CA1272847A - Ethylene copolymerization process - Google Patents
Ethylene copolymerization processInfo
- Publication number
- CA1272847A CA1272847A CA000510667A CA510667A CA1272847A CA 1272847 A CA1272847 A CA 1272847A CA 000510667 A CA000510667 A CA 000510667A CA 510667 A CA510667 A CA 510667A CA 1272847 A CA1272847 A CA 1272847A
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- vanadium
- promoter
- alphaolefin
- molar ratio
- reaction medium
- Prior art date
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Abstract
ABSTRACT
A process for the copolymerization of ethylene with at least one comonomer selected from the group consisting of copolymerizable mono-alphaolefins and nonconjugated polyenes which process is performed in the presence of a liquid aliphatic hydrocarbon reaction medium comprising a liquid alphaolefin utilizing a catalyst composition comprising a vanadium catalyst, an organoaluminum cocata-lyst, and a promoter which is a derivative of certain 4/4,4-trihalobut-2-enoic acids, wherein the molar ratio of promoter to vanadium is about 6:1 or greater.
A process for the copolymerization of ethylene with at least one comonomer selected from the group consisting of copolymerizable mono-alphaolefins and nonconjugated polyenes which process is performed in the presence of a liquid aliphatic hydrocarbon reaction medium comprising a liquid alphaolefin utilizing a catalyst composition comprising a vanadium catalyst, an organoaluminum cocata-lyst, and a promoter which is a derivative of certain 4/4,4-trihalobut-2-enoic acids, wherein the molar ratio of promoter to vanadium is about 6:1 or greater.
Description
ETHYLENE COPOLYMERIZ~TION PROCESS
.
Field of the Invention This invention relates to a process for the copolym-erization of ethylene with at least one comonomer selected from the group consisting of copolymerizable mono-alphaolefins and nonconjugated polyenes which process is performed in the presence of a liquid reaction o medium comprising a liquid alphaolefin utilizing a catalyst composition comprising a vanadium catalyst, an organoaluminum cocatalyst, and a promoter which is a derivative of certain 4,4,4-trihalobut-2-enoic acids, wherein the molar ratio of promoter to vanadium is about 6:1 or greater.
Background of the Invention The use of catalyst compositions comprised of a vanadium compound catalyst and an organoaluminum coca-talyst to copolymerize ethylene with alphaolefins and/or nonconjugated dienes has long been known. Thus, for example, Natta et al in U.S. Patent 3,260,708 disclose a process for copolymerizing ethylene with an aliphatic alphaolefin and a nonconjugated cyclic polyene, which process employs a vanad1um compound catalyst and an organoaluminum cocatalyst. Somewhat similarly, Diliddo ~ `r . :
: , , : ' .
.: . - , .
' ' ' ' . " " ' '. ~:,', , ' . ' . ' ' - . : ' , . :
~L~7~
et al in U.S. Patent 3,644,311 disclose that th~ inclu-sion of from 5 to 75 percent of an aliphatic hydrocarbor.
solubilizing agent containing 6 to 10 carbon atoms in an ethylene/propylene/polyene polymerization reaction comprising a catalyst composition including a vanadium catalyst and an organoaluminum cocatalyst will reduce polymer buildup within the polymerization reactor.
However, while such two-component catalyst systems will produce polymer, the amount of polymer produced per gram of vanadium is relatively small. Moreover, a relatively substantial amount of vanadium residue is present in the product polymer, and, consequently, removal of this residue is required in order to avoid polymer degradation.
In order to increase catalyst efficiency and to reduce the amount of vanadium residue in the polymers produced, it has become known to employ certain promoter compounds in conjunction with the vanadium/organo-aluminum catalyst composition.
Among the multitudes of promoter compounds which have been disclosed in the prior art are esters and halides of perchlorocrotonic acid. Thus, Emde et al in U.S. Patent 3,622,54~ disclose the use of such compounds as promoters for the copolymerization of ethylene with alphaolefins and/or polyenes in processes employing a vanadium catalyst and an organoaluminum cocatalyst.
However, this patent warns (at col. 1, lines 52-53) that "extremely high concentrations cause trouble with the . .
.
.
., ~7~fl7 activator (i.e., the perchlorocrotonic ester or halide) resulting in a decrease of the activity below 1", and indicates that preferred concentrations are below 5 millimoles of activator per millimole of vanadium compound.
Sunseri, in U.S. Patent 3, 645,993, discloses that a series of halogenated compounds, in particular chlorocrotonyl chloride and alkyl perchlor-ocrotonates (among others), may be employed as promoters for ethylene/alphaolefin/polyene polymerization in molar ratios of 1-30 moles promoter per mole vanadium wherein such promoters are employed in conjunction with certain nitrogen-containing acid scavengers, preferably ammonia, aniline or pyridine. Somewhat similarly, Bond et al (in U.S. Patent 4,022,961) and Hall (in U.S. Patent 4~156,767) show examples of ethylene/alphaolefin/polyene polymerization employing butyl perchlorocrotonate (BPCC) as an accelerator in BPCC:vanadium ratios of up to 7.6:1 and 7:1 respectively wherein nitrogen-containing acid scavengers are additionally employed. It is noteworthy that Bond et al, Hall and Sunseri all state that the reaction solvent may be any suitable inert organic solvent which is liquid under reaction conditions.
The use of such nitrogen-containing acid scavengers apparently stems from the disclosure of Boozer in U.S.
Patent 3,574,176 wherein it is indicated that the use of such compounds (in the absence of a promoter) will decrease gel formation in the polymer, and, in some ~ . .
`, ' . ' '` ` : ' ' .
- . . .
` ~ . ., instances, increase the catalyst mileage. However, it is to be noted that many of these nitrogen containing compounds are toxic and present a potential health hazard. Thus, the American Conference of Governmental and Industrial Hygienists h~s proposed short term exposure limits of 35 ppm for ammonia, 5 ppm for aniline and homologues and 10 ppm for pyridine wherein ppm is parts of vapor or gas per million parts of contaminated air by volume at 25C and 760 mm Hg pressure. Even further reduced limits are proposed for long term expo-sure.
Schaum et al in U.S. Patent 3,600,368 disclose the use of promoters which can be perchlorocrotonic acid derivatives, in promoter to vanadium molar ratios of 5-50:1 in halogenated reaction media such as methylene chloride, ethyl chloride, and the like. It is noteworthy that at column 3, lines 18-21 this patent teaches away from the use of hydrocarbon reaction media (which are employed in all the above patents) indicating that yields in such hydrocarbon media are increased by about 200%
only.
A second class of compounds which have been employed as promoters for alphaolefin polymerization is disclosed by Zaar et al in U.S. Patent 4,361,686. These compounds are of the formula FICC12-CCl = CCl-COOR wherein R is alkyl, cycloalkyl, aryl, alkaryl or aralkyl (optionally halogenated or aliphatically substituted) and is preferably methyl or n-butyl. It is noteworthy that it .
- . .' ' :
is declared that the use of this class of accelerators is advantageously conducted in the presence o~ inert solvents, e.g., saturated hydrocarbons or aryl compounds such as benzene, toluene and the like, rather ~han in liquified monomers under pressure.
A third class of promoter compounds are o~ the formula:
~1 Rl R2 wherein: n is 1, 2, 3 or 4; X, Xl and x2 are halogen;
A is oxygen, sulfur or halogen; Rl is hydrogen, Cl-C16 alkyl or -CooR4 wherein R4 is Cl-C18 alkyl, C3-C18 alkenyl, C5-C6 cycloalkyl, C7-C9 aralkyl or C6-C10 aryl; R2 is hydrogen or Cl-C16 alkyl; with the provisos that (a) when n is 1 and A is halogen, there is no R3; ~b) when n is 1 and A
is oxygen or sulfur, R is hydrogen, Cl-C18 alkyl, C6-C10 aryl, C7-Cg alkylaryl, C7-C9 aryl-alkyl, C3-C6 alkenyl, Cl-C18 haloalkyl~
C6-C10 haloaryl, C7-Cg haloalkylaryl or C7-C9 haloarylalkyl; (c~ when n is 2, A is oxygen or sulfur, and R3 is C2-C12 alkylene, C4-C6 oxydialkylene, or C4-C6 thiodialkylene; and (d) when n is 3 or 4, A
'~ ' .
..
-:; ' .' '' ' ~ , ' , , ~' . :. : .
'3~7;~
is oxygen or sulfur, and R3 is a Cn-C12 alkyl radical having the valence n.
While the above three classes of promoter compounds will increase the yield of polymer produced by vanadium/organoaluminum catalyst systems, it would nonetheless be desirable to further increase the yield of polymer produced and/or to reduce the need for using potentially hazardous chemicals.
It has now been unexpectedly found that when the promoters of the first and third classes above are employed in promoter to vanadium ratios of about 6:1 or greater in the presence of a liquid aliphatic hydrocarbon reaction medium comprising a liquid alphaolefin, the productivi~y of the catalyst is unexpectedly enhanced.
Description of the Invention This invention is directed to a process for the production of a copolymer of ethylene with at least one comonomer selected from the group consisting of copolymerizable mono-alphaolefins and nonconjugated polyenes, which process comprises reacting ethylene with said at least one comonomer in a liquid aliphatic hydro-carbon reaction medium comprising a liquid alphaolefin in the presence of a catalyst composition comprising:
(a) a vanadium-containing compound;
(b) an organoaluminum compound; and (c) a promoter having the structure:
.
- - . . .: ' .'. ' ' ' :
. . . . . .
