CA1114098A - Process for producing ethylene copolymers - Google Patents
Process for producing ethylene copolymersInfo
- Publication number
- CA1114098A CA1114098A CA325,070A CA325070A CA1114098A CA 1114098 A CA1114098 A CA 1114098A CA 325070 A CA325070 A CA 325070A CA 1114098 A CA1114098 A CA 1114098A
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- Prior art keywords
- titanium
- compound
- process according
- unsaturated hydrocarbon
- hydrocarbon monomer
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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
- C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F210/16—Copolymers of ethene with alpha-alkenes, e.g. EP rubbers
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
ABSTRACT OF THE DISCLOSURE
A process for producing ethylene copolymers having a density of 0.900 - 0.940 by copolymerizing ethylene with other unsaturated hydrocarbon monomer in the presence of a catalyst comprising a titanium and/or vanadium compound and an organo aluminum compound, which comprises using a titanium and/or vanadium compound supported on a magnesium compound as a catalyst component and carrying out the copolymerization reaction in a liquid phase of said unsaturated hydrocarbon monomer.
The polymer produced according to this process has a variety of advantages over conventional high-pressure low-density polyethylenes in that it has a higher strength, a higher stiffness, a higher softening point, a higher cold resistance (particularly low-temperature impact resistance), a higher melt extensi-bility, a higher stress cracking resistance, etc., so that it can be put to use not only in the application fields of conventional high-pressure low-density polyethylenes but also in a wide variety of novel application fields.
A process for producing ethylene copolymers having a density of 0.900 - 0.940 by copolymerizing ethylene with other unsaturated hydrocarbon monomer in the presence of a catalyst comprising a titanium and/or vanadium compound and an organo aluminum compound, which comprises using a titanium and/or vanadium compound supported on a magnesium compound as a catalyst component and carrying out the copolymerization reaction in a liquid phase of said unsaturated hydrocarbon monomer.
The polymer produced according to this process has a variety of advantages over conventional high-pressure low-density polyethylenes in that it has a higher strength, a higher stiffness, a higher softening point, a higher cold resistance (particularly low-temperature impact resistance), a higher melt extensi-bility, a higher stress cracking resistance, etc., so that it can be put to use not only in the application fields of conventional high-pressure low-density polyethylenes but also in a wide variety of novel application fields.
Description
1 This invention relates to a process for produc-ing an ethylene copolymer having a density of 0.900 -0.940 by copolymerizing ethylene with other unsaturated hydrocarbon monomer in a liquid phase of said unsaturated hydrocarbon monomer.
Medium-density ethylene polymers can be produced by copolymerizing ethylene with an ~-olefin such as l-butene ln the state of slurry in an inert hydrocarbon solvent by the low-moderate pressure process. However, 10 in this case, the resulting polymer deposits on the inner wall of reactor to produce troubles about heat conduction, agitation, discharge of polymer, etc. In addition, the resulting polymer particles tend to be bulky and irregular which decreases space yield and 15 incurs troubles about transportation of polymer.
Therefore, a commercial production according to this process encounters difficulty in respect of cost and many other problems.
Apart from above, the polymerization of 20 propylene in liquid propylene and its copolymerization with a samll quantity of other unsaturated hydrocarbon monomer in liquid propylene (hereinafter referred to as bulk polymerization) are disclosed and extensively practised industrially. Homopolymerization of l-butene ; 25 in liquid l-butene and copolymerization of l-butene 1- ~
~ ' f ''': ' ' ~ . ' '' :
,. ' ' ~
' ~, ~ ' ' '' '; :
- ' : ' ' : , 9fl 1 with a small quantity of unsaturated hydrocarbon monomer such as propylene, decene, octadecene or the like in liquid l-butene are also disclosed.
Nevertheless, production of low-density or medium-density ethylene polymer having an ethylene content of overwhelming majority by bulk copolymerization of ethylene with an unsaturated hydrocarbon monomer in the liquid medium of said unsaturated hydrocarbon monomer has not yet been practised industrially.
On the other hand, it is well known that a catalyst system comprising a combination of a compound of transition metal belonging to Group IVb-VIb of the periodic table and an organometallic compound of a metal belonging to Group I-III of the periodic table (the so-called Ziegler catalyst) is effective for the polymerization of olefins. Further, many studies have hitherto been conducted with respect to the catalysts comprising a transition metal compound supported on a carrier to reveal that inorganic compounds such as oxides, hydroxides, chlorides and carbonates of metals or silicon as well as mixtures or double salts thereof are effective as the carrier. For example, magnesium chloride, double oxide of magnesium and aluminum, double oxide of magnesium and calcium and the like are known to be effective as the carrier.
; However, the catalyst for use in the production of polyolefin is desired to have a catalytic activity as high as possible. In fact, even the catalysts ~ .
, .. . . , . .. .. - . . , , , : . . . -.
. ~' ' ~' . , . : ' .
l mentioned above are still insufficient in catalytic activity. When applied to the production of low-medium density ethylene polymers, these catalysts cannot prevent the aforementioned difficulties encountered in the slurry polymerization in an inert hydrocarbon solvent, so that they cannot be said to be satisfactory industrially.
Previously (Belg. Pat. No. 849,503) the present inventors discovered that a catalyst obtainable by combining an organoaluminum compound with a solid catalyst component prepared by supporting a titanium and/or vanadium compound on a solid product obtainable by reacting an organomagnesium compound with a halogenated aluminum compound and/or a halogenated silicon compound can aot as a catalyst of very high activity for the polymerization of olefins. The inventors have conducted further advanced studies concerning the polymerization of olefin by the use of the above-mentloned high active catalyst. As the result, it has been found that, if the above-mentioned catalyst is used, a low-density or medium-denslty ethylene polymer can be produced with a very high activity and without any deashing process by bulk-copolymerizing ethylene with an unsaturated hydrocarbon ~; 25 monomer in a liquid phase comprising said unsaturated ` hydrocarbon monomer, and further that, in the polymeri-~; ~ zation reaction, a polymer having better slurry characteristics and a high bulk density can be obtained -: " '. ' . , , !
i. : ' ~ ' ' ' ~ ' ' "'. ~ ' ~ ' , ... ,, ' .
" . ' . . . ' - ~, ~.~1.4~
l with a less adhesion of polymer to the inner wall of reactor.
Thus, it is an object of the present invention to provide a process for producing, with a high activity, an ethylene polymer having good slurry characteristics by copolymerizing a large quantity of ethylene with a small quantity of unsaturated hydrocarbon monomer in the liquid phase of unsaturated hydrocarbon monomer.
Other ob~ects and advantages of the present invention will be apparent from the following descriptions:
According to the present invention, there is : provided a process for producing a low-denslty or medium-density ethylene polymer having a density of 0.900 - 0.940 which comprlses copolymerizing ethylene with other unsaturated hydrocarbon monomer in a liquid pha~e comprising said unsaturated hydrocarbon monomer in the presence of a catalyst system comprising an organo-aluminum compound and a solid catalyst component prepared by supporting a titanium and/or vanadium compound on a solid product obtainable by reacting an organomagnesium compound with a halogenated aluminum . compound represented by the following general formula:
: R nAlX3_n .~ 25 wherein Rl is an alkyl, aryl or alkenyl group having up to 20 carbon atoms, X is a halogen atom and n is a number defined by O ~ n ~ 3, and/or with a halogenated silicon ....
:. , , . . : . -~: , . . . ~ ~ ., .
~, . . . : - , . ~ . . - . , , - - . - . -.
, . ,,: , , - , , . - : , .
. , . - , . . . . .. :
.. , - .... , - . ..
., - , . ~ . .
4~ ~ ~
l compound represented by the following general formula:
R2mSiX4 m wherein R2 is an alkyl, aryl or alkenyl group having up to 20 carbon atoms, X is a halogen atom and m is a number defined by 0 _ m < 4.
