CA1085811A - Process for preparing polyolefins - Google Patents
Process for preparing polyolefinsInfo
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- CA1085811A CA1085811A CA269,137A CA269137A CA1085811A CA 1085811 A CA1085811 A CA 1085811A CA 269137 A CA269137 A CA 269137A CA 1085811 A CA1085811 A CA 1085811A
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- vanadium
- titanium
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
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- Organic Chemistry (AREA)
- Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
Abstract
ABSTRACT OF THE DISCLOSURE
A process is provided for preparing polyolefins. The process comprises polymerizing or copolymerizing an olefins or olefins using, an a novel catalyst, a transition metal compound component and an organometallic compound of groups I- IV of the Periodic Table. The transition metal compound component is a substance which is obtained by contacting the following compounds (1) and (2), namely: (1) a compound which is obtained by reacting an organomagnesium compound represented by the general formula RMgX, wherein R is an alkyl or aryl group having 1 to 20 carbon atoms and X is a halogen, with an alum-inum compound represented by the general formula A1R'nX3-n, wherein R' is an alkyl or aryl group having 1 to 20 carbon atoms, X is halogen and n is 0 ? n ? 3, and subsequently re-acting that reaction product with a hydroxy compound represented by the general formula R"OH wherein R" is a hydrocarbon radical having 1 to 20 carbon atoms; and (2) a titanium compound and/
or a vanadium compound. By this process, the olefin polymer-ization or copolymerization proceeds with a remarkably high activity of the catalyst. The bulk density of the resulting polymer is remarkable high. Moreover, a polymer having a high merit index can be prepared at a lower hydrogen concentration than heretofore.
A process is provided for preparing polyolefins. The process comprises polymerizing or copolymerizing an olefins or olefins using, an a novel catalyst, a transition metal compound component and an organometallic compound of groups I- IV of the Periodic Table. The transition metal compound component is a substance which is obtained by contacting the following compounds (1) and (2), namely: (1) a compound which is obtained by reacting an organomagnesium compound represented by the general formula RMgX, wherein R is an alkyl or aryl group having 1 to 20 carbon atoms and X is a halogen, with an alum-inum compound represented by the general formula A1R'nX3-n, wherein R' is an alkyl or aryl group having 1 to 20 carbon atoms, X is halogen and n is 0 ? n ? 3, and subsequently re-acting that reaction product with a hydroxy compound represented by the general formula R"OH wherein R" is a hydrocarbon radical having 1 to 20 carbon atoms; and (2) a titanium compound and/
or a vanadium compound. By this process, the olefin polymer-ization or copolymerization proceeds with a remarkably high activity of the catalyst. The bulk density of the resulting polymer is remarkable high. Moreover, a polymer having a high merit index can be prepared at a lower hydrogen concentration than heretofore.
Description
'rllifi invention re'la~es to a no~e~ catalyst Lmd t:o a l~ro-:ess Eor preparing polyo]ef:Lns us:Lng such novel catalyst.
Since ~he discovery of the ~act that a catalyst system compris-ing an organometa:Llic compound and a transition metal compolmd can be an e~cellent catalyst for olefln polymerization (see Japanese Patent Publi-cations 1545/57, 1546/57 and 2045/57), many improved catalysts for olefin polymeriz,ation have been proposed. In the polyolefin manufacturing pro-cess, however, it is desirable that the catalyst activity be as high as possible. Specially, in recent years there has been an increasing demand 10 for the development of a catalyst whose activity is high enough to dis-pense with the catalyst removing step. When viewed from this standpoint, many of the aforementioned improved catalysts are still low in activity and hence a further improvement has been desired.
Furthermore, many of the aforementioned catalyst systems have drawbacks, in that the bulk density of the resulting polymer is low, in that there is a difficulty in the handling of polymer slurry in the poly-olefin manufacturing process, in that the output per unit volume of the polymerization vessel is small, and in that the handling of a polymer powder is difficult.
An object of a main aspect of this invention is to provide a novel catalyst whereby many of the above problems may be minimized or i even overcome.
An object of another aspect of this invention is to provide an improved olefin polymerization or copolymerization process using the said catalyst.
sy one aspeet of this invention, then, a'polymerization catalyst is provided eomprising: (A) a transition metal com-pouna eomponent; and (B) an organometallie eompound of Groups I - IV of the Periodie Table; the transition metal eompound being obtained by eontaeting (l) a eompound obtained by re-aeting an organomagnesium eompound represented by the general formula RMgX, wherein R is an alkyl or aryl group having l to 20 earbon atoms and X is a halogen, with an aluminum eompound represented by the general formula AlR' X3 ~ ~ ~e~ 8i~
. :: , , ;,...
:: -. : ~
.: ' ' '.: : : .
5i8:~
R' is an alkyl or aryl group having 1 to 20 carbon atoms, X is a halogen and n is 0<n(3, and subsequently reacting that reaction product with a hydroxy compound represented by the general formula R"OH, wherein R" is a hydrocarbon radical having 1 to 20 carbon atoms selected from the group consisting of alkyl, alkënyl, aryl ana aralkyl or a substituted hydrocar-bon group containing hetero elements selected from the group consisting of oxygen, nitrogen, sulfur and chloride, with (2) at least one of a titanium compound and a vanadium compound.
By one variant, the RMgX and the AlR' X3 are used in a ration such that the Mg/Al atomic ratio is in the range of from 10/1 to 1/50, and the two are reacted together for one minute to 20 hours at a temperature in the range of from -100C.
to 200C.
By another variant, the reaction product of the RMgX and the AlR' X3 , and the R"OH are used in a ratio such that the (R+R')/OH mole ratio is in the range d from 10/1 to 1/20, and the two are reacted together for one minute to 20 hours at a temperature in the range of from -100C. to 200C.
By still another variant, the treatment of contacting the compound (1) which is obtained by the reaction of the RMgX
and the AlR' X3 and the subsequent reaction with the R"OH, with the titanium compound and/or vanadium compound, is a co-; pulverization of the compounds (1) and (2) which is conducted for 0.5 to 50 hours in an inert gas atmosphere at a temperature in the range of from 0C. to 200C.
By yet another variant, the content of titanium or van-adium in the transition metal compound component is in the range of from 0.5 to 20 weight percent.
By a further variant, the organometallic compound is either an organoaluminum compound or an organozinc compound.
