CA2062611A1 - Process for producing ethylene-.alpha.-olefin copolymers - Google Patents
Process for producing ethylene-.alpha.-olefin copolymersInfo
- Publication number
- CA2062611A1 CA2062611A1 CA002062611A CA2062611A CA2062611A1 CA 2062611 A1 CA2062611 A1 CA 2062611A1 CA 002062611 A CA002062611 A CA 002062611A CA 2062611 A CA2062611 A CA 2062611A CA 2062611 A1 CA2062611 A1 CA 2062611A1
- Authority
- CA
- Canada
- Prior art keywords
- titanium
- tetrakis
- process according
- ethylene
- olefin
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Abandoned
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F210/02—Ethene
-
- 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
Abstract
ABSTRACT
A process for producing an ethylene-.alpha.-olefin copolymer which comprises copolymerizing ethylene and an .alpha.-olefin at a temperature higher than 120°C by using a catalyst system comprising a specified titanium amide compound represented by general formula (R1R2N)4-nTiYn and an oxygen-containing alkylaluminum compound. According to the above process, there can be obtained ethylene-.alpha.-olefin copolymers narrow in composition distribution, high in molecular weight and excellent in weather resistance, colorizability, corrosion resistance and dynamic properties.
A process for producing an ethylene-.alpha.-olefin copolymer which comprises copolymerizing ethylene and an .alpha.-olefin at a temperature higher than 120°C by using a catalyst system comprising a specified titanium amide compound represented by general formula (R1R2N)4-nTiYn and an oxygen-containing alkylaluminum compound. According to the above process, there can be obtained ethylene-.alpha.-olefin copolymers narrow in composition distribution, high in molecular weight and excellent in weather resistance, colorizability, corrosion resistance and dynamic properties.
Description
BACKGROI)ND OF THE INVENTION
Field of the Invention This invention relates to a process for producing ethylene-a-olefin copolymers using a no~el Ziegler catalyst system. Particularly, this in~enti~n relates to a process for producing ethylene-~-olefin copolymers at a temperature higher than 1~0~ by using a polymerization catalyst comprising a titanium amicle compound and an oxygen-containing alkylaluminum compound.
More particularly, this invention relates to a process for producing ethylene-a-olefin copol~mers narrow in composi-tion distribution, high in molecular weight and excellent in weather resistance, colorizability, corrosion resist-ance and dynamic properties by using a novel catalyst ;,.,~
system.
:, ~
Description of the Prior Art ~Olefin copolymers are used in very many fields ; such as film, laminate, electric wire coating, injection molded products, special molded products, and the like.
;~20 It is generally known in these fields that a product excellent .in transparency, impact resistance and blocking ;resistance can be obtained by using a polymer narrow in molecular weight distribution or composition di~tribution.
Particularly in the case of copolymers, the molecular ~ "
;, . . :
,, ~ , h ~
1 weight distribution and composition distribution exercise an increasing influence up~n the propertie~ of ole~in copolymer as the content of copolymerized olefin increases. Thus, an olefin copolymer narrow in m~lecular weight distribution and composition di tribution is waited for.
As a process for producing olefin copolymers, the method of using the ~o-called Ziegler-Natta catalyst comprising a transition metal of Group IV to VI oF ~he periodic table and an organometallic compound of a metal of Group I to III is generally widely known.
As the process or producing an olefin copol~mer at high tempexatures by using these Ziegler type catalyst, the following two processes are practised today.
The first process is usually called "solution process" which comprises polymerizing or copol~merizing olefins in a solvent such as cyclohexane or the like. In this process, an olefin is polymerized at a temperature of 120 to 250C and a pressure of 5 to 50 kg/cm2 by the use of a Ziegler type catalyst to form a solution of polymer.
Thc second process is usually ralled "high pressure ion process" which comprises polymerizing or copolymerizing olefins in the absence of solvent at a high temperature and a high pressure to form a polymer in a 25 molten state.
These high temperature solution polymerization process and high pressure ion polymerization process using a Ziegler catalyst are known to have a merit that the ~!
, ~ :`
; "' ~ . ` - . :
. .
,~: ' : `
, ~2~
l reactor is compact and comonomer can be selected with a high degree of freedom.
On Ziegler type solid catalyst for use at high temperature, a variety of improvements have been proposed up to date as described in, for example, Japanese Patent Application KOKAI (Laid-Open) Nos. 51-144397, 54-52192, 56~18607, 56-99209, 57-87405, 57-153007, 57-190009 and 58-208803. Ho~ever, all these techniques give a polymer broad in composition distribution and are unsatisfactory in transparency and dynamic properties of the for~ed polymers.
~:~ On the other hand, as a method for obtaining an olefin polymer narrow in molecular weight distribution and composition distribution, a process for polymerizing an olefin by usi.ng a catalyst formed from a vanadium type catalyst component and an organoaluminum compound catalyst component is known However, this process is disadvan-:~ tageous in that activity per transition metal is low anr .
the activity furth~r decreases when polymerization is : 20 carried out at a high temperature of 120C or abo~e.
.; :
In order to solve such a probleml processesusing a catalyst system comprisin~ a titanium compound or zirconium compound and an aluminum compound have been disclosed up to today, and recent~y, a process using a catalyst system comprising a titanium compound or ~: zirconium compound and aluminoxane has been proposed ~ [Japanese Patent Application KOHYO ~International Laid-.~ Open) No. l-~Q3788; Japanese Patent Application KOXAI
:~ - 3 -, .- :
. :
.
,, .:
1 (Laid-Open) No. 62-121708].
However, when such a catalyst system is used in the high temperature solution pol~merization process, the ~ormed copol~mer i5 low in molecular weight and cannot be said to be satisfactory in practical properties. ~urther, such a catalyst system is not su~ficient in the ab.ility to copolymerize a-olefins. Thus, expensive ~-olefin must be fed into the polymerization system in a large amount, which is undesirable in economical point of view.
As processes for homo- or co-polymerizing olefins by using a catalyst system comprising a compound having titanium-nitrogen bond and an organoaluminum compound, a process using a catalyst system comprising a ~ solid component prepared by supporting a titanium amide :~ 15 compound on magnesium halide and an organoaluminum ~ compound (EP-A-0 320169; Italian Patent No. 867243), a , , process using a catalyst system comprising a titanium diphenylamide compound and an organoaluminum compound EP-A-0 104374; Japanese Patent Application XOKOKU
(Examined Publication) No. 42-11646)l a process using a ~; catalyst system comprising an aryl substituent-containing titanium amide compound and an organoaluminum compound , ~Japanese Patent Application KOKOKU (E.xamined Publication) No. 42~22691], and a process using a catalyst system comprising a lower alkyl-containing titanium amide ,,, , compound such as dimethylamidotitanium trichloride and the ~,,.
~: like and an organoaluminum compound [J. of Polym. Sci.
~' Part A-l, 241, 6 (1968)3 have been proposed.
,;
!~. .:`~
" :~ ', : . :
.,,~: ~ , 1 Howe~er, if a copolymerization of ethylene and ~olefin is carried ou~ with the catalyst systems disclosed in these papers, no satisfactory result has been obtained. Thus, according to the process disclQsed in EP-A-0 320169 and Italian Patent No. 867243, the formed ethylene-a-olefin copolymer has a broad composition distribution. According to the processes disclosed in EP-A-0 104374, Japanese Patent Application KOKOKV
(Examined Publication) Nos. 42-11646 and 42-22691 and J.
Polym. Sci. Part ~-1, 241, 6 ~1968), catalyst activity, copolymerizability and narrowness of composition distribution are unsatisfactory.
In order to solve the above-mentioned problems, ; the present inventors previously proposed ~Japanese Patent Application KOKAI (Laid-Open) ~o. 2-774123 a process for copolymerizing ethylene and a~olefin to give a copolymer having a narrow composition distribution which comprises using a catalyst system comprising an organoaluminum compound and a liq~id catalyst component comprising a titanium compound represented by the following general formula:
(R R N)4-(m+n~TiXmYn wherein R1 and R2 each represent a saturated hydrocarbon group having 8 to 30 carbon atoms, X represents a halogen atom, Y represents an alkoxy group, m is a number satisfy-ing 1 s m < 3, and n is a number satisfying 0 < n ~ 2, : ~ .
'"
, 1 and (m+n) satisfies 1 < ~m+n) _ 3.
However, this process had a fault that, if the catalyst system was used a~ a high temperature, the catalyst activity was very low and the ability to copoly-m~rize a-olefin was low, and the resulting polymer was unsatisfactory in composition distribution.
SUMMARY OF THE INV~NTION
In ~iew of the above-rnentioned present status of things, the problem to be solved by this invention or the : 10 object of this invention consists in providing a process for producing an ethylene-~-olefin copolymer which com-prises using a novel catalyst system, by the use of which a high catalyst activity per transition metal can be exhibited at high temperatures and an ethylene-a olefin copolymer narrow in composition distribution, high in ~ molecular weight and excellen~ in weather resistance, j colorizability, corrosion resistance and dynamic proper-ties can be obtained.
:Thus, this invention relates to a process for producing an ethylene-a-olefin copolymer which comprise~
copolymerizing ethylene and an a-olefin at a polyme:riza-tion temperature higher than 120C by using a catalyst system comprising as catalyst component (A) a titanium amide compound represented by the following general formula:
~R1R2N)4_nTiYn ~; - 6 - :
:
,:~i~ :
Field of the Invention This invention relates to a process for producing ethylene-a-olefin copolymers using a no~el Ziegler catalyst system. Particularly, this in~enti~n relates to a process for producing ethylene-~-olefin copolymers at a temperature higher than 1~0~ by using a polymerization catalyst comprising a titanium amicle compound and an oxygen-containing alkylaluminum compound.
More particularly, this invention relates to a process for producing ethylene-a-olefin copol~mers narrow in composi-tion distribution, high in molecular weight and excellent in weather resistance, colorizability, corrosion resist-ance and dynamic properties by using a novel catalyst ;,.,~
system.
:, ~
Description of the Prior Art ~Olefin copolymers are used in very many fields ; such as film, laminate, electric wire coating, injection molded products, special molded products, and the like.
;~20 It is generally known in these fields that a product excellent .in transparency, impact resistance and blocking ;resistance can be obtained by using a polymer narrow in molecular weight distribution or composition di~tribution.
Particularly in the case of copolymers, the molecular ~ "
;, . . :
,, ~ , h ~
1 weight distribution and composition distribution exercise an increasing influence up~n the propertie~ of ole~in copolymer as the content of copolymerized olefin increases. Thus, an olefin copolymer narrow in m~lecular weight distribution and composition di tribution is waited for.
As a process for producing olefin copolymers, the method of using the ~o-called Ziegler-Natta catalyst comprising a transition metal of Group IV to VI oF ~he periodic table and an organometallic compound of a metal of Group I to III is generally widely known.
As the process or producing an olefin copol~mer at high tempexatures by using these Ziegler type catalyst, the following two processes are practised today.
The first process is usually called "solution process" which comprises polymerizing or copol~merizing olefins in a solvent such as cyclohexane or the like. In this process, an olefin is polymerized at a temperature of 120 to 250C and a pressure of 5 to 50 kg/cm2 by the use of a Ziegler type catalyst to form a solution of polymer.
Thc second process is usually ralled "high pressure ion process" which comprises polymerizing or copolymerizing olefins in the absence of solvent at a high temperature and a high pressure to form a polymer in a 25 molten state.