The unsaturated hydrocarbon monomers used in the liquid state in the present invention are C3-C8 ~-olefins. Examples of said unsaturated hydrocarbon monomer include propylene, l-butene, 1-pentene, l-hexene, l-octene and the like, among which l-butene is particu-larly preferable.
me ethylene polymer constructing the ob~ect of this invention is a copolymer of a major percentage (preferably, 80 - 99%) by mole of ethylene and a minor percentage (preferably, l - 20%) by mole of at least one kind of unsaturated hydrocarbon monomer. Density of the copolymer can be controlled mainly by varying the quantity of unsaturated hydrocarbon monomer to be copolymerized with ethylene. Density of the ethylene homopolymer obtainable with the catalyst system of this invention depends on its molecular weight. Roughly speaking, however, the density is about 0.96. It is possible to lower the density of copolymer arbitrarily by lncreasing the content of unsaturated hydrocarbon monomer used as comonomer. In order to obtain a polymer having a density falling in the intended range, it is necessary to introduce l - 20 mole-% of unsaturated ;~: - 5 -:
., . , ~ . . . ~. , ' : .
. . . ~ .
~ . . . , ~
- . ~ . .
4t~
1 hydrocarbon monomer into the ethylene copolymer. The amount of unsaturated hydrocarbon monomer to be introduced necessary for obtaining the same density varies depending on the species of monomer. mere is a general tendency that a monomer having a longer side chain after being polymerized may be introduced into copolymer in a smaller amount by mole. For example, when the comonomer is l-butene, one must introduce about 5 - 18 mole-% of l-butene into the copolmer in order to produce a low-density ethylene polymer having a density of 0.900 - 0.925, while one must introduce about
Medium-density ethylene polymers can be produced by copolymerizing ethylene with an ~-olefin such as l-butene ln the state of slurry in an inert hydrocarbon solvent by the low-moderate pressure process. However, 10 in this case, the resulting polymer deposits on the inner wall of reactor to produce troubles about heat conduction, agitation, discharge of polymer, etc. In addition, the resulting polymer particles tend to be bulky and irregular which decreases space yield and 15 incurs troubles about transportation of polymer.
Therefore, a commercial production according to this process encounters difficulty in respect of cost and many other problems.
Apart from above, the polymerization of 20 propylene in liquid propylene and its copolymerization with a samll quantity of other unsaturated hydrocarbon monomer in liquid propylene (hereinafter referred to as bulk polymerization) are disclosed and extensively practised industrially. Homopolymerization of l-butene ; 25 in liquid l-butene and copolymerization of l-butene 1- ~
~ ' f ''': ' ' ~ . ' '' :
,. ' ' ~
' ~, ~ ' ' '' '; :
- ' : ' ' : , 9fl 1 with a small quantity of unsaturated hydrocarbon monomer such as propylene, decene, octadecene or the like in liquid l-butene are also disclosed.
Nevertheless, production of low-density or medium-density ethylene polymer having an ethylene content of overwhelming majority by bulk copolymerization of ethylene with an unsaturated hydrocarbon monomer in the liquid medium of said unsaturated hydrocarbon monomer has not yet been practised industrially.
On the other hand, it is well known that a catalyst system comprising a combination of a compound of transition metal belonging to Group IVb-VIb of the periodic table and an organometallic compound of a metal belonging to Group I-III of the periodic table (the so-called Ziegler catalyst) is effective for the polymerization of olefins. Further, many studies have hitherto been conducted with respect to the catalysts comprising a transition metal compound supported on a carrier to reveal that inorganic compounds such as oxides, hydroxides, chlorides and carbonates of metals or silicon as well as mixtures or double salts thereof are effective as the carrier. For example, magnesium chloride, double oxide of magnesium and aluminum, double oxide of magnesium and calcium and the like are known to be effective as the carrier.
; However, the catalyst for use in the production of polyolefin is desired to have a catalytic activity as high as possible. In fact, even the catalysts ~ .
, .. . . , . .. .. - . . , , , : . . . -.
. ~' ' ~' . , . : ' .
l mentioned above are still insufficient in catalytic activity. When applied to the production of low-medium density ethylene polymers, these catalysts cannot prevent the aforementioned difficulties encountered in the slurry polymerization in an inert hydrocarbon solvent, so that they cannot be said to be satisfactory industrially.
Previously (Belg. Pat. No. 849,503) the present inventors discovered that a catalyst obtainable by combining an organoaluminum compound with a solid catalyst component prepared by supporting a titanium and/or vanadium compound on a solid product obtainable by reacting an organomagnesium compound with a halogenated aluminum compound and/or a halogenated silicon compound can aot as a catalyst of very high activity for the polymerization of olefins. The inventors have conducted further advanced studies concerning the polymerization of olefin by the use of the above-mentloned high active catalyst. As the result, it has been found that, if the above-mentioned catalyst is used, a low-density or medium-denslty ethylene polymer can be produced with a very high activity and without any deashing process by bulk-copolymerizing ethylene with an unsaturated hydrocarbon ~; 25 monomer in a liquid phase comprising said unsaturated ` hydrocarbon monomer, and further that, in the polymeri-~; ~ zation reaction, a polymer having better slurry characteristics and a high bulk density can be obtained -: " '. ' . , , !
i. : ' ~ ' ' ' ~ ' ' "'. ~ ' ~ ' , ... ,, ' .
" . ' . . . ' - ~, ~.~1.4~
l with a less adhesion of polymer to the inner wall of reactor.
Thus, it is an object of the present invention to provide a process for producing, with a high activity, an ethylene polymer having good slurry characteristics by copolymerizing a large quantity of ethylene with a small quantity of unsaturated hydrocarbon monomer in the liquid phase of unsaturated hydrocarbon monomer.
Other ob~ects and advantages of the present invention will be apparent from the following descriptions:
According to the present invention, there is : provided a process for producing a low-denslty or medium-density ethylene polymer having a density of 0.900 - 0.940 which comprlses copolymerizing ethylene with other unsaturated hydrocarbon monomer in a liquid pha~e comprising said unsaturated hydrocarbon monomer in the presence of a catalyst system comprising an organo-aluminum compound and a solid catalyst component prepared by supporting a titanium and/or vanadium compound on a solid product obtainable by reacting an organomagnesium compound with a halogenated aluminum . compound represented by the following general formula:
: R nAlX3_n .~ 25 wherein Rl is an alkyl, aryl or alkenyl group having up to 20 carbon atoms, X is a halogen atom and n is a number defined by O ~ n ~ 3, and/or with a halogenated silicon ....
:. , , . . : . -~: , . . . ~ ~ ., .
~, . . . : - , . ~ . . - . , , - - . - . -.
, . ,,: , , - , , . - : , .
. , . - , . . . . .. :
.. , - .... , - . ..
., - , . ~ . .
4~ ~ ~
l compound represented by the following general formula:
R2mSiX4 m wherein R2 is an alkyl, aryl or alkenyl group having up to 20 carbon atoms, X is a halogen atom and m is a number defined by 0 _ m < 4.
The unsaturated hydrocarbon monomers used in the liquid state in the present invention are C3-C8 ~-olefins. Examples of said unsaturated hydrocarbon monomer include propylene, l-butene, 1-pentene, l-hexene, l-octene and the like, among which l-butene is particu-larly preferable.
me ethylene polymer constructing the ob~ect of this invention is a copolymer of a major percentage (preferably, 80 - 99%) by mole of ethylene and a minor percentage (preferably, l - 20%) by mole of at least one kind of unsaturated hydrocarbon monomer. Density of the copolymer can be controlled mainly by varying the quantity of unsaturated hydrocarbon monomer to be copolymerized with ethylene. Density of the ethylene homopolymer obtainable with the catalyst system of this invention depends on its molecular weight. Roughly speaking, however, the density is about 0.96. It is possible to lower the density of copolymer arbitrarily by lncreasing the content of unsaturated hydrocarbon monomer used as comonomer. In order to obtain a polymer having a density falling in the intended range, it is necessary to introduce l - 20 mole-% of unsaturated ;~: - 5 -:
., . , ~ . . . ~. , ' : .
. . . ~ .
~ . . . , ~
- . ~ . .