Since ~he discovery of the ~act that a catalyst system compris-ing an organometa:Llic compound and a transition metal compolmd can be an e~cellent catalyst for olefln polymerization (see Japanese Patent Publi-cations 1545/57, 1546/57 and 2045/57), many improved catalysts for olefin polymeriz,ation have been proposed. In the polyolefin manufacturing pro-cess, however, it is desirable that the catalyst activity be as high as possible. Specially, in recent years there has been an increasing demand 10 for the development of a catalyst whose activity is high enough to dis-pense with the catalyst removing step. When viewed from this standpoint, many of the aforementioned improved catalysts are still low in activity and hence a further improvement has been desired.
Furthermore, many of the aforementioned catalyst systems have drawbacks, in that the bulk density of the resulting polymer is low, in that there is a difficulty in the handling of polymer slurry in the poly-olefin manufacturing process, in that the output per unit volume of the polymerization vessel is small, and in that the handling of a polymer powder is difficult.
An object of a main aspect of this invention is to provide a novel catalyst whereby many of the above problems may be minimized or i even overcome.
An object of another aspect of this invention is to provide an improved olefin polymerization or copolymerization process using the said catalyst.
sy one aspeet of this invention, then, a'polymerization catalyst is provided eomprising: (A) a transition metal com-pouna eomponent; and (B) an organometallie eompound of Groups I - IV of the Periodie Table; the transition metal eompound being obtained by eontaeting (l) a eompound obtained by re-aeting an organomagnesium eompound represented by the general formula RMgX, wherein R is an alkyl or aryl group having l to 20 earbon atoms and X is a halogen, with an aluminum eompound represented by the general formula AlR' X3 ~ ~ ~e~ 8i~
. :: , , ;,...
:: -. : ~
.: ' ' '.: : : .
5i8:~
R' is an alkyl or aryl group having 1 to 20 carbon atoms, X is a halogen and n is 0<n(3, and subsequently reacting that reaction product with a hydroxy compound represented by the general formula R"OH, wherein R" is a hydrocarbon radical having 1 to 20 carbon atoms selected from the group consisting of alkyl, alkënyl, aryl ana aralkyl or a substituted hydrocar-bon group containing hetero elements selected from the group consisting of oxygen, nitrogen, sulfur and chloride, with (2) at least one of a titanium compound and a vanadium compound.
By one variant, the RMgX and the AlR' X3 are used in a ration such that the Mg/Al atomic ratio is in the range of from 10/1 to 1/50, and the two are reacted together for one minute to 20 hours at a temperature in the range of from -100C.
to 200C.
By another variant, the reaction product of the RMgX and the AlR' X3 , and the R"OH are used in a ratio such that the (R+R')/OH mole ratio is in the range d from 10/1 to 1/20, and the two are reacted together for one minute to 20 hours at a temperature in the range of from -100C. to 200C.
By still another variant, the treatment of contacting the compound (1) which is obtained by the reaction of the RMgX
and the AlR' X3 and the subsequent reaction with the R"OH, with the titanium compound and/or vanadium compound, is a co-; pulverization of the compounds (1) and (2) which is conducted for 0.5 to 50 hours in an inert gas atmosphere at a temperature in the range of from 0C. to 200C.
By yet another variant, the content of titanium or van-adium in the transition metal compound component is in the range of from 0.5 to 20 weight percent.
By a further variant, the organometallic compound is either an organoaluminum compound or an organozinc compound.
- 2 -. :.. . :: , . : .
; -: : . .. ....
By yet a still Eurther variant, the organometallic corn-pound is used in an amount of from 0;1 to 1,000 mole per mole of the titanium compound and/or vanadium compound.
By another aspect of this invention, a process is pro-vided for preparing polyolefins by polymerizing or copolymer-izing olefin(s) using as a catalyst a transition metal compound component and an organometallie compound of Groups I - IV of the Periodic Table, the transition metal compound component being obtained by eontacting a titanium compound and/or a 1~ vanadium compound with a eompound as earrier, the compound as carrier being obtained by reacting an organomagnesium eompound represented by the general formula RMgX wherein R is an alkyl or aryl group having 1 to 20 earbon atoms and X is a halogen, with an aluminum eompound represented by the general formula AlR' X3 wherein R' is an alkyl or aryl group having 1 to 20 carbon atoms, X is a halogen and n is 0~n~3, and subseque~tly reaeting the reaetion produet with a hydroxy eompound represented by the general formula R"OH wherein R" is a hyarocarbon radical having 1 to 20 carbon atoms selected from the group consisting of alkyl, alkenyl, aryl and aralkyl or a substituted hydro-carbon group containing hetero elements selected from the group consisting of oxygen, nitrogen sulfur and chloride.
By a variant of this aspect, the olefin polymerization or copolymerization is conducted at a temperature in the range of from 20C. to 300C. and at a-pressue in the range of from the atmospherie pressure to 70 kg/em .
By another variant of this aspect, the olefin polymer-ization or copolymerization is conducted with hydrogen added into the polymerization system.
By the use of the catalyst of an aspect of this invent-on, it becomes possible to effect an olefin polymerization or - 2a -3S8~
copolymeri~ation according to another aspect of this invent-ion with a remarkably high activity of the catalyst, and the bulk density of the resulting polymer is rernarkably high.
As another advantage of the process of an aspect of the present invention, a polymerhaving a high melt index can be prepared easily, that i$, a polymer of the same melt index can be obtained at a lower hydrogen concentration; this is advantageous both economically and also for productivity.
Although the details of the structure of the carrier which is used in the catalys-t of an aspect of the present in-vention and which is obtained, as mentioned above, by the reaction of the compounds of RMgX, AlR' X3 and R"OH, are not clear, it is presumed that a novel carrier is produced by the reaction of the three.
The reaction ratio of the compounds RMgX and AlR' X3 employed B
.. .
., ,: . ' ' ,. .. , , ' , .
58~l~
in providing the catalyst of an aspect of the present invention can be ~idely selected, it being desirable that the Mg/Al atomic ratio be.in the range of from 10/1 to l/50, preferably from 5/1 to 1/10 and more prefer-ably from 3/1 to 1/2. Also, the reaction ratio between these reactants and the compound R"OH can widely be selected, a desirable (R+R')/OH mole ratio being in the range of from lO/l to 1/20, preferably from 2/1 to - 1/10 and more preferably from 1/1 to 1/5. All these reactions are carried out in either the absence of solvent or in the presence of an inert diluent at a temperature in the range of from -100C. to 200C., prefer-ably from -20C. to 100C. and more preferably from 0C. to 100C. The reaction time is not specially restricted; usually a reaction time ranging from 1 minute to 20 hours and preferably from 10 minutes to 10 hours is desirable. .