I 1 IRl I 2 3~R3 wherein:
n is 1, 2, 3 or 4;
X, Xl and x2 are halogen;
A is oxygen, sulfur or halogen;
Rl is hydrogen; halogen; Cl-C16 alkyl; or - CooR4 wherein R4 is Cl-C18 alkyl, C3-C18 alkenyl, C5-C6 cycloalkyl, C7-Cg aralkyl or C6 C10 aryl;
R2 is hydrogen, halogen or Cl C16 alkyl;
with the provisos that:
when n is 1 and A is halogen, there is no R3;
when n is 1 and A is oxygen or sulfur, R3 is hydrogen, Cl-C18 yl, C6 C10 aryl, C7-Cg alkylaryl, C7-Cg arylalkyl, C3-C6 alkenyl, Cl-C18 haloalkyl, C6-C10 haloaryl, C7-Cg haloaikylaryl or C7-C9~haloarylalkyl;
~ when n:is 2, A is oxygen or sufur, and~R3 i~s~C2-C12 alkylene, C4-C6 oxydialkylene, or C4-C6 thiodial-kylene; and when n is 3 or 4, A is oxygen or sulfur, and R3 is a Cn-C12 alkyl radical having the valence n;
wherein the molar ratio of said promoter to the vanadium in said vanadium-containing compound is about 6:1 or greater;
with the proviso that when said comonomer consists of mono-alphaolefin, the molar ratio in the reactor of ethylene to comonomer is about 3:1 or less.
In its preferred embodiment, this invention relates to a process for the production of a copolymer of ethylene with at least one comonomer selected from the group consisting of (i) at least one copolymerizable mono-alphaolefin selected from the group consisting of propylene, l-butene and l-pentene; and (ii) at least one nonconjugated polyene selected from the group consisting of 5-ethylidene-2-norbornene, dicyclopentadiene and 1,4-hexadiene;
in a liquid aliphatic hydrocarbon reaction medium comprising at least one liquid alphaolefin selected from the group consiting of propylene, l-butene and l-pentene;
in the presence of a catalyst composition comprising:
(a) a vanadlum-containlng compound;~
(b) an:organoalumlnum~compound; and . - ~ : : .
. .. . . .
-. : . . ; ..
(c) a promoter selected from the group con-sisting o~ butyl 4,l~,4-trichlorobut-2-enoate, methyl 2-methyl-4,4,4-trichloro-but-2-enoate, ethyl 4,~,4-trichlorobut-
.
Field of the Invention This invention relates to a process for the copolym-erization of ethylene with at least one comonomer selected from the group consisting of copolymerizable mono-alphaolefins and nonconjugated polyenes which process is performed in the presence of a liquid reaction o medium comprising a liquid alphaolefin utilizing a catalyst composition comprising a vanadium catalyst, an organoaluminum cocatalyst, and a promoter which is a derivative of certain 4,4,4-trihalobut-2-enoic acids, wherein the molar ratio of promoter to vanadium is about 6:1 or greater.
Background of the Invention The use of catalyst compositions comprised of a vanadium compound catalyst and an organoaluminum coca-talyst to copolymerize ethylene with alphaolefins and/or nonconjugated dienes has long been known. Thus, for example, Natta et al in U.S. Patent 3,260,708 disclose a process for copolymerizing ethylene with an aliphatic alphaolefin and a nonconjugated cyclic polyene, which process employs a vanad1um compound catalyst and an organoaluminum cocatalyst. Somewhat similarly, Diliddo ~ `r . :
: , , : ' .
.: . - , .
' ' ' ' . " " ' '. ~:,', , ' . ' . ' ' - . : ' , . :
~L~7~
et al in U.S. Patent 3,644,311 disclose that th~ inclu-sion of from 5 to 75 percent of an aliphatic hydrocarbor.
solubilizing agent containing 6 to 10 carbon atoms in an ethylene/propylene/polyene polymerization reaction comprising a catalyst composition including a vanadium catalyst and an organoaluminum cocatalyst will reduce polymer buildup within the polymerization reactor.
However, while such two-component catalyst systems will produce polymer, the amount of polymer produced per gram of vanadium is relatively small. Moreover, a relatively substantial amount of vanadium residue is present in the product polymer, and, consequently, removal of this residue is required in order to avoid polymer degradation.
In order to increase catalyst efficiency and to reduce the amount of vanadium residue in the polymers produced, it has become known to employ certain promoter compounds in conjunction with the vanadium/organo-aluminum catalyst composition.
Among the multitudes of promoter compounds which have been disclosed in the prior art are esters and halides of perchlorocrotonic acid. Thus, Emde et al in U.S. Patent 3,622,54~ disclose the use of such compounds as promoters for the copolymerization of ethylene with alphaolefins and/or polyenes in processes employing a vanadium catalyst and an organoaluminum cocatalyst.
However, this patent warns (at col. 1, lines 52-53) that "extremely high concentrations cause trouble with the . .
.
.
., ~7~fl7 activator (i.e., the perchlorocrotonic ester or halide) resulting in a decrease of the activity below 1", and indicates that preferred concentrations are below 5 millimoles of activator per millimole of vanadium compound.
Sunseri, in U.S. Patent 3, 645,993, discloses that a series of halogenated compounds, in particular chlorocrotonyl chloride and alkyl perchlor-ocrotonates (among others), may be employed as promoters for ethylene/alphaolefin/polyene polymerization in molar ratios of 1-30 moles promoter per mole vanadium wherein such promoters are employed in conjunction with certain nitrogen-containing acid scavengers, preferably ammonia, aniline or pyridine. Somewhat similarly, Bond et al (in U.S. Patent 4,022,961) and Hall (in U.S. Patent 4~156,767) show examples of ethylene/alphaolefin/polyene polymerization employing butyl perchlorocrotonate (BPCC) as an accelerator in BPCC:vanadium ratios of up to 7.6:1 and 7:1 respectively wherein nitrogen-containing acid scavengers are additionally employed. It is noteworthy that Bond et al, Hall and Sunseri all state that the reaction solvent may be any suitable inert organic solvent which is liquid under reaction conditions.
The use of such nitrogen-containing acid scavengers apparently stems from the disclosure of Boozer in U.S.
Patent 3,574,176 wherein it is indicated that the use of such compounds (in the absence of a promoter) will decrease gel formation in the polymer, and, in some ~ . .
`, ' . ' '` ` : ' ' .
- . . .
` ~ . ., instances, increase the catalyst mileage. However, it is to be noted that many of these nitrogen containing compounds are toxic and present a potential health hazard. Thus, the American Conference of Governmental and Industrial Hygienists h~s proposed short term exposure limits of 35 ppm for ammonia, 5 ppm for aniline and homologues and 10 ppm for pyridine wherein ppm is parts of vapor or gas per million parts of contaminated air by volume at 25C and 760 mm Hg pressure. Even further reduced limits are proposed for long term expo-sure.
Schaum et al in U.S. Patent 3,600,368 disclose the use of promoters which can be perchlorocrotonic acid derivatives, in promoter to vanadium molar ratios of 5-50:1 in halogenated reaction media such as methylene chloride, ethyl chloride, and the like. It is noteworthy that at column 3, lines 18-21 this patent teaches away from the use of hydrocarbon reaction media (which are employed in all the above patents) indicating that yields in such hydrocarbon media are increased by about 200%
only.
A second class of compounds which have been employed as promoters for alphaolefin polymerization is disclosed by Zaar et al in U.S. Patent 4,361,686. These compounds are of the formula FICC12-CCl = CCl-COOR wherein R is alkyl, cycloalkyl, aryl, alkaryl or aralkyl (optionally halogenated or aliphatically substituted) and is preferably methyl or n-butyl. It is noteworthy that it .
- . .' ' :
is declared that the use of this class of accelerators is advantageously conducted in the presence o~ inert solvents, e.g., saturated hydrocarbons or aryl compounds such as benzene, toluene and the like, rather ~han in liquified monomers under pressure.
A third class of promoter compounds are o~ the formula:
~1 Rl R2 wherein: n is 1, 2, 3 or 4; X, Xl and x2 are halogen;
A is oxygen, sulfur or halogen; Rl is hydrogen, Cl-C16 alkyl or -CooR4 wherein R4 is Cl-C18 alkyl, C3-C18 alkenyl, C5-C6 cycloalkyl, C7-C9 aralkyl or C6-C10 aryl; R2 is hydrogen or Cl-C16 alkyl; with the provisos that (a) when n is 1 and A is halogen, there is no R3; ~b) when n is 1 and A
is oxygen or sulfur, R is hydrogen, Cl-C18 alkyl, C6-C10 aryl, C7-Cg alkylaryl, C7-C9 aryl-alkyl, C3-C6 alkenyl, Cl-C18 haloalkyl~
C6-C10 haloaryl, C7-Cg haloalkylaryl or C7-C9 haloarylalkyl; (c~ when n is 2, A is oxygen or sulfur, and R3 is C2-C12 alkylene, C4-C6 oxydialkylene, or C4-C6 thiodialkylene; and (d) when n is 3 or 4, A
'~ ' .
..
-:; ' .' '' ' ~ , ' , , ~' . :. : .
'3~7;~
is oxygen or sulfur, and R3 is a Cn-C12 alkyl radical having the valence n.
While the above three classes of promoter compounds will increase the yield of polymer produced by vanadium/organoaluminum catalyst systems, it would nonetheless be desirable to further increase the yield of polymer produced and/or to reduce the need for using potentially hazardous chemicals.