4t~
1 hydrocarbon monomer into the ethylene copolymer. The amount of unsaturated hydrocarbon monomer to be introduced necessary for obtaining the same density varies depending on the species of monomer. mere is a general tendency that a monomer having a longer side chain after being polymerized may be introduced into copolymer in a smaller amount by mole. For example, when the comonomer is l-butene, one must introduce about 5 - 18 mole-% of l-butene into the copolmer in order to produce a low-density ethylene polymer having a density of 0.900 - 0.925, while one must introduce about
2 - 5 mole-~ of l-butene in order to produce a medium-density ethylene polymer having a density of 0.926 -0.940. Since C3-C8 ~-olefins show different monomer reactlvity ratio from species to species in the ;~ copolymerization reaction with ethylene in the presence of the catalyst of this invention, the partlal pressure of ethylene to be fed into reactor is greatly dependent ; on the kind of C3-C8 olefin. On the other hand, the ; 20 proportion of unsaturated hydrocarbon monomer to be copolymerized is dependent on the ratio between an unsaturated hydrocarbon monomer and ethylene in liquid phase. In other words, a higher partial pressure o~
, , , ~. ~ ., ethylene gives a higher ethylene content of the copolymer.
Accordingly, a copolymer having an intended content of the unsaturated hydrocarbon monomer unit can be produced at will by changing the partial pressure of ethylene appropriately.
.. . - :-. . . - - -. : .
.. ~. , ... . . , . - . . . , ~ ..
. . , ... ~ . :. - . - . - ... . .. . , . ~ .
... . . , , . . .. . .: . , . -,,. . .. - .. ; . . , ~ .. : : ... . , : :
. - . . - , . . , , . . , -. . - . , 1 The polymer slurry of this invention obtainable by the bulk copolymerization in an unsaturated hydrocarbon monomer such as l-butene has a great merit as compared with a polymer slurry obtainable by conventional suspen-sion polymerization process (or solvent polymerization) in which the polymerization is carried out in general -in the medium of liquid saturated hydrocarbon having 5 - 7 carbon atoms, in that the polymer can be isolated merely by a simple procedure of removing the unreacted unsaturated hydrocarbon monomer.
Thus, the necessary procedures are only to copolymerlze a lique~ied unsaturated hydrocarbon monomer with ethylene under an elevated pressure and to recover and reuse the unreacted monomer after the reaction. In this case, recovery of solvent is unnecessary unlike conventional solvent polymerization, and the charge system attached to the polymerization reactor can be simplified. Therefore, the process provided herein is considerably simple and economical.
The polymer produced according to the process of this invention has a variety of advantages over conventional high-pressure low-density polyethylenes in that it has a higher strength, a higher stiffness, a higher softening point, a higher cold resistance (particularly low-temperature impact resistance), a higher melt extensibility, a higher stress cracking resistance, etc., so that it can be put to use in the application fields of conventional high-pressure -.
. : ~
~ 7 ~
. ,., , . ~ - .. . .
, . .. .
.
.
: , I . .', ' . ~ ~ ~
. ~ .
..
, , , . - -.~ ' . '. - :
ofl 1 low-density polyethylenes but also in a wide variety of novel application fields.
The catalyst used in this invention comprises a combination of an organoaluminum compound and a solid catalyst component prepared by supporting a tltanium compound and/or a vanadium compound on a solid product obtainable by reacting an organomagnesium compound with a halogenated aluminum compound represented by the following general formula:
RlnAlX3 n whereln R is an alkyl, cycloalkyl, aryl or alkenyl group having up to 20 carbon atoms, X is a halogen atom .
and n is a number defined by 0 _ n < 3, or with a halogenated silicon compound represented by the following general formula:
R msix4-m wherein R2 is an alkyl, cycloalkyl, aryl or alkenyl group having up to 20 carbon atoms, X is a halogen atom and m is a number defined by 0 < m < 4.
In this invention, the organomagnesium compound used for the synthesis of catalyst may be selected from any forms of organomagnesium compounds obtainable by reacting an organic halogen compound with metallic magnesium.
As said organomagnesium compound, Grignard compounds represented by the following general formula:
, . .
:. ... . . ~ .. . . - . . . . ..
, ~ : , , , , - . . :.
., ., .. , . ... , . . .. .. ... ~... ..... . .. - .... ..
, . , . . . . .. ,. . - .
. .
- . . - . . . .. -.: . - . .
- . .. .. . :: . .. .: - . - : :
.. : .. . . . ~ . :, ~ - . .: .- .
fl l R3MgX
wherein R3 is an alkyl, aryl or alkenyl group having up to 20 carbon atoms, and X is a halogen atom, and organo-magnesium compounds represented by the following general formula:
R32Mg can be used preferably.
Said organomagnesium compound includes all the possible compositions expressed by the following equilibrium equation:
2R3MgX ~ R32Mg + MgX2 ~ R32Mg.MgX2 notwithstanding whether or not said organomagnesium compound has been prepared in the presence of ether ~W. Shlenk et al., Ber., 62, 920 (1929); ibid. 64, 739 ( 19 31 ) ~ 7rct ~,~
Herein, R3 represents an alkyl, aryl~ror alkenyl group having up to 20 carbon atoms~ such as methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, n-amyl, lso-amyl, n-hexyl, n-octyl, 2-ethylhexyl, phenyl, benzyl and the like. Concrete ~ examples of said organomagnesium compound, expressed ;~ in terms of Grignard compounds, include ethylmagnesium ; chloride, ethylmagnesium bromide, n-propylmagnesium . .
~ chloride, n-butylmagnesium chloride, tert-butylmagnesium ., ........... . . ... -`;~ - . - ~ .. ' .. . . :
.: . . . . . . . . .
~ .. ~......... . . . ~ .
l chloride, n-amylmagnesium chloride, phenylmagnesium bromide and the like.
Organomagnesium compounds represented by the general ~ormula R32Mg are also included in the organo-magnesium compounds of this invention, as indicated bythe aforementioned equilibrium equation. Their concrete examples include diethylmagnesium, dipropylmagnesium, dibutylmagnesium, diamylmagnesium, dihexylmagnesium~
dioctylmagnesium, diphenylmagnesium, dibenzylmagnesium and the li~e.
These organomagnesium compounds are synthesized and used in the presence of an ethereal solvent such as ethyl ether, propyl ether, butyl ether, amyl ether, tetrahydrofuran, dioxane and the like; hydrocarbon solvents such as hexane, heptane, octane, cyclohexane, benzene, toluene, xylene and the like; or a mixture of an ethereal solvent and a hydrocarbon solvent. Among these solvents, ethereal solvents are particularly preferable.
The halogenated aluminum compound represented by general formula R nAlX3 n includes all the compounds having an aluminum-halogen bond (Al-X). A compound having a larger number of halogen atoms gives a better result, and anhydrous aluminum chloride is most preferable. m e halogenated silicon compound represented by general formula R2mSiX4 m includes all the compounds having a silicon-halogen bond (Si-X). A compound having a larger number of halogen atoms gives a better result, and silicon tetrachloride is most preferable. In the general . ~ . . - - .
. , . .. : : . .: .. .: .. . - . . : , . : :
.. .: .: . ~ - . : ~ .
. ~ : . . , . ' ' ' ' -. ~
.
4~?~
1 formulas~ R~ and ~2 represent an alkyl, cycloalkyl, ¦ aryl~or alkenyl group having up to 20 carbon atoms.
Concrete examples of Rl and R2 include methyl, ethyl, n-propyl, iso-propyl, n-butyl, sec-butyl, tert-butyl, n-amyl, iso-amyl, n-hexyl, n-heptyl, n-octyl, vinyl, allyl, cyclopentyl, cyclohexyl, phenyl, benzyl and the like. X represents halogen atom, of which concrete examples include chlorine, bromine and iodine. n represents a number defined by 0 < n < 3, and m represents a number defined by 0 < m < 4. Concrete examples of said halogenated aluminum compound include anhydrous aluminum chloride, aluminum bromide, aluminum iodide, diethyl-aluminum chloride, ethylaluminum dichloride, ethylaluminum sesquichloride, dibutylaluminum chloride, butylaluminum dichloride, dihexylaluminum bromide, hexylaluminum dlbromide and the like. Concrete examples of said halogenated silicon compound include silicon tetra-chloride, silicon tetrabromide, methylsilyl trichloride, dimethylsllyl dichloride, trimethylsilyl chloride, ethylsilyl trichloride, diethylsilyl dichloride, triethylsilyl chloride, propylsilyl tribromide, dipropylsilyl dibromide, tripropylsilyl bromide, dibutylsilyl dichloride, tributylsilyl chloride, vinylsilyl trichloride and the like.