Examples of organomagnesium compounds represented by the general formula RMgX wherein R is an alkyl or aryl group having l to 20 carbon atoms, preferably 1 to 8 carbon atoms and X is a halogen, include those compounds usually known as Grignard compounds~; Examples are methylmag-nesium chloride, methylmagnesium bromide, methylmagnesium iodide, ethyl-magnesium chloride, ethylmagnesium bromide, ethylmagnesium iodide, n-propylmagnesium chloride, n-propylmagnesium bromide, n-propylmagnesium iodide, n-butylmagnesium chloride, n-butylmagnesium bromide, n-butyl-magnesium.iodide, isobutylmagnesium chloride, isobutylmagnesium bromide, isobutylmagnesium iodide, hexylmagnesium chloride, hexylmagnesium bromide, hexylmagnesium iodide, octylmagnesium chloride, octylmagnesium bromide, phenylmagnesium chloride, and phenylmagnesium bromide, and ether complexes thereof. Examples of such ether compounds are dimethyl ether, diethyl ether, diisopropyl ether, dibutyl ether, methyl ethyl ether, diallyl ether, tetrahydrofuran, dioxane and anisole.
Examples of aluminum compounds represented by the general for-mula AlR'nX3 n wherein R~ is an alkyl or aryl group having 1 to 20 carbon atoms, X is a halogen and n is o C n ~ 3, include trimethylaluminum, triethylaluminum, triisobutylaluminum, trihexylaluminum, tridecylaluminum, diethylaluminum chloride, diisobutylaluminum chloride, ethylaluminuTQ
sesquichloride, methylaluminum dichloride, ethylaluminum dichloride, isobutylaluminum dichloride, aluminum chloride, aluminum bromide, aluminum iodide, and mixtures thereof. Alkylaluminum halides are specially desirable.
The hydroxy compound represented by the general formula R"OH
contains a hydrocarbon group having 1 to 20 carbon atoms~ preferably 1 to 10 carbon atoms. Such hydrocarbon group (R") is preferably selected from the group consisting of alkyl, alkenyl, aryl and aralkyl, but may be a substituted hydrocarbon group containing hetero elements, e.g., oxygen, nitrogen, sulfur and chloride. Typical examples of the compound represented by the general formula R"OH include methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, iso-butyl alcohol, t-butyl alcohol, n-amyl alcohol, iso-amyl alcohol, t-amyl alcohol, n-hexyl alcohol, n-heptyl alcohol, n-octyl alcohol, n-decyl aleohol, allyl alcohol, benzyl alcohol, cyclohexanol, phenol, chlorophenol, methyl Cellosolve (the Trade Mark for ethylene glycol monomethyl ether), ethanol amine and mixtures thereof. ~
~ell-known methods may be used as the procedure for supporting, by eontacting, a titanium compound and/or a vanadium compound on the carrier which has been prepared from the compounds of RMg~, AlR' X3 n and R"OH in the manner mentioned above. For example, the method which may be used involves reacting a titanium compound and/or a vanadium-compound in the presence or absence of solvent and preferably with heat applied;
another method involves pulverizing the carrier and transition metal com-pound or compounds together. The latter method is used specially prefer-ably in the procedure for preparing the catalyst of an aspect of the present invention, because the catalyst can be prepared with only a small amount of transition metal compound or compounds added and consequently the step of washing out the transition metal compound or compounds can be omitted, which is convenient. The apparatus used for the copulverization i~ not specially restricted. Ball mill, vibration mill, rod mill, and impact mill are usually employed. Conditions such as, for example, temperature and time ~or the pulverization caQ be determined easlly by those skilled in the art according to the pulverization method.
The conditions generally adopted involve pulverization tempera-tures ranging from 0 to 200C. and preferably ~rom 20 to 100C., and pulverization times ranging from 0.5 to 50 hours and preferably from 1 to 30 hours. The operation should be conducted in an inert gas atmosphere and moisture should be avoided as far as possible.
The amount of a titanlum compound and/or a vanadium compound to be supported is preferably adjusted so that the amount of titanium and/or vanadium in the resulting product is in the range of from 0.5 to 20 weight percent. In order to obtain a well-balanced activity per titanium andlor vanadium and per solid, a range of from 1 to 8 weight percent is specially preferred.
The titanîum compounds and/or vanadium compounds which may be used in the catalyst of aspects of the present invention are generally those that can be used as a component of a Ziçgler catalyst. Examples are tetravalent titanium compounds, e.g. titanium tetrachloride, titanium tetrabromide, titanium tetraiodide, methoxytitanium trichloride, dimeth-oxytitanium dichloride, tetramethoxy titanium, ethoxytitanium trichloride,diethoxytitanium dichloride, tetraethoxtitanium, isopropoxytitanium tri-chloride, diisopropoxytitanium dichloride, di-n-butoxytitanium dichloride, tetra-n-butoxytitanium, t-butoxytitanium trichloride,- tetraphenoxytitanium, ethoxyisopropoxytitanium dichloride; trivalent titanium compounds9 e.g., titanium trlchloride, titanium tribromide, and titanium trichloride-aluminum trichloride eutectic mi*ture; trivalent vanadium compounds, e.g., vanadium trichloride and vanadium tribromide; tetravalent vanadium compounds9 e.g.9 vanadium tetrachloride and vanadium tetrabromide; and pentavalent vanadium compounds, e.g., vanadium oxychloride, vanadium oxybromide, orthomethyl vanadate and orthoethyl vanadate.
The olefin polymerization reaction according to an aspect of this invention using the catalyst of an aspect of the present invention is carried out in the same manner as in the conventiona]. olefin pol~l-merization reaction using a Ziegler'catalyst; that is, a substantially oxygen- and moisture-free condition is maintained throughout the reaction.
The conditions for the olefin polymerization involve temperatures ranging from 20 to 300~C. and preferably from 50 to 180C., and pressures ranging from the atmospheric pressure to 70 kg/cm2.G and preferably from 2 to 60 kg/cm .G. The molecular weight'can be adjusted to a certain extent by changing the polymerization conditions, e.g., the polymeriza-tion temperature and the mole ratio of catalyst, but it is more effective-ly ad~usted by the addition of hydrogen into the polymeri~ation system.With the catalyst of an aspect of the present invention, two or more stage polymerization reactions ha~ing different hydrogen concentrations and different polymerization temperatures can of course be made.
The process of an aspect of the present invention can be applied to the polymerization of all o].efins that are polymerizable with Ziegler ; catalysts. For example, it is suitably used for the homopolymerization of ~-olefins, e.g., ethylene, propylene, and l-butene, and the copolymeriaa-tion of ethylene and propylene, ethylene and l-butene, and propylen~'and l-butene3 and also for the copolymerization of an olefin and a diene com-pound, e.g., ethylene and 1,4-hexadiene, and ethylene and ethylidene-norbornene.