It has now been unexpectedly found that when the promoters of the first and third classes above are employed in promoter to vanadium ratios of about 6:1 or greater in the presence of a liquid aliphatic hydrocarbon reaction medium comprising a liquid alphaolefin, the productivi~y of the catalyst is unexpectedly enhanced.
Description of the Invention This invention is directed to a process for the production of a copolymer of ethylene with at least one comonomer selected from the group consisting of copolymerizable mono-alphaolefins and nonconjugated polyenes, which process comprises reacting ethylene with said at least one comonomer in a liquid aliphatic hydro-carbon reaction medium comprising a liquid alphaolefin in the presence of a catalyst composition comprising:
(a) a vanadium-containing compound;
(b) an organoaluminum compound; and (c) a promoter having the structure:
.
- - . . .: ' .'. ' ' ' :
. . . . . .
I 1 IRl I 2 3~R3 wherein:
n is 1, 2, 3 or 4;
X, Xl and x2 are halogen;
A is oxygen, sulfur or halogen;
Rl is hydrogen; halogen; Cl-C16 alkyl; or - CooR4 wherein R4 is Cl-C18 alkyl, C3-C18 alkenyl, C5-C6 cycloalkyl, C7-Cg aralkyl or C6 C10 aryl;
R2 is hydrogen, halogen or Cl C16 alkyl;
with the provisos that:
when n is 1 and A is halogen, there is no R3;
when n is 1 and A is oxygen or sulfur, R3 is hydrogen, Cl-C18 yl, C6 C10 aryl, C7-Cg alkylaryl, C7-Cg arylalkyl, C3-C6 alkenyl, Cl-C18 haloalkyl, C6-C10 haloaryl, C7-Cg haloaikylaryl or C7-C9~haloarylalkyl;
~ when n:is 2, A is oxygen or sufur, and~R3 i~s~C2-C12 alkylene, C4-C6 oxydialkylene, or C4-C6 thiodial-kylene; and when n is 3 or 4, A is oxygen or sulfur, and R3 is a Cn-C12 alkyl radical having the valence n;
wherein the molar ratio of said promoter to the vanadium in said vanadium-containing compound is about 6:1 or greater;
with the proviso that when said comonomer consists of mono-alphaolefin, the molar ratio in the reactor of ethylene to comonomer is about 3:1 or less.
In its preferred embodiment, this invention relates to a process for the production of a copolymer of ethylene with at least one comonomer selected from the group consisting of (i) at least one copolymerizable mono-alphaolefin selected from the group consisting of propylene, l-butene and l-pentene; and (ii) at least one nonconjugated polyene selected from the group consisting of 5-ethylidene-2-norbornene, dicyclopentadiene and 1,4-hexadiene;
in a liquid aliphatic hydrocarbon reaction medium comprising at least one liquid alphaolefin selected from the group consiting of propylene, l-butene and l-pentene;
in the presence of a catalyst composition comprising:
(a) a vanadlum-containlng compound;~
(b) an:organoalumlnum~compound; and . - ~ : : .
. .. . . .
-. : . . ; ..
(c) a promoter selected from the group con-sisting o~ butyl 4,l~,4-trichlorobut-2-enoate, methyl 2-methyl-4,4,4-trichloro-but-2-enoate, ethyl 4,~,4-trichlorobut-
2-enoate, 2-ethylhexyl 4,4,4-trichloro-but-2-enoate and butyl perchlorocrotonate;
wherein the molar ratio of said promoter to the vanadiu~ in said vanadium-contaIning compound is abo~t 6:1 or greater with the proviso that when said comonomer consists of a mono-alphaolefin, the molar ratio in the reactor of ethylene to comonomer is a~out 3:1 or less.
The process of this invention involves the copolymerization of ethylene with at least one comonomer selected from the group consisting of copolymerizable mono-alphaolefins and nonconjugated polyenes in the presence of (l) a specified reaction medium and (2) a specified catalyst composition.
The copolymerizable mono-alphaolefins which may be employed in the process of this invention are compounds of the formula CH2 = CHR wherein R is an alkyl radical containing from one to ten carbon atoms. When R contains more than 2 carbon atoms such radical may be straight chain or branched. Preferred mono-alphaolefins include propylene, l-butene, l-pentene, l-hexene, 3-methyl-l-pentene, l-heptene, l-octene and l-decene.
`
' ~ ~ 7~ ~ 7 The polyenes which may be employed in the process of this invention are nonconjugated. Illustrative of such nonconjugated polyenes are aliphatic dienes such as the cis- and trans- isomers of 17 4-hexadiene, 1,5-hexadiene, 1,4-pentadiene, 2-methyl-1,4-pentadiene, 3 methyl-1,4-hexadiene, 4-methyl-1,4-hexadiene, 1,9-decadiene, exo-and endo-dicyclopentadiene and the like; exo- and endo-alkenylnorbornenes~ such as 5-propenyl-, 5-(buten-2-yl)-, and 5-~2-methylbuten-[2']-yl)norbornene and the like;
alkylalkenylnorbornenes, such as 5-methyl-6-propenylnor-bornene and the like; alkylidenenorbornenes, such as 5-methylene-, 5-ethylidene-, and 5-isopropylidene-2-nor-bornene, vinylnorbornene, cyclohexenylnorbornene and the like; alkylnorbornadienes, such as methyl-, ethyl-, and propylnorbornadiene and the like; and cyclodienes such as 1,5-cyclooctadiene, 1,4-cyclooctadiene and the like.
Preferably, the process of this invention is employed to produce a terpolymer of ethylene, propylene and a non-conjugated diene. Most preferably, the 2~ non-conJugated diene is 5-ethylidene-2-norbornene, 1,4-hexadiene or dicyclopentadiene when such terpolymers are formed.
The liquid aliphatic hydrocarbon reaction medium employed in the practice of this invention is comprised of a liquid alphaolefin. As is employed herein, the term "liquid aliphatic hydrocarbon reaction medium" refers to a reaction medium the major portion of which is comprised of aliphatic liquids which contain hydrogen and carbon - . .. : :. . , : :
only. It is to be understood that the reaction medium may contain a minor amount of other nonreactive hydrocar-bons such as benzene, toluene and the like.
Typically, the reaction medium will be comprised of ~i) from about 15 to 100 weight percent of an alphaolefin of the formula CH2 = CHR wherein R is Cl - C10 alkyl and (ii) from O to about 85 weight percent of an aliphatic C3-C10 hydrocarbon which is inert to the pol~erization reaction. Illustrative of the aliphatic compounds which may be employed are alkanes such as butane, isobutane, pentane, hexane, heptane, 2-ethylhexane and the like; cycloalkanes such as cyclo-pentane and the like; alkenes such as 2-pentene and the like; and cycloalkenes such as cyclohexene and the like.
Although a mixture of mono-alphaolefins may be employed as the reaction medium it is preferred that only a single mono-alphaolefin be employed. Propylene is the preferred mono-alphaolefin.
When the reaction medium of this invention further comprises an aliphatic C3-C12 hydrocarbon, it is pre-erred that such hydrocarbon comprise a C5-C10 linear or branched alkane.
Preferably, the reaçtion medlum mixture is comprised of from about 20 to about 80 weight percent of one or ~5 more non-alphaolefinic aliphatic hydrocarbons and o from about 20 to about 80 weight percent of propylene. More preferably, the reaction medium is comprised of from about 25 to about 6~0 weight percent propylene and of from . ~:
., ~ ~ . .
. . .
.: , . .
- '- . ' ' ,', .' ~ " .
,, ~ ' ' ''~' ' ' -:~ :
7~ ~ 7 about 40 ~o about 75 weight percent non-alphaolefin aliphatic hydrocarbon.
The copolymerization of this invention is performed in the presence of a reaction medium which comprises a liquid mono-alphaolefin. In some embodiments, this mono-alphaolefin may comprise a compound which is a liquid at atmospheric pressure, such as l-octene. In such circumstances, the polymerization may be performed at atmospheric pressure. In other embodiments, the mono-alphaolefin may comprise a compound which is not a liquidat atmospheric pressure, such as propylene. In these latter circumstances, the reaction is generally performed at superatmospheric pressure.
Moreover, it is within the scope of this invention to form the liquid mono-alphaolefin in situ, e.g., by (1) saturating a liquid alkane (such as pentane, hexane, heptane or the like) with a mono-alphaolefin (such as propylene); (2) feeding the saturated liquid into a pressure vessel/reactor; (3) pressurizing said pressure vessel/reactor with additional mono-alphaolefin gas to the extent that liquid mono-alphaolefin is formed; and (4) conducting the polymerization under such increased pressure.
The catalyst composition employed in the process of this invention is comprised of a vanadium compound catalyst, an organoaluminum cocatalyst and a promoter.
Any of the vanadium compounds known to the art to be - useful as components of coordination catalysts for : , ., ' ' ' ' ~, . :
7~
polymerizing alphaolefins can be used. These include vanadium halides, vanadium oxyhalides, addition complexes of vanadium halides with oxygen- and nitrogen-containing ligands, chelate complexes of vanadium with 1,3-diketone compounds and compounds such as alkyl vanadate esters.