The synthetic reactions of the catalyst are all carried out in an atmosphere of inert gas such as nitrogen, argon or the like. The reaction between the organomagnesium compound and the halogenated aluminum .
.
.
::~ , . . - : - -- , . ' :
- ~ . , . . ~ -' 1 compound and/or halogenated silicon compound is prefer-ably carried out in a solvent at a temperature of 0 -100C, though the reaction may be carried out at a high temperature of 100C or above. The solvents usable in this reaction include aliphatic hydrocarbons such as pentane, hexane, heptane, octane and the like; aromatic hydrocarbons such as benzene, toluene, xylene and the like, alicyclic hydrocarbons such as cyclohexane, cyclopentane and the like; ethereal solvents such as ethyl ether, butyl ether, amyl ether, tetrahydrofuran, dioxane and the like; and mixtures of hydrocarbon solvents and ethereal solvents Among these solvents, ethereal solvents are particularly preferable.
Said organomagnesium compound is reacted with sald halogenated aluminum compound and/or said halogenated silicon compound in a proportion of 0.1 - 10.0 and preferably 0.5 - 2.0, by mole. The reaction product is precipitated in the form of a solid.
The reaction product obtained as above is isoIated and then used as a carrier. Concretely speaking, the reaction product is used after being filtered, or subsequently thoroughly washed with a purified hydro- -carbon diluent, or further dried. Then, a titanium compound and/or a vanadium compound is supported on the carrier synthesized as above.
Examples of the titanium compound and the vanadium compound to be supported on the carrier include titanium trichloride, titanium compounds represented by the , ~: : - . .. . - .. . : .
; ` ' ~'', ' ,' . ~ ' ' ' ' . ' . . : , .: . , ' - . - .
l general formula Ti(oR4)4 pXp, vanadium tetrachloride, vanadium oxytrichloride and the like.
In the general formula Ti(oR4)4 pXp, R4 represents an alkyl or cycloalkyl group having up to 20 carbon atoms, or phenyl group, X represents a halogen atom, and p represents a number defined by 0 < p < 4.
Concrete examples of titanium compound represented by this general formula include titanium tetrachloride, titanium tetrabromide, titanium tetraiodide, tetraethoxytitanium, ethoxytitanium trichloride, diethoxytitanium dichloride, triethoxytitanium chloride, propoxytitanium trichloride, butoxytitanium trichloride, phenoxytitanium trichloride, ethoxytitanium tribromide, dipropoxytitanium dibromide, tributoxytitanium bromide and the like, among which titanium tetrachloride is particularly preferable in respect of activity and particle characteristics.
In supporting said titanium compound and/or vanadium compound on the carrier, one may adopt disclosed processes such as lmpregnation, kneading, co-precipitation and the like. A particularly superior process for this purpose comprises contacting said titanium compound and/or vanadium compound with said carrier in the absence of solvent or in the presence of appropriate inert solvent. Preferably, this supporting reaction is conducted at a temperature ranging from room temperature (about 20C) to 150C. After completion of the reaction, the reaction product is collected by filtration, . .
~ 4~
1 thoroughly washed with a purified hydrocarbon diluent and then put to use directly, or put to use after an additional drying. The amount o~ said titanium compound ~nd/or vanadium compound to be supported on the carrier is controlled so that the amount of titanium and/or vanadium atoms contained in the resulting solid product falls within the range of 0.1 - 30% by weight usually, and pre~erably in the range o~ 0.5 - 15% by weight.
In this invention, a greater specific surface area of the solid catalyst component is more desirable. The solid catalyst component obtainable according to the above-mentioned process has a great speci~ic surface area, which sometimes exceeds 200 m2/g.
me organoaluminum compound which constitutes a catalyst system ln the polymerizatlon reaction in combination with the above-mentioned solid catalyst component includes trialkylaluminums such as triethyl-aluminum, tri-n-propylaluminum, tri-n-butylaluminum, tri-n-hexylaluminum and the like; dialkylaluminum monohalides such as diethylaluminum monochloride, di-n-propylaluminum monochloride, di-n-butylaluminum monochloride, di-n-hexylaluminum monochloride and the llke; alkylaluminum dihalides such as ethylaluminum dichloride, n-propylaluminum dichloride, n-butylaluminum dichloride, n-hexylaluminum dichloride and the like;
and alkylaluminum sesquihalides such as ethylaluminum sesquichloride, n-propylaluminum sesquichloride, 1 .
n-butylaluminum sesquichloride~ n-hexylaluminum : - 14 -... ,. . . . ~
~J 14~
1 sesquichloride and the like. These organoaluminum compounds may be used either alone or in combination of two or more.
The molar ratio between ~he solid catalyst component and the organoaluminum compound (Ti and/or V : Al) used for the polymerization of olefins can vary widely from about 10 : 1 to 1 : 1000, pre~erably from 2 : 1 to 1 : 100.
The catalyst of this invention has a very hlgh activity and, at the same time, the polymerization reaction is carried out in the state of bulk copolymeri-zation. Owing to these facts, the catalyst can exhibit a very high efficiency throughout the operation.
It is not difficult to make the content of transltlon metal ln the polymer produced by the process of thls lnventlon as low as about 10 ppm or less, and sometimes it can be lessened to about 2 ppm or less, so that one can omit the catalyst removal process without lncurrlng any problem about product quality.
When the buIk copolymerization of this lnvention is carried out in a lower unsaturated hydrocarbon monomer havlng 4 - 6 carbon atoms such as l-butene, the resulting polymer has only a small quantlty of fraction soluble into the liquid phase so that there is observed neither increase of viscosity nor stlckiness of cake due to the formation of low molecular weight soluble fraction in the plymerization reactor. me polymer particles have good characteristics ;. . ~ " . . .
- .
. .
.
. - . -. - ` ` ` .. .. . . .
. ~ . . . . .
" . . . .. .
, . . . . ` . . ` .
~ ~4q~
1 and the production efficiency per unit volume of reaction space can be enhanced. Therefore, a more advantageous result can be obtained.
In the process of this invention, the polymerization temperature may be selected arbitrarily from temperature range of -20 to 120C. A temperature range of 50 to 70C is particularly preferable.
The reaction pressure is preferably in the range of 1 - 100 kg/cm2 and particularly in the range of 10 - 50 kg/cm2.
Molecular weight of the resulting polymer can be controlled by introducing hydrogen into the polymerization reaction system. Since the amount of hydrogen to be introduced varies depending upon polymerization conditions and intended molecular weight of polymer, it is necessary to control its supply appropriately in accordance with the object.
It is conventional to use an inert solvent as a carrier for supplying catalyst. Examples of said inert solvent include aliphatic hydrocarbons such as pentane, hexane, heptane, octane and the like; alicyclic hydrocarbons such as cyclohexane, cycloheptane and the like; and aromatic hydrocarbons such as benzene, -toluene, xylene and the like.
The following examples will illustrate this invention in more detail. The examples are presented in no 11mitative way, unless the essentiality of this invention is exceeded.
, , , .. , ,.... ,- :
. . , :. ., . , : :
: ... . . - : . :
: , .... - . , ,-, ~.. . , - , - . . .: . -,. , . . . - - :. . . . . .
. , , ., , . - ,, . ,.. . , , . ,, , . . ,., .... " . . .
1 In the examples, the characteristics of polymer were measured by the following procedure.
Content of l-butene in copolymer was determined by measuring infrared absorption spectrum of a film, evaluating the absorbance with regard to the peak of 762 cm 1, and then calculating the content of ethyl group according to the following equation:
C2H5/1000C = td x log(Io/I) - 18.4 wherein t is thickness o~ specimen (cm), d is density (g/cm3), I is intensity of transmittent light, Io is lntensity of incident light, and C2H5/1000C is the number of ethyl group per 1000 carbon atoms.
Density and melt index (MI) were determined according to JIS K-6760. Bulk density was determined according to JIS K-6721.
;
Example 1 .~ .