Examples of organometallic compounds which may be used in the preparation of the catalyst of an aspect of the present invention are exem~lified organometallic compounds of Groups I - IV of the Periodic '~
Table which are known to be a component of Ziegler catalyst. Organo-aluminum and organozinc compounds are specially preferred. Examples ~nclude organoaluminum compounds represented by the general formulae R3Al, R2AlX, RAlX2, R2AlOR, RAl(OR)2, RAl(OR)X and R3Al2X3 wherein R is an alkyl or aryl group having l to 20 carbon atoms and which may be the same or different and X is a halogen, and organozinc compounds represented by the'general formula R2Zn wherein R is an alkyl group having l to 20 carbon atoms and which may be the same or different, e.g., triethylaluminum, triisobutylaluminum, trihexylaluminum~ trioctylaluminum, tridecyl-aluminum, diethylaluminum chloride, ethylaluminum sesequichloride, diethylzinc, and mixtures thereof. The amount of these organometallic compounds used in the catalyst of an aspect of the present invention is not specially restricted, but usually these compounds can be used in amounts of 0.1 to 1,000 moles per mole of transition metal compound or compounds ~namely, a titanium compound and/or a vanadium compound).
The following examples are further illustrative of aspects of the present invention.
Example 1 (a) Catalyst Preparation A 500 ml flask equipped with a stirrer was purged with nitrogen, in which was then placed 0.2 mole of a tetrahydrofuran solution of ethylmagnesium chloride (2 moles/ liter). Thereafter, 0.2 mole of ethylaluminum dichloride (in n-hexane) was added with stirring under an ice-cooled condition. After reaction for 3 hours under reflex condition, 0.4 mole of ethanol was added, followed by a further reaction for 4 hours under reflux condition. Then the solvents, tetrahydrofuran and n-hexane, were removed and drying was applied at 150C. under reduced pressure.
~0.
To 10 g of the carrler prepared ahove was added 1.86 8 of titanium tetrachloride and the mixture was then suh~ected to a ball milling for 16 hours with1n a 400 ml stainless steel pot at room temperature under a nitrogen atmosphere, the stainless steel pot containing 25 stalnless steel balls each 1/2 inch in diameter. In 1 g of the solid powder obtained after the ball milllng was contained 40 mg of titanium.
(b) Polymerization A 2 liter stainless steel autoclave equipped with an induction stirrer was purged with nitrogen7 in which were then placed 1,000 ml of hexane, 1 millimole of triethylaluminum and 20 mg of the solid prepared above, and the temperature was ~aised to 90C while stirring was applied. The system, which was at a pressure of 2 kg/cm .G
with the vapor pressure of hexane, was pressurized with hydrogen to a total pressure of 5~2 kg/cm .G and then with ethylene to a total pressure of 10 kg/cm .G while polymerization was started. The poly merization was continued for 1 hr. while ethylene was introduced continuously so as to maintain the total pressure at 10 kg/cm2.G.
Then the polymer slurry was transferred into a beaker and hexane removed under reduced pressure to yield 173 g of a white polyethylene having a melt index of 9,3 and a bulk density of 0.35. The catalyst activlty was 45,000 g polyethylene/g Ti-hr-C2H4 pressure, 1~800 g polyethylene/g solid-hr-C2H4 pressure, T~e polyethylene having a high bulk density was obtained with an extremely high catalyst activity.
2~
Example 2 For the preparation of carrier and catalyst, the same procedure as in Example 1 was repeated except that there were used b~tylmagnesium chlorlde in pLace of ethylmagnesium chloride and 1.0 mole, in place of 0.4 mole, of ethanol. Polymerization was conducted for 1 hr. in the same manner as in Example 1 to yield 245 g of a white polyethylene havlng a melt index of 11.5 and a bulk density of ~.39. The catalyst activity was extremely high, it was 2,550 g polyethylene/g solid-hr-C2H4 pressure, 63,800 g polyethylene/g Ti-hr-C2H4 pre8sure.
Example 3 The reaction between an organomagnesium compound and an aluminum compound was conducted in th~ same procedure as in Example 1 excep~ that there were used 0.15 mole of a diethyl ether solution of butylmagnesium chlorlde in place of 0.2 mole of the tetrahydrofuran solution of ethylmagnesium chloride and 0.05 mole of aluminum trichloride in place of ethylaluminum dichloride and that the reaction was made for 4 hrs. under reflux of diethyl ether Then, 0.25 mole of ethanol was added and a further reaction was made in the same manner as in Example 1. Thereafterp titanium tetrachloride was supported in the same way as in Example 1 t~ give a solid containing 39 mg of titanium per g of the solid.
Using the solid catalyst prepared above, polymerization ~0 was made in the same procedure as in Example 1 to yield 306 g of a white polyethylene having a melt index of 12.4 and a bulk density of 0.38. The catalyst activity was 3,190 g polyethylene/g solid-hr~C2H4 pressure, 819800 g polyethylene/g Ti-hr-C2H4 pressure. Thus! both the catalyst activity and the bulk density were extremely high.
~5 Example 4 For the preparation of carrier and catalyst~ the same procedure as in Example 1 was repeated except that there were used 0.2 mole of a die~hyl ether solution of ethylmagnesium bromide in place of the tetrahydrofuran solutlon of ethylmagnesium chloride and that the 5~
reaction between an organomagnesium compound and an alumln~m compound was made for 4 hrs. under reflux of diethyl ether and also except that the subsequent addition was of 0.8 mole of methanol. Then, polymerizatlon was made using the catalyst prepared above in the same manner as in Example 1 to yield 212 g of a white polyethylene having a melt index of 12.1 and a bulk density of 0.38. The catalyst activity was 2,210 g polyethylene/g solid.hr-C2H4 pressure, 55,200 g polyethylene/g Ti.hr-C2H4 pressure. Thus, the catalyst activity was extremely high and also the bulk density was high.
Example 5 Using 20 mg of the catalyst prepared in Example 1, 1 millimole of triethylaluminum and 1,000 ml of hexane, hydrogen was introduced at 90C to a pressure of 5.2 kg/cm .G and then an ethylene- !
propylene mixture contalning 2 mole % of propylene was introduced so as to maintain the pressure of the autoclave at 10 kg/cm2.G~ while poly-merization was made for 1 hr., to yield 174 g of'~ white polymer having a melt lndex of 9,1 and a bulk density of 0,36 and containing 4.8 methyl groups per 1~000 car~on atoms. The catalyst activiLy was 1~810 g ~0 polyethylenel~ solid-hr pressure, 45r300 g polyethylene/g Ti-hr pressure.
Thus, the catalyst activity ~as extremely high and also the bulk density was high.
