 to 5 hours.
16 The contacting with component E should preferably be carried 17 out more than once. Where the previous contacting has been carried 18 out in a hydrocarbon, the contact product should be separated from the 19 hydrocarbon prior to the subsequent contacting.
Where the contacting with component E is carried out more 21 than once, it is recommended that the contact product 2 be contacted 22 with a halogenated hydrocarbon or a halide of an element selected from 23 the group consisting of the elements of Groups IIa, IVa, and Va of the 24 periodic table of elements at the interval of the contacting. This will improve the catalytic performance of the resulting catalyst 26 component-27 The halogenated hydrocarbon used in this step is a mono- and 28 polyhalogen substitute of saturated or unsaturated aliphatic, 29 alicyclic, or aromatic hydrocarbon having 1 to 12 carbon atoms.
Examples of aliphatic compounds include methyl chloride, methyl 31 bromide, methyl iodide, methylene chloride, methylene bromide, 32 methylene iodide, chloroform, bromoform, iodoform, carbon 33 tetrachloride, carbon tetrabromide, carbon tetraiodide9 ethyl 34 chloride, ethyl bromide, ethyl iodide, 1,2 dichloroethane, 1,2-dibromoethane, 1,2-diiodoethane, methylchloroform, 36 methylbromoform, methyliodoform, 191,2-trichloroethylene, 37 1,1,2-tribromoethylene, 1,1,2,2-tetrachloroethylene, 38 pentachloroethane, hexachloroethane, hexabromoethane, - lo -1 n-propylchloride, 1,2-dichloropropane, hexachloropropylene, 2 octachloropropane, decabromobutane, and chlorinated paraffin.
3 Examples of alicyclic compound include chlorocyclopropane, 4 tetrachlorocyclopentane, hexachloropentadiene, and hexachlorocyclohexane. Examples of aromatic compounds include 6 chlorobenzene, bromobenzene, o-dichlorobenzene, p-dichlorobenzene, 7 hexachlorobenzene, hexabromobenzene, benzotrichloride, and 8 p-chlorobenzotrichloride. These compounds may be used individually or 9 in combination with one another.
The halide of an element selected from the elements in Groups 11 IIIa, IVa, and Va of the periodic table of elements (referred to as 12 metal halide hereinafter) includes, for example, halides, fluorides, 13 bromides, and iodides ob B, Al, Ga~ In, Tl, Si, Ge, Sn, Pb, As, Sb, 14 and Bi. Preferable among them are BCl3, BI3, AlCl3, AlBr3, AlI3, GaCl3, GaBr3, InCl3, TiC13, SiC14, S 4, 5 16 and SbF5.
17 The contacting with a halogenated hydrocarbon (component F) 18 is accomplished by contacting the solids (which has been separated 19 from the contact product with component E) with component F.
The solids and component F may be contacted with each other 21 as such or in a hydrocarbon. The contacting may be accomplished by 22 mechanical copulverizing or mixing and stirring.
23 Component F is used in an amount of more than O.l mol, 24 preferably 0.5 to 200 mol, fDr l gram atom of magnesium in the solid.
The contacting is accomplished at 0 to 200C for O.l to l5 hours, 26 preferably 25 to 90C for 0.5 to 5 hours.
27 The solid may be contacted with a metal halide (component G) 28 in the same manner as used for contacting the solid with component F.
29 Component G is used in an amount more than O.l mol, preferably 0.5 to l50 mol, for l gram atom of magnesium in the solid. The contacting is 31 accomplished at 0 to 200C for O.l to 15 hours, preferably 25 to 32 90C for 0.5 to 5 hours.
33 The solid substance obtained as mentioned above is washed, if 34 required, with an inert hydrocarbon such as hexane, heptane, octane, cyclohexane, benzene, toluene, and xylene, followed by drying, whereby 36 there is obtained the catalyst component of this invention.
37 The catalyst component of this invention is powder having a 38 specific surface area of 50 to 650 m2/g as measured by BET method at 1 the adsorption temperature of liquid nitrogen, a pore volume of 0.05 2 to 0.40 cc/g, and a narrow particle size distribution.
3 Catalyst for Polymerization of Olefin 4 The catalyst component of this invention is combined with an organoaluminum compound to be made into a catalyst for 6 homopolymerization of an olefin or for copolymerization of an olefin 7 and other olefin.
8 Organoaluminum Compound 9 The organoaluminum compound to be combined with the catalyst component may be the same one as used in the preparation of the 11 catalyst component.
12 Preferable among them is trialkyl aluminum, particularly 13 triethyl aluminum and triisobutyl aluminum. The trialkyl aluminum can 14 be used in combination with the other organoaluminum compound such as commercially available diethyl aluminum chloride, ethyl aluminum 16 dichloride, ethyl a1uminum sesquichloride, diethyl aluminum ethoxide, 17 and diethyl aluminum hydride, and a mixture or complex thereof.
18 In addition, the organoaluminum compound may be used alone or 19 in combination with an electron donor compound. Any electron donor compound used in the preparation of the catalyst component of this 21 invention may be used. Preferable ones are carboxylic acid esters, 22 alcohols, ethers, and ketones. The electron donor compound may be 23 used when an organoaluminum compound is used in combination with the 24 catalyst component, or may be used after being contacted with an organoaluminum beforehand.
26 The organoaluminum compound is used in an amount of l to 2000 27 gram mol, preferably 20 to 500 gram mol, for l gram atom of titanium 28 in the catalyst component.
29 The ratio of the organoaluminum compound to the electron donor compound is such that aluminum in the organoaluminum compound is 31 O.l to 40 gram atom, preferably l to 25 gram atom, for l mol of the 32 electron donor compound.
33 Polymerization of Olefin 34 The catalyst composed of the catalyst component prepared as mentioned above and an organoaluminum compound (and an electron donor 36 compound) is useful as a catalyst for homopolymerization of monoolefin 37 or copolymerization of monoolefin and other monoolefin or diolefin.
38 It exhibits outstanding performance as a catalyst for ~2~
1 homopolymerization of an alpha-olefin of carbon number 3 to 6, such as 2 propylene, l-butene, 4-methyl-l-pentene, and l-hexene, or random or 3 block copolymerization of the above-mentioned alpha-olefins with one 4 another or with ethylene; and for homopolymerization of ethylene or random or block copolymerization of ethylene with an alpha-olefin of 6 carbon number 3 to lO, such as propylene, l-butene, 7 4-methyl-l-pentene, l-hexene, and l-octene.
8 The polymerization may be performed either in gas phase or 9 liquid phase. The liquid phase polymerization may be accomplished in an inert hydrocarbon such as n-butane, isobutane, n-pentane, 11 isopentane, hexane, heptane, octane, cyclohexane, benzene, toluene, 12 and xylene, or in the liquid monomer. The polymerization temperature 13 is usually -80C to +l50C, preferably 40C to l20C. The ~ polymerization pressure is l to 60 atm. The molecular weight modification of the resulting polymer is accomplished in the presence 16 of hydrogen or other known molecular weight modifiers. In the 17 copolymerization of olefin, the quantity of other olefin to be 18 copolymerized is usually less than 30 wt%, particularly 0.5 to l5 wt%, 19 based on the olefin. The polymerization with the catalyst system of this invention may be performed continuously or batchwise under the 21 commonly used conditions. The copolymerization may be accomplished in 22 one step or in two or more steps.
23 Effect of InventiOn 24 The catalyst component of this invention is useful for the product-.on of polyolefins, particularly isotactic polypropylene, 26 ethylene-propylene random copolymer, and ethylene-propylene block 27 cOpolymer.
28 The polymerization catalyst made from the catalyst component 29 of this invention exhibits a high catalytic activity and stereoregularities and keeps its high activity for a long time during 31 polymerization. It provides polymer powder having a high bulk density 32 and flowability.
33 Examples 34 The invention is described in more detail with reference to the following examples and application examples. The scope of this 36 invention is not limited by these examples. Percent (%) in the 37 examples and application examples means wt%, unless otherwise 38 indicated-~22~
1 The specific surface area (S.A.) and pore volume (P.V.) of 2 the catalyst component were measured by using SORPTOMATIC, Model 1810, 3 made by CARL0 ERBA.
4 The catalytic activity Kc is the quantity (g) of polymer formed per l 9 of catalyst, and Kt is the quantity (kg) of polymer 6 formed per l 9 of titanium in the catalyst.
7 The heptane insoluble (referred to as HI hereinafter) which 8 indicates the ratio of crystalline fractions in the polymer is the 9 quantity of residues which remain after extraction for 6 hours with boiling n-heptane in a Soxhlet apparatus of improved typeO
11 The melt flow rate (MFR) and melt index (Ml) were measured 12 according to ASTM-Dl238. The bulk density was measured according to 13 ASTM-Dl895-69, Method A.
14 Example l Contacting of Magnesium Diethoxide with Trichlorosilane 16 Into a 2-liter glass reactor equipped with a reflux 17 condenser, dropping funnel, and stirrer and replaced with nitrogen 18 were charged l20 9 (l.05 mol) of commercial magnesium diethoxide and 19 680 ml of n-heptane. With stirring at room temperature, a mixture of 356 9 (2.63 mol) of trichlorosilane and 250 ml of n-heptane was added 21 dropwise from the dropping funnel over 45 minutes. Stirring was 22 continued for 6 hours at 70C. During the reaction, a gas composed 23 mainly of ethylene and ethyl chloride formed. The resulting solids 24 were filtered off at 70C and then washed by stirring in 600 ml of n-hexane at 65C for lO minutes. The supernatant liquid was removed 26 by decantation. Washing with n-hexane was repeated 4 times, and the 27 solids were dried at 60C for l hour under reduced pressure. Thus 28 there was obtained l64 9 of solid component (I). This solid component 29 was found to contain l2.9% of magnesium, l4.l% of silicon, and 45.7%
of chlorine, and to have a specific surface area of 3l m2/g and a 31 pore volume of 0.08 cc/g.