These high temperature solution polymerization process and high pressure ion polymerization process using a Ziegler catalyst are known to have a merit that the ~!
, ~ :`
; "' ~ . ` - . :
. .
,~: ' : `
, ~2~
l reactor is compact and comonomer can be selected with a high degree of freedom.
On Ziegler type solid catalyst for use at high temperature, a variety of improvements have been proposed up to date as described in, for example, Japanese Patent Application KOKAI (Laid-Open) Nos. 51-144397, 54-52192, 56~18607, 56-99209, 57-87405, 57-153007, 57-190009 and 58-208803. Ho~ever, all these techniques give a polymer broad in composition distribution and are unsatisfactory in transparency and dynamic properties of the for~ed polymers.
~:~ On the other hand, as a method for obtaining an olefin polymer narrow in molecular weight distribution and composition distribution, a process for polymerizing an olefin by usi.ng a catalyst formed from a vanadium type catalyst component and an organoaluminum compound catalyst component is known However, this process is disadvan-:~ tageous in that activity per transition metal is low anr .
the activity furth~r decreases when polymerization is : 20 carried out at a high temperature of 120C or abo~e.
.; :
In order to solve such a probleml processesusing a catalyst system comprisin~ a titanium compound or zirconium compound and an aluminum compound have been disclosed up to today, and recent~y, a process using a catalyst system comprising a titanium compound or ~: zirconium compound and aluminoxane has been proposed ~ [Japanese Patent Application KOHYO ~International Laid-.~ Open) No. l-~Q3788; Japanese Patent Application KOXAI
:~ - 3 -, .- :
. :
.
,, .:
1 (Laid-Open) No. 62-121708].
However, when such a catalyst system is used in the high temperature solution pol~merization process, the ~ormed copol~mer i5 low in molecular weight and cannot be said to be satisfactory in practical properties. ~urther, such a catalyst system is not su~ficient in the ab.ility to copolymerize a-olefins. Thus, expensive ~-olefin must be fed into the polymerization system in a large amount, which is undesirable in economical point of view.
As processes for homo- or co-polymerizing olefins by using a catalyst system comprising a compound having titanium-nitrogen bond and an organoaluminum compound, a process using a catalyst system comprising a ~ solid component prepared by supporting a titanium amide :~ 15 compound on magnesium halide and an organoaluminum ~ compound (EP-A-0 320169; Italian Patent No. 867243), a , , process using a catalyst system comprising a titanium diphenylamide compound and an organoaluminum compound EP-A-0 104374; Japanese Patent Application XOKOKU
(Examined Publication) No. 42-11646)l a process using a ~; catalyst system comprising an aryl substituent-containing titanium amide compound and an organoaluminum compound , ~Japanese Patent Application KOKOKU (E.xamined Publication) No. 42~22691], and a process using a catalyst system comprising a lower alkyl-containing titanium amide ,,, , compound such as dimethylamidotitanium trichloride and the ~,,.
~: like and an organoaluminum compound [J. of Polym. Sci.
~' Part A-l, 241, 6 (1968)3 have been proposed.
,;
!~. .:`~
" :~ ', : . :
.,,~: ~ , 1 Howe~er, if a copolymerization of ethylene and ~olefin is carried ou~ with the catalyst systems disclosed in these papers, no satisfactory result has been obtained. Thus, according to the process disclQsed in EP-A-0 320169 and Italian Patent No. 867243, the formed ethylene-a-olefin copolymer has a broad composition distribution. According to the processes disclosed in EP-A-0 104374, Japanese Patent Application KOKOKV
(Examined Publication) Nos. 42-11646 and 42-22691 and J.
Polym. Sci. Part ~-1, 241, 6 ~1968), catalyst activity, copolymerizability and narrowness of composition distribution are unsatisfactory.
In order to solve the above-mentioned problems, ; the present inventors previously proposed ~Japanese Patent Application KOKAI (Laid-Open) ~o. 2-774123 a process for copolymerizing ethylene and a~olefin to give a copolymer having a narrow composition distribution which comprises using a catalyst system comprising an organoaluminum compound and a liq~id catalyst component comprising a titanium compound represented by the following general formula:
(R R N)4-(m+n~TiXmYn wherein R1 and R2 each represent a saturated hydrocarbon group having 8 to 30 carbon atoms, X represents a halogen atom, Y represents an alkoxy group, m is a number satisfy-ing 1 s m < 3, and n is a number satisfying 0 < n ~ 2, : ~ .
'"
, 1 and (m+n) satisfies 1 < ~m+n) _ 3.
However, this process had a fault that, if the catalyst system was used a~ a high temperature, the catalyst activity was very low and the ability to copoly-m~rize a-olefin was low, and the resulting polymer was unsatisfactory in composition distribution.
SUMMARY OF THE INV~NTION
In ~iew of the above-rnentioned present status of things, the problem to be solved by this invention or the : 10 object of this invention consists in providing a process for producing an ethylene-~-olefin copolymer which com-prises using a novel catalyst system, by the use of which a high catalyst activity per transition metal can be exhibited at high temperatures and an ethylene-a olefin copolymer narrow in composition distribution, high in ~ molecular weight and excellen~ in weather resistance, j colorizability, corrosion resistance and dynamic proper-ties can be obtained.
:Thus, this invention relates to a process for producing an ethylene-a-olefin copolymer which comprise~
copolymerizing ethylene and an a-olefin at a polyme:riza-tion temperature higher than 120C by using a catalyst system comprising as catalyst component (A) a titanium amide compound represented by the following general formula:
~R1R2N)4_nTiYn ~; - 6 - :
:
,:~i~ :
2 ~
1 wherein Rl and R2 each represent a hydrocarbon group having 1 to 30 carbon atoms, Y represents an alkoxy group and n represents a number satisfying 0 < n < 3, and, as catalyst component ~B) an oxygen-containing alkylaluminum compound..
BRIEF DESCRI PTION OF THE DRAWINGS
Figure 1 is a differential scanning calorimeter (DSC) chart illustrating the melting behavior of ~he copolymer obtained in Example 1.
Figure 2 is a DSC chart illustrating the:melting behavior of the copolymer obtained in Comparative Example 7.
Figure 3 is a DSC chart illustrating the melting behavior of the copolymer obtained in Comparative Example `~ . 15 8.
Figure 4 is a flo~ chart diagram for facili-tating unders~anding of this invention. This flow chart diagram is nothing more than one typical example of the embodiments of this in~ention, and this in~ention is by no means limited by it.
DETAILED DESCRIPTION OF THE INVENTION
; The catalyst component (A) used in this invention is constituted of a nitrogen-containing titanium ~ compound represented by the following general formula:
:: ~RlR2N~4_nTiYn _ 7 ,~ , ; . . , ::
~ . . . . .
1 r ~. 3.
l wherein Rl and R2, identical or diferent from each other, each represents a hydrocarbon group having 1 to 30 carbon atoms, Y represents an alkoxy group, and n represents a number satisfying 0 n < 3.
R1 and R2 are not critical, but preferably alkyl group and aryl group, and the catalyst compenent (A~ may be in any ~f liquid and solid states.
As examples of the alkoxy group~ methoxy, ethoxy, propoxy, butoxy, 2-ethylhexoxy, decoxy and the like can be referred to. From the viewpoint of catalyst performances, the alkoxy group is not critical. The alkoxy group preferably has l to 12 carbon atoms.
~: Concrete preferable examples of such titanium ~` amide compound (A) include the followings:
;~: 15 tetrakis(dimethylamino)titanium, tetrakis(diethylamino)titanium, : tetrakis(dipropylamino)titanium, , : tetrakis(dibutylamino)ti~anium, tetrakis(dihexylamino)titanium, tetrakis(diphenylamino)titanium, tetrakis(dioctylamino)titanium, tetrakis(didecylamino)titanium, tetrakis(dioctadecylamino)titanium, - methoxytris(dimethylamino)titanium, ethoxytris(dimethylamino)titanium, - butoxytris(dimethylamino)titanium~
hexoxytris(dimethylamino)titanium, 2-ethylhexoxytris(dimethylamino~titanium, " ~
:: :
-, ` ~' ~ ' . . ' 2 ~ ~ ~
1 decoxytri~(dimethylamino~titanium, methoxytris(diethylamino)titanium, ethoxytris(diethylamino)titanium, butoxytris(diethylamino)titanium, hexoxytris(diethylamino)titanium, 2-ethylhexoxytris(diethylamino)titanium, decoxytris(diethylamino)titani~n, methoxytris(dipropylamino)titanium, ethoxytris~dipropylamino)titanium, butoxytris(dipropylamino)titanium, hexoxytris(dipropylamino)titanium, 2-ethylhexoxytris(dipropylamino~titanium, ~ decoxytris(dipropylamino)titanium, -~ methoxytris(dibutylamino)titanium~
-~ 15 ethoxytris(dibutylamino)titanium, butoxytris(dlbutylamino)titanium, hexoxytris(dibutylamino~titanium, 2-ethylhexoxytri 9 (dibutylamino)titanium, decoxytris(dibutylamino)ti~anium, methoxytris(dihexylami~o)titanium, ethoxytris(dihexylamino)titanium, ~ butoxytris(dihexylamino)titaniuml - hexoxytris~dihexylamino)titanium, 2-ethylhexoxytris(dihexylamino)titanium, decoxytris(dihexylamino)titanium, methoxytris(diphenylamino)titanium, ~: ~ ethoxytris(dlphenylamino)titanium, . butoxytris~diphenylamino)titanium, : _ 9 _ :~ :
~ $~.~6 1 hexoxytris(diphenylamino)titanium, 2-ethylhexoxytris(diphenylamino~itanium, decoxytris(diphenylamino)titanium, methoxytris~dioctylamino)titanium, ethoxytris(dioctylamino)titanium, ~toxytris(dioctylamino)ti~ani~m, hexoxytris(didecylamino~tita~ium, ~-ethylhexoxytris(didecylamino)~itanium, decoxytris(dioctylamino~titanium, methoxytris(didecylamino)titanium, etho~ytris(didecylamino)titanium, butoxytris(didecylamino)titanium, hexoxytris~didecylamino3titanium, 2-ethylhexoxytris(didecylamino)titanium, decoxytris~didecylamino)tit~nium, methoxytris (di~tadecy~ ~o) titanium~
: ethoxytris(dioctadecylamino)titanium, butoxytris(dioctadecylamino)titanium, , ~ hexoxytris(dioctadecylamino)titanium, 2-ethylhexoxytris(dioctadecylamino)titanium, decoxytris(dioctadecylamino)titanium, and the like.
Among these compounds, preferable are tetrakis-~i (dimethylamino)titanium, tetrakis(diethylamino)titaniumr tetrakis(dipropylamino)titanium, tetrakis(dibutylamino)-:~ titanium, tetrakis(dihexylamino)titanium, tetrakis(di-phenylamino~titanium, tetrakis~dioctylamino)titanium, tetrakis(didecylamino)titanium, tetrakis(dioctadecyl-.,'. - 10 -";
, .
f ~
1 amino)titanium and the like.
As the method for synthesizing these titanium amide compounds (A3, the methods mentioned in Japanese Patent Application KOKOKU (Examined Publication) Nos. 41-5397 and 42-11646, H. Burger et al., ~. of Organomet.
Chem., 108 (1976~, 69-84, H. Burger et al., J. of Organomet. Chem., 20 ~1969), 129-139, etc. can be adopted.