Suitable vanadium compounds include, for example, VC14, VOCl3, vanadium tris(acetylacetonate), vanadium oxybis~acetylacetonate), trimethyl vanadate, triisopropyl vanadate, tetrakis(beta-ethoxyethoxy)vanadium, allyl vanadate, tri-n-octadecyl vanadate, tetrahydrofuranate of VCl3, bis(gamma-isopropoxy)vanadium dibromide, beta-ethoxy ethoxyvanadium trichloride, 2,2-dime~hyl-1,3-propylenedioxyvanadyl fluoride, fluorovanadyl bis(acetyl-acetonate), diethoxyvanadyl fluoride, vanadium tris(then-oyl trifluoroacetonate), vanadium tris(trifluoroacetyl-acetonate), pyridinate of VC13, trimethylaminate of VC13, tris(2~ethylhexyl) vanadate, VI4, VBr4, VOBr3, VOI3 and dibromovanadyl acetylacetonate. Of the above compounds, the preferred vanadium catalysts are VC14, VOC13 and vanadium tris(acetylacetonate).
In addition, there may be employed vanadium com-pounds having one of the following structural formulas:
VO(OR)3, VO(OR)Cl2, VO(S-CS-NR2)2, VO(O-CO-R)3 and VO[SPS(OR)2]3 wherein R in each of the above recited formulas is an alkyl radical of 1-16 carbon atoms, and a compound having the formula (O)nV(OCH2R~p(OR')qXm where R is a tertiary alkyl having 4-18 carbon atoms; R'is Cl-C18 alkyl .
' ' .
, .
- ~- - ,, , : .
and if q is 2, R can be linear or branched C2-C8 alkylene; X is chlorine, bromine or iodine; n is O or l; if n is O then m is 0,1,2 or 3; p is an integer of l to 4; q is 1, 2 or 3 with the proviso that p + q + m = 3 or 4; if n is l then m is 0,1 or 2, p is 1, 2 or 3, q is l, 2 or 3, with the proviso that p + q + m = 1, 2 or 3.
The cocatalyst of the process of this invention is an organoaluminum compound. Preferably, the organoalu-minum compound of the instant invention is a trialkyl-aluminum or an alkylaluminum halide. Of the trialkyl-aluminums, triethylaluminum is particularly preferred.
l~ Of the halide compounds, the chlorides are most pre-ferred. Among the alkylaluminum chlorides preferred for use in this invention are ethylaluminum sesquichloride, ethylaluminum dichloride, diethylaluminum chloride and diisobutylaluminum chloride. Of all the above mentioned organoaluminum compounds, ethylaluminum sesquichloride and diethylaluminum chloride are most preferred.
The promoters employed in the catalyst composition of this invention are compounds of the formula:
_ _ .
~l Rl R2 x f c~- B - A - R
:
: ~
wherein:
n is 1, 2, 3 or 4;
X, Xl and x2 are halogen;
A is oxygen, sulfur or halogen;
Rl is hydrogen, halogen, Cl-C16 alkyl or -CooR4 wherein R4 is Cl-C18 alkyl, C3-Clg alkenyl~ C5-C6 cycloalkyl, C7-Cg aralkyl or C6-C10 aryl;
R is hydrogen, halogen or Cl-C16 alkyl;
with the provisos that:
when n is 1 and A is halogen, there is no R3;
when n is 1 and A is oxygen or sulfur, R3 is hydrogen, Cl-C18 alkyl, C6-C10 aryl, C7-Cg alkylaryl, C7-Cg arylalkyl, C3-C6 alkenyl, Cl-C18 haloalkyl, C6-C10 haloaryl, C7-Cg haloalkylaryl or C7-Cg haloarylalkyl;
when n is 2, A is oxygen or sulfur, and R is C2-C12 alkylene, C4-C6 oxydialkylene, or C4-C6 thiodialky-lene;
. - .
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' ' - " ': ,' ., ' ',. :. : . ' ' ' ' ~ ~ 7~
when n is 3 or 4, A is oxygen or sulfur, and R3 is a Cn-C12 alkyl radical having the valence n.
Preferably, the promoters of this invention are compounds having the above structure whexein:
n is 1 or 2;
X, Xl and x2 are chlorine;
A is oxygen, Rl is hydrogen, chlorine, Cl-C8 alkyl, or CoOR4 wherein R4 is Cl-C8 alkyl, cycloalkyl, benzyl or phenyl;
R is hydrogen, chlorine or Cl-C8 alkyl;
with the provi.sos that:
when n is 19 R3 is Cl-C12 alkyl, phenyl, tolyl, benzyl, allyl, Cl-C2 haloalkyl or halophenyl;
and when n is 2, R3 is C2-C6 alkylene, oxydiethylene or thiodiethylene.
Most preferably,:the promoter is selected from the group consisting of butyl 4,4,4-trichlorobut-2-enoate, methyl 2-methyl-4,4,4-trichlorobut-2-enoate, ethyl 4,4,4-trichlorbut-~2-enoate, 2-ethylhexyl 4,4,4-trichlorobut 2-enoate~and butyl perchlorocrotonate.
; ~
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- . : , . ..
, .. . . . :
Several of these promoters, such as esters and halides of perchlorocrotonic acid, are known compounds and may be readily synthesized by those skilled in the art of organic chemistry. Others of these promoters are described in copending Canadian Patent Application No.
443,255, filed on December 14, 1983.
In general, these other promoters may be prepared by reacting a compound of the formula:
- Rl R2 \ C = C ~ nR3 wherein n, A, Rl, R2 and R3 are as defined above, with a compound of the formula C(X)(Xl)~X2)(X3) wherein X, Xl, X2, and X3 are all halogen, in the presence of a catalyst such as RuC12[(C6H5)3P]3 to produce a compound of the formula:
~o E x ~ 2 and dehydrohalogenating said compound, e.g., by treatment with an appropriate base The acid halide promoter compounds may be produced by reacting the appropriate carboxylic acid with a sulfonyl halide or a phosphorous trihalide or pentahalide.
, It is a further feature of the process of this invention that the molar ratio of promoter compound to the vanadium in the vanadium-containing compound is ~reater than about 6:1 and is preferably in the range of between about 6:1 and about 150:1. More preferably, the molar ratio of the promoter compound to vanadium in the vanadium-containing compound is the range of between about 8:1 and about 120:1. Still more preferably, this molar ratio is in the range of between about 12:1 and about lO0:1. Most preferably, the molar ratio is in the range`of about 24:1 and about 80:1.
The catalyst, cocatalyst and promoter are preferably present in the polymerization reaction such that the molar ratio of cocatalyst to catalyst plus promoter is in the range of between about 1.5:1 and about 500:1. More preferably, this molar ratio is in the range of between about 1.5:1 and about 100:1. Most preferably, this molar ratio is in the range of between about 2.5:1 and about 10:1 .
The process of this invention is typically performed as follows. The catalyst composition, reaction medium and comonomers are introduced into the reaction vessel, which is typically a pressure vessel made of a non-reactive material such as stainless steel. In order to obtain best results, it is preferred that the alphaolefin be anhydrous and thus it is preferable that such monomer be dried, e.g. by passing it through molecular sieves, prior to its introduction into the reactor. Preferably, . ~ . .
`' ;~' -' ' '' ~ ' the water content in the alphaolefin should be no more than ten parts per million by weight.
During such introduction, care should be taken to avoid premixing the promoter with the organoaluminum cocatalyst lest deactivation of the catalyst composition occur.
In a preferred embodiment of the instant invention, hydrogen gas is an added reactant in the polymerization reaction. Hydrogen gas is employed to improve the regulation of the molecular weight of the polymer produced in the reaction. Specifically, lower molecular weights are obtainable when hydrogen gas is utilized. It is emphasized that the use of hydrogen gas as a reactant is not essential.
It is to be understood that the addition of a nitrogen-containing acid scavenger compound is not required in the practice of this invention. However, if desired, small amounts of such compounds may be added to the reaction medium.
In general, the catalyst concentration may range between about l x 10 8 and about 3 x lO 1 mole of vanadium per liter of total reaction medium (i.e. reac-tion medium plus monomer plus catalyst composition).
Preferably, between about l x 10 7 and about 1 x 10 2 mole vanadium per liter of total reaction medium is present. Most pre~erably, between about l x lO 6 and about 5 x 10 3 mole vanadium per liter ~otal reaction medium is employed.
.
" ' ' :, ' .
, When the comonomer which is copolymerized with ethylene consists of mono-alphaolefin, the molar ratio in the reactor of ethylene to comonomer is about 3:1 or less. More preferably, such molar ratio is 1:1 or less, and most preferably such molar ratio is 1:3 or less.
The polymerization reaction of this invention occurs in the liquid state at a temperature in the range of between about -25C and about 70C. More preferably, the temperature range of this reaction is between about -20 and about 50C. Reaction time may vary from several minutes or less to several hours or more depending on factors such as reaction batch size, reac~ion tempera-ture, the particular reactants selected, and other similar factors. If desired, the reaction may be moni-tored by sampling or by reaction mixture solids measure-ment.
The reaction product is typically isolated by floccing, decantation or filtering.
The polymer produced by the process of this invention will frequently possess a vanadium concentration which is low enough that washing of the product to reduce the vanadium levels therein so as to avoid degeneration thereof is typically not necessary.
Moreover, the polymer produced by the process of this invention is generally essentially gel free.
By making adjustments well known to those skilled in the art of polymerization, the process of this invention may be operated in a batch or a continuous manner.
. . ~ .
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.
E~A~PLES
The following Examples are intended to further illus~rate the invention and are not intended to limit the scope of the invention in any manner.
Preparation of Butyl 4,4,4-trichlorobut-2-enoate (BTCB).