,
; -: : . .. ....
By yet a still Eurther variant, the organometallic corn-pound is used in an amount of from 0;1 to 1,000 mole per mole of the titanium compound and/or vanadium compound.
By another aspect of this invention, a process is pro-vided for preparing polyolefins by polymerizing or copolymer-izing olefin(s) using as a catalyst a transition metal compound component and an organometallie compound of Groups I - IV of the Periodic Table, the transition metal compound component being obtained by eontacting a titanium compound and/or a 1~ vanadium compound with a eompound as earrier, the compound as carrier being obtained by reacting an organomagnesium eompound represented by the general formula RMgX wherein R is an alkyl or aryl group having 1 to 20 earbon atoms and X is a halogen, with an aluminum eompound represented by the general formula AlR' X3 wherein R' is an alkyl or aryl group having 1 to 20 carbon atoms, X is a halogen and n is 0~n~3, and subseque~tly reaeting the reaetion produet with a hydroxy eompound represented by the general formula R"OH wherein R" is a hyarocarbon radical having 1 to 20 carbon atoms selected from the group consisting of alkyl, alkenyl, aryl and aralkyl or a substituted hydro-carbon group containing hetero elements selected from the group consisting of oxygen, nitrogen sulfur and chloride.
By a variant of this aspect, the olefin polymerization or copolymerization is conducted at a temperature in the range of from 20C. to 300C. and at a-pressue in the range of from the atmospherie pressure to 70 kg/em .
By another variant of this aspect, the olefin polymer-ization or copolymerization is conducted with hydrogen added into the polymerization system.
By the use of the catalyst of an aspect of this invent-on, it becomes possible to effect an olefin polymerization or - 2a -3S8~
copolymeri~ation according to another aspect of this invent-ion with a remarkably high activity of the catalyst, and the bulk density of the resulting polymer is rernarkably high.
As another advantage of the process of an aspect of the present invention, a polymerhaving a high melt index can be prepared easily, that i$, a polymer of the same melt index can be obtained at a lower hydrogen concentration; this is advantageous both economically and also for productivity.
Although the details of the structure of the carrier which is used in the catalys-t of an aspect of the present in-vention and which is obtained, as mentioned above, by the reaction of the compounds of RMgX, AlR' X3 and R"OH, are not clear, it is presumed that a novel carrier is produced by the reaction of the three.
The reaction ratio of the compounds RMgX and AlR' X3 employed B
.. .
., ,: . ' ' ,. .. , , ' , .
58~l~
in providing the catalyst of an aspect of the present invention can be ~idely selected, it being desirable that the Mg/Al atomic ratio be.in the range of from 10/1 to l/50, preferably from 5/1 to 1/10 and more prefer-ably from 3/1 to 1/2. Also, the reaction ratio between these reactants and the compound R"OH can widely be selected, a desirable (R+R')/OH mole ratio being in the range of from lO/l to 1/20, preferably from 2/1 to - 1/10 and more preferably from 1/1 to 1/5. All these reactions are carried out in either the absence of solvent or in the presence of an inert diluent at a temperature in the range of from -100C. to 200C., prefer-ably from -20C. to 100C. and more preferably from 0C. to 100C. The reaction time is not specially restricted; usually a reaction time ranging from 1 minute to 20 hours and preferably from 10 minutes to 10 hours is desirable. .
Examples of organomagnesium compounds represented by the general formula RMgX wherein R is an alkyl or aryl group having l to 20 carbon atoms, preferably 1 to 8 carbon atoms and X is a halogen, include those compounds usually known as Grignard compounds~; Examples are methylmag-nesium chloride, methylmagnesium bromide, methylmagnesium iodide, ethyl-magnesium chloride, ethylmagnesium bromide, ethylmagnesium iodide, n-propylmagnesium chloride, n-propylmagnesium bromide, n-propylmagnesium iodide, n-butylmagnesium chloride, n-butylmagnesium bromide, n-butyl-magnesium.iodide, isobutylmagnesium chloride, isobutylmagnesium bromide, isobutylmagnesium iodide, hexylmagnesium chloride, hexylmagnesium bromide, hexylmagnesium iodide, octylmagnesium chloride, octylmagnesium bromide, phenylmagnesium chloride, and phenylmagnesium bromide, and ether complexes thereof. Examples of such ether compounds are dimethyl ether, diethyl ether, diisopropyl ether, dibutyl ether, methyl ethyl ether, diallyl ether, tetrahydrofuran, dioxane and anisole.
Examples of aluminum compounds represented by the general for-mula AlR'nX3 n wherein R~ is an alkyl or aryl group having 1 to 20 carbon atoms, X is a halogen and n is o C n ~ 3, include trimethylaluminum, triethylaluminum, triisobutylaluminum, trihexylaluminum, tridecylaluminum, diethylaluminum chloride, diisobutylaluminum chloride, ethylaluminuTQ
sesquichloride, methylaluminum dichloride, ethylaluminum dichloride, isobutylaluminum dichloride, aluminum chloride, aluminum bromide, aluminum iodide, and mixtures thereof. Alkylaluminum halides are specially desirable.
The hydroxy compound represented by the general formula R"OH
contains a hydrocarbon group having 1 to 20 carbon atoms~ preferably 1 to 10 carbon atoms. Such hydrocarbon group (R") is preferably selected from the group consisting of alkyl, alkenyl, aryl and aralkyl, but may be a substituted hydrocarbon group containing hetero elements, e.g., oxygen, nitrogen, sulfur and chloride. Typical examples of the compound represented by the general formula R"OH include methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, iso-butyl alcohol, t-butyl alcohol, n-amyl alcohol, iso-amyl alcohol, t-amyl alcohol, n-hexyl alcohol, n-heptyl alcohol, n-octyl alcohol, n-decyl aleohol, allyl alcohol, benzyl alcohol, cyclohexanol, phenol, chlorophenol, methyl Cellosolve (the Trade Mark for ethylene glycol monomethyl ether), ethanol amine and mixtures thereof. ~
~ell-known methods may be used as the procedure for supporting, by eontacting, a titanium compound and/or a vanadium compound on the carrier which has been prepared from the compounds of RMg~, AlR' X3 n and R"OH in the manner mentioned above. For example, the method which may be used involves reacting a titanium compound and/or a vanadium-compound in the presence or absence of solvent and preferably with heat applied;
another method involves pulverizing the carrier and transition metal com-pound or compounds together. The latter method is used specially prefer-ably in the procedure for preparing the catalyst of an aspect of the present invention, because the catalyst can be prepared with only a small amount of transition metal compound or compounds added and consequently the step of washing out the transition metal compound or compounds can be omitted, which is convenient. The apparatus used for the copulverization i~ not specially restricted. Ball mill, vibration mill, rod mill, and impact mill are usually employed. Conditions such as, for example, temperature and time ~or the pulverization caQ be determined easlly by those skilled in the art according to the pulverization method.