32 Contacting with Benzoic Anhydride 33 l8 9 of the solid component (I) WdS placed in a 300-ml 3~ stainless steel (SUS3l6) mill pot containing lO0 pieces of stainless steel (SUS3l6) balls, 12 mm in diameter, under the nitrogen 36 atmosphere. Then 4.5 9 of ben~oic anhydride was added to the mill 37 pot. The mill pot was mounted on a shaker and shaken for l hour for 38 crushing. Thus there was obtained a solid component (II).
~' 1 Contacting with Triethyl Aluminum 2 7.0 9 of the solid component (II) was placed in a 200-ml 3 glass reactor equipped with a stirrer and dropping funnel under the 4 nitrogen atmosphere. Then 60 ml of n-heptane was added, followed by stirring to make slurry. Then a mixture of l.0 ml of triethyl 6 aluminum and 30 ml of n-heptane was added dropwise at room temperature 7 over l5 minutes. Reaction was continued at 50C for l hour. The 8 resulting solid substance was filtered off at 50C, followed by 9 washing four times with 90 ml portions of n-hexane at 50C. Thus there was obtained a solid component (III) in the form of slurry.
11 Contactiny with Titanium Tetrachloride 12 To the solid component (III) were added 40 ml of toluene and 13 60 ml of titanium tetrachloride, followed by stirring at 90C for 2 14 hours. The resulting solid substance was filtered off at 90C and washed 7 times with 90 ml portions of n-hexane at room temperature.
16 After drying at room temperature for l hour under reduced pressure, 17 there was obtained 5.4 9 of catalyst component containing 2.6% of 18 titanium, 17.2% of magnesium, 57.2% of chlorine, and 3.0% of silicon.
19 The specific surface area was 318 m2tg and the pore volume was 0.28 cc/g-21 Example 2 22 8.5 9 of the solid component (I) obtained in Example l was 23 placed in a 200-ml glass reactor equipped with a stirrer under the 24 nitrogen atmosphere. Then 90 ml of n-heptane and 3.0 9 of benzoyl chloride were added, followed by reaction at 70C for 2 hours. The 26 reaction product was washed 3 times with 90 ml portions of n-heptane 27 at 65C. Thus there was obtained the solid component (II). To this 28 solid component (II) were added 90 ml of n-heptane and 2.2 ml of 29 triethyl aluminum, followed by reaction at 50C for l hour. The reaction product was washed 5 times with 90 ml portions of n-heptane 31 to give the solid component (III) in the form of slurry. This solid 32 component (III) was contacted with titanium tetrachloride and treated 33 in the same way as in Example l. There was obtained a catalyst 34 component having the composition as shown in Table l.
ExamPle 3 36 The solid component (III) obtained in Example l was placed in 37 a 200-ml glass reactor eqwipped with a stirrer under the nitrogen 38 atmosphere. Then 40 ml of toluene and 60 ml of titanium tetrachloride were added, followed by stirring at 90C for 2 hours. After removal 2 of the supernatant liquid by decantation, the reaction product was 3 washed 4 times with 90 ml portions of toluene at 60C. Then 40 ml 4 of toluene and 60 ml of titanium tetrachloride were added again, followed by stirring at 90C for 2 hours.
6 The resulting solid substance was filtered off at 90C and 7 washed 7 times with 90 ml portions of n-hexane at room temperature, 8 followed by drying for l hour at room temperature under reduced 9 pressure. Thus there was obtained a catalyst component having the composition as shown in Table l.
11 Example 4 12 A catalyst component was prepared in the same way as in 13 Example 3 by contacting the solid component (III) obtained in Example 14 2 with titanium tetrachloride twice. The composition of the catalyst component is shown in Table l.
16 Example 5 17 The solid component (II) was obtained in the same way as in 18 Example l, except that benzoic anhydride was replaced by ethyl 19 benzoate. The solid component (II) was contacted with triethyl aluminum in the same way as in Example l to give the solid component 21 (III).
22 A catalyst cornponent was prepared in the same way as in 23 Example 3 by contacting this solid component (III) with titanium 24 tetrachloride twice. The composition of the catalyst component is shown in Table l.
26 Example 6 27 The solid component (II) was obtained in the same way as in 28 Example l, except that benzoic anhydride was replaced by 3.0 9 of 29 p-cresol and 4.5 ml of ethyl benzoate. The solid component (II) was contacted with triethyl aluminum in the same way as in Example l to 31 give the solid component (III).
32 A catalyst component was prepared in the same way as in 33 Example 3 by contacting this solid component (III) with titanium 34 tetrachloride twice. The composition of the catalyst component is shown in Table l.
36 Example 7 37 The solid component (III) was obtained in the same way as in 38 Example l by contacting the solid component (II) obtained in Example l ~%~
- l6 -1 with ethyl aluminum dichloride in place of triethyl aluminum. This 2 solid component (III) was then contacted with titanium tetrachloride 3 twice in the same way as in Example 3 to give a catalyst component.
4 The composition of the catalyst component is shown in Table l.
Example 8 6 The solid component (III) was obtained in the same way as in 7 Example 2 by contacting the solid component (II) obtained in Example 2 8 with diethyl aluminum chloride in place of triethyl aluminum. This 9 solid component (III) was then contacted with titanium tetrachloride twice in the same way as in Example 3 to give a catalyst component.
11 The composition of the catalyst component is shown in Table l.
12 Example 9 13 The solid component (III) was prepared in the same way as in 14 Example l, except that trichlorosile was replaced by metnyldichlorosilane. This solid component (III) was contacted with 16 titanium tetrachloride twice in the same way as in Example 3 to give a 17 catalyst component having the composition as shown in Table l.
18 Example lO
19 The solid component (I) was prepared in the same way as in Example l, except that trichlorosilane was replaced by 21 methyldichlorosilane. The solid component (II) was prepared in the 22 same way as in Example 2 by contacting with benzoyl chloride. The 23 solid component (III) was prepared by contacting with diethyl aluminum 24 chloride in the same way as in Example 8.
This solid component (III) was contacted with titanium 26 tetrachloride twice in the same way as in Example 3 to give a catalyst 27 component having the composition as shown in Table l.
28 Example ll 29 To the solid component (III) obtained in Example 7 were added 40 ml of toluene and 60 ml of titanium tetrachloride, followed by 31 stirring at 90C for 2 hours. After removal of the supernatant 32 liquid by decantation, 80 ml of toluene and 6.2 9 of hexachloroethane 33 were added, followed by reaction at 60C for l hour. After washing 34 4 times with 90 ml portions of toluene at 60C, 40 ml of toluene and 60 ml of titanium tetrachloride were added again, followed by stirring 36 at 90C for 2 hours.
- l7 -1 The resulting solid substance was filtered off at 90C and 2 washed 7 times with 90 ml portions of n-hexane at room temperature, 3 followed by drying for l hour at room temperature under reduced 4 pressur~. Thus there was obtained a catalyst component having the composition as shown in Table l.
6 Examples 12 and 13 7 The solid component (III) obtained in Example 2 was placed in 8 a 200-ml glass reactor equipped with a stirrer under the nitrogen 9 atmosphere. Then 40 ml of toluene and 60 ml of titanium tetrachloride were added, followed by stirring at 90C for 2 hours. After removal 11 Of the supernatant liquid by decantation, 85 ml of toluene and 6.3 9 12 of silicon tetrachloride (Example l2) or 5.2 9 of tin tetrachloride 13 (Example l3) were added, followed by stirring at 60C for l hour.
14 The reaction product was washed 4 times with 90 ml portions of toluene at 60C. Then 40 ml of toluene and 60 ml of titanium tetrachloride 16 were added, followed by stirring at 90C for 2 hours. The resulting 17 solid substance was filtered off at 90C and washed 7 times with 90 18 ml portions of n-hexane at room temperature, followed by drying for l 19 hour at room temperature under reduced pressure. Thus there was obtained a catalyst component having the composition as shown in Table 21 l.
22 Comparative Example l 23 Into the same mill pot as used in Example l were charged 24 under tbe nitrogen atmosphere 3l.5 9 of commercial magnesium diethoxide and lO.0 9 of benzoic anhydride. The mill pot was shaken 26 on a shaker for 15 hours.
27 5.0 9 of the resulting ground solid was placed in a 500-ml 28 glass container equipped with a stirrer, and 330 ml of n-heptane was 29 added and then 9 ml of titanium tetrachloride was added dropwise over l5 minutes. Further, 35 ml of trichlorosilane was added dropwise in 31 the same way, followed by stirring at 90C for 2 hours.
32 The resulting solid substance was filtered off at 90C and 33 washed 6 times with l50 ml portions of n-hexane at room temperature.
34 The solid substance was dried at room temperature for l hour under reduced pressure. Table l shows the compositions of the resulting 36 catalyst component.
37 Comparative Example 2 38 A catalyst component having the composition as shown in Table 1 1 was prepared in the same way as in Comparative Example 1, except 2 that benzoic anhydride was replaced by 7.5 ml of ethyl benzoate.