128 grams (1 mole) of freshly distilled butyl acrylate was reacted with 300 ml of carbon tetrachloride in the presence of 1.92 grams (2 millimoles) of dichloro-tris[triphenylphosphine]ruthenium, under nitrogen, in a three necked (1 liter round bottom) flask, equipped with a condenser, an overhead mechanical stirrer and a thermo-meter. The reaction mixture was heated to reflux (80C) for about 1 hour, at which time the mi~ture turned brownish in color. The mixture was cooled to room temperature, and excess CC14 was removed using a rotary evaporator. The catalyst was precipitated by addition of n-heptane which was separated by decantation from the remaining supernatant brown viscous material. The brown ~0 viscous reaction product (n-butyl-2,4,4,4-tetrachloro-butyrate) was isolated by evaporation of the n-heptane (using a rotary evaporator). It weighed 275 grams (97%
yield).
Infrared analysis (IR) of the product did not show an absorption attributable to vinylic type unsaturation indicating the absence of an acrylic double bond. After distillation, at 95-100C and 0.5 mm Hgy the reaction product was a clear, colorless oil.
',', . : ' ' ' ' ' .
One mole (289 grams) of butyl 2,4,4,4-tetrachloro-butyrate (produced as described above), triethylamine (138 ml, 1 mole) and benzene (500 ml) were placed in a three-necked round bottom 2-liter flask equipped with an overhead mechanical stirrer, a condenser and a thermo-meter. This reaction mixture was heated at reflux (80C) ~o-- 50 hours. After adding an additional 30 ml (0.2 mole) of triethylamine reflux was continued for another 2~ hours.
After ~his total of 70 hours at reflux, a dark brownish material was obtained. The reaction product was filtered. The solid (C2H5)3NHCl salt was removed leaving a solution from which the benzene solvent was removed by a rotary evaporator. The resultant dark brown viscous material ~234 grams, 95% yield) was distilled ~72-74C at 0.3 mm Hg). The product, butyl 4,4,4-trichlorobut-2-enoate (82% trans) was a colorless, clear viscous oil (90% yield). The elemental analysis for this compound appears in Table I. The nuclear magnetic 2~ resonance (NMR) spectral (lH and 13C) data, which appear in Table II, were consistent with this compound.
lABLE I
Elemental Analysis Calculated % Found D
C H Cl C H Cl . . .
39.134.52 ~l3.32 39.10 4.44 43.32 - - ' -' - ' ' , ~ .
~7~ 7 TABLE II
N.~l.R. SPECTROSCOPY DATA*
~, ._ . _ (in parts per million) H - NMR
. . . _ . . _ . . . _ 0.97 (t,3H), 1.42 (m, 2H), 1.68 (m, 2H) 4.2 (t,2H), 6.39 (d, lH), 7.20 (d, lH) CIS (J = 9 HZ) TRANS
(J = 15 HZ) 13.58, 19.04, 530.53, 65.32, 92.17, 121.73, 145.97 ! 164.63 * In the above Table the following abbreviations have the following meanings:
s - singlet d - doublet t - triplet m - multiplee ~
; ~ :
:
, - -'- - ~ ':' ' ' ' " '-. ~' . ' . . . ~
Pre~ ration of EPDM
Seven thousand grams of liquid propylene were added to a dry 5-gallon stainless steel jacketed reactor provided with a stirrer. The propylene was charged into the reactor while a cooling medium flowed in the jacketed portion of the reactor. After 1.75 moles of hydrogen had been charged into the reactor, ethylene was added until a pressure of about 110 psig was recorded. This pressure was maintained t~ about 10 psig) for the duration of the polymerization . To this was added 3.5 millimoles of ethyl aluminum sesquichloride (EASC) and isopentane (120 ml). Stirring was initiated upon addition of the EASC at 175 rpm. With the temperature in the reactor set at -8C, cooling was discontinued and a solution com-prising 0.873 millimole of vanadium oxytrichloride (VOC13~, 36 millimoles of 5-ethylidene-2-norbornene (ENB), and 3.5 millimoles of butyl perchlorocrotonate (BPCC) in 280 ml of isopentane was incrementally added to the reaction mass by means of a positive displacement pump. The addition of the solution initiated the reac-tion. After polymerization had been carried out for about 60 minutes, the reaction was terminated by passing the reaction medium which contained the product polymer into an isopropanol solution containing about 0.5 weight percent of an antioxidant composed of a trialkylaryl phosphite and a styrenated para-cresol. The polymer was separated from the reaction medium and analyzed.
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.. . .
.
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In Examples 3 and 4 and in Comparative Experiment A, the process of Example 2 was repeated except that the amounts of catalyst, cocatalyst and promoter were as listed in Table III below.
A summary of Examples 2 - 4 and Comparative Experiment A, including the analysis of the EPDM polymer product, appears in Table III.
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.
.
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TABLE III
Example No. A _2 3 4 Catalyst VOC13 VOCl VOCl VOCl mmoles .873 .4313 753 08 3 Promoter BPCC BPCC BPCC BPCC
mmoles 3.5 6.9 2.4 5.1 Cocatalyst EASC EASC EASC EASC
equivalent mmoles 23.686.66 6.66 6.66 Pro./Cat. Molar Ratio 4:1 16:1 32:1 64:1 Yield g EPr~i 454 560 208 682 Calculated Results Cat. Eff. g EPDM/g V* 10,200 25,500 54,400 166,700 Vanadium Res., ppm ** 98 39 18 6 EPDM Characteristics Ethylene/Propylene Wt 38:62 43:57 49:51 50:50 Ratio Intrinsic Viscosity (in tetralin at 135C) 5.3 4.46 3.8 1.8 Iodine No. 7.2 5.2 3.2 1.7 * Based upon yield of EPDM.
0 ** Based upon assumption that all vanadium remained in EPDM.
The above results indicate that catalyst efficiency is dramatically increased when BPCC is employed as a catalyst promoter in the process of this invention.
To a 2 liter Parr bomb reactor equipped with a stirrer and cooling jacket were added 500 grams of liquid :. ~ . ,. ', ' ', ' ' ::' ' , - ~ ,- ~ ., .
' .
&`~7 propylene. The propylene was charged into the reactor while a cooling medium flowed through the jacket. The reactor, which had an initial pressure of about 115 psig, was first pressurized to about 135 psig with hydrogen~
and ~hen further pressurized to about 1l~5 psig with ethylene. To this was added 0.74 millimole of ethyl aluminum sesquichloride (EASC) in 20 cc of toluene.
Agitation was begun and a solution comprising 0.0125 millimole of bis-neopentyl chlorovanadate (BNCV), 3.6 ml of 5-ethylidene-2-norbornene (ENB) and 0.1-millimole of butyl 4,4,4-trichlorobut-2-enoate (BTCB) (produced in accordance with the method of Example l) in 25 cc of toluene was incrementally added to the reaction mass.
During the polymerization, the reaction temperature was maintained at about 0C and the reaction pressure at about 165 ~5 psig. After polymerization had been carried out for about 1 hour, the reaction was terminated by the addition of an isopropanol solution containing about 0.5 weight percent of an antioxidant composed of trialkylaryl phosphite and a styrenated para-cresol. The polymer was separated from the reaction medium and analyzed. The results of such analysis are presented in Table IV.
In Example 6, a process similar to that of Example 5 was followed with butyl perchlorocrotonate (BPCC) being 30employed in place of BTCB. The results of Example 6 are also summarized in TabIe IV.
TABLE IV
:
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':
Example No. 5 6 -Catalyst BNCV BNCV
~moles O.0125 0.0125 Prcmoter BTCB BPCC
nmoles 0.1 0.1 Cocatalyst EASC EASC
equivalent mmoles 0.74 0.74 Pro./Cat. Molar Ratio8/1 8/1 Yield g EPDM 91.6 87.6 Calculated Results Cat. Eff. g E~l/g V*143,700 137,700 Vanadium Res., ppm **7.0 7.3 EPDMlCharacteristics Ethylene/Propylene Wt Ratio 62/38 54/46 Intrinsic Viscosity (in tetralin at 135C)1.89 2.02 Iodine No. 3.1 2.9 * Based upon yield of EPDM.
** Based upon assumption that all vanadium remained in EPDM.
The above results show that additional promoters, such as BTCB, will perform admirably when employed in the process of this invention.
Preparation of EPDM
FolIowing a procedure essentially similar to that of Examples 2-4 and Comparative Experiment A respectively, EPDM is produced employing butyl 4,4,4-trichlorobut-2-~: .
:.: . . .
-. :. ., : ' .
enoate (BTCB) which is produced in accordance with the procedure in Example 1. It is seen that the catalyst efficiency is greater when the molar ratio of catalyst promoter (BTCB) to vanadium exceeds 6:1.
Examples 10 - 13 Synthesis of EPDM
A ten-gallon jacketed reactor provided with a radial turbine was cleaned and dried. With the radial turbine lQ operated at 250 rpm, 12,120 grams of n-pentane, 4,040 grams of liquid propylene, 70 milliliters of 5-ethyli-dene-2-norbornene (ENB), 147 milliliters of a solution which comprised 71.9 mmoles of diethyl aluminum chloride ~DEAC) in n-pentane, 210 grams of ethylene gas and 2 moles (4 grams) of hydrogen gas were added to the reactor.
With the reactor contents maintained at 25C, a catalyst solution was added to the reaction medium. The catalyst solution comprised 29 milliliters of 0.025 ~l VOC13, 46.5 milliliters of 0.5 M BPCC, 100 milliliters of ENB, and 281 milliliters of n-pentane. This catalyst solution was initially added at a rate of 3.4 ml/min.