The conditions generally adopted involve pulverization tempera-tures ranging from 0 to 200C. and preferably ~rom 20 to 100C., and pulverization times ranging from 0.5 to 50 hours and preferably from 1 to 30 hours. The operation should be conducted in an inert gas atmosphere and moisture should be avoided as far as possible.
The amount of a titanlum compound and/or a vanadium compound to be supported is preferably adjusted so that the amount of titanium and/or vanadium in the resulting product is in the range of from 0.5 to 20 weight percent. In order to obtain a well-balanced activity per titanium andlor vanadium and per solid, a range of from 1 to 8 weight percent is specially preferred.
The titanîum compounds and/or vanadium compounds which may be used in the catalyst of aspects of the present invention are generally those that can be used as a component of a Ziçgler catalyst. Examples are tetravalent titanium compounds, e.g. titanium tetrachloride, titanium tetrabromide, titanium tetraiodide, methoxytitanium trichloride, dimeth-oxytitanium dichloride, tetramethoxy titanium, ethoxytitanium trichloride,diethoxytitanium dichloride, tetraethoxtitanium, isopropoxytitanium tri-chloride, diisopropoxytitanium dichloride, di-n-butoxytitanium dichloride, tetra-n-butoxytitanium, t-butoxytitanium trichloride,- tetraphenoxytitanium, ethoxyisopropoxytitanium dichloride; trivalent titanium compounds9 e.g., titanium trlchloride, titanium tribromide, and titanium trichloride-aluminum trichloride eutectic mi*ture; trivalent vanadium compounds, e.g., vanadium trichloride and vanadium tribromide; tetravalent vanadium compounds9 e.g.9 vanadium tetrachloride and vanadium tetrabromide; and pentavalent vanadium compounds, e.g., vanadium oxychloride, vanadium oxybromide, orthomethyl vanadate and orthoethyl vanadate.
The olefin polymerization reaction according to an aspect of this invention using the catalyst of an aspect of the present invention is carried out in the same manner as in the conventiona]. olefin pol~l-merization reaction using a Ziegler'catalyst; that is, a substantially oxygen- and moisture-free condition is maintained throughout the reaction.
The conditions for the olefin polymerization involve temperatures ranging from 20 to 300~C. and preferably from 50 to 180C., and pressures ranging from the atmospheric pressure to 70 kg/cm2.G and preferably from 2 to 60 kg/cm .G. The molecular weight'can be adjusted to a certain extent by changing the polymerization conditions, e.g., the polymeriza-tion temperature and the mole ratio of catalyst, but it is more effective-ly ad~usted by the addition of hydrogen into the polymeri~ation system.With the catalyst of an aspect of the present invention, two or more stage polymerization reactions ha~ing different hydrogen concentrations and different polymerization temperatures can of course be made.
The process of an aspect of the present invention can be applied to the polymerization of all o].efins that are polymerizable with Ziegler ; catalysts. For example, it is suitably used for the homopolymerization of ~-olefins, e.g., ethylene, propylene, and l-butene, and the copolymeriaa-tion of ethylene and propylene, ethylene and l-butene, and propylen~'and l-butene3 and also for the copolymerization of an olefin and a diene com-pound, e.g., ethylene and 1,4-hexadiene, and ethylene and ethylidene-norbornene.
Examples of organometallic compounds which may be used in the preparation of the catalyst of an aspect of the present invention are exem~lified organometallic compounds of Groups I - IV of the Periodic '~
Table which are known to be a component of Ziegler catalyst. Organo-aluminum and organozinc compounds are specially preferred. Examples ~nclude organoaluminum compounds represented by the general formulae R3Al, R2AlX, RAlX2, R2AlOR, RAl(OR)2, RAl(OR)X and R3Al2X3 wherein R is an alkyl or aryl group having l to 20 carbon atoms and which may be the same or different and X is a halogen, and organozinc compounds represented by the'general formula R2Zn wherein R is an alkyl group having l to 20 carbon atoms and which may be the same or different, e.g., triethylaluminum, triisobutylaluminum, trihexylaluminum~ trioctylaluminum, tridecyl-aluminum, diethylaluminum chloride, ethylaluminum sesequichloride, diethylzinc, and mixtures thereof. The amount of these organometallic compounds used in the catalyst of an aspect of the present invention is not specially restricted, but usually these compounds can be used in amounts of 0.1 to 1,000 moles per mole of transition metal compound or compounds ~namely, a titanium compound and/or a vanadium compound).
The following examples are further illustrative of aspects of the present invention.
Example 1 (a) Catalyst Preparation A 500 ml flask equipped with a stirrer was purged with nitrogen, in which was then placed 0.2 mole of a tetrahydrofuran solution of ethylmagnesium chloride (2 moles/ liter). Thereafter, 0.2 mole of ethylaluminum dichloride (in n-hexane) was added with stirring under an ice-cooled condition. After reaction for 3 hours under reflex condition, 0.4 mole of ethanol was added, followed by a further reaction for 4 hours under reflux condition. Then the solvents, tetrahydrofuran and n-hexane, were removed and drying was applied at 150C. under reduced pressure.
~0.
To 10 g of the carrler prepared ahove was added 1.86 8 of titanium tetrachloride and the mixture was then suh~ected to a ball milling for 16 hours with1n a 400 ml stainless steel pot at room temperature under a nitrogen atmosphere, the stainless steel pot containing 25 stalnless steel balls each 1/2 inch in diameter. In 1 g of the solid powder obtained after the ball milllng was contained 40 mg of titanium.
(b) Polymerization A 2 liter stainless steel autoclave equipped with an induction stirrer was purged with nitrogen7 in which were then placed 1,000 ml of hexane, 1 millimole of triethylaluminum and 20 mg of the solid prepared above, and the temperature was ~aised to 90C while stirring was applied. The system, which was at a pressure of 2 kg/cm .G
with the vapor pressure of hexane, was pressurized with hydrogen to a total pressure of 5~2 kg/cm .G and then with ethylene to a total pressure of 10 kg/cm .G while polymerization was started. The poly merization was continued for 1 hr. while ethylene was introduced continuously so as to maintain the total pressure at 10 kg/cm2.G.