~L2~
Table 1 Silicon Compound-Catalyst Component treated Solid ~ Composition (%) Example My~ Sl Cl ~9 1 12.g 14.2 45.7 17.2 2.6 3.0 57.2 2 12.9 14.1 45.7 16.8 2.5 3.4 56.8 3 12.9 14.1 45.7 17.4 2.4 4.2 58.3 4 12.9 14.1 45.7 17.6 2.5 3.8 57.2 12.9 14.1 45.7 17.2 2.2 3.5 57.1 6 12.9 14.1 45.7 17.1 2.6 3.7 56.8 7 12.9 14.1 45.7 17.4 2.1 3.2 57.1 8 12.9 14.1 45.7 17.2 2.2 3.8 57.6 9 12.8 14.2 48.3 17.3 2.5 3.3 57.0 12.8 14.2 48.3 18.1 2.3 3.4 56.9 11 12.9 14.1 45.7 17.6 2.1 3.6 57.2 12 12.9 14.1 45.7 16.9 2.0 3.5 56.9 Comparative Example 1 - - - 15.2 5.3 0.6 44.1 2 - - - 14.3 5.9 0.6 42.6 2 ~ 3~;
1 Application Example l 2 Polymerization of Propylene 3 l9.3 mg of catalyst component obtained in Example l, 2.6 ml 4 of triethyl aluminum (abbreviated as TEAL hereinafter) solution in n-heptane, and 0.l4 ml of ethyl p-methoxybenzoate were mixed. After 6 standing for 5 minutes, the mixture was added to a 1.5-liter stainless 7 steel (SUS 32) autoclave equipped with a stirrer under the nitrogen 8 atmosphere. (The n-heptane solution of TEAL çontains l mol of TEAL in 9 l liter of n-heptane, and 2.6 ml of the solution corresponds to 250 gram atom of aluminum for l gram atom of titanium in the catalyst 11 component. 0.l4 ml of ethyl p-methoxybenzoate corresponds to 0.33 mol 12 for l gram atom of aluminum in TEAL.) Then, 0.6 liter of hydrogen as 13 the molecular weight modifier and 0.8 liter of liquefied propylene 14 were forced into the autoclave. The reaction system was heated to 70C, and the polymerization of propylene was carried out for l 16 hour. After the polymerization was complete, unreacted propylene was 17 purged. Thus there was obtained 26l 9 of white polypropylene powder 18 having an HI of 94.0% (heptane insolubles indicating the crystalline 19 fraction in the polymer), an MFR of 2.8 (melt flow rate), and a bulk density of 0.38 g/cm3.
21 Kc = l3,500 [quantity (9) of polymer formed per l 9 of catalyst]
22 Kt = 5l9 [quantity (kg) of polymer formed per l 9 of Ti in the 23 catalyst]
2~ Application Examples 2 to l5 Polymerization of propylene was carried out in the same way 26 as in Application Example l, except that the catalyst component 27 obtained in Example l was replaced by those which were obtained in 28 Examples 2 to l3 and Comparative Examples l and 2. The results are 29 shown in Table 2.
~2~
Table 2 MFR Bulk Application Catalyst Kc Kt Hl (9/lO density Example Component ~ (k~) (X) min) (g/cm3) 1 Example 1 13,500 519 9408 2.8 0.38 2 Example 2 12,600 504 95.2 3.2 0.38 3 Example 3 14,800 617 95.2 3.1 0.39 4 Example 4 14,500 580 95.5 2.7 0.39 Example 5 15,400 700 95.0 2.6 0.39 6 Example 6 16,200 623 95.5 2.4 0.39 7 Example 7 14,000 667 95.9 202 0.38 8 Example 8 14,800 673 96.0 2.2 0.39 9 Example 9 14,000 560 95.4 2.5 0.39 Example 10 13,800600 95.5 2.1 0.38 11 Example 11 15,500738 95.0 2.6 0.39 12 Example 12 15,800790 95.6 2.4 0.39 13 Example 13 15,600650 95.3 2.9 0.39 14 Comparative Example 1 480 9 86.7 - -Comparative Example 2 600 10 85.1
11 Background Technology 12 Heretofore, it has been known that a contact product of a 13 halogen-free magnesium compound and a titanium compound is useful as a 14 catalyst component for the polymerization of olefins. However, it is low in catalytic performance, and attempts have been made for 16 improvement. Such attempts include a process in which Mg(OR)2 is 17 contacted with titanium tetrahalide in the presence of a halogenated 18 silane represented by SiXpR4 p (X = halogen, R = hydrocarbyl 19 radical) or in the presence of said halogenated silane and an electron donor compound (Japanese Patent Laid-open No. 98076/1977), a process 21 in which a magnesium compound having the Mg-0-R linkage is contacted 22 with a halogenating agent such as a silicon compound represented by 23 the formula XmSiRn (X and R being as defined above) in the 24 presence of an electron donor compound (Japanese Patent Laid-open No.
~3094/l978), a process in which the solid reaction product of a 26 halogenated aluminum, an organic compound having the Si-0 bond, and 27 magnesium alcoholate is contacted with a tetravalent titanium compound 28 having at least one halogen atom (Japanese Patent Laid-open No.
29 78287/1978), a process in which the reaction product of a magnesium compound, titanium compound, and silicon compound is contacted with at 31 least one kind of halogenated aluminum compound (Japanese Patent 32 Laid-open No. 155205/1981).
33 The catalyst components obtained according to the 34 above-mentioned processes, however, are poor in catalytic activity and stereoregularity and provide polymers having a low bulk density. In 36 addition to the above-mentioned catalyst components, there is known ~%~
1 one which is obtained by contacting a magnesium compound, an electron 2 donor compound, a silicon compound having the Si-H bond, and a 3 titanium ha1ide compound all together tJapanese Patent Laid-open No.
4 92009/1982). According to this process, the magnesium compound is essentially a magnesium halide and the silicon compound and titanium 6 halide are used simultaneously for contacting. Therefore, the 7 resulting product is not necessarily satisfactory.
8 Summary of the Invention 9 In order to produce from a halogen-free magnesium compound a catalyst component which can be made into a catalyst which exhibits 11 high stereoregularity and high catalytic activity and provides olefin 12 polymers having a high bulk density, the present inventors carried out 13 extensive researches, which led to the findings that the object can be 14 achieved with a solid substance obtained by reacting a magnesium hydrocarbyl oxide with a silicon compound having at least one 16 hydrogen-silicon bond, contacting the reaction product with an 17 electron donor compound, contacting the resulting contact product with 18 an organoaluminum compound and finally contacting with a titanium 19 compound. The present invention has been completed based on these findin9S-21 The essence of this invention resides in a catalyst component 22 for polymerization of olefins which is prepared by reacting a 23 magnesium hydrocarbyl oxide with a silicon compound having at least 24 one hydrogen-silicon bond, contacting the reaction product with an electron donor compound, and contacting the resulting contact product 26 with an organoaluminum compound and further with a titanium compound.
27 Raw Materials for Catalyst Component 28 The raw materials used for preparing the catalyst component 29 of this invention are described below.
(A) Magnesium Alkoxide 31 The magnesium hydrocarbyl oxide used in this invention is 32 represented by the formula Mg(OR)(OR'), wherein R and R' are alkyl, 33 alkenyl, cycloalkyl, aryl, or aralkyl groups having l to 20 carbon 34 atoms, preferably l to lO carbon atoms, and R and R' may be the same or different.
36 These compounds include, for e~ample, Mg(OCH3)2, Mg(C2H5)2, Mg 37 (OCH3)(0C2H5), Mg(Oi-C3H7)2~ Mg(OC3H7)2~ 9( 4 9 2 38 Mg(Oi-C4Hg)2, Mg(OC4Hg)(O-iC4H9) 9 Mg(OC4~9)(Osec-C~Hg), ~2Z~
1 Mg(oc6Hl3)2~ Mg(CgHl7)2~ M9(C6Hll)2' Mg( 6 5)2 2 Mg(oc6H4cH3)2~ and M9(0CH2C6H5)2 3 These magnesium hydrocarbyl oxides should preferably be dried 4 before use, and more preferably be dried with heating under reduced pressure. These magnesium hydrocarbyl oxides may be obtained 6 commercially or may be synthesized according to the known methods.
7 These magnesium hydrocarbyl oxides may be contacted ~ith an 8 inorganic or organic inert solid substance prior to use.
9 Suitable inorganic solid substances include metal compounds in the form of sulfate, hydroxide, carbonate, phosphate, or silicate.
11 Examples of such compounds include Mg(OH)2, BaC03, and Ca3(P04)2.
12 Suitable organic solid substances include low-molecular 13 aromatic hydrocarbons such as durene, anthracene, napthalene, and 14 diphenyl. They also include high-molecular compounds such as polyethylene, polypropylene, polyvinyl toluene, polystyrene, 16 polymethyl methacrylate, polyamide, polyester, and polyvinyl chloride.
17 (B) Silicon Compound 18 The silicon compound used in this invention may be any 1g compound having the hydrogen-silicon bond. It is represented by the formula HmRnSiXr, wherein R is (l) a hydrocarbon group, (2) R'0-21 (R' is a nydrocarbon group), (3) R R N- (R and R are 22 hydrocarbcln groups), or (4) R4Coo- (R4 is a hydrogen atom or 23 hydrocarbon group); X is a halogen atom, and m is l to 3, 0 ' r ~ 4, 24 and m + n + r = 4. When n is greater than l, R may be the same or different.
26 The hydrocarbon groups represented by R, Rl, R2, R3, 27 and R4 include alkyl, alkenyl, cycloalkyl, aryl, and aralkyl groups 28 of carbon number l to 16. The alkyl group includes, for example, 29 methyl, ethyl, propyl, n-butyl, isobutyl 9 n-hexyl, n-octyl, 2-ethylhexyl, and n-decyl. The alkenyl group includes, for example, 31 vinyl, allyl, isopropenyl, propenyl, and butenyl. The cycloalkyl 32 group includes, for example, cyclopentyl and cyclohexyl. The aryl 33 group includes, for example, phenyl, tolyl, and xylyl. The aralkyl 34 group includes, for example, benzyl, phenetyl, and phenylpropyl.