However, as the run continued, the rate of addition of catalyst was reduced. The run was conducted for 38 minutes during which time 76.5 milliliters of catalyst solution was added to the reactor.
The reaction was terminated by passing the reaction m~dium into an lsopr~panol solutlon containing about 0.S
:
, . ' -- . . . : , weight percent of an antioxidant composed of a trialkyl-aryl phosphite and a styrenated para-cresol. The EPDM
polymer produced by this reaction was separated, dried, weighed and analyzed.
In Examples 11 - 13 other runs were conducted as described in Example 10 except that the relative ratios of n-pentane and liquid propylene were altered as shown in Table V. The analyses of the polymers produced are also provided in Table V.
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TABLE V
Example No. 10 11 12 13 -Catalyst VOC13 VOC13 VOC13 VOC13 mmoles .177 .144 .227 .270 Promoter BPCC BPCC BPCC BPCC
mmoles 3.74 4.60 7.26 8.64 Coca~alyst DEAC DEAC DEAC DEAC
mmoles 71.9 71.9 66.0 71.9 Molar Ratio Pro./Cat. 32:1 32:1 32:1 32:1 Reaction Medium, wt. ~ n-Pentane 75 60 55 40 wt. % Propylene 25 40 45 60 Yield, grams 2,026 1,804 1,866 2,242 Calculated_Results Catalyst Eff.*
g EPDM/g V 338,800 246,300 161,600 163~300 V residue in Polymer, ppm** 3 4 6 6 EPDM Analysis Intrinsic Viscosity (in tetralin at 135C) 1.85 2.1 2.3 3.2 Iodine No. 7.8 6.8 9.5 5.0 * Based on yield of EPDM
** Based on assumption that all vanadium is in the polymer.
The above results indicate that high catalyst efficiencies are achieved and polymers having low vana-dium residues are produced employing the process of this invention.
, - . . . .
. ~, . . `;, ,~ . " '. . -
wherein the molar ratio of said promoter to the vanadiu~ in said vanadium-contaIning compound is abo~t 6:1 or greater with the proviso that when said comonomer consists of a mono-alphaolefin, the molar ratio in the reactor of ethylene to comonomer is a~out 3:1 or less.
The process of this invention involves the copolymerization of ethylene with at least one comonomer selected from the group consisting of copolymerizable mono-alphaolefins and nonconjugated polyenes in the presence of (l) a specified reaction medium and (2) a specified catalyst composition.
The copolymerizable mono-alphaolefins which may be employed in the process of this invention are compounds of the formula CH2 = CHR wherein R is an alkyl radical containing from one to ten carbon atoms. When R contains more than 2 carbon atoms such radical may be straight chain or branched. Preferred mono-alphaolefins include propylene, l-butene, l-pentene, l-hexene, 3-methyl-l-pentene, l-heptene, l-octene and l-decene.
`
' ~ ~ 7~ ~ 7 The polyenes which may be employed in the process of this invention are nonconjugated. Illustrative of such nonconjugated polyenes are aliphatic dienes such as the cis- and trans- isomers of 17 4-hexadiene, 1,5-hexadiene, 1,4-pentadiene, 2-methyl-1,4-pentadiene, 3 methyl-1,4-hexadiene, 4-methyl-1,4-hexadiene, 1,9-decadiene, exo-and endo-dicyclopentadiene and the like; exo- and endo-alkenylnorbornenes~ such as 5-propenyl-, 5-(buten-2-yl)-, and 5-~2-methylbuten-[2']-yl)norbornene and the like;
alkylalkenylnorbornenes, such as 5-methyl-6-propenylnor-bornene and the like; alkylidenenorbornenes, such as 5-methylene-, 5-ethylidene-, and 5-isopropylidene-2-nor-bornene, vinylnorbornene, cyclohexenylnorbornene and the like; alkylnorbornadienes, such as methyl-, ethyl-, and propylnorbornadiene and the like; and cyclodienes such as 1,5-cyclooctadiene, 1,4-cyclooctadiene and the like.
Preferably, the process of this invention is employed to produce a terpolymer of ethylene, propylene and a non-conjugated diene. Most preferably, the 2~ non-conJugated diene is 5-ethylidene-2-norbornene, 1,4-hexadiene or dicyclopentadiene when such terpolymers are formed.
The liquid aliphatic hydrocarbon reaction medium employed in the practice of this invention is comprised of a liquid alphaolefin. As is employed herein, the term "liquid aliphatic hydrocarbon reaction medium" refers to a reaction medium the major portion of which is comprised of aliphatic liquids which contain hydrogen and carbon - . .. : :. . , : :
only. It is to be understood that the reaction medium may contain a minor amount of other nonreactive hydrocar-bons such as benzene, toluene and the like.
Typically, the reaction medium will be comprised of ~i) from about 15 to 100 weight percent of an alphaolefin of the formula CH2 = CHR wherein R is Cl - C10 alkyl and (ii) from O to about 85 weight percent of an aliphatic C3-C10 hydrocarbon which is inert to the pol~erization reaction. Illustrative of the aliphatic compounds which may be employed are alkanes such as butane, isobutane, pentane, hexane, heptane, 2-ethylhexane and the like; cycloalkanes such as cyclo-pentane and the like; alkenes such as 2-pentene and the like; and cycloalkenes such as cyclohexene and the like.
Although a mixture of mono-alphaolefins may be employed as the reaction medium it is preferred that only a single mono-alphaolefin be employed. Propylene is the preferred mono-alphaolefin.
When the reaction medium of this invention further comprises an aliphatic C3-C12 hydrocarbon, it is pre-erred that such hydrocarbon comprise a C5-C10 linear or branched alkane.
Preferably, the reaçtion medlum mixture is comprised of from about 20 to about 80 weight percent of one or ~5 more non-alphaolefinic aliphatic hydrocarbons and o from about 20 to about 80 weight percent of propylene. More preferably, the reaction medium is comprised of from about 25 to about 6~0 weight percent propylene and of from . ~:
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.: , . .
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,, ~ ' ' ''~' ' ' -:~ :
7~ ~ 7 about 40 ~o about 75 weight percent non-alphaolefin aliphatic hydrocarbon.
The copolymerization of this invention is performed in the presence of a reaction medium which comprises a liquid mono-alphaolefin. In some embodiments, this mono-alphaolefin may comprise a compound which is a liquid at atmospheric pressure, such as l-octene. In such circumstances, the polymerization may be performed at atmospheric pressure. In other embodiments, the mono-alphaolefin may comprise a compound which is not a liquidat atmospheric pressure, such as propylene. In these latter circumstances, the reaction is generally performed at superatmospheric pressure.
Moreover, it is within the scope of this invention to form the liquid mono-alphaolefin in situ, e.g., by (1) saturating a liquid alkane (such as pentane, hexane, heptane or the like) with a mono-alphaolefin (such as propylene); (2) feeding the saturated liquid into a pressure vessel/reactor; (3) pressurizing said pressure vessel/reactor with additional mono-alphaolefin gas to the extent that liquid mono-alphaolefin is formed; and (4) conducting the polymerization under such increased pressure.
The catalyst composition employed in the process of this invention is comprised of a vanadium compound catalyst, an organoaluminum cocatalyst and a promoter.
Any of the vanadium compounds known to the art to be - useful as components of coordination catalysts for : , ., ' ' ' ' ~, . :
7~
polymerizing alphaolefins can be used. These include vanadium halides, vanadium oxyhalides, addition complexes of vanadium halides with oxygen- and nitrogen-containing ligands, chelate complexes of vanadium with 1,3-diketone compounds and compounds such as alkyl vanadate esters.
Suitable vanadium compounds include, for example, VC14, VOCl3, vanadium tris(acetylacetonate), vanadium oxybis~acetylacetonate), trimethyl vanadate, triisopropyl vanadate, tetrakis(beta-ethoxyethoxy)vanadium, allyl vanadate, tri-n-octadecyl vanadate, tetrahydrofuranate of VCl3, bis(gamma-isopropoxy)vanadium dibromide, beta-ethoxy ethoxyvanadium trichloride, 2,2-dime~hyl-1,3-propylenedioxyvanadyl fluoride, fluorovanadyl bis(acetyl-acetonate), diethoxyvanadyl fluoride, vanadium tris(then-oyl trifluoroacetonate), vanadium tris(trifluoroacetyl-acetonate), pyridinate of VC13, trimethylaminate of VC13, tris(2~ethylhexyl) vanadate, VI4, VBr4, VOBr3, VOI3 and dibromovanadyl acetylacetonate. Of the above compounds, the preferred vanadium catalysts are VC14, VOC13 and vanadium tris(acetylacetonate).
In addition, there may be employed vanadium com-pounds having one of the following structural formulas:
VO(OR)3, VO(OR)Cl2, VO(S-CS-NR2)2, VO(O-CO-R)3 and VO[SPS(OR)2]3 wherein R in each of the above recited formulas is an alkyl radical of 1-16 carbon atoms, and a compound having the formula (O)nV(OCH2R~p(OR')qXm where R is a tertiary alkyl having 4-18 carbon atoms; R'is Cl-C18 alkyl .
' ' .
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and if q is 2, R can be linear or branched C2-C8 alkylene; X is chlorine, bromine or iodine; n is O or l; if n is O then m is 0,1,2 or 3; p is an integer of l to 4; q is 1, 2 or 3 with the proviso that p + q + m = 3 or 4; if n is l then m is 0,1 or 2, p is 1, 2 or 3, q is l, 2 or 3, with the proviso that p + q + m = 1, 2 or 3.