(1) Synthesis of Organomagnesium Compound 16.0 g of chipped magnesium for the prepa-ration of Grignard reagent was placed in a four-necked flask having a capacity of 500 ml and equipped with a stirrer, a reflux condenser and a dropping funnel, and the inner atmosphere of the system was thoroughly replaced with nitrogen to remove air and moisture completely. 0.65 mole of n-butyl chloride and 300 ml of n-butyl ether were charged into the dropping funnel, :
-~ - 17 -,. . .~ ,.. , , . , .. .- " . .. .
:,, ~ , -, . :, , , . . , , ~ . , : :, . . ,., ,, -., . :. ,. . : ., . - ~ - , ... .,: . , - . : : : -: - - .
,, .,: , . . . .
: ,.. , . . - , . . : - . :: ~: : : - . -" :. : - . : , -, . . . ~ . , . , , --. : ., . ~ ,: . , , , .: - . . . .
;. . ~ .. - . . . . . . . .
.. .. : :~: .. : . . . . . ..
1 after which their about 30 ml was dropped onto the magnesium in the flask to start the reaction (when the reaction did not start, the bottom of flask was gently heated in order to start the reaction).
After start of the reaction, the dropping was continued so as to keep a mild progress of the reaction.
After completion of the dropping, the reaction was eontinued for an additional about one hour at 60 C. Then the reaction mixture was cooled to room temperature and the unreacted magnesium was filtered off by means of a glass filter.
The n-butylmagnesium chloride present in n-butyl ether was hydrolyzed with 1 N sulfuric acid and back-titrated with 1 N sodium hydroxide to determine lts concentration by the use of phenol-phtalein as an indicator. Thus, its concentration was found to be 2.00 moles/liter.
(2) Synthesis of Solid Catalyst Component The inner atmosphere of a four-necked flask having a capacity of 500 ml and equipped with a stirrer, a dropping funnel and a thermometer was thoroughly replaced with nitrogen to remove air and moisture.
35 g of anhydrous aluminum chloride, which had been purified by sublimation in advance, was introduced into the flask and dissolved into 150 ml of n-butyl ether while cooled with ice. Then, 132 ml (0.264 ~ole) of the ethereal solution of n-butylmagnesium :
. : , , , ~. . ,, .. , . . ... . , - . ~-.'.: .: . ,' :. . . '.. ' . '. '. ' . .
, ., .. - .. ...
.. . . . . . . . .
,: : - . . :
. . - .. . ~, . ; . . , 1 chloride synthesized in (1) was slowly dropped from the dropping funnel to yield a white precipitate.
The mixture was reacted at an ice-cooled temperature for one hour, and then at 50C for an additional
, , , ~. ~ ., ethylene gives a higher ethylene content of the copolymer.
Accordingly, a copolymer having an intended content of the unsaturated hydrocarbon monomer unit can be produced at will by changing the partial pressure of ethylene appropriately.
.. . - :-. . . - - -. : .
.. ~. , ... . . , . - . . . , ~ ..
. . , ... ~ . :. - . - . - ... . .. . , . ~ .
... . . , , . . .. . .: . , . -,,. . .. - .. ; . . , ~ .. : : ... . , : :
. - . . - , . . , , . . , -. . - . , 1 The polymer slurry of this invention obtainable by the bulk copolymerization in an unsaturated hydrocarbon monomer such as l-butene has a great merit as compared with a polymer slurry obtainable by conventional suspen-sion polymerization process (or solvent polymerization) in which the polymerization is carried out in general -in the medium of liquid saturated hydrocarbon having 5 - 7 carbon atoms, in that the polymer can be isolated merely by a simple procedure of removing the unreacted unsaturated hydrocarbon monomer.
Thus, the necessary procedures are only to copolymerlze a lique~ied unsaturated hydrocarbon monomer with ethylene under an elevated pressure and to recover and reuse the unreacted monomer after the reaction. In this case, recovery of solvent is unnecessary unlike conventional solvent polymerization, and the charge system attached to the polymerization reactor can be simplified. Therefore, the process provided herein is considerably simple and economical.
The polymer produced according to the process of this invention has a variety of advantages over conventional high-pressure low-density polyethylenes in that it has a higher strength, a higher stiffness, a higher softening point, a higher cold resistance (particularly low-temperature impact resistance), a higher melt extensibility, a higher stress cracking resistance, etc., so that it can be put to use in the application fields of conventional high-pressure -.
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ofl 1 low-density polyethylenes but also in a wide variety of novel application fields.
The catalyst used in this invention comprises a combination of an organoaluminum compound and a solid catalyst component prepared by supporting a tltanium compound and/or a vanadium compound on a solid product obtainable by reacting an organomagnesium compound with a halogenated aluminum compound represented by the following general formula:
RlnAlX3 n whereln R is an alkyl, cycloalkyl, aryl or alkenyl group having up to 20 carbon atoms, X is a halogen atom .
and n is a number defined by 0 _ n < 3, or with a halogenated silicon compound represented by the following general formula:
R msix4-m wherein R2 is an alkyl, cycloalkyl, aryl or alkenyl group having up to 20 carbon atoms, X is a halogen atom and m is a number defined by 0 < m < 4.
In this invention, the organomagnesium compound used for the synthesis of catalyst may be selected from any forms of organomagnesium compounds obtainable by reacting an organic halogen compound with metallic magnesium.
As said organomagnesium compound, Grignard compounds represented by the following general formula:
, . .
:. ... . . ~ .. . . - . . . . ..
, ~ : , , , , - . . :.
., ., .. , . ... , . . .. .. ... ~... ..... . .. - .... ..
, . , . . . . .. ,. . - .
. .
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- . .. .. . :: . .. .: - . - : :
.. : .. . . . ~ . :, ~ - . .: .- .
fl l R3MgX
wherein R3 is an alkyl, aryl or alkenyl group having up to 20 carbon atoms, and X is a halogen atom, and organo-magnesium compounds represented by the following general formula:
R32Mg can be used preferably.
Said organomagnesium compound includes all the possible compositions expressed by the following equilibrium equation:
2R3MgX ~ R32Mg + MgX2 ~ R32Mg.MgX2 notwithstanding whether or not said organomagnesium compound has been prepared in the presence of ether ~W. Shlenk et al., Ber., 62, 920 (1929); ibid. 64, 739 ( 19 31 ) ~ 7rct ~,~
Herein, R3 represents an alkyl, aryl~ror alkenyl group having up to 20 carbon atoms~ such as methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, n-amyl, lso-amyl, n-hexyl, n-octyl, 2-ethylhexyl, phenyl, benzyl and the like. Concrete ~ examples of said organomagnesium compound, expressed ;~ in terms of Grignard compounds, include ethylmagnesium ; chloride, ethylmagnesium bromide, n-propylmagnesium . .
~ chloride, n-butylmagnesium chloride, tert-butylmagnesium ., ........... . . ... -`;~ - . - ~ .. ' .. . . :
.: . . . . . . . . .
~ .. ~......... . . . ~ .
l chloride, n-amylmagnesium chloride, phenylmagnesium bromide and the like.
Organomagnesium compounds represented by the general ~ormula R32Mg are also included in the organo-magnesium compounds of this invention, as indicated bythe aforementioned equilibrium equation. Their concrete examples include diethylmagnesium, dipropylmagnesium, dibutylmagnesium, diamylmagnesium, dihexylmagnesium~
dioctylmagnesium, diphenylmagnesium, dibenzylmagnesium and the li~e.
These organomagnesium compounds are synthesized and used in the presence of an ethereal solvent such as ethyl ether, propyl ether, butyl ether, amyl ether, tetrahydrofuran, dioxane and the like; hydrocarbon solvents such as hexane, heptane, octane, cyclohexane, benzene, toluene, xylene and the like; or a mixture of an ethereal solvent and a hydrocarbon solvent. Among these solvents, ethereal solvents are particularly preferable.
The halogenated aluminum compound represented by general formula R nAlX3 n includes all the compounds having an aluminum-halogen bond (Al-X). A compound having a larger number of halogen atoms gives a better result, and anhydrous aluminum chloride is most preferable. m e halogenated silicon compound represented by general formula R2mSiX4 m includes all the compounds having a silicon-halogen bond (Si-X). A compound having a larger number of halogen atoms gives a better result, and silicon tetrachloride is most preferable. In the general . ~ . . - - .