Preferable among them are lower alkyl groups such as methyl, 36 ethyl, propyl, isopropyl, n-butyl, isobutyl, and t-butyl, and aryl 37 groups such as phenyl and tolyl.
9~
1 X denotes halogen atoms such as chlorine, bromine, and 2 iodine. The preferred halogen is chlorine.
3 The si1icon compounds are exemplified by HSiC13, H2SiC12, 4 H3SiCl, HCH3SiC12, HC2H5SiC12, H(t C4Hg)SiC12~ HC6 5 C 2' H(CH3)2SiCl, H(i-C3H7)2SiCl, H2C2H5SiCl, H2(n-C4Hg)SiCl, 6 H2(C6H4CH3)SiCl, HSi(CH3)3, HSiCH3(0CH32, HSiCH3(0C2H5)2, ( 3)3, (C2H5)2SiH2, HSi(CH3)2(0C2H5), HSi(CH3)2[N(CH3)2], 3( 2 5)2~ HSiC2~l5(0C2H5)2~ HSiCH3[N(CH3)2]2' C6H5SiH
9 HSi(C2H5)3~ HSi(OC2Hs)3~ HSi(CH3)2[N(C2H5)2]~ [ ( 3 2 3 6 5 3 H2' C6H5(CH3)2siH~ (n-C3H7)3SiH~ HSiCl(C6H ) 11 H2Si(C6H5)2, HSi(C6H5)2CH3, (n-C5H11o)3si , ( 6 5 3 12 (n-C5Hll)3SiH. Another example of the compounds not covered by 13 the above formula include (ClCh2CH20)2-CH3SiH, HSi(OCH2CH2Cl)3, [ (CH3)2Si]20, [H(CH3)2Si]2~H, (CH3)35iOSi(CH3) H
[H(CH3)2si]2C6H4~ [H(cH3)2sio]2si(cH3)2~ [(CH3)3sio]2sjHcH3, 16 [(CH3)3SiO]3SiH, and [Si(CH3)(H)0]5.
17 Preferable among these halogenated silicon compounds are 18 those which are represented by the formula in which R is a 19 hydrocarbon, n is O to 2, and r is 1 to 3. They are HSiC13, H2SiC12, H3SiCl, HCH3SiC12, HC2H5SiC12, H(t C4Hg)S 2' 6 5 2 21 H(CH32SiCl, H(i-C3H7)2SiCl, H2C2H5SiCl, H2(n-C4Hg)SiCl, 22 H2(C6H4C~3)SiCl, and HSiCl(C6H5)2. Most preferable among them are 23 HSiC13, HCH3SiC12, and H(CH3)2SiCl. Especially preferred among the 24 silicon c~mpounds is HSiC13.
(C) Electron Donor Compound 26 The electron donor compound used in this invention includes 27 carboxylic acids, carboxylic anhydrides, carboxylic esters, carboxylic 28 acid halides, alcohols, ethers, ketones, amines, amides, nitriles, 29 aldehydes, alcoholates, phosphoamides, thioethers, thioesters, and carbonic esters, and phosphorus, arsenic, and antimony compounas in 31 which these atoms are bonded to an organic group through a carbon or 32 oxygen. Preferable among them are carboxylic esters, carboxylic 33 anhydrides, carboxylic acid halides, alcohol, and ethers.
34 Examples of carboxylic esters include butyl formate, ethyl acetate, butyl acetate, ethyl acrylate, ethyl butyrate, isobutyl 36 isobutyrate, methyl methacrylate, diethyl maleate, diethyl tartrate, 37 ethyl cyclohexanecarbonate, ethyl benzoate, ethyl p-methoxybenzoate, 38 methyl p-methylbenzoate, ethyl p-tert-butylbenzoate, dibutyl ~2~
1 phthalate, dia11yl phthalate, and ethyl alpha-naphthoate. They are 2 not limitative. Preferable among them are alkyl esters of aromatic 3 carboxylic acid, particularly Cl 8 alkyl esters of benzoic acid or 4 nucleus-substituted benzoic acid such as p-methylbenzoic acid and p-methoxy benzoic acid.
6 Examples of the carboxylic anhydride include aliphatic 7 monocarboxylic anhydrides such as acetic anhydride, propionic 8 anhydride, butyric anhydride, valeric anhydride, and caproic 9 anhydride; aliphatic olefinmonocarboxylic anhydride such as acrylic anhydride, crotonic anhydride, and methacrylic anhydride; alicyclic 11 carboxylic anhydrides such as cyclohexanemonocarboxylic anhydride, 12 cyclohexenemonocarboxylic anhydride, cis-1,2-cyclohexanedicarboxylic 13 anhydride, and cis-4-cyclohexene-1,2-dicarboxylic anhydride; aromatic 14 monocarboxylic anhydrides such as benzoic anhydride, p-toluylic anhydride, p-ethylbenzoic anhydride, and p-methoxybenzoic anhydride;
16 and aromatic dicarboxylic anhydrides such as phthalic anhydride.
17 Examples of the carboxylic acid halides include aliphatic 18 monocarboxylic acid halides (acid chlorides such as acetyl chloride, 19 propionyl chloride, n-butyl chloride; and acid bromides such as acetyl bromide and n-butyl bromide; and acid iodides such as acetyl iodide 21 and n-butyl iodide), aliphatic monoolefincarboxylic acid halides (acid 22 chlorides such as acryl chloride, crotonyl chloride, and methacryl 23 chloride; acid bromides such as acryl bromide and methacryl bromide;
24 and acid iodides such as acryl iodide and methacryl iodide), alicyclic carboxylic acid halides (cyclohexane-carboxylic acid chloride, 26 cis-4-methylcyclohexanecarboxylic acid chloride, 27 l-cyclohexenecarboxylic acid chloride, cyclohexanecarboxylic acid 28 bromide, and cis-4-methylhexenecarboxylic acid bromide), aromatic 29 monocarboxylic acid halides (acid chlorides such as benzoyl chloride, p-toluic acid chloride, p-ethylbenzoic acid chloride, and 31 p-methoxybenzoic acid chloride; acid bromides such as benzoyl bromide;
32 and acid iodides such as benzoyl iodide), and aromatic dicarboxylic 33 acid halides such as phthalic acid dichloride.
34 The alcohols are represented by the formula ROH, wherein R is an alkyl, alkenyl, cycloalkyl, aryl, or aralkyl group of carbon number 36 l to l2. Examples of the alcohols include methanol, ethanol, 37 propanol, isopropanol, butanol, isobutanol, pentanol, hexanol, 38 octanol, 2-ethylhexanol, cyclohexanol, benzyl alcohol, allyl alcohol, phenol, cresol, xylenol, ethylphenol, isopropylphenol, 2 p-t-butylphenol, n octylphenol, and naphthol.
3 The ethers are represented by the formula ROR', wherein R and 4 R' are alkyl9 alkenyl, cycloalkyl, aryl, or aralkyl groups of carbon number l to 12, and R and R' may be the same or different. Examples 6 of the ethers include diethyl ether, diisopropyl ether, dibutyl ether, 7 diisobutyl ether, diisoamyl ether, di-2-ethylhexyl ether, diallyl 8 ether, ethyl allyl ether, butyl allyl ether, diphenyl ether, anisole, 9 and ethyl phenyl ether.
(D) Organoaluminum Compound 11 The organoaluminum compound (component D) used in this 12 invention is one which is represented by the formula RnAlX3 n' 13 wherein R is an alkyl group or aryl group, X is a halogen atom, alkoxy 14 group, or hydrogen atom, n is an arbitrary number in the range of l ' n ' 3. Preferred ones are alkyl aluminum compounds and a mixture 16 thereof or complex thereof having l to 18 carbon atoms, preferably 2 17 to 6 carbon atoms, such as trialkyl aluminum, dialkyl aluminum 18 rnonohalide, monoalkyl aluminum dihalide, alkyl aluminum sesquihalide, 19 dialkyl aluminum monoalkoxide, and dialkyl aluminum monohydride.
Examples of such compounds include trialkyl aluminum such as trimethyl 21 aluminum, triethyl aluminum, tripropyl aluminum, triisobutyl aluminum, 22 and trihexyl aluminum; dialkyl aluminum monohalide such as dimethyl 23 aluminum chloride, diethyl aluminum iodide, and diisobutyl aluminum 24 chloride; monoalkyl aluminum dihalide such as methyl aluminum dichloride, ethyl aluminum dichloride, methyl aluminum dibromide, 26 ethyl aluminum dibromide, ethyl aluminum diiodide, and isobutyl 27 aluminum dichloride; alkyl aluminum sesquihalide such as ethyl 28 aluminum sesquichloride; dialkyl aluminum monoalkoxide such as 29 dimethyl aluminum methoxide, diethyl aluminum ethoxide, diethyl aluminum phenoxide, dipropyl aluminum ethoxide, diisobutyl aluminum 31 ethoxide, and diisobutyl aluminum phenoxide; and dialkyl aluminum 32 hydride such as dimethyl aluminum hydride, diethyl aluminum hydride, 33 dipropyl aluminum hydride, and diisobutyl aluminum hydride.
34 Particularly preferable among them are triethyl aluminum, diethyaluminum chloride, ethylaluminum sesquichloride, and 36 ethylaluminum dichloride.
1 (E) Titanium Compound 2 The titanium compound used in this invention includes 3 divalent, trivalent, and tetravalent titanium compounds. They are 4 exemplified by titanium tetrachloride, titanium tetrabromide, trichloroethoxytitanium, dichlorodibutoxytitanium, 6 dichlorodiphenoxytitanium, chlorotiethoxytitanium, 7 chlorotributoxytitanium, tetrabutoxytitanium, and titanium 8 trichloride. Preferable among them are tetravalent titanium halides 9 such as titanium tetrachloride, trichloroethoxytitanium, dichlorobutoxytitanium, and dichlorodiphenoxytitanium, and most 11 preferable is titanium tetrachloride.