The cocatalyst of the process of this invention is an organoaluminum compound. Preferably, the organoalu-minum compound of the instant invention is a trialkyl-aluminum or an alkylaluminum halide. Of the trialkyl-aluminums, triethylaluminum is particularly preferred.
l~ Of the halide compounds, the chlorides are most pre-ferred. Among the alkylaluminum chlorides preferred for use in this invention are ethylaluminum sesquichloride, ethylaluminum dichloride, diethylaluminum chloride and diisobutylaluminum chloride. Of all the above mentioned organoaluminum compounds, ethylaluminum sesquichloride and diethylaluminum chloride are most preferred.
The promoters employed in the catalyst composition of this invention are compounds of the formula:
_ _ .
~l Rl R2 x f c~- B - A - R
:
: ~
wherein:
n is 1, 2, 3 or 4;
X, Xl and x2 are halogen;
A is oxygen, sulfur or halogen;
Rl is hydrogen, halogen, Cl-C16 alkyl or -CooR4 wherein R4 is Cl-C18 alkyl, C3-Clg alkenyl~ C5-C6 cycloalkyl, C7-Cg aralkyl or C6-C10 aryl;
R is hydrogen, halogen or Cl-C16 alkyl;
with the provisos that:
when n is 1 and A is halogen, there is no R3;
when n is 1 and A is oxygen or sulfur, R3 is hydrogen, Cl-C18 alkyl, C6-C10 aryl, C7-Cg alkylaryl, C7-Cg arylalkyl, C3-C6 alkenyl, Cl-C18 haloalkyl, C6-C10 haloaryl, C7-Cg haloalkylaryl or C7-Cg haloarylalkyl;
when n is 2, A is oxygen or sulfur, and R is C2-C12 alkylene, C4-C6 oxydialkylene, or C4-C6 thiodialky-lene;
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when n is 3 or 4, A is oxygen or sulfur, and R3 is a Cn-C12 alkyl radical having the valence n.
Preferably, the promoters of this invention are compounds having the above structure whexein:
n is 1 or 2;
X, Xl and x2 are chlorine;
A is oxygen, Rl is hydrogen, chlorine, Cl-C8 alkyl, or CoOR4 wherein R4 is Cl-C8 alkyl, cycloalkyl, benzyl or phenyl;
R is hydrogen, chlorine or Cl-C8 alkyl;
with the provi.sos that:
when n is 19 R3 is Cl-C12 alkyl, phenyl, tolyl, benzyl, allyl, Cl-C2 haloalkyl or halophenyl;
and when n is 2, R3 is C2-C6 alkylene, oxydiethylene or thiodiethylene.
Most preferably,:the promoter is selected from the group consisting of butyl 4,4,4-trichlorobut-2-enoate, methyl 2-methyl-4,4,4-trichlorobut-2-enoate, ethyl 4,4,4-trichlorbut-~2-enoate, 2-ethylhexyl 4,4,4-trichlorobut 2-enoate~and butyl perchlorocrotonate.
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Several of these promoters, such as esters and halides of perchlorocrotonic acid, are known compounds and may be readily synthesized by those skilled in the art of organic chemistry. Others of these promoters are described in copending Canadian Patent Application No.
443,255, filed on December 14, 1983.
In general, these other promoters may be prepared by reacting a compound of the formula:
- Rl R2 \ C = C ~ nR3 wherein n, A, Rl, R2 and R3 are as defined above, with a compound of the formula C(X)(Xl)~X2)(X3) wherein X, Xl, X2, and X3 are all halogen, in the presence of a catalyst such as RuC12[(C6H5)3P]3 to produce a compound of the formula:
~o E x ~ 2 and dehydrohalogenating said compound, e.g., by treatment with an appropriate base The acid halide promoter compounds may be produced by reacting the appropriate carboxylic acid with a sulfonyl halide or a phosphorous trihalide or pentahalide.
, It is a further feature of the process of this invention that the molar ratio of promoter compound to the vanadium in the vanadium-containing compound is ~reater than about 6:1 and is preferably in the range of between about 6:1 and about 150:1. More preferably, the molar ratio of the promoter compound to vanadium in the vanadium-containing compound is the range of between about 8:1 and about 120:1. Still more preferably, this molar ratio is in the range of between about 12:1 and about lO0:1. Most preferably, the molar ratio is in the range`of about 24:1 and about 80:1.
The catalyst, cocatalyst and promoter are preferably present in the polymerization reaction such that the molar ratio of cocatalyst to catalyst plus promoter is in the range of between about 1.5:1 and about 500:1. More preferably, this molar ratio is in the range of between about 1.5:1 and about 100:1. Most preferably, this molar ratio is in the range of between about 2.5:1 and about 10:1 .
The process of this invention is typically performed as follows. The catalyst composition, reaction medium and comonomers are introduced into the reaction vessel, which is typically a pressure vessel made of a non-reactive material such as stainless steel. In order to obtain best results, it is preferred that the alphaolefin be anhydrous and thus it is preferable that such monomer be dried, e.g. by passing it through molecular sieves, prior to its introduction into the reactor. Preferably, . ~ . .
`' ;~' -' ' '' ~ ' the water content in the alphaolefin should be no more than ten parts per million by weight.
During such introduction, care should be taken to avoid premixing the promoter with the organoaluminum cocatalyst lest deactivation of the catalyst composition occur.
In a preferred embodiment of the instant invention, hydrogen gas is an added reactant in the polymerization reaction. Hydrogen gas is employed to improve the regulation of the molecular weight of the polymer produced in the reaction. Specifically, lower molecular weights are obtainable when hydrogen gas is utilized. It is emphasized that the use of hydrogen gas as a reactant is not essential.
It is to be understood that the addition of a nitrogen-containing acid scavenger compound is not required in the practice of this invention. However, if desired, small amounts of such compounds may be added to the reaction medium.
In general, the catalyst concentration may range between about l x 10 8 and about 3 x lO 1 mole of vanadium per liter of total reaction medium (i.e. reac-tion medium plus monomer plus catalyst composition).
Preferably, between about l x 10 7 and about 1 x 10 2 mole vanadium per liter of total reaction medium is present. Most pre~erably, between about l x lO 6 and about 5 x 10 3 mole vanadium per liter ~otal reaction medium is employed.
.
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, When the comonomer which is copolymerized with ethylene consists of mono-alphaolefin, the molar ratio in the reactor of ethylene to comonomer is about 3:1 or less. More preferably, such molar ratio is 1:1 or less, and most preferably such molar ratio is 1:3 or less.
The polymerization reaction of this invention occurs in the liquid state at a temperature in the range of between about -25C and about 70C. More preferably, the temperature range of this reaction is between about -20 and about 50C. Reaction time may vary from several minutes or less to several hours or more depending on factors such as reaction batch size, reac~ion tempera-ture, the particular reactants selected, and other similar factors. If desired, the reaction may be moni-tored by sampling or by reaction mixture solids measure-ment.
The reaction product is typically isolated by floccing, decantation or filtering.
The polymer produced by the process of this invention will frequently possess a vanadium concentration which is low enough that washing of the product to reduce the vanadium levels therein so as to avoid degeneration thereof is typically not necessary.
Moreover, the polymer produced by the process of this invention is generally essentially gel free.
By making adjustments well known to those skilled in the art of polymerization, the process of this invention may be operated in a batch or a continuous manner.
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E~A~PLES
The following Examples are intended to further illus~rate the invention and are not intended to limit the scope of the invention in any manner.
Preparation of Butyl 4,4,4-trichlorobut-2-enoate (BTCB).
128 grams (1 mole) of freshly distilled butyl acrylate was reacted with 300 ml of carbon tetrachloride in the presence of 1.92 grams (2 millimoles) of dichloro-tris[triphenylphosphine]ruthenium, under nitrogen, in a three necked (1 liter round bottom) flask, equipped with a condenser, an overhead mechanical stirrer and a thermo-meter. The reaction mixture was heated to reflux (80C) for about 1 hour, at which time the mi~ture turned brownish in color. The mixture was cooled to room temperature, and excess CC14 was removed using a rotary evaporator. The catalyst was precipitated by addition of n-heptane which was separated by decantation from the remaining supernatant brown viscous material. The brown ~0 viscous reaction product (n-butyl-2,4,4,4-tetrachloro-butyrate) was isolated by evaporation of the n-heptane (using a rotary evaporator). It weighed 275 grams (97%
yield).
Infrared analysis (IR) of the product did not show an absorption attributable to vinylic type unsaturation indicating the absence of an acrylic double bond. After distillation, at 95-100C and 0.5 mm Hgy the reaction product was a clear, colorless oil.
',', . : ' ' ' ' ' .
One mole (289 grams) of butyl 2,4,4,4-tetrachloro-butyrate (produced as described above), triethylamine (138 ml, 1 mole) and benzene (500 ml) were placed in a three-necked round bottom 2-liter flask equipped with an overhead mechanical stirrer, a condenser and a thermo-meter. This reaction mixture was heated at reflux (80C) ~o-- 50 hours. After adding an additional 30 ml (0.2 mole) of triethylamine reflux was continued for another 2~ hours.