In this invention, the synthesis was carried out according to these methods by reacting (i) a secon~ary amine compound represented by the following general formula:
` R4R5NH
.
wherein ~4 and R5 each represent a hydrocarhon group having 1 to 30 carbon atoms, with (ii) an alkyl-(alkali metal~ represented by the following ~ormula:
. :
. R6M
.:
wherein ~6 represents a hydrocarbon group having 1 to 30 carbon atoms and M represents an alkali metal such as Li, K and the like, to synthesize an alkali metal amide compound, and subsequently reacting said alkali metal amide compound with (iii) ~anium tetrahalide represented by the following general formula.
~ TiX4 ;, :
.....
:: . : . :
. ~ -. .
,: ~ ~ ' . ': ~
. ... .
l wherein X represents a halogen atom such as chlorine, bromine, iodine and the like and preferably chlorine.
As examples of the oxygen-containing alkyl-aluminum compound used in this invention as catalyst component (B) of the polymerization catalyst system, cyclic and acyclic aluminoxanes of which structures are represented ~y the following general formulas:
~A1(~3)-]k and ~32Al~Al(R3)-O]kAl~R32 wherein R3 represents a hydrocarbon group having 1 to 8 carbon atoms and k is an integer of 1 or greater, preferably 2 to 30, can be referred to. More specif.i-; cally, concrete examples of said oxygen-conkaining :;~ alkylaluminum compound include t~tramethyladialuminoxane, tetraethyldialuminoxane, tetrabutyldialuminoxane, tetrahe~yldialuminoxane, methylaluminoxane, ~:~ 15 ethylaluminoxane, butylaluminoxane, hexylaluminoxane and ~: the like, among which methylaluminoxane is particularly preferable.
The alumino~anes are poduced by various methods. Preferably, they are produced by contacting water with a æolution of a trialkylaluminum such as trimethylaluminum in an appropriate organic solvent such as toluene or aliphatic hydrocarbon. For example, an alkylaluminum is treated with water in the form of wetting solvent. According to another preferable method~ an - 12 ~
'~.' 2 ~
1 alkylaluminum such as trimethylaluminum is contacted with a hydrated salt such as copper sulfate hydrate or ferrous sulfate hydrate. Production of aluminoxane in the presence of ferrous sulfate hydrate is most preferable.
S According to this method, a dilute solution of trimethyl-aluminum in, for example, toluene is treated with ferrous sulfate hydrate represented by FeSO4O7H2O. Preferably, 6 to 7 moles of trimethylaluminum is treated with about one mole of ferruus sulfate hydrate. Occurrence of the reaction can be proved by generation of methane gas.
The amount of component tB) can be varied in so wide a range as 1 to 10,000 moles, preferably 1 to 1,000 moles and more preferably 1 to 500 moles, per one mole of titanium atom in component (A).
In this invention, the method for feeding the catalyst components into polymerization reactor is not particularly critical, except that they ha~e to be fed in an inert gas such as nitrogen, argon and the like in a moisture-free state.
The catalyst components (A) and (B) may be fed either separately or after mutually contacting them previously.
In this invention, the conditions of polymer-ization are as follows. ~hus, the polymerization temperature is .120C or above, preferably 135C to 350C, and more preferably 150C to 270C. As for the polymerization pressure, it is 5 to 100 kg/cm2 and preferably 10 to 50 kg/cm2 in the ca~e of solution ,.
;
l process; and 350 to 3,500 kg/cm2 and preferably 700 to 1,800 kg/cm2 in the case of high pressure ion process. As for the mode of polymerization, batch-wise process and continuous process are both adop~a~le.
In the solution process pol~merization using a catalyst system of this invention, the sol~ent is usually select~d from hydrocarbon solvents such as hexane, cyclo-hexane, heptane~ kerosine fractions, toluene and the like.
~he ~-olefins usable in this invention are those having 3 to 20 carbon atoms, preferably 3 to 10 carbon atoms, such as propylene, butene-l, 4-methylpentene-1, ; hexene-l, octene-1, vinylcyclohexane and the like.
This invention is particularly successfully applicable to pxoduction of ethylene-a-olefin copolymers lS constituted of at least eo~ by mole of ethylene and a residual quantity of a~ least one a-olefin, particularly those ~uch as propylene, ~utene-1, 4-methylpentene-1, hexene-1, octene-l and the like.
It is also possible to add a chaln transfer agent such as hydrogen and the like in order to regulate the molecular weight of polymer.
Next, this invention will be illustrated in more detail by way of the following examples and comparative examples~
Properties of polymers referxed to in the exam-ples were measured according to the following methods.
Thus, a-olefin content was determined from the characteristic absorptions of ethylene and a-olefin by the : :~
: - 14 _ ~ , . . .
.
:
~7~ ~2$~
l use of infrared spectrophotometer JASC0-30~ manufactured by NIPPON BUNKO ~OGYO CO.
Intrinsic viscosity ~n ] was measured with Vbbellohde viscometer in tetralin solution at 135C.
As the measure for expressing composition distribu~ion, average melting pOillt <Tm> was used, which was determined from a measurement using a differential scanning calorimeter (DSC3 and a calculation according to the following equation. A smaller value of <~m> means a narrower composition distribu~ion.
~Hi x tl) ~Tm> =
:~ ~Hi wherein 50C < ti c 130C/ and Hi is energy o melting (W/g) at temperature Ti.
~ .
~:~ Example 1 (1) S~ntheses of catalyst components : 15 Synthesis of titanium amide compound (A)~
After replacing the inner atmosphere of a 300 ml flask equipped with a stirrer/ a dropping funnel and a thermometer with argon gas, 18.1 ml (60 mmoles) of dioctylamine and 150 ml of hexane were charged into the flask.
; Then, 60 mmoles of butyllithiu~ diluted with 38.7 ml of hexane was dropwise added from the dropping funnel into the flask over a period of 30 minutes while ', ~ 15 _ ::
~2~i 1 keeping ~he temperature of the solution in the flask at 5C. Aftar dropping it, the resulting mixture was reacted first at 5C for 2 hours and thereafter at 30C for 2 hours.
Then, 1.65 ml (15 mmoles) of titanium tetra-chloride was dropwise added from the dropping funnel into the reacte~ mixture over a period of 30 minutes while keeping the temperature a~ 5C. Af ter dropping it, the resulting mixture was further reacted first at 5C for one hour and thereafter at 30C for 2 hours to obtain 15 mmoles (yield of this reaction was assumed to be 100~) of titanium amide compound (A) represented by a composition formula ~C8H17)2N]4Ti (catalyst concentration: 0.062 mmole Ti/ml).
; 15 (2~ Polymerization of ethylene After vacuum-drying an autoclave having an inner volume of 400 ml and equipped with a s~irrer and replacing its inner atmosphere w.ith argon gas, 140 ml of toluene as : a solvent and 480 mmoles of l-hexene as an a-olefin were charged, and tempera~ure of the reactor was elevated to : 180~C. Then, ethylene was fed at a controlled ethylene pressure of 25 kg/cm2. After the system had been stabilized, 8 mmoles of methylaluminoxane ~MAO) manufactured by TOSOH-AKZO Co. as an organoaluminum compound was fed, and subse~uently 0~08 mmole of the c~mpound represented by the composition formula ~: ~(C8H17)2N]4Ti synthesized in Paragraph (1) was fed as a catalyst component. Then, a polymerization reaction was ~!,. "~
'.,. ~ :
' : ~
1 carried out for 2 minutes at a controlled temperature of 180C. As a result, 22,000 g of a copolymer was obtained per 1 mole of transition metal ~catalyst activity: 22,000 g-copolymer/mole-M). The results are shown in Table 1.
Pigure 1 illustrates the melting beha~ior of the copolymer obtained herein measured by DSC. In E'igure 1, abscissa expresses temperature ~C~ and ordinate expresses energy of melting (~w). I~ can be said that when the melting peak of Figure 1 appears at a lower temperature position, the composition distribution of polymer is narrower. In the case of the copolymer obtained herein, the composition distribution was very narrow.
, Comparative F.xample l A polymeriæation of ethylene was carried out in the same manner a~ in Example 1-(2), except that 8 mmoles of triisobutylaluminum (TIBA) was used as an organo-aluminum compound in place of MAO. As a result, polymer was hardly obtained.
.~
Comparative Example 2 A polymerization of ethylene was carried out in the same manner as in Example 1-(2), except that 8 mmoles of ethylaluminum dichloride (EADC) was used as an organoaluminum compound in place of the MAO. As a result, 31,000 g of a polymer was obtained per 1 mole of tran-sition metal. However, molecular weight of the polymer ~ expressed in terms of [ n] was 0.04 which was much lower ; - 17 -, ~ - : . ., - - ~ .
1 than that in Example 1.
Comparative Example 3 Polymerization of ethylene:
After vacuum-drying an autoclave having an inner volume oE 400 ml and equipped with a stirrer and replacing its inner atmosphere with argon gas, 140 ml of toluene as a solvent and 48~ mmoles of l-h~xene as an a-olefin were charged, and t~mperature of the reactor was elevated to BO~C. Then, ethylene was fed at a controlled ethylene pressure of 5.0 kg/cm~. After the system had been stabilized, 8 mmoles of MAO was charged as an organo-aluminum compound, and subsequently O.08 mmole of the ; compound represented by the composition fo~mula ~(C8H17)2N~4Ti syn~hesized in Exampl2 1-(1) was added as a catalyst component. Then, a polymerization reaction was ~ carried out for 2 minutes at a controlled temperature of :; 80C. As a result, polymer was hardly obtained.
Example 2 ~: A polymerization of ethylene was carried out in the same manner as in Example 1-~2), except that a polymerization temperature of 200C was adopted. As a resultl a polymer having a narrow composition distribution was obtained as in Example 1.
~, 1 i l ;: Comparative Example 4 ` 25 A polymerization of ethylene was carried out in ~ ~ .
- ' 1 the same manner as in Example 2, except that 0.08 mmole of biscyclopentadienyl zirconium dichloride (Cp2ZrCl~) was used as a catalyst component in place of the titanium amide compound ~A) used in Example 2. As a result, molecular weight of the polymer expressed in terms of ~]
was 0.17 which was much lowe.r than that in Example 2.
Comparati~e Example 5 (1) Synthesis of catalyst component Synthesis of titanium amide compound:
After raplacing the inner atmosphere of a lO0 ml flask equipped with a stirrer, a droppin~ funnel and a thermometer with argon gas, 6.0 ml (20 mmoles~ of dioctyl-amine and 50 ml of hexane were char~ed.
Thenr 20 ~moles of butyllithium diluted with 12.9 ml of hexane was dropwise added from the dropping funn~l into the flask over a period of 30 minutes, while keeping the inner temperature of the flask at 5C. After ~: droppinq it, the resulting mixture was reacted f~rst at : 5C ~or 2 hours and thereafter at 30C for 2 hours.
Then, 2.2 ml (20 mmoles) of titanium tetra-chloride was dropwise added from the dropping funnel into the reacted mixture obtained above over a period of 30 minutes, while keeping the temperature of the mixture at 5C. After dropping it, the resulting mixture was reacted first at SC for one hour and thereafter at 30C for 2 hours, to obtain 20 mmoles (yield of this reaction was assumed to be 100%) of a titanium amide compound .~ - lg -~., 1~`
1 represented by a composition formula (C8H~7)2NTiC13.