Then the polymer slurry was transferred into a beaker and hexane removed under reduced pressure to yield 173 g of a white polyethylene having a melt index of 9,3 and a bulk density of 0.35. The catalyst activlty was 45,000 g polyethylene/g Ti-hr-C2H4 pressure, 1~800 g polyethylene/g solid-hr-C2H4 pressure, T~e polyethylene having a high bulk density was obtained with an extremely high catalyst activity.
2~
Example 2 For the preparation of carrier and catalyst, the same procedure as in Example 1 was repeated except that there were used b~tylmagnesium chlorlde in pLace of ethylmagnesium chloride and 1.0 mole, in place of 0.4 mole, of ethanol. Polymerization was conducted for 1 hr. in the same manner as in Example 1 to yield 245 g of a white polyethylene havlng a melt index of 11.5 and a bulk density of ~.39. The catalyst activity was extremely high, it was 2,550 g polyethylene/g solid-hr-C2H4 pressure, 63,800 g polyethylene/g Ti-hr-C2H4 pre8sure.
Example 3 The reaction between an organomagnesium compound and an aluminum compound was conducted in th~ same procedure as in Example 1 excep~ that there were used 0.15 mole of a diethyl ether solution of butylmagnesium chlorlde in place of 0.2 mole of the tetrahydrofuran solution of ethylmagnesium chloride and 0.05 mole of aluminum trichloride in place of ethylaluminum dichloride and that the reaction was made for 4 hrs. under reflux of diethyl ether Then, 0.25 mole of ethanol was added and a further reaction was made in the same manner as in Example 1. Thereafterp titanium tetrachloride was supported in the same way as in Example 1 t~ give a solid containing 39 mg of titanium per g of the solid.
Using the solid catalyst prepared above, polymerization ~0 was made in the same procedure as in Example 1 to yield 306 g of a white polyethylene having a melt index of 12.4 and a bulk density of 0.38. The catalyst activity was 3,190 g polyethylene/g solid-hr~C2H4 pressure, 819800 g polyethylene/g Ti-hr-C2H4 pressure. Thus! both the catalyst activity and the bulk density were extremely high.
~5 Example 4 For the preparation of carrier and catalyst~ the same procedure as in Example 1 was repeated except that there were used 0.2 mole of a die~hyl ether solution of ethylmagnesium bromide in place of the tetrahydrofuran solutlon of ethylmagnesium chloride and that the 5~
reaction between an organomagnesium compound and an alumln~m compound was made for 4 hrs. under reflux of diethyl ether and also except that the subsequent addition was of 0.8 mole of methanol. Then, polymerizatlon was made using the catalyst prepared above in the same manner as in Example 1 to yield 212 g of a white polyethylene having a melt index of 12.1 and a bulk density of 0.38. The catalyst activity was 2,210 g polyethylene/g solid.hr-C2H4 pressure, 55,200 g polyethylene/g Ti.hr-C2H4 pressure. Thus, the catalyst activity was extremely high and also the bulk density was high.
Example 5 Using 20 mg of the catalyst prepared in Example 1, 1 millimole of triethylaluminum and 1,000 ml of hexane, hydrogen was introduced at 90C to a pressure of 5.2 kg/cm .G and then an ethylene- !
propylene mixture contalning 2 mole % of propylene was introduced so as to maintain the pressure of the autoclave at 10 kg/cm2.G~ while poly-merization was made for 1 hr., to yield 174 g of'~ white polymer having a melt lndex of 9,1 and a bulk density of 0,36 and containing 4.8 methyl groups per 1~000 car~on atoms. The catalyst activiLy was 1~810 g ~0 polyethylenel~ solid-hr pressure, 45r300 g polyethylene/g Ti-hr pressure.
Thus, the catalyst activity ~as extremely high and also the bulk density was high.
,
Claims (16)
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. A polymerization catalyst comprising:
(A) a transition metal compound component;
and (B) an organometallic compound of Groups I - IV of the Periodic Table; said transition metal compound being obtained by contacting (1) a compound obtained by reacting an organomagnesium com-pound represented by the general formula RMgX, wherein R is an alkyl or aryl group having 1 to 20 carbon atoms and x is a halogen, with an aluminum compound represented by the gener-al formula A1R'nX3-n' wherein R' is an alkyl or aryl group having 1 to 20 carbon atoms, X is a halogen and n is 0?n?3, and subsequently reacting that reaction product with a hydroxy compound represented by the general formula R"OH, wherein R"
is a hydrocarbon radical having 1 to 20 carbon atoms selected from the group consisting of alkyl, alkenyl, aryl and aralkyl or a substituted hydrocarbon group containing hetero elements selected from the group consisting of oxygen, nitrogen, sul-fur and chloride, with (2) at least one of a titanium compound and a vanadium com-pound.
(A) a transition metal compound component;
and (B) an organometallic compound of Groups I - IV of the Periodic Table; said transition metal compound being obtained by contacting (1) a compound obtained by reacting an organomagnesium com-pound represented by the general formula RMgX, wherein R is an alkyl or aryl group having 1 to 20 carbon atoms and x is a halogen, with an aluminum compound represented by the gener-al formula A1R'nX3-n' wherein R' is an alkyl or aryl group having 1 to 20 carbon atoms, X is a halogen and n is 0?n?3, and subsequently reacting that reaction product with a hydroxy compound represented by the general formula R"OH, wherein R"
is a hydrocarbon radical having 1 to 20 carbon atoms selected from the group consisting of alkyl, alkenyl, aryl and aralkyl or a substituted hydrocarbon group containing hetero elements selected from the group consisting of oxygen, nitrogen, sul-fur and chloride, with (2) at least one of a titanium compound and a vanadium com-pound.
2. The catalyst of claim 1 wherein said RMgX and said A1R'nX3-n are used in a ratio such that the Mg/Al atomic ratio is in the range of from 10/1 to 1/50, and the two are reacted together for one minute to 20 hours at a temperature in the range of from -100°C. to 200°C.
3. The catalyst of claim 1 wherein the reaction product of said RMgX and said A1R'nX3-n, and said R"OH are used in a ratio such that the (R+R')/OH mole ratio is in the range of from 10/1 to 1/20, and the two are reacted together for one minute to 20 hours at a tempersture in the range of from -100°C. to 200°C.
4. The catalyst of claim 1 wherein the treatment of con-tacting said compound (1) which is obtained by the reaction of said RMgX and said A1R'nX3-n and the subsequent reaction with said R"OH, with said titanium compound and/or vanadium compound, is a copulverization of said compounds (1) and (2) which is conducted for 0.5 to 50 hours in an inert gas at-mosphere at a temperature in the range of from 0°C. to 200°C.
5. The catalyst of claim 1 wherein the content of titanium or vanadium in said transition metal compound component is in the range of from 0.5 to 20 weight percent.