. , . .. : : . .: .. .: .. . - . . : , . : :
.. .: .: . ~ - . : ~ .
. ~ : . . , . ' ' ' ' -. ~
.
4~?~
1 formulas~ R~ and ~2 represent an alkyl, cycloalkyl, ¦ aryl~or alkenyl group having up to 20 carbon atoms.
Concrete examples of Rl and R2 include methyl, ethyl, n-propyl, iso-propyl, n-butyl, sec-butyl, tert-butyl, n-amyl, iso-amyl, n-hexyl, n-heptyl, n-octyl, vinyl, allyl, cyclopentyl, cyclohexyl, phenyl, benzyl and the like. X represents halogen atom, of which concrete examples include chlorine, bromine and iodine. n represents a number defined by 0 < n < 3, and m represents a number defined by 0 < m < 4. Concrete examples of said halogenated aluminum compound include anhydrous aluminum chloride, aluminum bromide, aluminum iodide, diethyl-aluminum chloride, ethylaluminum dichloride, ethylaluminum sesquichloride, dibutylaluminum chloride, butylaluminum dichloride, dihexylaluminum bromide, hexylaluminum dlbromide and the like. Concrete examples of said halogenated silicon compound include silicon tetra-chloride, silicon tetrabromide, methylsilyl trichloride, dimethylsllyl dichloride, trimethylsilyl chloride, ethylsilyl trichloride, diethylsilyl dichloride, triethylsilyl chloride, propylsilyl tribromide, dipropylsilyl dibromide, tripropylsilyl bromide, dibutylsilyl dichloride, tributylsilyl chloride, vinylsilyl trichloride and the like.
The synthetic reactions of the catalyst are all carried out in an atmosphere of inert gas such as nitrogen, argon or the like. The reaction between the organomagnesium compound and the halogenated aluminum .
.
.
::~ , . . - : - -- , . ' :
- ~ . , . . ~ -' 1 compound and/or halogenated silicon compound is prefer-ably carried out in a solvent at a temperature of 0 -100C, though the reaction may be carried out at a high temperature of 100C or above. The solvents usable in this reaction include aliphatic hydrocarbons such as pentane, hexane, heptane, octane and the like; aromatic hydrocarbons such as benzene, toluene, xylene and the like, alicyclic hydrocarbons such as cyclohexane, cyclopentane and the like; ethereal solvents such as ethyl ether, butyl ether, amyl ether, tetrahydrofuran, dioxane and the like; and mixtures of hydrocarbon solvents and ethereal solvents Among these solvents, ethereal solvents are particularly preferable.
Said organomagnesium compound is reacted with sald halogenated aluminum compound and/or said halogenated silicon compound in a proportion of 0.1 - 10.0 and preferably 0.5 - 2.0, by mole. The reaction product is precipitated in the form of a solid.
The reaction product obtained as above is isoIated and then used as a carrier. Concretely speaking, the reaction product is used after being filtered, or subsequently thoroughly washed with a purified hydro- -carbon diluent, or further dried. Then, a titanium compound and/or a vanadium compound is supported on the carrier synthesized as above.
Examples of the titanium compound and the vanadium compound to be supported on the carrier include titanium trichloride, titanium compounds represented by the , ~: : - . .. . - .. . : .
; ` ' ~'', ' ,' . ~ ' ' ' ' . ' . . : , .: . , ' - . - .
l general formula Ti(oR4)4 pXp, vanadium tetrachloride, vanadium oxytrichloride and the like.
In the general formula Ti(oR4)4 pXp, R4 represents an alkyl or cycloalkyl group having up to 20 carbon atoms, or phenyl group, X represents a halogen atom, and p represents a number defined by 0 < p < 4.
Concrete examples of titanium compound represented by this general formula include titanium tetrachloride, titanium tetrabromide, titanium tetraiodide, tetraethoxytitanium, ethoxytitanium trichloride, diethoxytitanium dichloride, triethoxytitanium chloride, propoxytitanium trichloride, butoxytitanium trichloride, phenoxytitanium trichloride, ethoxytitanium tribromide, dipropoxytitanium dibromide, tributoxytitanium bromide and the like, among which titanium tetrachloride is particularly preferable in respect of activity and particle characteristics.
In supporting said titanium compound and/or vanadium compound on the carrier, one may adopt disclosed processes such as lmpregnation, kneading, co-precipitation and the like. A particularly superior process for this purpose comprises contacting said titanium compound and/or vanadium compound with said carrier in the absence of solvent or in the presence of appropriate inert solvent. Preferably, this supporting reaction is conducted at a temperature ranging from room temperature (about 20C) to 150C. After completion of the reaction, the reaction product is collected by filtration, . .
~ 4~
1 thoroughly washed with a purified hydrocarbon diluent and then put to use directly, or put to use after an additional drying. The amount o~ said titanium compound ~nd/or vanadium compound to be supported on the carrier is controlled so that the amount of titanium and/or vanadium atoms contained in the resulting solid product falls within the range of 0.1 - 30% by weight usually, and pre~erably in the range o~ 0.5 - 15% by weight.
In this invention, a greater specific surface area of the solid catalyst component is more desirable. The solid catalyst component obtainable according to the above-mentioned process has a great speci~ic surface area, which sometimes exceeds 200 m2/g.
me organoaluminum compound which constitutes a catalyst system ln the polymerizatlon reaction in combination with the above-mentioned solid catalyst component includes trialkylaluminums such as triethyl-aluminum, tri-n-propylaluminum, tri-n-butylaluminum, tri-n-hexylaluminum and the like; dialkylaluminum monohalides such as diethylaluminum monochloride, di-n-propylaluminum monochloride, di-n-butylaluminum monochloride, di-n-hexylaluminum monochloride and the llke; alkylaluminum dihalides such as ethylaluminum dichloride, n-propylaluminum dichloride, n-butylaluminum dichloride, n-hexylaluminum dichloride and the like;
and alkylaluminum sesquihalides such as ethylaluminum sesquichloride, n-propylaluminum sesquichloride, 1 .
n-butylaluminum sesquichloride~ n-hexylaluminum : - 14 -... ,. . . . ~
~J 14~
1 sesquichloride and the like. These organoaluminum compounds may be used either alone or in combination of two or more.
The molar ratio between ~he solid catalyst component and the organoaluminum compound (Ti and/or V : Al) used for the polymerization of olefins can vary widely from about 10 : 1 to 1 : 1000, pre~erably from 2 : 1 to 1 : 100.
The catalyst of this invention has a very hlgh activity and, at the same time, the polymerization reaction is carried out in the state of bulk copolymeri-zation. Owing to these facts, the catalyst can exhibit a very high efficiency throughout the operation.
It is not difficult to make the content of transltlon metal ln the polymer produced by the process of thls lnventlon as low as about 10 ppm or less, and sometimes it can be lessened to about 2 ppm or less, so that one can omit the catalyst removal process without lncurrlng any problem about product quality.
When the buIk copolymerization of this lnvention is carried out in a lower unsaturated hydrocarbon monomer havlng 4 - 6 carbon atoms such as l-butene, the resulting polymer has only a small quantlty of fraction soluble into the liquid phase so that there is observed neither increase of viscosity nor stlckiness of cake due to the formation of low molecular weight soluble fraction in the plymerization reactor. me polymer particles have good characteristics ;. . ~ " . . .
- .
. .
.
. - . -. - ` ` ` .. .. . . .
. ~ . . . . .
" . . . .. .
, . . . . ` . . ` .
~ ~4q~
1 and the production efficiency per unit volume of reaction space can be enhanced. Therefore, a more advantageous result can be obtained.
In the process of this invention, the polymerization temperature may be selected arbitrarily from temperature range of -20 to 120C. A temperature range of 50 to 70C is particularly preferable.
The reaction pressure is preferably in the range of 1 - 100 kg/cm2 and particularly in the range of 10 - 50 kg/cm2.
Molecular weight of the resulting polymer can be controlled by introducing hydrogen into the polymerization reaction system. Since the amount of hydrogen to be introduced varies depending upon polymerization conditions and intended molecular weight of polymer, it is necessary to control its supply appropriately in accordance with the object.