12 Preparation of Catalyst Component 13 The catalyst component of this invention is prepared by 14 reacting a magnesium hydrocarbyl oxide (component A) with a silicon compound (component B), contacting the reaction product with an 16 electron donor compound containing at least one H-Si bond (component 17 C), and contacting the resulting contact product with an 18 organoaluminum compound (component D) and further with a titanium 19 compound (component E). The process is described below.
(1) Reaction of Magnesium Alkoxide with Silicon Compound 21 The reaction of a magnesium hydrocarbyl oxide (component A) 22 with a silicon compound containing at least one H-Si bond (component 23 B) is accomplished by contacting the two components with each other.
24 The contacting can be accomplished by mixing/stirring or mechanically copulverizing the two compounds in the presence or absence of a 26 hydrocarbon. Preferably, the two components should be mixed and 27 stirred in a hydrocarbon.
28 The preferred hydrocarbon is a saturated aliphatic, saturated 29 alicyclic, or aromatic hydrocarbon of carbon number 6 to 12 such as hexane, heptane, octane, cyclohexane, benzene, toluene, and xylene.
31 One mol of component A is contacted with 0.5 to 10 mol, 32 preferably 1 to 50 mol of component B. Usually, the contacting is 33 performed at O to 200C for 0.5 to 100 hours. More than one kind 34 each of component A and component B may be used.
The hydrocarbon may be used in any amount; but it should 36 preferably be less than 100 ml for 1 9 of component A.
37 The quantity of silicon atom in the reaction product, which 38 is insoluble in an inert solvent, particularly n-hexane or n-heptane, 1 at 65C, is more than 8 wt %.
2 The contact product of component A and component B is 3 separated from the reaction system, and is used for the subsequent 4 contacting. If necessary, it may be washed with an inert hydrocarbon such as one which is used in the contacting of component A and 6 component B, prior to the subsequent contacting~ This washing may be 7 carried out with heating.
8 (2) Contacting with Electron Donor Compound 9 The contacting of the reaction product obtained in the above step (l) with an electron donor compound (component C) may be 11 accomplished by mixing and stirring them together in the presence or 12 absence of an inert hydrocarbon, or by mechanically copulverizing 13 them. The inert hydrocarbon includes hexane, heptane, octane, 14 cyclohexane, benzene, toluene, and xylene.
The contacting by mechanical copulverization should be 16 carried out at O to 100C for O.l to lOO hours. The contacting by 17 mere stirring should be carried out at O to 150C for 0.5 to lO
18 hourS-19 Component C is used in an amount of O.Ol to lO gram mol, particularly 0.05 to l gram mol, for l gram atom of magnesium in the 21 reaction product of magnesium alkoxide and silicon compound.
22 (3) Contacting with Organoaluminum Compound 23 Ihe contact product (contact product l) obtained in the above 24 step (2) is subsequently contacted with an organoaluminum compound (component D). Before being contacted with component D, the contact 26 product l may be washed with a proper cleaning agent such as the 27 above-mentioned inert hydrocarbon. The contact product l and 28 component D may be contacted with each other as such; but it is 29 preferable that they are mixed and stirred in a hydrocarbon. The hydrocarbon includes hexane, heptane, octane, cyclohexane, benzene, 31 toluene, and xylene.
32 Component D is used in an amount of O.l to 20 mol, preferably 33 0.5 to 5 mol, for l mol of component C in the contact product l.
34 The contacting in a hydrocarbon should be carried out at O to 100C for O.l to l5 hours, and preferably at lO to 70C for 0.5 to 36 5 hours.
37 More than one kind of component D may be used simultaneously;
38 and the contacting with component D may be carried out more than once.
1 (4) Contactin~ with Titanium Compound 2 The contact product (contact product 2) obtained in the above 3 step (3) is then contacted with a titanium compound (component E).
4 Prior to contacting with component E, the contact product 2 may be washed with a proper cleaning agent such as the above-mentioned inert 6 hydrocarbon.
7 The contact product 2 and component E may be contacted with 8 each other as such; but it is preferable that they are mixed and 9 stirred in a hydrocarbon. The hydrocarbon includes hexane, heptane, octane, cyclohexane, benzene, toluene, and xylene.
11 Component E is used in an amount more than 0.1 gram moT, 12 preferably 1 to S0 gram mol, for 1 gram atom of magnesium in the 13 contact product 2.
14 The contacting should be carried out at 0 to 200C for 0.5 to 20 hours, and preferably at 60 to 150C for 1 to 5 hours.
16 The contacting with component E should preferably be carried 17 out more than once. Where the previous contacting has been carried 18 out in a hydrocarbon, the contact product should be separated from the 19 hydrocarbon prior to the subsequent contacting.
Where the contacting with component E is carried out more 21 than once, it is recommended that the contact product 2 be contacted 22 with a halogenated hydrocarbon or a halide of an element selected from 23 the group consisting of the elements of Groups IIa, IVa, and Va of the 24 periodic table of elements at the interval of the contacting. This will improve the catalytic performance of the resulting catalyst 26 component-27 The halogenated hydrocarbon used in this step is a mono- and 28 polyhalogen substitute of saturated or unsaturated aliphatic, 29 alicyclic, or aromatic hydrocarbon having 1 to 12 carbon atoms.
Examples of aliphatic compounds include methyl chloride, methyl 31 bromide, methyl iodide, methylene chloride, methylene bromide, 32 methylene iodide, chloroform, bromoform, iodoform, carbon 33 tetrachloride, carbon tetrabromide, carbon tetraiodide9 ethyl 34 chloride, ethyl bromide, ethyl iodide, 1,2 dichloroethane, 1,2-dibromoethane, 1,2-diiodoethane, methylchloroform, 36 methylbromoform, methyliodoform, 191,2-trichloroethylene, 37 1,1,2-tribromoethylene, 1,1,2,2-tetrachloroethylene, 38 pentachloroethane, hexachloroethane, hexabromoethane, - lo -1 n-propylchloride, 1,2-dichloropropane, hexachloropropylene, 2 octachloropropane, decabromobutane, and chlorinated paraffin.
3 Examples of alicyclic compound include chlorocyclopropane, 4 tetrachlorocyclopentane, hexachloropentadiene, and hexachlorocyclohexane. Examples of aromatic compounds include 6 chlorobenzene, bromobenzene, o-dichlorobenzene, p-dichlorobenzene, 7 hexachlorobenzene, hexabromobenzene, benzotrichloride, and 8 p-chlorobenzotrichloride. These compounds may be used individually or 9 in combination with one another.
The halide of an element selected from the elements in Groups 11 IIIa, IVa, and Va of the periodic table of elements (referred to as 12 metal halide hereinafter) includes, for example, halides, fluorides, 13 bromides, and iodides ob B, Al, Ga~ In, Tl, Si, Ge, Sn, Pb, As, Sb, 14 and Bi. Preferable among them are BCl3, BI3, AlCl3, AlBr3, AlI3, GaCl3, GaBr3, InCl3, TiC13, SiC14, S 4, 5 16 and SbF5.
17 The contacting with a halogenated hydrocarbon (component F) 18 is accomplished by contacting the solids (which has been separated 19 from the contact product with component E) with component F.
The solids and component F may be contacted with each other 21 as such or in a hydrocarbon. The contacting may be accomplished by 22 mechanical copulverizing or mixing and stirring.
23 Component F is used in an amount of more than O.l mol, 24 preferably 0.5 to 200 mol, fDr l gram atom of magnesium in the solid.
The contacting is accomplished at 0 to 200C for O.l to l5 hours, 26 preferably 25 to 90C for 0.5 to 5 hours.
27 The solid may be contacted with a metal halide (component G) 28 in the same manner as used for contacting the solid with component F.
29 Component G is used in an amount more than O.l mol, preferably 0.5 to l50 mol, for l gram atom of magnesium in the solid. The contacting is 31 accomplished at 0 to 200C for O.l to 15 hours, preferably 25 to 32 90C for 0.5 to 5 hours.
33 The solid substance obtained as mentioned above is washed, if 34 required, with an inert hydrocarbon such as hexane, heptane, octane, cyclohexane, benzene, toluene, and xylene, followed by drying, whereby 36 there is obtained the catalyst component of this invention.
37 The catalyst component of this invention is powder having a 38 specific surface area of 50 to 650 m2/g as measured by BET method at 1 the adsorption temperature of liquid nitrogen, a pore volume of 0.05 2 to 0.40 cc/g, and a narrow particle size distribution.
3 Catalyst for Polymerization of Olefin 4 The catalyst component of this invention is combined with an organoaluminum compound to be made into a catalyst for 6 homopolymerization of an olefin or for copolymerization of an olefin 7 and other olefin.
8 Organoaluminum Compound 9 The organoaluminum compound to be combined with the catalyst component may be the same one as used in the preparation of the 11 catalyst component.
12 Preferable among them is trialkyl aluminum, particularly 13 triethyl aluminum and triisobutyl aluminum. The trialkyl aluminum can 14 be used in combination with the other organoaluminum compound such as commercially available diethyl aluminum chloride, ethyl aluminum 16 dichloride, ethyl a1uminum sesquichloride, diethyl aluminum ethoxide, 17 and diethyl aluminum hydride, and a mixture or complex thereof.
18 In addition, the organoaluminum compound may be used alone or 19 in combination with an electron donor compound. Any electron donor compound used in the preparation of the catalyst component of this 21 invention may be used. Preferable ones are carboxylic acid esters, 22 alcohols, ethers, and ketones. The electron donor compound may be 23 used when an organoaluminum compound is used in combination with the 24 catalyst component, or may be used after being contacted with an organoaluminum beforehand.