(2) Polymerization of ethylene A polymexization was carried out in the same manner as in Example 1-(2), excep~ that 0.03 mmole of the compound represented by the composition formula (C8H17)2NTiC13 synthesized in Paragraph ~1) wa~ used as a catalyst component in place of the compound represent~d by the composition formula [~C~H17)2N~4Ti. The results are shown in Table 1. The polymer obtained herein had a broad composition distribution.
Comparative Example 6 A polymerization of ethylene was carried out in : the same manner as in Comparative E~ample 5-(2), except that 8 mmol~s of TIBA was u~ed as an organoaluminum compound in place of MA0. Results of the polymerization are shown in Table 1. Polymerization activity of the catalyst was very low, and the polymer obta.ined had a broad composition distri~ution.
, . .
Comparative Example 7 A polymeriæation of ethylene was carried out in the same manner as in Example 1-(2), except that 0.08 mmole of titanium tetrachloride was used as a catalyst ; component in place of the compound represented by the composition formula [~C8H17)2N]4Ti. Results of the polymerization are shown in Table 1, and the DSC chart of , ~:
. .
j . : .
,j~-1 the polymer is shown in Figure 2. It is apparent there-from that the catalyst used herein was low in copolymeriz-: ing ability and the polymer obtained herein had a bro~d composition distribution.
Comparative Example 8tl) Synthesis of catalyst component After replacing the inner atmosphere of a iO0 ml flask equipped with a stirrer, a dropping ~unnel and a thermometer with argon gas, 3~8 ml (20 mmoles) of decyl alcohol and 50 ml of hexane were charged.
Then, 20 mmoles of butyllithium diluted with 12.9 ml of hexane was dropwise added from the dropping funnel into the flask over a period of 3~ minutes, while keeping the inner temperature of the flask at 5C. After dropping it, the resulting mixture was reacted first at 5C for 2 hours and thereafter at 30C for 2 hours.
~ hen, 0.55 ml (5 mmoles) of titanium tetra-; chloride was dropwise added from the dropping funnel into the reacted mixture over a period of 30 minutes, while keeping the inner temperature at 5C. After dropping it,the resulting mixture was reacted first at 5C for one hour and thereafter at 30C for 2 hour~ to obtain 5 mmoles (yield of this reaction was assumed to be 100%) of a titanium compound represented by a composition formula ; 25 (CloH2lo)4~i -(2) Polymerizatlon of ethylene A polymerization was carried out in the same : .
, - 21 -?~
,~ . , , , ` : ' ~2~
1 manner as in Example 1-(2), except that the compound represented by the composition formula (CloH21O~4Ti synthesized in Paragraph (1~ was used as a ca~alyst component in place of the compound represented by the composition formula [(C8H17)2NJ~Ti. The results of the polymerization are shown in Table 1, and DSC chart of the polymer thus obtained is shown in Figure 3. It is apparent therefrom that the catalyst activity per transi-tion metal was lower than that of Example 1 and the polymer obtained herein had a broad composition distribu-tion.
~xample 3 (1) Synthesis of catalyst component Synthesis of titanium amide compound (A):
A~ter replacing the inner atmosphere of a 300 ml flask equipped with a stirrer, a dropping funnel and a : thermometer with argon gas, 6.3 ml (60 mmoles) of diethyl-amine and 150 ml of hexane were charged.
~hen, 60 mmoles of butyllithium diluted with 38.7 ml of hexane was dropwise added from the dropping funnel into the flask over a period of 30 minutes, while ; keeping the temperature of the solution in the flask at SC. After dropping it, the resulting mixture was reacted first at 5C for 2 hours and thereafter at 30C for 2 hours.
Then, 1.65 ml (15 mmoles) of titanium tetra-chloride was dropwise added from the dropping funnel into .~' - . ~ , ~ - . .
: -, , ~ ~ .
2 ~
1 the reacted mixtuxe over a period of 30 minutes, while keeping the temperature of the mixture at 5C. After dropping it, the resulting mixture was reacted first a~
5C for one hour and thereafter at 30C for 2 hours to obtain 15 mmoles (yield of this reaction was assumed to be 100%) of a titanium amide co~pound (A~ represented by a composition f~rmula E (C2H5)2N~4~i-: (2) Polymerization of ethylene A polymerization was carried out in the same manner as in Example 1-(23, except that 0.08 ~mole of the compound represented by the composition formula [~C2H5)2N~4Ti s~nthesized in Paragraph tl3 was ued as a catalyst component in place of the compound represented by the composition formula r (C~H17)2N~4Ti. Thus, a polymer : 15 having a narrow composition distribution was obtained as in Example 1.
~ Comparative Example 9 : A polymerization of ethylene ~as carried ~ut in .~
the same manner as in Example 3-(2), except that 8 mmoles of TIBA was used as an organoaluminum compound in place of ; MAO. As a result, polymer was hardly obtained.
Comparative Example 10 (1) Synthesis of catalyst component ::~ Synthesis of titanium amide compound:
25After replacing the inner atmosphere of a 100 ml flask equipped with a stirrer, a dropping funnel and a ' _ 23 -,'~,, .
~ ' -: , .
1 thermometer with argon gas, 2.1 ml (20 mmoles) of diethyl-amine and 50 ml of hexane were charged.
Then, 20 mmoles of butyllithium diluted with 12.9 ml of hexane was dropwise added from the dropping funnel into the flask over a period of 30 minutes, while keeping the inner temperature o~ the flask at 5C. After dropping it, the resulting mixture was reacted first at 5C for 2 hours and thereafter at 3~C for 2 hours.
Then, 2.2 ml (20 mmoles) of titanium tetra-chloride was dropwise added from the dropping fu~nel intothe reacted mixture over a period of 30 minutes, while keeping the inner temperature of the flask at 5C. After dropping it, the resulting mixture was reacted first at SC for one hour and thereafter at 30C for 2 hours.
After the reaction, the mixture was allowed to ~tand to separate the solid from the liquid. The separated solid was twice washed with each 50 ml portion ~;~ of hexane and dried under reduced pressure to obtaln 4.5 g of a solid titanium amide compound represented by a composition formula (C2H5)2NTiC13.
(2) Polymexization of ethylene A polymerization was carried out in the same manner as in Example 1 (2), except that 0.08 mmole of the compound represented by -the composition formula (C2H5)2NTiC13 was used as the catalyst compon~nt in place of the ~(C8H17)2NI4Ti. The polymer thus obtained had a ~; broad composition distribution.
~; .
,:
. ' 1 Comparative Example 11 A polymerization of ethylene was carried out in the same manner as in Comparative Example 10-(2)l except that 8 mmoles of TIBA was used as an organoaluminum compound in place of MAO. The result of the polymeri-zation are shown in Table 1. It is apparent that the catalyst used herein had a very low polymerization activity, and the polymer obtained herein had a broad composition distribution.
Comparative ~xample 12 (1) S~nthesis of catalyst component Synthesis of titanium amide compound:
After replacing the inner atmosphere of a 200 ml flask e~uipped with a stirrer, a dropping funnel and a thermometer with argon gas, 2.7 ~ (16 mmoles) of diphenyl-amine and 100 ml of hexane were charge~l.
Then, 16 mmoles of butyll.ithium diluted with 10.3 ml of hexane was dropwise added from the dropping funnel into the flask over a period of 30 minutes, while . 20 keeping the inner temperature of the flask at 5C. After :dropping it, the resulting mixture was reacted first at 5C for 2 hours and thereafter at 30C for 2 hours.
Then, 1.76 ml (16 mmoles) of titanium tetrachloride was dropwise added from the dropping funnel into the reacted mixture obtained above over a period of 30 minutes, whiie keeping the temperature of the mixture at 5C. A~ter dropping it, the resulting mixture was ; - ~5 -, ~2~
l reacted first at 5C for one hour and thereafter at 30C
for 2 hours, to o~tain 16 mmoles (yield of this reaction was assumed to be 100%) of a titanium amide compound represented b~ a composition formula (C6H5)2NTiCl3.
(2~ Polymerization of ethylene A polymerization was carried QU't in the same manner as in Example 1-(2~, except that 0.08 mmole of the compound represented by the comp~sition formula (C6H5)2NTiC13 synthesized in Paragraph (1~ was used in place of the compound represented by the composition formula [(C8H17)2N]4Ti and 8 mmoles of triethylal~ninum (TEA) was used a~ an organoaluminum compound in place of MAO. The results are shown in Table 1. The catalyst used herein had a very low pol~merization activity and the polymer obtained herein had a broad composition distribution.
Example 4 (1) Synthesis of catalyst component Synthesi~ of titanium amide compound ~A):
, :
:~ 20 After replacing the inner atmosphere of a 300 ml ~Iask equippPd with a stirrer, a dropping funnel and a thermometer with argon gas, 2.7 g (16 mmoles) of diphenyl- :
amine and 200 ml of hexane were charged.
Then, 16 mmoles of butyllithium diluted with 10.3 ml of hexane was dropwise added from the dropping funnel into the flask over a period of 30 minutes, while keeping the inner temperature of the flask at 5C. After ~ 26 -;;', : , ~ : ~. -- . ::
; , . . .
: ` ::
" ~, ' ': : ` '' : , 2~2~1~
1 dropping it, the resulting mixture was reacted first at 5C for 2 hours and thereafter at 30C for 2 hours.
Then, 0.44 ml (4 mmoles) of titanium tetrachloride was dropwise added f:rom the dropping funnel into the reacted mixture obtained above over a period of 30 minutes, while Xeeping the temperature of the mixture at 5C. After dropping it, the result.ing mLxture was reacted first at 5C ~or one hvur and thereafter at 30C
for 2 hours, to obtain 4 mmoles (yield o this reaction was assumed to be 100%) of a solid titanium amide compound (A) represented by a composition formula [C~H5)2N]4Ti.
(2) Polymerization of ethylene A polymerization was carried out in the same manner as in Example 1-t2), Pxcept that 0.08 mmole of the compound represented by the composition formula ~(C6HS)2~4~L synthesized in Paragraph (1) was used as a ~:; ca~alyst component in place of the compound represented ~y the composition formula [(C8~17)2~]4Ti' ~he~p ym obtained herein had a narrow composition distribution as ~`~ 20 in Example 1.
~: Comparative Example 13 A polymerization of ethylene was carried out in the same manner as in Example 4 (2), except that 8 mmoles of diethylaluminum chloride (DEAC) was used as an organo-:: 25 aluminum compound in place of MA0. The results of the polymerization are shown in Table 1. The catalyst used herein was much lower ~han the catalyst used in Example 4 ~; - 27 ~
., .~
~:
, 2 ~
1 in polymerization activity, and the polymer obtained herein had a broad composition distribution.
Example 5 (1) Synthesis of catalyst component Synthesis of titani~m amide compound (A):
Ater replacing the inner atmosphere of a 300 ml flask equipped with a stirrer, a dropping funnel and a thermometer with argon gas~ 10.5 ml (60 mmoles~ of diiso-butylamine and 150 ml of hexane were charged.
Then, 60 ~moles of butyllithium diluted with : 38.7 ml of hexane was dropwise added from the dropping funnel into the flask over a period of 30 minutes, while ., keeping the inner temperature of khe 1as]c at 5C. After dropping it, the resulting mixture was reacted first at 5~C for 2 hours and thereafter at 30C for 2 hours.