It is conventional to use an inert solvent as a carrier for supplying catalyst. Examples of said inert solvent include aliphatic hydrocarbons such as pentane, hexane, heptane, octane and the like; alicyclic hydrocarbons such as cyclohexane, cycloheptane and the like; and aromatic hydrocarbons such as benzene, -toluene, xylene and the like.
The following examples will illustrate this invention in more detail. The examples are presented in no 11mitative way, unless the essentiality of this invention is exceeded.
, , , .. , ,.... ,- :
. . , :. ., . , : :
: ... . . - : . :
: , .... - . , ,-, ~.. . , - , - . . .: . -,. , . . . - - :. . . . . .
. , , ., , . - ,, . ,.. . , , . ,, , . . ,., .... " . . .
1 In the examples, the characteristics of polymer were measured by the following procedure.
Content of l-butene in copolymer was determined by measuring infrared absorption spectrum of a film, evaluating the absorbance with regard to the peak of 762 cm 1, and then calculating the content of ethyl group according to the following equation:
C2H5/1000C = td x log(Io/I) - 18.4 wherein t is thickness o~ specimen (cm), d is density (g/cm3), I is intensity of transmittent light, Io is lntensity of incident light, and C2H5/1000C is the number of ethyl group per 1000 carbon atoms.
Density and melt index (MI) were determined according to JIS K-6760. Bulk density was determined according to JIS K-6721.
;
Example 1 .~ .
(1) Synthesis of Organomagnesium Compound 16.0 g of chipped magnesium for the prepa-ration of Grignard reagent was placed in a four-necked flask having a capacity of 500 ml and equipped with a stirrer, a reflux condenser and a dropping funnel, and the inner atmosphere of the system was thoroughly replaced with nitrogen to remove air and moisture completely. 0.65 mole of n-butyl chloride and 300 ml of n-butyl ether were charged into the dropping funnel, :
-~ - 17 -,. . .~ ,.. , , . , .. .- " . .. .
:,, ~ , -, . :, , , . . , , ~ . , : :, . . ,., ,, -., . :. ,. . : ., . - ~ - , ... .,: . , - . : : : -: - - .
,, .,: , . . . .
: ,.. , . . - , . . : - . :: ~: : : - . -" :. : - . : , -, . . . ~ . , . , , --. : ., . ~ ,: . , , , .: - . . . .
;. . ~ .. - . . . . . . . .
.. .. : :~: .. : . . . . . ..
1 after which their about 30 ml was dropped onto the magnesium in the flask to start the reaction (when the reaction did not start, the bottom of flask was gently heated in order to start the reaction).
After start of the reaction, the dropping was continued so as to keep a mild progress of the reaction.
After completion of the dropping, the reaction was eontinued for an additional about one hour at 60 C. Then the reaction mixture was cooled to room temperature and the unreacted magnesium was filtered off by means of a glass filter.
The n-butylmagnesium chloride present in n-butyl ether was hydrolyzed with 1 N sulfuric acid and back-titrated with 1 N sodium hydroxide to determine lts concentration by the use of phenol-phtalein as an indicator. Thus, its concentration was found to be 2.00 moles/liter.
(2) Synthesis of Solid Catalyst Component The inner atmosphere of a four-necked flask having a capacity of 500 ml and equipped with a stirrer, a dropping funnel and a thermometer was thoroughly replaced with nitrogen to remove air and moisture.
35 g of anhydrous aluminum chloride, which had been purified by sublimation in advance, was introduced into the flask and dissolved into 150 ml of n-butyl ether while cooled with ice. Then, 132 ml (0.264 ~ole) of the ethereal solution of n-butylmagnesium :
. : , , , ~. . ,, .. , . . ... . , - . ~-.'.: .: . ,' :. . . '.. ' . '. '. ' . .
, ., .. - .. ...
.. . . . . . . . .
,: : - . . :
. . - .. . ~, . ; . . , 1 chloride synthesized in (1) was slowly dropped from the dropping funnel to yield a white precipitate.
The mixture was reacted at an ice-cooled temperature for one hour, and then at 50C for an additional
3 hours. After the reaction, the resulting white colored solid was separated, washed and dried under reduced pressure to give 32.5 g of a white colored solid. Its 10 g was taken in a four-necked flask having a capacity of 100 ml, dipped in 50 ml of titanium tetrachloride, and reacted at 130C
for one hour with stirring. After completion of the reaction, it was repeatedly washed with n-heptane until the washing became free from titanium tetrachloride, and then it was dried under reduced pressure to give 7.5 g of a solid catalyst component. In 1 g of the resulting solid product, 25 mg of titanium atom was supported, and the solid product had a specific surface area of 230 m2/g.
(3~ Polymerization Inner atmosphere of a stainless-made autoclave having a capacity of 5 liters and equipped with an electromagnetic stirrer was replaced with dry nitrogen completely, after which 1,250 g of l-butene was charged into the autoclave. Then, hydrogen was fed up to a partical pressure of 2 kg/cm and 15 mmoles of triethylaluminum was added.
m e temperature was elevated to 50C, ethylene was ` fed up to a partial pressure of 18 kg/cm2, and then .
, , . , . .. , , '' , ~ , . ' ': ' - .. .
.. . , . . . , . : - :
, . .. : . .. . :: -- . ~ :-. . .- - . .. . .
1 9.9 mg of the aforementioned solid catalyst component suspended with 20 ml of heptane was added to start the polymerization. me polymerization was continued at 50C for 4.9 hours, while keeping the total pressure constant by supplying ethylene.
After the polymerization was continued for an appointed period o~ time, the polymerization was stopped with isopropyl alcohol and the unreacted monomer was purged.
The resulting polymer was washed with methanol and dried under reduced pressure at 60C to give 559 g of a copolymer. The copolymer contained 5.5 mole-%
of l-butene. It had a density of 0.923 g/cm3, MI of 0.24 g/10 min. and a bulk density of 0.33 g/cm3.
In this reaction, the catalyst exhibited an activity of 11,500 g copolymer/g solid.hr or 461,000 g copolymer/g Ti-hr.
Examples 2-6 Using the same solid catalyst compnent as in Example 1, polymerization was carried out by the same procedure as above. m e results obtained were as shown in Table 1.
Examples 7-9 Catalyst was prepared and polymerization -was carried out in the same manner as in Example 1.
m e results obtained were as shown in Table 2.
.
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for one hour with stirring. After completion of the reaction, it was repeatedly washed with n-heptane until the washing became free from titanium tetrachloride, and then it was dried under reduced pressure to give 7.5 g of a solid catalyst component. In 1 g of the resulting solid product, 25 mg of titanium atom was supported, and the solid product had a specific surface area of 230 m2/g.
(3~ Polymerization Inner atmosphere of a stainless-made autoclave having a capacity of 5 liters and equipped with an electromagnetic stirrer was replaced with dry nitrogen completely, after which 1,250 g of l-butene was charged into the autoclave. Then, hydrogen was fed up to a partical pressure of 2 kg/cm and 15 mmoles of triethylaluminum was added.
m e temperature was elevated to 50C, ethylene was ` fed up to a partial pressure of 18 kg/cm2, and then .
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1 9.9 mg of the aforementioned solid catalyst component suspended with 20 ml of heptane was added to start the polymerization. me polymerization was continued at 50C for 4.9 hours, while keeping the total pressure constant by supplying ethylene.
After the polymerization was continued for an appointed period o~ time, the polymerization was stopped with isopropyl alcohol and the unreacted monomer was purged.
The resulting polymer was washed with methanol and dried under reduced pressure at 60C to give 559 g of a copolymer. The copolymer contained 5.5 mole-%
of l-butene. It had a density of 0.923 g/cm3, MI of 0.24 g/10 min. and a bulk density of 0.33 g/cm3.
In this reaction, the catalyst exhibited an activity of 11,500 g copolymer/g solid.hr or 461,000 g copolymer/g Ti-hr.
Examples 2-6 Using the same solid catalyst compnent as in Example 1, polymerization was carried out by the same procedure as above. m e results obtained were as shown in Table 1.
Examples 7-9 Catalyst was prepared and polymerization -was carried out in the same manner as in Example 1.
m e results obtained were as shown in Table 2.