26 The organoaluminum compound is used in an amount of l to 2000 27 gram mol, preferably 20 to 500 gram mol, for l gram atom of titanium 28 in the catalyst component.
29 The ratio of the organoaluminum compound to the electron donor compound is such that aluminum in the organoaluminum compound is 31 O.l to 40 gram atom, preferably l to 25 gram atom, for l mol of the 32 electron donor compound.
33 Polymerization of Olefin 34 The catalyst composed of the catalyst component prepared as mentioned above and an organoaluminum compound (and an electron donor 36 compound) is useful as a catalyst for homopolymerization of monoolefin 37 or copolymerization of monoolefin and other monoolefin or diolefin.
38 It exhibits outstanding performance as a catalyst for ~2~
1 homopolymerization of an alpha-olefin of carbon number 3 to 6, such as 2 propylene, l-butene, 4-methyl-l-pentene, and l-hexene, or random or 3 block copolymerization of the above-mentioned alpha-olefins with one 4 another or with ethylene; and for homopolymerization of ethylene or random or block copolymerization of ethylene with an alpha-olefin of 6 carbon number 3 to lO, such as propylene, l-butene, 7 4-methyl-l-pentene, l-hexene, and l-octene.
8 The polymerization may be performed either in gas phase or 9 liquid phase. The liquid phase polymerization may be accomplished in an inert hydrocarbon such as n-butane, isobutane, n-pentane, 11 isopentane, hexane, heptane, octane, cyclohexane, benzene, toluene, 12 and xylene, or in the liquid monomer. The polymerization temperature 13 is usually -80C to +l50C, preferably 40C to l20C. The ~ polymerization pressure is l to 60 atm. The molecular weight modification of the resulting polymer is accomplished in the presence 16 of hydrogen or other known molecular weight modifiers. In the 17 copolymerization of olefin, the quantity of other olefin to be 18 copolymerized is usually less than 30 wt%, particularly 0.5 to l5 wt%, 19 based on the olefin. The polymerization with the catalyst system of this invention may be performed continuously or batchwise under the 21 commonly used conditions. The copolymerization may be accomplished in 22 one step or in two or more steps.
23 Effect of InventiOn 24 The catalyst component of this invention is useful for the product-.on of polyolefins, particularly isotactic polypropylene, 26 ethylene-propylene random copolymer, and ethylene-propylene block 27 cOpolymer.
28 The polymerization catalyst made from the catalyst component 29 of this invention exhibits a high catalytic activity and stereoregularities and keeps its high activity for a long time during 31 polymerization. It provides polymer powder having a high bulk density 32 and flowability.
33 Examples 34 The invention is described in more detail with reference to the following examples and application examples. The scope of this 36 invention is not limited by these examples. Percent (%) in the 37 examples and application examples means wt%, unless otherwise 38 indicated-~22~
1 The specific surface area (S.A.) and pore volume (P.V.) of 2 the catalyst component were measured by using SORPTOMATIC, Model 1810, 3 made by CARL0 ERBA.
4 The catalytic activity Kc is the quantity (g) of polymer formed per l 9 of catalyst, and Kt is the quantity (kg) of polymer 6 formed per l 9 of titanium in the catalyst.
7 The heptane insoluble (referred to as HI hereinafter) which 8 indicates the ratio of crystalline fractions in the polymer is the 9 quantity of residues which remain after extraction for 6 hours with boiling n-heptane in a Soxhlet apparatus of improved typeO
11 The melt flow rate (MFR) and melt index (Ml) were measured 12 according to ASTM-Dl238. The bulk density was measured according to 13 ASTM-Dl895-69, Method A.
14 Example l Contacting of Magnesium Diethoxide with Trichlorosilane 16 Into a 2-liter glass reactor equipped with a reflux 17 condenser, dropping funnel, and stirrer and replaced with nitrogen 18 were charged l20 9 (l.05 mol) of commercial magnesium diethoxide and 19 680 ml of n-heptane. With stirring at room temperature, a mixture of 356 9 (2.63 mol) of trichlorosilane and 250 ml of n-heptane was added 21 dropwise from the dropping funnel over 45 minutes. Stirring was 22 continued for 6 hours at 70C. During the reaction, a gas composed 23 mainly of ethylene and ethyl chloride formed. The resulting solids 24 were filtered off at 70C and then washed by stirring in 600 ml of n-hexane at 65C for lO minutes. The supernatant liquid was removed 26 by decantation. Washing with n-hexane was repeated 4 times, and the 27 solids were dried at 60C for l hour under reduced pressure. Thus 28 there was obtained l64 9 of solid component (I). This solid component 29 was found to contain l2.9% of magnesium, l4.l% of silicon, and 45.7%
of chlorine, and to have a specific surface area of 3l m2/g and a 31 pore volume of 0.08 cc/g.
32 Contacting with Benzoic Anhydride 33 l8 9 of the solid component (I) WdS placed in a 300-ml 3~ stainless steel (SUS3l6) mill pot containing lO0 pieces of stainless steel (SUS3l6) balls, 12 mm in diameter, under the nitrogen 36 atmosphere. Then 4.5 9 of ben~oic anhydride was added to the mill 37 pot. The mill pot was mounted on a shaker and shaken for l hour for 38 crushing. Thus there was obtained a solid component (II).
~' 1 Contacting with Triethyl Aluminum 2 7.0 9 of the solid component (II) was placed in a 200-ml 3 glass reactor equipped with a stirrer and dropping funnel under the 4 nitrogen atmosphere. Then 60 ml of n-heptane was added, followed by stirring to make slurry. Then a mixture of l.0 ml of triethyl 6 aluminum and 30 ml of n-heptane was added dropwise at room temperature 7 over l5 minutes. Reaction was continued at 50C for l hour. The 8 resulting solid substance was filtered off at 50C, followed by 9 washing four times with 90 ml portions of n-hexane at 50C. Thus there was obtained a solid component (III) in the form of slurry.
11 Contactiny with Titanium Tetrachloride 12 To the solid component (III) were added 40 ml of toluene and 13 60 ml of titanium tetrachloride, followed by stirring at 90C for 2 14 hours. The resulting solid substance was filtered off at 90C and washed 7 times with 90 ml portions of n-hexane at room temperature.
16 After drying at room temperature for l hour under reduced pressure, 17 there was obtained 5.4 9 of catalyst component containing 2.6% of 18 titanium, 17.2% of magnesium, 57.2% of chlorine, and 3.0% of silicon.
19 The specific surface area was 318 m2tg and the pore volume was 0.28 cc/g-21 Example 2 22 8.5 9 of the solid component (I) obtained in Example l was 23 placed in a 200-ml glass reactor equipped with a stirrer under the 24 nitrogen atmosphere. Then 90 ml of n-heptane and 3.0 9 of benzoyl chloride were added, followed by reaction at 70C for 2 hours. The 26 reaction product was washed 3 times with 90 ml portions of n-heptane 27 at 65C. Thus there was obtained the solid component (II). To this 28 solid component (II) were added 90 ml of n-heptane and 2.2 ml of 29 triethyl aluminum, followed by reaction at 50C for l hour. The reaction product was washed 5 times with 90 ml portions of n-heptane 31 to give the solid component (III) in the form of slurry. This solid 32 component (III) was contacted with titanium tetrachloride and treated 33 in the same way as in Example l. There was obtained a catalyst 34 component having the composition as shown in Table l.
ExamPle 3 36 The solid component (III) obtained in Example l was placed in 37 a 200-ml glass reactor eqwipped with a stirrer under the nitrogen 38 atmosphere. Then 40 ml of toluene and 60 ml of titanium tetrachloride were added, followed by stirring at 90C for 2 hours. After removal 2 of the supernatant liquid by decantation, the reaction product was 3 washed 4 times with 90 ml portions of toluene at 60C. Then 40 ml 4 of toluene and 60 ml of titanium tetrachloride were added again, followed by stirring at 90C for 2 hours.
6 The resulting solid substance was filtered off at 90C and 7 washed 7 times with 90 ml portions of n-hexane at room temperature, 8 followed by drying for l hour at room temperature under reduced 9 pressure. Thus there was obtained a catalyst component having the composition as shown in Table l.
11 Example 4 12 A catalyst component was prepared in the same way as in 13 Example 3 by contacting the solid component (III) obtained in Example 14 2 with titanium tetrachloride twice. The composition of the catalyst component is shown in Table l.
16 Example 5 17 The solid component (II) was obtained in the same way as in 18 Example l, except that benzoic anhydride was replaced by ethyl 19 benzoate. The solid component (II) was contacted with triethyl aluminum in the same way as in Example l to give the solid component 21 (III).
22 A catalyst cornponent was prepared in the same way as in 23 Example 3 by contacting this solid component (III) with titanium 24 tetrachloride twice. The composition of the catalyst component is shown in Table l.
26 Example 6 27 The solid component (II) was obtained in the same way as in 28 Example l, except that benzoic anhydride was replaced by 3.0 9 of 29 p-cresol and 4.5 ml of ethyl benzoate. The solid component (II) was contacted with triethyl aluminum in the same way as in Example l to 31 give the solid component (III).
32 A catalyst component was prepared in the same way as in 33 Example 3 by contacting this solid component (III) with titanium 34 tetrachloride twice. The composition of the catalyst component is shown in Table l.
36 Example 7 37 The solid component (III) was obtained in the same way as in 38 Example l by contacting the solid component (II) obtained in Example l ~%~
- l6 -1 with ethyl aluminum dichloride in place of triethyl aluminum. This 2 solid component (III) was then contacted with titanium tetrachloride 3 twice in the same way as in Example 3 to give a catalyst component.