~: Then, 1.65 ml (15 mmoles) of titanium tetra-chloride was dropwise added from the dropping funnel into ~` the reacted mixture obtained above over a period of 30 ~ minutes, while keeping the temperature of the mixture at ; ~ 20 5C. After droppin~ it, the resulting mixture was reacted first at 5C for one hour and thereafter at 3~C for 2 hours, to obtain 15 mmoles (yield of this reaction was assumed to be 100%) of solid titanium amide compound (A) represented by a composition formula {[(C~3)2CHCH2]2N}4Ti.
~: 25 (2) Polymerization of ethylene A polymerization was carried out in the same ; manner as in Example 1 (2), except that 0.08 mmole of the 2~ _ . .
:~ . . . .
~2~
1 compound represented by the composition formula {[tCH3)2CHCH2]~N}~Ti synthesized in Paragraph (1) was used as a ca~alyst component in place of the compound represented by the composition fo.rmula [(C8H17~2N]4Ti.
The polymer obtained herein had a narrow composition distribution as in Example 1.
Comparative Example 14 (1) Synthesis of catalyst component Synthesis of titanium amide compound:
After replacing the inner atmosphere of a 300 ml fla~k equipped with a stirrer, a dxopping funnel and a thermometer with argon gas, 0.41 ml (10 mmoles) of methyl alcohol and 25 ml of hexane were charged.
Then, 10 mmoles of butyllithium diluted with 6.5 ml of hexane was dropwise added from the dropping funnel into the flask over a period of 30 minutes, while keeping the inner temperature of the flask at 5C. After dropping it, the resulting mixture was reacted first at 5C for 2 hours and thereafter at 30C for 2 hours.
; 20 Then, 10 mmoles of the comound represented by the composition formula (C8H17)2NTiC13 synthesized by the same method as in Comparative Example 5-(1) was dropwise added from the dropping funnel into the reacted mixture obtained above over a period of 30 minutes, while keeping the temperature of the mixture at 5C. After dropping it, the resulting mixture was reacted first at 5C for one hour and thereafter at 30C for 2 hours, to obtain 10 ~: :
.
, ; ~
, . . - . . .
. . .
~2~ ~ ~
1 mmoles (yield of this reaction was assumed to be 100~) of titanium amide compound represented by a composition formula (C8H17)2N~i(OCH3)C12 (2) Polymerization of ethylene A polymerization was carried out in the same manner as in Example 1-(2), except that 0.08 mmole of the compound represented by the composition ormula (C8H17~2NTi(OCH3)C12 synthesized in Paragraph (1) was used : as a catalyst component in place of the compound represented by the composition formula [(C8H17)2N]4Ti.
The polymer obtained herein had a broad composition di~tribution.
.
Example 6 A copolymerization o~ ethylene and l-butene was carried out in the same manner as in Example 1 by using the same catalyst system as used in Example 1. A polymer narrow in composition distribution was obtained as in Example 1.
Example 7 A copolymerization of ethylene and 4~
methylpentene-1 was carried out in the same manner as in Example 1 by using the same catalyst system AS used in Example 1. A polymer narrow in composition distribution was obtained as in Example 1.
.
, - 3~ -~:
~ ~ ' .
- ~ .
, 2 ~ ~ ~
1 Example 8 A copolymerization of ethylene and 1-decene was carried out in the same manner as in E~maple 1 ~y using the same catalyst system as used in Example 1. A polymer narrow in composition distribution was obtained as in Example 1.
The conditions and results of polymerization in :~ all the examples mentioned abo~e are summarized in Table ~.~
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1 wherein Rl and R2 each represent a hydrocarbon group having 1 to 30 carbon atoms, Y represents an alkoxy group and n represents a number satisfying 0 < n < 3, and, as catalyst component ~B) an oxygen-containing alkylaluminum compound..
BRIEF DESCRI PTION OF THE DRAWINGS
Figure 1 is a differential scanning calorimeter (DSC) chart illustrating the melting behavior of ~he copolymer obtained in Example 1.
Figure 2 is a DSC chart illustrating the:melting behavior of the copolymer obtained in Comparative Example 7.
Figure 3 is a DSC chart illustrating the melting behavior of the copolymer obtained in Comparative Example `~ . 15 8.
Figure 4 is a flo~ chart diagram for facili-tating unders~anding of this invention. This flow chart diagram is nothing more than one typical example of the embodiments of this in~ention, and this in~ention is by no means limited by it.
DETAILED DESCRIPTION OF THE INVENTION
; The catalyst component (A) used in this invention is constituted of a nitrogen-containing titanium ~ compound represented by the following general formula:
:: ~RlR2N~4_nTiYn _ 7 ,~ , ; . . , ::
~ . . . . .
1 r ~. 3.
l wherein Rl and R2, identical or diferent from each other, each represents a hydrocarbon group having 1 to 30 carbon atoms, Y represents an alkoxy group, and n represents a number satisfying 0 n < 3.
R1 and R2 are not critical, but preferably alkyl group and aryl group, and the catalyst compenent (A~ may be in any ~f liquid and solid states.
As examples of the alkoxy group~ methoxy, ethoxy, propoxy, butoxy, 2-ethylhexoxy, decoxy and the like can be referred to. From the viewpoint of catalyst performances, the alkoxy group is not critical. The alkoxy group preferably has l to 12 carbon atoms.
~: Concrete preferable examples of such titanium ~` amide compound (A) include the followings:
;~: 15 tetrakis(dimethylamino)titanium, tetrakis(diethylamino)titanium, : tetrakis(dipropylamino)titanium, , : tetrakis(dibutylamino)ti~anium, tetrakis(dihexylamino)titanium, tetrakis(diphenylamino)titanium, tetrakis(dioctylamino)titanium, tetrakis(didecylamino)titanium, tetrakis(dioctadecylamino)titanium, - methoxytris(dimethylamino)titanium, ethoxytris(dimethylamino)titanium, - butoxytris(dimethylamino)titanium~
hexoxytris(dimethylamino)titanium, 2-ethylhexoxytris(dimethylamino~titanium, " ~
:: :
-, ` ~' ~ ' . . ' 2 ~ ~ ~
1 decoxytri~(dimethylamino~titanium, methoxytris(diethylamino)titanium, ethoxytris(diethylamino)titanium, butoxytris(diethylamino)titanium, hexoxytris(diethylamino)titanium, 2-ethylhexoxytris(diethylamino)titanium, decoxytris(diethylamino)titani~n, methoxytris(dipropylamino)titanium, ethoxytris~dipropylamino)titanium, butoxytris(dipropylamino)titanium, hexoxytris(dipropylamino)titanium, 2-ethylhexoxytris(dipropylamino~titanium, ~ decoxytris(dipropylamino)titanium, -~ methoxytris(dibutylamino)titanium~
-~ 15 ethoxytris(dibutylamino)titanium, butoxytris(dlbutylamino)titanium, hexoxytris(dibutylamino~titanium, 2-ethylhexoxytri 9 (dibutylamino)titanium, decoxytris(dibutylamino)ti~anium, methoxytris(dihexylami~o)titanium, ethoxytris(dihexylamino)titanium, ~ butoxytris(dihexylamino)titaniuml - hexoxytris~dihexylamino)titanium, 2-ethylhexoxytris(dihexylamino)titanium, decoxytris(dihexylamino)titanium, methoxytris(diphenylamino)titanium, ~: ~ ethoxytris(dlphenylamino)titanium, . butoxytris~diphenylamino)titanium, : _ 9 _ :~ :
~ $~.~6 1 hexoxytris(diphenylamino)titanium, 2-ethylhexoxytris(diphenylamino~itanium, decoxytris(diphenylamino)titanium, methoxytris~dioctylamino)titanium, ethoxytris(dioctylamino)titanium, ~toxytris(dioctylamino)ti~ani~m, hexoxytris(didecylamino~tita~ium, ~-ethylhexoxytris(didecylamino)~itanium, decoxytris(dioctylamino~titanium, methoxytris(didecylamino)titanium, etho~ytris(didecylamino)titanium, butoxytris(didecylamino)titanium, hexoxytris~didecylamino3titanium, 2-ethylhexoxytris(didecylamino)titanium, decoxytris~didecylamino)tit~nium, methoxytris (di~tadecy~ ~o) titanium~
: ethoxytris(dioctadecylamino)titanium, butoxytris(dioctadecylamino)titanium, , ~ hexoxytris(dioctadecylamino)titanium, 2-ethylhexoxytris(dioctadecylamino)titanium, decoxytris(dioctadecylamino)titanium, and the like.
Among these compounds, preferable are tetrakis-~i (dimethylamino)titanium, tetrakis(diethylamino)titaniumr tetrakis(dipropylamino)titanium, tetrakis(dibutylamino)-:~ titanium, tetrakis(dihexylamino)titanium, tetrakis(di-phenylamino~titanium, tetrakis~dioctylamino)titanium, tetrakis(didecylamino)titanium, tetrakis(dioctadecyl-.,'. - 10 -";
, .
f ~
1 amino)titanium and the like.
As the method for synthesizing these titanium amide compounds (A3, the methods mentioned in Japanese Patent Application KOKOKU (Examined Publication) Nos. 41-5397 and 42-11646, H. Burger et al., ~. of Organomet.
Chem., 108 (1976~, 69-84, H. Burger et al., J. of Organomet. Chem., 20 ~1969), 129-139, etc. can be adopted.
In this invention, the synthesis was carried out according to these methods by reacting (i) a secon~ary amine compound represented by the following general formula:
` R4R5NH
.
wherein ~4 and R5 each represent a hydrocarhon group having 1 to 30 carbon atoms, with (ii) an alkyl-(alkali metal~ represented by the following ~ormula:
. :
. R6M
.:
wherein ~6 represents a hydrocarbon group having 1 to 30 carbon atoms and M represents an alkali metal such as Li, K and the like, to synthesize an alkali metal amide compound, and subsequently reacting said alkali metal amide compound with (iii) ~anium tetrahalide represented by the following general formula.
~ TiX4 ;, :
.....
:: . : . :
. ~ -. .
,: ~ ~ ' . ': ~
. ... .
l wherein X represents a halogen atom such as chlorine, bromine, iodine and the like and preferably chlorine.
As examples of the oxygen-containing alkyl-aluminum compound used in this invention as catalyst component (B) of the polymerization catalyst system, cyclic and acyclic aluminoxanes of which structures are represented ~y the following general formulas:
~A1(~3)-]k and ~32Al~Al(R3)-O]kAl~R32 wherein R3 represents a hydrocarbon group having 1 to 8 carbon atoms and k is an integer of 1 or greater, preferably 2 to 30, can be referred to. More specif.i-; cally, concrete examples of said oxygen-conkaining :;~ alkylaluminum compound include t~tramethyladialuminoxane, tetraethyldialuminoxane, tetrabutyldialuminoxane, tetrahe~yldialuminoxane, methylaluminoxane, ~:~ 15 ethylaluminoxane, butylaluminoxane, hexylaluminoxane and ~: the like, among which methylaluminoxane is particularly preferable.
The alumino~anes are poduced by various methods. Preferably, they are produced by contacting water with a æolution of a trialkylaluminum such as trimethylaluminum in an appropriate organic solvent such as toluene or aliphatic hydrocarbon. For example, an alkylaluminum is treated with water in the form of wetting solvent. According to another preferable method~ an - 12 ~
'~.' 2 ~
1 alkylaluminum such as trimethylaluminum is contacted with a hydrated salt such as copper sulfate hydrate or ferrous sulfate hydrate. Production of aluminoxane in the presence of ferrous sulfate hydrate is most preferable.