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Claims (11)
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. A process for producing an ethylene copolymer having a density of 0.900-0.940 by copolymerizing ethylene with another unsaturated hydrocarbon monomer in the presence of a catalyst comprising a titanium and/or vanadium compound and an organoaluminum compound, which comprises using a titanium and/
or vanadium compound supported on a magnesium compound as a catalyst component and carrying out the copolymerization reaction in a liquid phase of said unsaturated hydrocarbon monomer said magnesium compound being a solid product obtainable by reacting an organomagnesium compound with a halogenated aluminum compound and/or a halogenated silicon compound represented by the follow-ing general formula:
and/or wherein R1 and R2 are an alkyl, cycloalkyl, aryl or alkenyl group having up to 20 carbon atoms; X is a halogen atom; and n and m are numbers defined by 0 ? n<3 and 0 ? m<4, respectively.
or vanadium compound supported on a magnesium compound as a catalyst component and carrying out the copolymerization reaction in a liquid phase of said unsaturated hydrocarbon monomer said magnesium compound being a solid product obtainable by reacting an organomagnesium compound with a halogenated aluminum compound and/or a halogenated silicon compound represented by the follow-ing general formula:
and/or wherein R1 and R2 are an alkyl, cycloalkyl, aryl or alkenyl group having up to 20 carbon atoms; X is a halogen atom; and n and m are numbers defined by 0 ? n<3 and 0 ? m<4, respectively.
2. A process according to claim 1, wherein the magnesium compound is R3MgX and/or R32Mg wherein R3 is an alkyl, aryl or alkenyl group having up to 20 carbon atoms; and X is a halogen atom.
3. A process according to claim 2, wherein R3 is methyl, ethyl, n-propyl, iso-propyl, n-butyl, sec-butyl, tert-butyl, n-amyl, iso-amyl, n-hexyl, n-octyl, 2-ethylhexyl, phenyl or benzyl group.
4. A process according to claim 1 wherein said titanium or/and vanadium compound is a member selected from the group consisting of titanium trichloride, titanium compounds represented by the following general formula:
wherein R4 is an alkyl or cycloalkyl group having up to 20 carbon atoms, or phenyl group, X is halogen atom and p is a number defined by 0?p?4, vanadiumtetrachloride and vanadium oxy-trichloride.
wherein R4 is an alkyl or cycloalkyl group having up to 20 carbon atoms, or phenyl group, X is halogen atom and p is a number defined by 0?p?4, vanadiumtetrachloride and vanadium oxy-trichloride.
5. A process according to claim 4, wherein the titanium compound represented by general formula Ti(oR4)4-pXp is a member selected from the group consisting of titanium tetrachloride, titanium tetrabromide, titanium tetraiodide, tetraethoxytitanium, diethoxytitanium dichloride, triethoxytitanium chloride, pro-poxytitanium trichloride, butoxytitanium trichloride, phenoxy-titanium trichloride, ethoxytitanium tribromide, dipropoxy-titanium dibromide, and tributoxytitanium bromide.
6. A process according to claim 5, wherein the titanium compound is titanium tetrachloride.
7. A process according to claim 1, wherein said unsaturated hydrocarbon monomer is propylene, l-butene, l-pentene, l-hexene or l-octene.
8. A process according to claim 7 wherein the unsaturated hydrocarbon monomer is l-butene.
9. A process according to claim 1, 2 or 3, wherein the amount of supported titanium and/or vanadium compound is 0.1 -30% by weight as expressed in terms of titanium and/or vanadium atom containedin the solid product.
10. A process according to claim 1, 2 or 3, wherein said copolymerization reaction is carried out at a temperature of -20°C to 120°C under a reaction pressure of 1-100 kg/cm2.
11. A process according to claim 1, 2 or 3, wherein said copolymerization reaction is carried out in the presence of hydrogen.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP44387/78 | 1978-04-14 | ||
| JP4438778A JPS54135886A (en) | 1978-04-14 | 1978-04-14 | Preparation of ethylenic copolymer |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1114098A true CA1114098A (en) | 1981-12-08 |
Family
ID=12690088
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA325,070A Expired CA1114098A (en) | 1978-04-14 | 1979-04-06 | Process for producing ethylene copolymers |
Country Status (8)
| Country | Link |
|---|---|
| JP (1) | JPS54135886A (en) |
| BE (1) | BE875567A (en) |
| CA (1) | CA1114098A (en) |
| DE (1) | DE2915078A1 (en) |
| FR (1) | FR2422692B1 (en) |
| GB (1) | GB2019419B (en) |
| IT (1) | IT1120408B (en) |
| NL (1) | NL7902894A (en) |
Families Citing this family (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| IT1110494B (en) * | 1978-08-02 | 1985-12-23 | Montedison Spa | ETHYLENE POLYMERS AND PROCEDURE FOR THEIR PREPARATION |
| JPS5721408A (en) * | 1980-07-11 | 1982-02-04 | Asahi Chem Ind Co Ltd | Fine ethylene/alpha-olefin copolymer powder suitable as hot melt adhesive for cloth |
| CA1159198A (en) * | 1980-09-29 | 1983-12-20 | Akinobu Shiga | PROCESS FOR PRODUCING HIGHLY STEREOREGULA .alpha.-OLEFIN POLYMERS |
| JPS57105411A (en) * | 1980-12-23 | 1982-06-30 | Mitsubishi Petrochem Co Ltd | Ethylenic copolymer |
| JPS5811512A (en) * | 1981-07-10 | 1983-01-22 | Mitsubishi Chem Ind Ltd | Ethylenic copolymer |
| FR2509315A1 (en) * | 1981-07-10 | 1983-01-14 | Charbonnages Ste Chimique | HETEROGENEOUS COPOLYMERS OF ETHYLENE FOR THE MANUFACTURE OF FILMS |
| CA1190996A (en) * | 1982-04-22 | 1985-07-23 | Robert B. Steinert | Linear low density polyethylene process |
| JPS58189206A (en) * | 1982-04-30 | 1983-11-04 | Chisso Corp | Catalytic component for alpha-olefin polymerization |
| US5700895A (en) * | 1993-08-23 | 1997-12-23 | Sumitomo Chemical Company, Limited | Ethylene-α-olefin copolymer and molded article thereof |
| JP3344015B2 (en) * | 1993-08-23 | 2002-11-11 | 住友化学工業株式会社 | Ethylene-α-olefin copolymer and molded article molded from the copolymer |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1355245A (en) * | 1970-05-29 | 1974-06-05 | Mitsui Petrochemical Ind | Non-elastic ethylene copolymers and their preparation |
| IT1038179B (en) * | 1975-05-16 | 1979-11-20 | Montedison Spa | PROCEDURE FOR POLYMERIZATION OF ALPHA OLEFINS WITH AT LEAST THREEATONS OF CARBON |
| JPS5274684A (en) * | 1975-12-18 | 1977-06-22 | Sumitomo Chem Co Ltd | Process for polymerizing or copolymerizing olefins |
-
1978
- 1978-04-14 JP JP4438778A patent/JPS54135886A/en active Pending
-
1979
- 1979-04-06 CA CA325,070A patent/CA1114098A/en not_active Expired
- 1979-04-12 FR FR7909276A patent/FR2422692B1/en not_active Expired
- 1979-04-12 NL NL7902894A patent/NL7902894A/en not_active Application Discontinuation
- 1979-04-12 DE DE19792915078 patent/DE2915078A1/en not_active Withdrawn
- 1979-04-13 IT IT48733/79A patent/IT1120408B/en active
- 1979-04-13 BE BE0/194592A patent/BE875567A/en not_active IP Right Cessation
- 1979-04-17 GB GB7913210A patent/GB2019419B/en not_active Expired
Also Published As
| Publication number | Publication date |
|---|---|
| IT7948733A0 (en) | 1979-04-13 |
| NL7902894A (en) | 1979-10-16 |
| JPS54135886A (en) | 1979-10-22 |
| FR2422692B1 (en) | 1985-10-04 |
| GB2019419B (en) | 1982-09-22 |
| IT1120408B (en) | 1986-03-26 |
| BE875567A (en) | 1979-07-31 |
| FR2422692A1 (en) | 1979-11-09 |
| DE2915078A1 (en) | 1979-10-25 |
| GB2019419A (en) | 1979-10-31 |
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