4 The composition of the catalyst component is shown in Table l.
Example 8 6 The solid component (III) was obtained in the same way as in 7 Example 2 by contacting the solid component (II) obtained in Example 2 8 with diethyl aluminum chloride in place of triethyl aluminum. This 9 solid component (III) was then contacted with titanium tetrachloride twice in the same way as in Example 3 to give a catalyst component.
11 The composition of the catalyst component is shown in Table l.
12 Example 9 13 The solid component (III) was prepared in the same way as in 14 Example l, except that trichlorosile was replaced by metnyldichlorosilane. This solid component (III) was contacted with 16 titanium tetrachloride twice in the same way as in Example 3 to give a 17 catalyst component having the composition as shown in Table l.
18 Example lO
19 The solid component (I) was prepared in the same way as in Example l, except that trichlorosilane was replaced by 21 methyldichlorosilane. The solid component (II) was prepared in the 22 same way as in Example 2 by contacting with benzoyl chloride. The 23 solid component (III) was prepared by contacting with diethyl aluminum 24 chloride in the same way as in Example 8.
This solid component (III) was contacted with titanium 26 tetrachloride twice in the same way as in Example 3 to give a catalyst 27 component having the composition as shown in Table l.
28 Example ll 29 To the solid component (III) obtained in Example 7 were added 40 ml of toluene and 60 ml of titanium tetrachloride, followed by 31 stirring at 90C for 2 hours. After removal of the supernatant 32 liquid by decantation, 80 ml of toluene and 6.2 9 of hexachloroethane 33 were added, followed by reaction at 60C for l hour. After washing 34 4 times with 90 ml portions of toluene at 60C, 40 ml of toluene and 60 ml of titanium tetrachloride were added again, followed by stirring 36 at 90C for 2 hours.
- l7 -1 The resulting solid substance was filtered off at 90C and 2 washed 7 times with 90 ml portions of n-hexane at room temperature, 3 followed by drying for l hour at room temperature under reduced 4 pressur~. Thus there was obtained a catalyst component having the composition as shown in Table l.
6 Examples 12 and 13 7 The solid component (III) obtained in Example 2 was placed in 8 a 200-ml glass reactor equipped with a stirrer under the nitrogen 9 atmosphere. Then 40 ml of toluene and 60 ml of titanium tetrachloride were added, followed by stirring at 90C for 2 hours. After removal 11 Of the supernatant liquid by decantation, 85 ml of toluene and 6.3 9 12 of silicon tetrachloride (Example l2) or 5.2 9 of tin tetrachloride 13 (Example l3) were added, followed by stirring at 60C for l hour.
14 The reaction product was washed 4 times with 90 ml portions of toluene at 60C. Then 40 ml of toluene and 60 ml of titanium tetrachloride 16 were added, followed by stirring at 90C for 2 hours. The resulting 17 solid substance was filtered off at 90C and washed 7 times with 90 18 ml portions of n-hexane at room temperature, followed by drying for l 19 hour at room temperature under reduced pressure. Thus there was obtained a catalyst component having the composition as shown in Table 21 l.
22 Comparative Example l 23 Into the same mill pot as used in Example l were charged 24 under tbe nitrogen atmosphere 3l.5 9 of commercial magnesium diethoxide and lO.0 9 of benzoic anhydride. The mill pot was shaken 26 on a shaker for 15 hours.
27 5.0 9 of the resulting ground solid was placed in a 500-ml 28 glass container equipped with a stirrer, and 330 ml of n-heptane was 29 added and then 9 ml of titanium tetrachloride was added dropwise over l5 minutes. Further, 35 ml of trichlorosilane was added dropwise in 31 the same way, followed by stirring at 90C for 2 hours.
32 The resulting solid substance was filtered off at 90C and 33 washed 6 times with l50 ml portions of n-hexane at room temperature.
34 The solid substance was dried at room temperature for l hour under reduced pressure. Table l shows the compositions of the resulting 36 catalyst component.
37 Comparative Example 2 38 A catalyst component having the composition as shown in Table 1 1 was prepared in the same way as in Comparative Example 1, except 2 that benzoic anhydride was replaced by 7.5 ml of ethyl benzoate.
~L2~
Table 1 Silicon Compound-Catalyst Component treated Solid ~ Composition (%) Example My~ Sl Cl ~9 1 12.g 14.2 45.7 17.2 2.6 3.0 57.2 2 12.9 14.1 45.7 16.8 2.5 3.4 56.8 3 12.9 14.1 45.7 17.4 2.4 4.2 58.3 4 12.9 14.1 45.7 17.6 2.5 3.8 57.2 12.9 14.1 45.7 17.2 2.2 3.5 57.1 6 12.9 14.1 45.7 17.1 2.6 3.7 56.8 7 12.9 14.1 45.7 17.4 2.1 3.2 57.1 8 12.9 14.1 45.7 17.2 2.2 3.8 57.6 9 12.8 14.2 48.3 17.3 2.5 3.3 57.0 12.8 14.2 48.3 18.1 2.3 3.4 56.9 11 12.9 14.1 45.7 17.6 2.1 3.6 57.2 12 12.9 14.1 45.7 16.9 2.0 3.5 56.9 Comparative Example 1 - - - 15.2 5.3 0.6 44.1 2 - - - 14.3 5.9 0.6 42.6 2 ~ 3~;
1 Application Example l 2 Polymerization of Propylene 3 l9.3 mg of catalyst component obtained in Example l, 2.6 ml 4 of triethyl aluminum (abbreviated as TEAL hereinafter) solution in n-heptane, and 0.l4 ml of ethyl p-methoxybenzoate were mixed. After 6 standing for 5 minutes, the mixture was added to a 1.5-liter stainless 7 steel (SUS 32) autoclave equipped with a stirrer under the nitrogen 8 atmosphere. (The n-heptane solution of TEAL çontains l mol of TEAL in 9 l liter of n-heptane, and 2.6 ml of the solution corresponds to 250 gram atom of aluminum for l gram atom of titanium in the catalyst 11 component. 0.l4 ml of ethyl p-methoxybenzoate corresponds to 0.33 mol 12 for l gram atom of aluminum in TEAL.) Then, 0.6 liter of hydrogen as 13 the molecular weight modifier and 0.8 liter of liquefied propylene 14 were forced into the autoclave. The reaction system was heated to 70C, and the polymerization of propylene was carried out for l 16 hour. After the polymerization was complete, unreacted propylene was 17 purged. Thus there was obtained 26l 9 of white polypropylene powder 18 having an HI of 94.0% (heptane insolubles indicating the crystalline 19 fraction in the polymer), an MFR of 2.8 (melt flow rate), and a bulk density of 0.38 g/cm3.
21 Kc = l3,500 [quantity (9) of polymer formed per l 9 of catalyst]
22 Kt = 5l9 [quantity (kg) of polymer formed per l 9 of Ti in the 23 catalyst]
2~ Application Examples 2 to l5 Polymerization of propylene was carried out in the same way 26 as in Application Example l, except that the catalyst component 27 obtained in Example l was replaced by those which were obtained in 28 Examples 2 to l3 and Comparative Examples l and 2. The results are 29 shown in Table 2.
~2~
Table 2 MFR Bulk Application Catalyst Kc Kt Hl (9/lO density Example Component ~ (k~) (X) min) (g/cm3) 1 Example 1 13,500 519 9408 2.8 0.38 2 Example 2 12,600 504 95.2 3.2 0.38 3 Example 3 14,800 617 95.2 3.1 0.39 4 Example 4 14,500 580 95.5 2.7 0.39 Example 5 15,400 700 95.0 2.6 0.39 6 Example 6 16,200 623 95.5 2.4 0.39 7 Example 7 14,000 667 95.9 202 0.38 8 Example 8 14,800 673 96.0 2.2 0.39 9 Example 9 14,000 560 95.4 2.5 0.39 Example 10 13,800600 95.5 2.1 0.38 11 Example 11 15,500738 95.0 2.6 0.39 12 Example 12 15,800790 95.6 2.4 0.39 13 Example 13 15,600650 95.3 2.9 0.39 14 Comparative Example 1 480 9 86.7 - -Comparative Example 2 600 10 85.1
Claims (24)
PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. A catalyst component for the polymerization of olefins obtained by (1) reacting (A) Mg(OR)(OR') with (B) a silicon compound having at least one silicon-hydrogen bond, (2) contacting the reaction product with (C) an electron donor compound, (3) contacting the product from step (2) with an organoaluminum compound, and (4) contacting the step (3) product with a titanium compound, wherein R
and R' are radicals selected from alkyl, alkenyl, cycloalkyl, aryl and aralkyl radicals and R and R' may be the same or different.
and R' are radicals selected from alkyl, alkenyl, cycloalkyl, aryl and aralkyl radicals and R and R' may be the same or different.
2. The catalyst component of claim 1 wherein the titanium compound is selected from divalent, trivalent or tetravalent titanium halides, alkoxy titanium compounds and haloalkoxy titanium compounds.
.
.
3. The catalyst component of claim 2 wherein the titanium compound is titanium tetrachloride.
4. The catalyst component of claim 1 wherein the electron donors are selected from carboxylic acid esters, carboxylic acid and hydrides, carboxylic acid halides, alcohols and ethers.
5. The catalyst component of claim 4 wherein the electron donor is selected from benzoic anhydride, benzoyl chloride, ethyl benzoate, and p-cresol.
6. The catalyst component of claim 1 wherein the silicon compound is trichlorosilane.
7. The catalyst component of claim 1 wherein R and R' are alkyl radicals having from 1 to 8 carbon atoms.
8. The catalyst component of claim 7 wherein R and R' are ethyl.
9. The catalyst component of claim 1 wherein the organoaluminum compound is one of triethylaluminum, diethylaluminum ch1oride, ethylaluminum sesquichloride and ethylaluminum dichloride.