6. The catalyst of claim 1 wherein said organometallic compound is either an organo aluminum compound or an organo-zinc compound.
7. The catalyst of claim 1 wherein said organometallic compound is used in an amount of from 0 1 to 1,000 mole per mole of said titanium compound and/or vanadium compound.
8. A process for preparing polyolefins, which process comprises polymerizing or copolymerizing an olefin or olefins using, as a catalyst, a transition metal compound component and an organometallic compound of Groups I -IV of the Per-iodic Table, said transition metal compound component being a substance obtained by contacting the following compounds (1) and (2):
(1) a compound which is obtained by reacting an organomagnesium compound represented by the gen-eral formula RMgX wherein R is an alkyl or aryl group having 1 to 20 carbon atoms and X is a halogen, with an aluminum compound represented by the general formula A1R'nX3-n wherein R' is a halogen and n is 0?n?3, and subsequently reacting the reaction product with a hydroxy compound represented by the general formula R"OH wherein R' is a hydrocar-bon radical having 1 to 20 carbon atoms selected from the group consisting of alkyl, alkenyl, aryl and aralkyl or a substituted hydrocarbon group containing hetero elements selected from the group consisting of oxygen, nitrogen, sulfur and chloride;
and (2) a titanium compound and/or a vanadium compound.
(1) a compound which is obtained by reacting an organomagnesium compound represented by the gen-eral formula RMgX wherein R is an alkyl or aryl group having 1 to 20 carbon atoms and X is a halogen, with an aluminum compound represented by the general formula A1R'nX3-n wherein R' is a halogen and n is 0?n?3, and subsequently reacting the reaction product with a hydroxy compound represented by the general formula R"OH wherein R' is a hydrocar-bon radical having 1 to 20 carbon atoms selected from the group consisting of alkyl, alkenyl, aryl and aralkyl or a substituted hydrocarbon group containing hetero elements selected from the group consisting of oxygen, nitrogen, sulfur and chloride;
and (2) a titanium compound and/or a vanadium compound.
9. A process according to claim 8 wherein said RMgX and said A1R'nX3-n are used in a ratio such that the Mg/Al atomic ratio is in the range of from 10/1 to 1/50, and the two are reacted together for one minute to 20 hours at a temperature in the range of from -100°C. to 200°C.
10. A process according to claim 8 wherein the reaction product of said RMgX and said A1R'nX3-n, and said R"OH are used in a ratio such that the (R+R')/OH mole ratio is in the range of from 10/1 to 1/20, and the two are reacted together for one minute to 20 hours at a temperature in the range of from -100°C. to 200°C.
11. A process according to claim 8 wherein the treatment of contacting said compound (1) which is obtained by the reaction of said RMgX and said A1R'nX3-n and the subsequent reaction with said R"OH,with said titanium compound and/or vanadium compound, is a copulverization of said compounds (1) and (2) which is conducted for 0.5 to 50 hours in an inert gas atmosphere at a temperature in the range of from 0°C. to 200°C.
12. A process according to claim 8 wherein the content of titanium or vanadium in said transition metal compound component is in the range of from 0.5 to 20 weight percent.
13. A process according to claim 8 wherein said organometallic compound is either an organoaluminum compound or an organozinc compound.
14, A process according to claim 8 wherein said organometallic compound is used in an amount of from 0.1 to 1,000 mole per mole of said titanium compound and/or vanadium compound.
15. A process according to claim 8 wherein the olefin polymeriza-ation or copolymerization is conducted at a temperature in the range of from 20°C. to 300°C. and at a pressure in the range of from the atmos-pheric pressure to 70 kg/cm2.
16. A process according to claim 8 wherein the olefin polymeriza-tion or copolymerization is conducted with hydrogen added into the poly-merization system.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1470/1976 | 1976-01-09 | ||
| JP147076A JPS5285278A (en) | 1976-01-09 | 1976-01-09 | Production of polyolefin |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1085811A true CA1085811A (en) | 1980-09-16 |
Family
ID=11502339
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA269,137A Expired CA1085811A (en) | 1976-01-09 | 1977-01-04 | Process for preparing polyolefins |
Country Status (5)
| Country | Link |
|---|---|
| JP (1) | JPS5285278A (en) |
| CA (1) | CA1085811A (en) |
| DE (1) | DE2700163A1 (en) |
| FR (1) | FR2337737A1 (en) |
| IT (1) | IT1067562B (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA1104298A (en) * | 1978-02-23 | 1981-06-30 | Akinobu Shiga | Catalysts for the polymerization of olefins |
| JPS6050836U (en) * | 1983-09-19 | 1985-04-10 | 株式会社クボタ | Riding rice transplanter |
| CA1267646A (en) * | 1985-06-06 | 1990-04-10 | The Dow Chemical Company | Catalyst and method for producing relatively narrow molecular weight distribution olefin polymers |
| NL8700322A (en) * | 1987-02-11 | 1988-09-01 | Stamicarbon | CATALYST SYSTEM FOR (CO) POLYMERIZATION OF ETHENE IN SOLUTION. |
| JP6393707B2 (en) | 2016-04-28 | 2018-09-19 | 川崎重工業株式会社 | Spot joining apparatus, spot joining method and joint structure |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1275641A (en) * | 1969-01-06 | 1972-05-24 | Solvay | Catalysts for the polymerisation and copolymerisation of olefins |
| US3907759A (en) * | 1972-10-06 | 1975-09-23 | Nissan Chemical Ind Ltd | Catalyst for polymerization of olefins and process for polymerization of olefins with use of said catalyst |
| FR2212346B1 (en) * | 1972-12-28 | 1978-12-01 | Nippon Oil Co Ltd | |
| JPS5439876B2 (en) * | 1973-08-24 | 1979-11-30 | ||
| JPS5236791B2 (en) * | 1974-05-25 | 1977-09-17 |
-
1976
- 1976-01-09 JP JP147076A patent/JPS5285278A/en active Granted
- 1976-12-09 IT IT3021776A patent/IT1067562B/en active
- 1976-12-30 FR FR7639661A patent/FR2337737A1/en active Granted
-
1977
- 1977-01-04 CA CA269,137A patent/CA1085811A/en not_active Expired
- 1977-01-04 DE DE19772700163 patent/DE2700163A1/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS565405B2 (en) | 1981-02-04 |
| FR2337737A1 (en) | 1977-08-05 |
| JPS5285278A (en) | 1977-07-15 |
| DE2700163C2 (en) | 1989-02-16 |
| IT1067562B (en) | 1985-03-16 |
| FR2337737B1 (en) | 1980-10-10 |
| DE2700163A1 (en) | 1977-07-14 |
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