S According to this method, a dilute solution of trimethyl-aluminum in, for example, toluene is treated with ferrous sulfate hydrate represented by FeSO4O7H2O. Preferably, 6 to 7 moles of trimethylaluminum is treated with about one mole of ferruus sulfate hydrate. Occurrence of the reaction can be proved by generation of methane gas.
The amount of component tB) can be varied in so wide a range as 1 to 10,000 moles, preferably 1 to 1,000 moles and more preferably 1 to 500 moles, per one mole of titanium atom in component (A).
In this invention, the method for feeding the catalyst components into polymerization reactor is not particularly critical, except that they ha~e to be fed in an inert gas such as nitrogen, argon and the like in a moisture-free state.
The catalyst components (A) and (B) may be fed either separately or after mutually contacting them previously.
In this invention, the conditions of polymer-ization are as follows. ~hus, the polymerization temperature is .120C or above, preferably 135C to 350C, and more preferably 150C to 270C. As for the polymerization pressure, it is 5 to 100 kg/cm2 and preferably 10 to 50 kg/cm2 in the ca~e of solution ,.
;
l process; and 350 to 3,500 kg/cm2 and preferably 700 to 1,800 kg/cm2 in the case of high pressure ion process. As for the mode of polymerization, batch-wise process and continuous process are both adop~a~le.
In the solution process pol~merization using a catalyst system of this invention, the sol~ent is usually select~d from hydrocarbon solvents such as hexane, cyclo-hexane, heptane~ kerosine fractions, toluene and the like.
~he ~-olefins usable in this invention are those having 3 to 20 carbon atoms, preferably 3 to 10 carbon atoms, such as propylene, butene-l, 4-methylpentene-1, ; hexene-l, octene-1, vinylcyclohexane and the like.
This invention is particularly successfully applicable to pxoduction of ethylene-a-olefin copolymers lS constituted of at least eo~ by mole of ethylene and a residual quantity of a~ least one a-olefin, particularly those ~uch as propylene, ~utene-1, 4-methylpentene-1, hexene-1, octene-l and the like.
It is also possible to add a chaln transfer agent such as hydrogen and the like in order to regulate the molecular weight of polymer.
Next, this invention will be illustrated in more detail by way of the following examples and comparative examples~
Properties of polymers referxed to in the exam-ples were measured according to the following methods.
Thus, a-olefin content was determined from the characteristic absorptions of ethylene and a-olefin by the : :~
: - 14 _ ~ , . . .
.
:
~7~ ~2$~
l use of infrared spectrophotometer JASC0-30~ manufactured by NIPPON BUNKO ~OGYO CO.
Intrinsic viscosity ~n ] was measured with Vbbellohde viscometer in tetralin solution at 135C.
As the measure for expressing composition distribu~ion, average melting pOillt <Tm> was used, which was determined from a measurement using a differential scanning calorimeter (DSC3 and a calculation according to the following equation. A smaller value of <~m> means a narrower composition distribu~ion.
~Hi x tl) ~Tm> =
:~ ~Hi wherein 50C < ti c 130C/ and Hi is energy o melting (W/g) at temperature Ti.
~ .
~:~ Example 1 (1) S~ntheses of catalyst components : 15 Synthesis of titanium amide compound (A)~
After replacing the inner atmosphere of a 300 ml flask equipped with a stirrer/ a dropping funnel and a thermometer with argon gas, 18.1 ml (60 mmoles) of dioctylamine and 150 ml of hexane were charged into the flask.
; Then, 60 mmoles of butyllithiu~ diluted with 38.7 ml of hexane was dropwise added from the dropping funnel into the flask over a period of 30 minutes while ', ~ 15 _ ::
~2~i 1 keeping ~he temperature of the solution in the flask at 5C. Aftar dropping it, the resulting mixture was reacted first at 5C for 2 hours and thereafter at 30C for 2 hours.
Then, 1.65 ml (15 mmoles) of titanium tetra-chloride was dropwise added from the dropping funnel into the reacte~ mixture over a period of 30 minutes while keeping the temperature a~ 5C. Af ter dropping it, the resulting mixture was further reacted first at 5C for one hour and thereafter at 30C for 2 hours to obtain 15 mmoles (yield of this reaction was assumed to be 100~) of titanium amide compound (A) represented by a composition formula ~C8H17)2N]4Ti (catalyst concentration: 0.062 mmole Ti/ml).
; 15 (2~ Polymerization of ethylene After vacuum-drying an autoclave having an inner volume of 400 ml and equipped with a s~irrer and replacing its inner atmosphere w.ith argon gas, 140 ml of toluene as : a solvent and 480 mmoles of l-hexene as an a-olefin were charged, and tempera~ure of the reactor was elevated to : 180~C. Then, ethylene was fed at a controlled ethylene pressure of 25 kg/cm2. After the system had been stabilized, 8 mmoles of methylaluminoxane ~MAO) manufactured by TOSOH-AKZO Co. as an organoaluminum compound was fed, and subse~uently 0~08 mmole of the c~mpound represented by the composition formula ~: ~(C8H17)2N]4Ti synthesized in Paragraph (1) was fed as a catalyst component. Then, a polymerization reaction was ~!,. "~
'.,. ~ :
' : ~
1 carried out for 2 minutes at a controlled temperature of 180C. As a result, 22,000 g of a copolymer was obtained per 1 mole of transition metal ~catalyst activity: 22,000 g-copolymer/mole-M). The results are shown in Table 1.
Pigure 1 illustrates the melting beha~ior of the copolymer obtained herein measured by DSC. In E'igure 1, abscissa expresses temperature ~C~ and ordinate expresses energy of melting (~w). I~ can be said that when the melting peak of Figure 1 appears at a lower temperature position, the composition distribution of polymer is narrower. In the case of the copolymer obtained herein, the composition distribution was very narrow.
, Comparative F.xample l A polymeriæation of ethylene was carried out in the same manner a~ in Example 1-(2), except that 8 mmoles of triisobutylaluminum (TIBA) was used as an organo-aluminum compound in place of MAO. As a result, polymer was hardly obtained.
.~
Comparative Example 2 A polymerization of ethylene was carried out in the same manner as in Example 1-(2), except that 8 mmoles of ethylaluminum dichloride (EADC) was used as an organoaluminum compound in place of the MAO. As a result, 31,000 g of a polymer was obtained per 1 mole of tran-sition metal. However, molecular weight of the polymer ~ expressed in terms of [ n] was 0.04 which was much lower ; - 17 -, ~ - : . ., - - ~ .
1 than that in Example 1.
Comparative Example 3 Polymerization of ethylene:
After vacuum-drying an autoclave having an inner volume oE 400 ml and equipped with a stirrer and replacing its inner atmosphere with argon gas, 140 ml of toluene as a solvent and 48~ mmoles of l-h~xene as an a-olefin were charged, and t~mperature of the reactor was elevated to BO~C. Then, ethylene was fed at a controlled ethylene pressure of 5.0 kg/cm~. After the system had been stabilized, 8 mmoles of MAO was charged as an organo-aluminum compound, and subsequently O.08 mmole of the ; compound represented by the composition fo~mula ~(C8H17)2N~4Ti syn~hesized in Exampl2 1-(1) was added as a catalyst component. Then, a polymerization reaction was ~ carried out for 2 minutes at a controlled temperature of :; 80C. As a result, polymer was hardly obtained.
Example 2 ~: A polymerization of ethylene was carried out in the same manner as in Example 1-~2), except that a polymerization temperature of 200C was adopted. As a resultl a polymer having a narrow composition distribution was obtained as in Example 1.
~, 1 i l ;: Comparative Example 4 ` 25 A polymerization of ethylene was carried out in ~ ~ .
- ' 1 the same manner as in Example 2, except that 0.08 mmole of biscyclopentadienyl zirconium dichloride (Cp2ZrCl~) was used as a catalyst component in place of the titanium amide compound ~A) used in Example 2. As a result, molecular weight of the polymer expressed in terms of ~]
was 0.17 which was much lowe.r than that in Example 2.
Comparati~e Example 5 (1) Synthesis of catalyst component Synthesis of titanium amide compound:
After raplacing the inner atmosphere of a lO0 ml flask equipped with a stirrer, a droppin~ funnel and a thermometer with argon gas, 6.0 ml (20 mmoles~ of dioctyl-amine and 50 ml of hexane were char~ed.
Thenr 20 ~moles of butyllithium diluted with 12.9 ml of hexane was dropwise added from the dropping funn~l into the flask over a period of 30 minutes, while keeping the inner temperature of the flask at 5C. After ~: droppinq it, the resulting mixture was reacted f~rst at : 5C ~or 2 hours and thereafter at 30C for 2 hours.
Then, 2.2 ml (20 mmoles) of titanium tetra-chloride was dropwise added from the dropping funnel into the reacted mixture obtained above over a period of 30 minutes, while keeping the temperature of the mixture at 5C. After dropping it, the resulting mixture was reacted first at SC for one hour and thereafter at 30C for 2 hours, to obtain 20 mmoles (yield of this reaction was assumed to be 100%) of a titanium amide compound .~ - lg -~., 1~`
1 represented by a composition formula (C8H~7)2NTiC13.
(2) Polymerization of ethylene A polymexization was carried out in the same manner as in Example 1-(2), excep~ that 0.03 mmole of the compound represented by the composition formula (C8H17)2NTiC13 synthesized in Paragraph ~1) wa~ used as a catalyst component in place of the compound represent~d by the composition formula [~C~H17)2N~4Ti. The results are shown in Table 1. The polymer obtained herein had a broad composition distribution.
Comparative Example 6 A polymerization of ethylene was carried out in : the same manner as in Comparative E~ample 5-(2), except that 8 mmol~s of TIBA was u~ed as an organoaluminum compound in place of MA0. Results of the polymerization are shown in Table 1. Polymerization activity of the catalyst was very low, and the polymer obta.ined had a broad composition distri~ution.
, . .
Comparative Example 7 A polymeriæation of ethylene was carried out in the same manner as in Example 1-(2), except that 0.08 mmole of titanium tetrachloride was used as a catalyst ; component in place of the compound represented by the composition formula [~C8H17)2N]4Ti. Results of the polymerization are shown in Table 1, and the DSC chart of , ~:
. .
j . : .
,j~-1 the polymer is shown in Figure 2. It is apparent there-from that the catalyst used herein was low in copolymeriz-: ing ability and the polymer obtained herein had a bro~d composition distribution.
Comparative Example 8tl) Synthesis of catalyst component After replacing the inner atmosphere of a iO0 ml flask equipped with a stirrer, a dropping ~unnel and a thermometer with argon gas, 3~8 ml (20 mmoles) of decyl alcohol and 50 ml of hexane were charged.
Then, 20 mmoles of butyllithium diluted with 12.9 ml of hexane was dropwise added from the dropping funnel into the flask over a period of 3~ minutes, while keeping the inner temperature of the flask at 5C. After dropping it, the resulting mixture was reacted first at 5C for 2 hours and thereafter at 30C for 2 hours.