10. The catalyst component of claim 1 wherein the step (3) product is contacted with the titanium compound two or more times.
11. The catalyst component of claim 10 wherein between at least one of a multiple titanium compound contacts, contacting the titanium compound contacted solid is treated with a halogenated hydrocarbon.
12. A catalyst system for the polymerization of olefins comprising the catalyst component of claim 1 and an organoaluminum cocatalyst.
13. A catalyst system for the polymerization of olefins comprising the catalyst component of claim 2 and an organoaluminum cocatalyst.
14. A catalyst system for the polymerization of olefins comprising the catalyst component of any one of claims 3, 4 or 5, and an organoaluminum cocatalyst.
15. A catalyst system for the polymerization of alphaolefins comprising the catalyst component of any one of claims 6, 7 or 8 and an organoaluminum cocatalyst.
16. A catalyst system for the polymerization of alphaolefins comprising the catalyst component of any one of claims 9, 10 or 11 and an organoaluminum cocatalyst.
17. A catalyst component for the polymerization of olefins obtained by (1) reacting (a) magnesium diethoxide with (b) trichlorosilane, (2) contacting the reaction product with (c) ethylbenzoate, (3) contacting the product from (2) with triethylaluminum, and (4) contacting the step (3) product with at least one treatment of titanium tetrachloride.
18. The catalyst component of claim 17 wherein the product from step (3) is contacted with titanium tetrachloride two times.
.
.
19. The catalyst component of claim 17 wherein one mol of component (a) is contacted with 0.5 to 10 mol component (b), the electron donor is used in an amount of 0.01 to 10 gram mol for 1 gram atom of magnesium in the reaction product of step 1, the organoaluminum compound is used in an amount of 0.1 to 20 mol per mol of electron donor compound and the titanium compound is used in the amount of more than 0.1 gram mol per 1 gram atom of magnesium in the contact product of step (3).
20. The catalyst component of claim 19 wherein the titanium compound is used in an amount of 1 to 50 gram mol per gram atom of magnesium.
21. A catalyst system for the polymerization of olefins comprising the catalyst component of claim 17 and an organoaluminum cocatalyst.
22. A catalyst system for the polymerization of olefins comprising the catalyst component of claim 18 and an organoaluminum cocatalyst.
23. A catalyst system for the polymerization of olefins comprising the catalyst component of claim 19 and an organoaluminum cocatalyst.
24. A catalyst system for the polymerization of olefins comprising the catalyst component of claim 20 and an organoaluminum cocatalyst.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP157,094/83 | 1983-08-30 | ||
| JP58157094A JPS6049007A (en) | 1983-08-30 | 1983-08-30 | Catalyst component for olefin polymerization |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1221956A true CA1221956A (en) | 1987-05-19 |
Family
ID=15642114
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000462037A Expired CA1221956A (en) | 1983-08-30 | 1984-08-29 | Catalyst component for polymerization of olefins |
Country Status (5)
| Country | Link |
|---|---|
| US (2) | US4551440A (en) |
| EP (1) | EP0136113B1 (en) |
| JP (1) | JPS6049007A (en) |
| CA (1) | CA1221956A (en) |
| DE (1) | DE3464372D1 (en) |
Families Citing this family (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0629288B2 (en) * | 1984-06-21 | 1994-04-20 | 東燃株式会社 | Olefin polymerization catalyst component |
| JPH0725807B2 (en) * | 1985-12-20 | 1995-03-22 | 東燃株式会社 | Method for producing catalyst component for olefin polymerization |
| US4738942A (en) * | 1985-12-23 | 1988-04-19 | Mobil Oil Corporation | Catalyst composition for polymerizing alpha-olefin polymers of relatively narrow molecular weight distribution and high melt index |
| US4885349A (en) * | 1985-12-23 | 1989-12-05 | Mobil Oil Corporation | Process for polymerizing alpha-olefin polymers of relatively narrow molecular weight distribution and high melt index |
| US5155187A (en) * | 1989-10-25 | 1992-10-13 | Quantum Chemical Corporation | Polymerization method |
| US5001099A (en) * | 1989-10-25 | 1991-03-19 | Quantum Chemical Corporation | Polymerization catalyst |
| US5126302A (en) * | 1990-04-30 | 1992-06-30 | Quantum Chemical Corporation | Olefin polymerization catalyst and methods |
| US5182341A (en) * | 1990-04-30 | 1993-01-26 | Masino Albert P | Olefin polymerization method |
| EP0846706B1 (en) * | 1996-12-06 | 2000-07-05 | Asahi Kasei Kogyo Kabushiki Kaisha | Olefin polymerization catalyst and preparation process of polyolefin using the same |
| US5990034A (en) | 1996-12-06 | 1999-11-23 | Asahi Kasei Kogyo Kabushiki Kaisha | Olefin polymerization catalyst |
| FI991069A0 (en) * | 1999-05-10 | 1999-05-10 | Borealis As | Preparation and use of a catalyst component comprising magnesium, titanium, halogen and an electron donor |
| KR100816951B1 (en) * | 2001-09-20 | 2008-03-25 | 삼성토탈 주식회사 | A method for ethylene polymerization and co-polymerization |
| JP5695869B2 (en) * | 2010-09-28 | 2015-04-08 | 日本ポリエチレン株式会社 | Ziegler-Natta catalyst reforming method, modified Ziegler-Natta catalyst, olefin polymerization method using the same, and obtained olefin polymer |
| EP3596136A1 (en) * | 2017-03-17 | 2020-01-22 | SABIC Global Technologies B.V. | Process for the polymerization of a polyolefin |
Family Cites Families (19)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3135809A (en) * | 1960-07-21 | 1964-06-02 | Southern Res Inst | Isomerization process |
| LU61816A1 (en) * | 1970-10-06 | 1972-06-28 | ||
| IT1042711B (en) * | 1975-09-19 | 1980-01-30 | Montedison Spa | COMPONENTS OF CATALYSTS FOR THE POLYMERIZATION OF OLEFINS |
| JPS5298076A (en) * | 1976-02-13 | 1977-08-17 | Mitsubishi Chem Ind Ltd | Preparation of polyolefins |
| JPS607642B2 (en) * | 1977-02-16 | 1985-02-26 | 旭化成株式会社 | Catalyst for production of polyalphaolefin |
| DE2742585A1 (en) * | 1976-09-28 | 1978-03-30 | Asahi Chemical Ind | NEW POLYMERIZATION CATALYSTS AND THEIR USE (I) |
| JPS6025441B2 (en) * | 1976-09-30 | 1985-06-18 | 三井化学株式会社 | Solid catalyst components and catalysts for olefin polymerization |
| US4242479A (en) * | 1976-12-23 | 1980-12-30 | Showa Yuka Kabushiki Kaisha | Process for producing an improved ethylenic polymer |
| IT1078995B (en) * | 1977-05-24 | 1985-05-08 | Montedison Spa | CATALYSTS FOR THE POLYMERIZATION OF OLEFINE |
| US4159256A (en) * | 1977-06-02 | 1979-06-26 | Asahi Kasei Kogyo Kabushiki Kaisha | Catalyst for polymerizing olefins and polymerization method of olefins carried out therewith |
| JPS584726B2 (en) * | 1978-03-15 | 1983-01-27 | 旭化成株式会社 | Olefin polymerization catalyst |
| IT1099416B (en) * | 1978-10-23 | 1985-09-18 | Montedison Spa | COMPONENTS AND CATALYSTS FOR THE POLYMERIZATION OF OLEFINS |
| US4324690A (en) * | 1979-02-15 | 1982-04-13 | Standard Oil Company (Indiana) | Alpha-olefin polymerization catalyst |
| US4250287A (en) * | 1980-03-14 | 1981-02-10 | Hercules Incorporated | 1-Olefin polymerization catalyst |
| JPS56155205A (en) * | 1980-05-02 | 1981-12-01 | Shindaikiyouwa Sekiyu Kagaku Kk | Production of polyolefin |
| JPS5763309A (en) * | 1980-10-03 | 1982-04-16 | Idemitsu Kosan Co Ltd | Polymerization of alpha-olefin |
| JPS57108107A (en) * | 1980-12-25 | 1982-07-06 | Asahi Chem Ind Co Ltd | Catalyst for olefin polymerization |
| ATE22452T1 (en) * | 1982-02-12 | 1986-10-15 | Mitsui Petrochemical Ind | PROCESS FOR PRODUCTION OF POLYMERS OF OLEFINS. |
| US4472521A (en) * | 1982-12-20 | 1984-09-18 | Stauffer Chemical Company | Supported catalyst for polymerization of olefins |
-
1983
- 1983-08-30 JP JP58157094A patent/JPS6049007A/en active Granted
-
1984
- 1984-08-20 US US06/642,463 patent/US4551440A/en not_active Expired - Fee Related
- 1984-08-29 CA CA000462037A patent/CA1221956A/en not_active Expired
- 1984-08-30 EP EP84305956A patent/EP0136113B1/en not_active Expired
- 1984-08-30 DE DE8484305956T patent/DE3464372D1/en not_active Expired
-
1985
- 1985-08-15 US US06/765,763 patent/US4588793A/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| US4588793A (en) | 1986-05-13 |
| EP0136113A3 (en) | 1985-05-29 |
| EP0136113B1 (en) | 1987-06-24 |
| US4551440A (en) | 1985-11-05 |
| EP0136113A2 (en) | 1985-04-03 |
| DE3464372D1 (en) | 1987-07-30 |
| JPS6049007A (en) | 1985-03-18 |
| JPH0149291B2 (en) | 1989-10-24 |
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