~ hen, 0.55 ml (5 mmoles) of titanium tetra-; chloride was dropwise added from the dropping funnel into the reacted mixture over a period of 30 minutes, while keeping the inner temperature at 5C. After dropping it,the resulting mixture was reacted first at 5C for one hour and thereafter at 30C for 2 hour~ to obtain 5 mmoles (yield of this reaction was assumed to be 100%) of a titanium compound represented by a composition formula ; 25 (CloH2lo)4~i -(2) Polymerizatlon of ethylene A polymerization was carried out in the same : .
, - 21 -?~
,~ . , , , ` : ' ~2~
1 manner as in Example 1-(2), except that the compound represented by the composition formula (CloH21O~4Ti synthesized in Paragraph (1~ was used as a ca~alyst component in place of the compound represented by the composition formula [(C8H17)2NJ~Ti. The results of the polymerization are shown in Table 1, and DSC chart of the polymer thus obtained is shown in Figure 3. It is apparent therefrom that the catalyst activity per transi-tion metal was lower than that of Example 1 and the polymer obtained herein had a broad composition distribu-tion.
~xample 3 (1) Synthesis of catalyst component Synthesis of titanium amide compound (A):
A~ter replacing the inner atmosphere of a 300 ml flask equipped with a stirrer, a dropping funnel and a : thermometer with argon gas, 6.3 ml (60 mmoles) of diethyl-amine and 150 ml of hexane were charged.
~hen, 60 mmoles of butyllithium diluted with 38.7 ml of hexane was dropwise added from the dropping funnel into the flask over a period of 30 minutes, while ; keeping the temperature of the solution in the flask at SC. After dropping it, the resulting mixture was reacted first at 5C for 2 hours and thereafter at 30C for 2 hours.
Then, 1.65 ml (15 mmoles) of titanium tetra-chloride was dropwise added from the dropping funnel into .~' - . ~ , ~ - . .
: -, , ~ ~ .
2 ~
1 the reacted mixtuxe over a period of 30 minutes, while keeping the temperature of the mixture at 5C. After dropping it, the resulting mixture was reacted first a~
5C for one hour and thereafter at 30C for 2 hours to obtain 15 mmoles (yield of this reaction was assumed to be 100%) of a titanium amide co~pound (A~ represented by a composition f~rmula E (C2H5)2N~4~i-: (2) Polymerization of ethylene A polymerization was carried out in the same manner as in Example 1-(23, except that 0.08 ~mole of the compound represented by the composition formula [~C2H5)2N~4Ti s~nthesized in Paragraph tl3 was ued as a catalyst component in place of the compound represented by the composition formula r (C~H17)2N~4Ti. Thus, a polymer : 15 having a narrow composition distribution was obtained as in Example 1.
~ Comparative Example 9 : A polymerization of ethylene ~as carried ~ut in .~
the same manner as in Example 3-(2), except that 8 mmoles of TIBA was used as an organoaluminum compound in place of ; MAO. As a result, polymer was hardly obtained.
Comparative Example 10 (1) Synthesis of catalyst component ::~ Synthesis of titanium amide compound:
25After replacing the inner atmosphere of a 100 ml flask equipped with a stirrer, a dropping funnel and a ' _ 23 -,'~,, .
~ ' -: , .
1 thermometer with argon gas, 2.1 ml (20 mmoles) of diethyl-amine and 50 ml of hexane were charged.
Then, 20 mmoles of butyllithium diluted with 12.9 ml of hexane was dropwise added from the dropping funnel into the flask over a period of 30 minutes, while keeping the inner temperature o~ the flask at 5C. After dropping it, the resulting mixture was reacted first at 5C for 2 hours and thereafter at 3~C for 2 hours.
Then, 2.2 ml (20 mmoles) of titanium tetra-chloride was dropwise added from the dropping fu~nel intothe reacted mixture over a period of 30 minutes, while keeping the inner temperature of the flask at 5C. After dropping it, the resulting mixture was reacted first at SC for one hour and thereafter at 30C for 2 hours.
After the reaction, the mixture was allowed to ~tand to separate the solid from the liquid. The separated solid was twice washed with each 50 ml portion ~;~ of hexane and dried under reduced pressure to obtaln 4.5 g of a solid titanium amide compound represented by a composition formula (C2H5)2NTiC13.
(2) Polymexization of ethylene A polymerization was carried out in the same manner as in Example 1 (2), except that 0.08 mmole of the compound represented by -the composition formula (C2H5)2NTiC13 was used as the catalyst compon~nt in place of the ~(C8H17)2NI4Ti. The polymer thus obtained had a ~; broad composition distribution.
~; .
,:
. ' 1 Comparative Example 11 A polymerization of ethylene was carried out in the same manner as in Comparative Example 10-(2)l except that 8 mmoles of TIBA was used as an organoaluminum compound in place of MAO. The result of the polymeri-zation are shown in Table 1. It is apparent that the catalyst used herein had a very low polymerization activity, and the polymer obtained herein had a broad composition distribution.
Comparative ~xample 12 (1) S~nthesis of catalyst component Synthesis of titanium amide compound:
After replacing the inner atmosphere of a 200 ml flask e~uipped with a stirrer, a dropping funnel and a thermometer with argon gas, 2.7 ~ (16 mmoles) of diphenyl-amine and 100 ml of hexane were charge~l.
Then, 16 mmoles of butyll.ithium diluted with 10.3 ml of hexane was dropwise added from the dropping funnel into the flask over a period of 30 minutes, while . 20 keeping the inner temperature of the flask at 5C. After :dropping it, the resulting mixture was reacted first at 5C for 2 hours and thereafter at 30C for 2 hours.
Then, 1.76 ml (16 mmoles) of titanium tetrachloride was dropwise added from the dropping funnel into the reacted mixture obtained above over a period of 30 minutes, whiie keeping the temperature of the mixture at 5C. A~ter dropping it, the resulting mixture was ; - ~5 -, ~2~
l reacted first at 5C for one hour and thereafter at 30C
for 2 hours, to o~tain 16 mmoles (yield of this reaction was assumed to be 100%) of a titanium amide compound represented b~ a composition formula (C6H5)2NTiCl3.
(2~ Polymerization of ethylene A polymerization was carried QU't in the same manner as in Example 1-(2~, except that 0.08 mmole of the compound represented by the comp~sition formula (C6H5)2NTiC13 synthesized in Paragraph (1~ was used in place of the compound represented by the composition formula [(C8H17)2N]4Ti and 8 mmoles of triethylal~ninum (TEA) was used a~ an organoaluminum compound in place of MAO. The results are shown in Table 1. The catalyst used herein had a very low pol~merization activity and the polymer obtained herein had a broad composition distribution.
Example 4 (1) Synthesis of catalyst component Synthesi~ of titanium amide compound ~A):
, :
:~ 20 After replacing the inner atmosphere of a 300 ml ~Iask equippPd with a stirrer, a dropping funnel and a thermometer with argon gas, 2.7 g (16 mmoles) of diphenyl- :
amine and 200 ml of hexane were charged.
Then, 16 mmoles of butyllithium diluted with 10.3 ml of hexane was dropwise added from the dropping funnel into the flask over a period of 30 minutes, while keeping the inner temperature of the flask at 5C. After ~ 26 -;;', : , ~ : ~. -- . ::
; , . . .
: ` ::
" ~, ' ': : ` '' : , 2~2~1~
1 dropping it, the resulting mixture was reacted first at 5C for 2 hours and thereafter at 30C for 2 hours.
Then, 0.44 ml (4 mmoles) of titanium tetrachloride was dropwise added f:rom the dropping funnel into the reacted mixture obtained above over a period of 30 minutes, while Xeeping the temperature of the mixture at 5C. After dropping it, the result.ing mLxture was reacted first at 5C ~or one hvur and thereafter at 30C
for 2 hours, to obtain 4 mmoles (yield o this reaction was assumed to be 100%) of a solid titanium amide compound (A) represented by a composition formula [C~H5)2N]4Ti.
(2) Polymerization of ethylene A polymerization was carried out in the same manner as in Example 1-t2), Pxcept that 0.08 mmole of the compound represented by the composition formula ~(C6HS)2~4~L synthesized in Paragraph (1) was used as a ~:; ca~alyst component in place of the compound represented ~y the composition formula [(C8~17)2~]4Ti' ~he~p ym obtained herein had a narrow composition distribution as ~`~ 20 in Example 1.
~: Comparative Example 13 A polymerization of ethylene was carried out in the same manner as in Example 4 (2), except that 8 mmoles of diethylaluminum chloride (DEAC) was used as an organo-:: 25 aluminum compound in place of MA0. The results of the polymerization are shown in Table 1. The catalyst used herein was much lower ~han the catalyst used in Example 4 ~; - 27 ~
., .~
~:
, 2 ~
1 in polymerization activity, and the polymer obtained herein had a broad composition distribution.
Example 5 (1) Synthesis of catalyst component Synthesis of titani~m amide compound (A):
Ater replacing the inner atmosphere of a 300 ml flask equipped with a stirrer, a dropping funnel and a thermometer with argon gas~ 10.5 ml (60 mmoles~ of diiso-butylamine and 150 ml of hexane were charged.
Then, 60 ~moles of butyllithium diluted with : 38.7 ml of hexane was dropwise added from the dropping funnel into the flask over a period of 30 minutes, while ., keeping the inner temperature of khe 1as]c at 5C. After dropping it, the resulting mixture was reacted first at 5~C for 2 hours and thereafter at 30C for 2 hours.
~: Then, 1.65 ml (15 mmoles) of titanium tetra-chloride was dropwise added from the dropping funnel into ~` the reacted mixture obtained above over a period of 30 ~ minutes, while keeping the temperature of the mixture at ; ~ 20 5C. After droppin~ it, the resulting mixture was reacted first at 5C for one hour and thereafter at 3~C for 2 hours, to obtain 15 mmoles (yield of this reaction was assumed to be 100%) of solid titanium amide compound (A) represented by a composition formula {[(C~3)2CHCH2]2N}4Ti.
~: 25 (2) Polymerization of ethylene A polymerization was carried out in the same ; manner as in Example 1 (2), except that 0.08 mmole of the 2~ _ . .
:~ . . . .
~2~
1 compound represented by the composition formula {[tCH3)2CHCH2]~N}~Ti synthesized in Paragraph (1) was used as a ca~alyst component in place of the compound represented by the composition fo.rmula [(C8H17~2N]4Ti.
The polymer obtained herein had a narrow composition distribution as in Example 1.
Comparative Example 14 (1) Synthesis of catalyst component Synthesis of titanium amide compound:
After replacing the inner atmosphere of a 300 ml fla~k equipped with a stirrer, a dxopping funnel and a thermometer with argon gas, 0.41 ml (10 mmoles) of methyl alcohol and 25 ml of hexane were charged.
Then, 10 mmoles of butyllithium diluted with 6.5 ml of hexane was dropwise added from the dropping funnel into the flask over a period of 30 minutes, while keeping the inner temperature of the flask at 5C. After dropping it, the resulting mixture was reacted first at 5C for 2 hours and thereafter at 30C for 2 hours.
; 20 Then, 10 mmoles of the comound represented by the composition formula (C8H17)2NTiC13 synthesized by the same method as in Comparative Example 5-(1) was dropwise added from the dropping funnel into the reacted mixture obtained above over a period of 30 minutes, while keeping the temperature of the mixture at 5C. After dropping it, the resulting mixture was reacted first at 5C for one hour and thereafter at 30C for 2 hours, to obtain 10 ~: :
.
, ; ~
, . . - . . .
. . .
~2~ ~ ~
1 mmoles (yield of this reaction was assumed to be 100~) of titanium amide compound represented by a composition formula (C8H17)2N~i(OCH3)C12 (2) Polymerization of ethylene A polymerization was carried out in the same manner as in Example 1-(2), except that 0.08 mmole of the compound represented by the composition ormula (C8H17~2NTi(OCH3)C12 synthesized in Paragraph (1) was used : as a catalyst component in place of the compound represented by the composition formula [(C8H17)2N]4Ti.
The polymer obtained herein had a broad composition di~tribution.
.
Example 6 A copolymerization o~ ethylene and l-butene was carried out in the same manner as in Example 1 by using the same catalyst system as used in Example 1. A polymer narrow in composition distribution was obtained as in Example 1.
Example 7 A copolymerization of ethylene and 4~
methylpentene-1 was carried out in the same manner as in Example 1 by using the same catalyst system AS used in Example 1. A polymer narrow in composition distribution was obtained as in Example 1.
.
, - 3~ -~:
~ ~ ' .
- ~ .
, 2 ~ ~ ~
1 Example 8 A copolymerization of ethylene and 1-decene was carried out in the same manner as in E~maple 1 ~y using the same catalyst system as used in Example 1. A polymer narrow in composition distribution was obtained as in Example 1.
The conditions and results of polymerization in :~ all the examples mentioned abo~e are summarized in Table ~.~
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Claims (13)
1. A process for producing an ethylene-.alpha.-olefin copolymer which comprises copolymerizing ethylene and an .alpha.-olefin at a polymerization temperature higher than 120°C
by using a catalyst system comprising (A) a titanium amide compound represented by the following general formula:
(R1R2N)4-nTiYn wherein R1 and R2 each represent a hydrocarbon group having 1 to 30 carbon atoms, Y represents an alkoxy group and n represents a number satisfying 0 ? n ? 3, and (B) an oxygen-containing alkylaluminum compound.
by using a catalyst system comprising (A) a titanium amide compound represented by the following general formula:
(R1R2N)4-nTiYn wherein R1 and R2 each represent a hydrocarbon group having 1 to 30 carbon atoms, Y represents an alkoxy group and n represents a number satisfying 0 ? n ? 3, and (B) an oxygen-containing alkylaluminum compound.
2. A process according to Claim 1, wherein the titanium amide compound (A) is tetrakis(dimethylamino)-titanium, tetrakis(diethylamino)titanium, tetrakis-(dipropylamino)titanium, tetrakis(dibutylamino)titanium, tetrakis(dihexylamino)titanium, tetrakis(diphenylamino)-titanium, tetrakis(dioctylamino)titanium, tetrakis-(didecylamino)titanium or tetrakis(dioctadecylamino)-titanium.
3. A process according to Claim 1, wherein said oxygen-containing alkylaluminum compound (B) is at least one member selected from the group consisting of cyclic and acyclic aluminoxanes of which structures are repre-sented by the following general formulas:
and wherein R3 represents a hydrocarbon group having 1 to 8 carbon atoms, and k represents an integer of 1 or greater.
and wherein R3 represents a hydrocarbon group having 1 to 8 carbon atoms, and k represents an integer of 1 or greater.
4. A process according to Claim 3, wherein the cyclic and acyclic aluminoxanes are tetramethyl adialuminoxane, tetraethyldialuminoxane, tetra-butyldialuminoxane, tetrahexyldialuminoxane, methyl-aluminoxane, ethylaluminoxane, butylaluminoxane or hexylalumioxane .
5. A process according to Claim 1, wherein the polymerization temperature is higher than 150°C.
6. A process according to Claim 1, wherein the amount of the compound (B) is 1 to 10,000 moles per one mole of titanium atom in the compound (A).
7. A process according to Claim 1, wherein the polymerization is carried out in a solution process using a hydrocarbon solvent or a high pressure ion process.
8. A process according to Claim 7, wherein the polymerization pressure is 5 to 100 kg/cm2 in the case of solution process.
9. A process according to Claim 7, wherein the polymerization pressure is 350 to 3,500 kg/cm2 in the case of high pressure ion process.
10. A process according to Claim l, wherein the .alpha.-olefin is those having 3 to 20 carbon atoms.
11. A process according to Claim 10, wherein a olefin is propylene, butene-1, 4-methylpentene-1, hexene-1, octene-1, or vinylcyclohexane.
12. A process according to Claim 1, wherein the ethylene-.alpha.-olefin copolymer constitutes of at least 80% by mole of ethylene and a residual quantity of at least one .alpha.-olefin.
13. A process according to Claim 7, wherein in the solution process, hexane, heptane, kerosin fraction or toluene is used as solvent.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP03-051128 | 1991-03-15 | ||
| JP3051128A JPH04285607A (en) | 1991-03-15 | 1991-03-15 | Production of ethylene-alpha-olefin copolymer |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2062611A1 true CA2062611A1 (en) | 1992-09-16 |
Family
ID=12878173
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002062611A Abandoned CA2062611A1 (en) | 1991-03-15 | 1992-03-10 | Process for producing ethylene-.alpha.-olefin copolymers |
Country Status (9)
| Country | Link |
|---|---|
| US (1) | US5258476A (en) |
| EP (1) | EP0509233B1 (en) |
| JP (1) | JPH04285607A (en) |
| KR (1) | KR920018097A (en) |
| CN (1) | CN1064871A (en) |
| CA (1) | CA2062611A1 (en) |
| DE (1) | DE69205873T2 (en) |
| NO (1) | NO180340C (en) |
| TW (1) | TW207550B (en) |
Families Citing this family (17)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3355534B2 (en) * | 1992-09-10 | 2002-12-09 | 住友化学工業株式会社 | Ethylene-α-olefin copolymer and molded article molded using the copolymer |
| JP3266942B2 (en) * | 1992-09-10 | 2002-03-18 | 住友化学工業株式会社 | High temperature and high pressure polymerization of ethylene |
| JP3332051B2 (en) * | 1992-12-18 | 2002-10-07 | 出光興産株式会社 | Polymerization catalyst and method for producing polymer using the catalyst system |
| US5527752A (en) * | 1995-03-29 | 1996-06-18 | Union Carbide Chemicals & Plastics Technology Corporation | Catalysts for the production of polyolefins |
| IT1276800B1 (en) * | 1995-06-30 | 1997-11-03 | Enichem Spa | PROCEDURE FOR THE PREPARATION OF (CO) POLYMERS OF -OLEFINS |
| US6169152B1 (en) | 1996-07-05 | 2001-01-02 | Jsr Corporation | Olefin polymerization catalyst comprising transition metal compound containing a cyclic ligand having at least two nitrogen atoms in its main chain skeleton |
| US6103657A (en) | 1997-07-02 | 2000-08-15 | Union Carbide Chemicals & Plastics Technology Corporation | Catalyst for the production of olefin polymers |
| US6136748A (en) * | 1997-07-02 | 2000-10-24 | Union Carbide Chemicals & Plastics Technology Corporation | Catalyst composition for the polymerization of olefins |
| US6096676A (en) * | 1997-07-02 | 2000-08-01 | Union Carbide Chemicals & Plastics Technology Corporation | Catalyst for the production of olefin polymers |
| US6339035B1 (en) * | 1999-02-22 | 2002-01-15 | Phillips Petroleum Company | Catalyst and process for polymerizing olefins |
| US6559088B1 (en) * | 1999-02-22 | 2003-05-06 | Fina Technology, Inc. | Ziegler-Natta catalyst with amine for polymerization |
| US6919467B2 (en) | 2001-12-18 | 2005-07-19 | Univation Technologies, Llc | Imino-amide catalyst compositions for the polymerization of olefins |
| US7001863B2 (en) | 2001-12-18 | 2006-02-21 | Univation Technologies, Llc | Monoamide based catalyst compositions for the polymerization of olefins |
| US6831187B2 (en) | 2001-12-18 | 2004-12-14 | Univation Technologies, Llc | Multimetallic catalyst compositions for the polymerization of olefins |
| US7199255B2 (en) | 2001-12-18 | 2007-04-03 | Univation Technologies, Llc | Imino-amide catalysts for olefin polymerization |
| US6864205B2 (en) | 2001-12-18 | 2005-03-08 | Univation Technologies, Llc | Heterocyclic-amide catalyst compositions for the polymerization of olefins |
| US7807760B2 (en) * | 2007-01-31 | 2010-10-05 | Sumitomo Chemical Company, Limited | Process for producing ethylene-α-olefin copolymer |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR1369866A (en) * | 1962-09-25 | 1964-08-14 | Snam Spa | Process for the catalytic polymerization of mono-olefins and di-olenes |
| NL160282C (en) * | 1969-06-24 | Montedison Spa | PROCEDURE TO PREPARE A CATALYST FOR THE POLYMERIZATION OF ALKINES. | |
| US4892914A (en) * | 1983-08-25 | 1990-01-09 | The Dow Chemical Company | Catalysts prepared from tetrakis(dialkylamide or diarylamide) derivatives of titanium and polymerization of olefins therewith |
| IL84798A (en) * | 1986-12-15 | 1991-09-16 | Montedison Spa | Production of crystalline vinyl aromatic polymers having mainly a syndiotactic structure |
| EP0320169B1 (en) * | 1987-11-30 | 1994-01-05 | The Dow Chemical Company | Catalysts prepared from tetrakis (dialkylamide and diarylamide) derivatives of titanium and polymerization of olefins therewith |
| US5039766A (en) * | 1988-06-28 | 1991-08-13 | Sumitomo Chemical Company, Limited | Liquid catalyst component, catalyst system containing said component and process for producing ethylene-alpha-olefin copolymer using said catalyst system |
-
1991
- 1991-03-15 JP JP3051128A patent/JPH04285607A/en active Pending
-
1992
- 1992-03-03 TW TW081101637A patent/TW207550B/zh active
- 1992-03-10 CA CA002062611A patent/CA2062611A1/en not_active Abandoned
- 1992-03-11 EP EP92104168A patent/EP0509233B1/en not_active Expired - Lifetime
- 1992-03-11 DE DE69205873T patent/DE69205873T2/en not_active Expired - Fee Related
- 1992-03-12 US US07/850,314 patent/US5258476A/en not_active Expired - Fee Related
- 1992-03-12 NO NO920965A patent/NO180340C/en unknown
- 1992-03-13 KR KR1019920004160A patent/KR920018097A/en not_active Application Discontinuation
- 1992-03-14 CN CN92101741A patent/CN1064871A/en active Pending
Also Published As
| Publication number | Publication date |
|---|---|
| EP0509233A3 (en) | 1992-12-09 |
| EP0509233A2 (en) | 1992-10-21 |
| JPH04285607A (en) | 1992-10-09 |
| NO180340B (en) | 1996-12-23 |
| DE69205873T2 (en) | 1996-04-04 |
| NO180340C (en) | 1997-04-02 |
| TW207550B (en) | 1993-06-11 |
| DE69205873D1 (en) | 1995-12-14 |
| EP0509233B1 (en) | 1995-11-08 |
| NO920965D0 (en) | 1992-03-12 |
| US5258476A (en) | 1993-11-02 |
| CN1064871A (en) | 1992-09-30 |
| NO920965L (en) | 1992-09-16 |
| KR920018097A (en) | 1992-10-21 |
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| Date | Code | Title | Description |
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