After ~his total of 70 hours at reflux, a dark brownish material was obtained. The reaction product was filtered. The solid (C2H5)3NHCl salt was removed leaving a solution from which the benzene solvent was removed by a rotary evaporator. The resultant dark brown viscous material ~234 grams, 95% yield) was distilled ~72-74C at 0.3 mm Hg). The product, butyl 4,4,4-trichlorobut-2-enoate (82% trans) was a colorless, clear viscous oil (90% yield). The elemental analysis for this compound appears in Table I. The nuclear magnetic 2~ resonance (NMR) spectral (lH and 13C) data, which appear in Table II, were consistent with this compound.
lABLE I
Elemental Analysis Calculated % Found D
C H Cl C H Cl . . .
39.134.52 ~l3.32 39.10 4.44 43.32 - - ' -' - ' ' , ~ .
~7~ 7 TABLE II
N.~l.R. SPECTROSCOPY DATA*
~, ._ . _ (in parts per million) H - NMR
. . . _ . . _ . . . _ 0.97 (t,3H), 1.42 (m, 2H), 1.68 (m, 2H) 4.2 (t,2H), 6.39 (d, lH), 7.20 (d, lH) CIS (J = 9 HZ) TRANS
(J = 15 HZ) 13.58, 19.04, 530.53, 65.32, 92.17, 121.73, 145.97 ! 164.63 * In the above Table the following abbreviations have the following meanings:
s - singlet d - doublet t - triplet m - multiplee ~
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Pre~ ration of EPDM
Seven thousand grams of liquid propylene were added to a dry 5-gallon stainless steel jacketed reactor provided with a stirrer. The propylene was charged into the reactor while a cooling medium flowed in the jacketed portion of the reactor. After 1.75 moles of hydrogen had been charged into the reactor, ethylene was added until a pressure of about 110 psig was recorded. This pressure was maintained t~ about 10 psig) for the duration of the polymerization . To this was added 3.5 millimoles of ethyl aluminum sesquichloride (EASC) and isopentane (120 ml). Stirring was initiated upon addition of the EASC at 175 rpm. With the temperature in the reactor set at -8C, cooling was discontinued and a solution com-prising 0.873 millimole of vanadium oxytrichloride (VOC13~, 36 millimoles of 5-ethylidene-2-norbornene (ENB), and 3.5 millimoles of butyl perchlorocrotonate (BPCC) in 280 ml of isopentane was incrementally added to the reaction mass by means of a positive displacement pump. The addition of the solution initiated the reac-tion. After polymerization had been carried out for about 60 minutes, the reaction was terminated by passing the reaction medium which contained the product polymer into an isopropanol solution containing about 0.5 weight percent of an antioxidant composed of a trialkylaryl phosphite and a styrenated para-cresol. The polymer was separated from the reaction medium and analyzed.
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In Examples 3 and 4 and in Comparative Experiment A, the process of Example 2 was repeated except that the amounts of catalyst, cocatalyst and promoter were as listed in Table III below.
A summary of Examples 2 - 4 and Comparative Experiment A, including the analysis of the EPDM polymer product, appears in Table III.
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TABLE III
Example No. A _2 3 4 Catalyst VOC13 VOCl VOCl VOCl mmoles .873 .4313 753 08 3 Promoter BPCC BPCC BPCC BPCC
mmoles 3.5 6.9 2.4 5.1 Cocatalyst EASC EASC EASC EASC
equivalent mmoles 23.686.66 6.66 6.66 Pro./Cat. Molar Ratio 4:1 16:1 32:1 64:1 Yield g EPr~i 454 560 208 682 Calculated Results Cat. Eff. g EPDM/g V* 10,200 25,500 54,400 166,700 Vanadium Res., ppm ** 98 39 18 6 EPDM Characteristics Ethylene/Propylene Wt 38:62 43:57 49:51 50:50 Ratio Intrinsic Viscosity (in tetralin at 135C) 5.3 4.46 3.8 1.8 Iodine No. 7.2 5.2 3.2 1.7 * Based upon yield of EPDM.
0 ** Based upon assumption that all vanadium remained in EPDM.
The above results indicate that catalyst efficiency is dramatically increased when BPCC is employed as a catalyst promoter in the process of this invention.
To a 2 liter Parr bomb reactor equipped with a stirrer and cooling jacket were added 500 grams of liquid :. ~ . ,. ', ' ', ' ' ::' ' , - ~ ,- ~ ., .
' .
&`~7 propylene. The propylene was charged into the reactor while a cooling medium flowed through the jacket. The reactor, which had an initial pressure of about 115 psig, was first pressurized to about 135 psig with hydrogen~
and ~hen further pressurized to about 1l~5 psig with ethylene. To this was added 0.74 millimole of ethyl aluminum sesquichloride (EASC) in 20 cc of toluene.
Agitation was begun and a solution comprising 0.0125 millimole of bis-neopentyl chlorovanadate (BNCV), 3.6 ml of 5-ethylidene-2-norbornene (ENB) and 0.1-millimole of butyl 4,4,4-trichlorobut-2-enoate (BTCB) (produced in accordance with the method of Example l) in 25 cc of toluene was incrementally added to the reaction mass.
During the polymerization, the reaction temperature was maintained at about 0C and the reaction pressure at about 165 ~5 psig. After polymerization had been carried out for about 1 hour, the reaction was terminated by the addition of an isopropanol solution containing about 0.5 weight percent of an antioxidant composed of trialkylaryl phosphite and a styrenated para-cresol. The polymer was separated from the reaction medium and analyzed. The results of such analysis are presented in Table IV.
In Example 6, a process similar to that of Example 5 was followed with butyl perchlorocrotonate (BPCC) being 30employed in place of BTCB. The results of Example 6 are also summarized in TabIe IV.
TABLE IV
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Example No. 5 6 -Catalyst BNCV BNCV
~moles O.0125 0.0125 Prcmoter BTCB BPCC
nmoles 0.1 0.1 Cocatalyst EASC EASC
equivalent mmoles 0.74 0.74 Pro./Cat. Molar Ratio8/1 8/1 Yield g EPDM 91.6 87.6 Calculated Results Cat. Eff. g E~l/g V*143,700 137,700 Vanadium Res., ppm **7.0 7.3 EPDMlCharacteristics Ethylene/Propylene Wt Ratio 62/38 54/46 Intrinsic Viscosity (in tetralin at 135C)1.89 2.02 Iodine No. 3.1 2.9 * Based upon yield of EPDM.
** Based upon assumption that all vanadium remained in EPDM.
The above results show that additional promoters, such as BTCB, will perform admirably when employed in the process of this invention.
Preparation of EPDM
FolIowing a procedure essentially similar to that of Examples 2-4 and Comparative Experiment A respectively, EPDM is produced employing butyl 4,4,4-trichlorobut-2-~: .
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enoate (BTCB) which is produced in accordance with the procedure in Example 1. It is seen that the catalyst efficiency is greater when the molar ratio of catalyst promoter (BTCB) to vanadium exceeds 6:1.
Examples 10 - 13 Synthesis of EPDM
A ten-gallon jacketed reactor provided with a radial turbine was cleaned and dried. With the radial turbine lQ operated at 250 rpm, 12,120 grams of n-pentane, 4,040 grams of liquid propylene, 70 milliliters of 5-ethyli-dene-2-norbornene (ENB), 147 milliliters of a solution which comprised 71.9 mmoles of diethyl aluminum chloride ~DEAC) in n-pentane, 210 grams of ethylene gas and 2 moles (4 grams) of hydrogen gas were added to the reactor.
With the reactor contents maintained at 25C, a catalyst solution was added to the reaction medium. The catalyst solution comprised 29 milliliters of 0.025 ~l VOC13, 46.5 milliliters of 0.5 M BPCC, 100 milliliters of ENB, and 281 milliliters of n-pentane. This catalyst solution was initially added at a rate of 3.4 ml/min.
However, as the run continued, the rate of addition of catalyst was reduced. The run was conducted for 38 minutes during which time 76.5 milliliters of catalyst solution was added to the reactor.
The reaction was terminated by passing the reaction m~dium into an lsopr~panol solutlon containing about 0.S
:
, . ' -- . . . : , weight percent of an antioxidant composed of a trialkyl-aryl phosphite and a styrenated para-cresol. The EPDM
polymer produced by this reaction was separated, dried, weighed and analyzed.
In Examples 11 - 13 other runs were conducted as described in Example 10 except that the relative ratios of n-pentane and liquid propylene were altered as shown in Table V. The analyses of the polymers produced are also provided in Table V.
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TABLE V
Example No. 10 11 12 13 -Catalyst VOC13 VOC13 VOC13 VOC13 mmoles .177 .144 .227 .270 Promoter BPCC BPCC BPCC BPCC
mmoles 3.74 4.60 7.26 8.64 Coca~alyst DEAC DEAC DEAC DEAC
mmoles 71.9 71.9 66.0 71.9 Molar Ratio Pro./Cat. 32:1 32:1 32:1 32:1 Reaction Medium, wt. ~ n-Pentane 75 60 55 40 wt. % Propylene 25 40 45 60 Yield, grams 2,026 1,804 1,866 2,242 Calculated_Results Catalyst Eff.*
g EPDM/g V 338,800 246,300 161,600 163~300 V residue in Polymer, ppm** 3 4 6 6 EPDM Analysis Intrinsic Viscosity (in tetralin at 135C) 1.85 2.1 2.3 3.2 Iodine No. 7.8 6.8 9.5 5.0 * Based on yield of EPDM
** Based on assumption that all vanadium is in the polymer.
The above results indicate that high catalyst efficiencies are achieved and polymers having low vana-dium residues are produced employing the process of this invention.
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Claims (36)
1. A process for the production of a copolymer of ethylene with at least one comonomer selected from the group consisting of copolymerizable mono-alphaolefins and nonconjugated polyenes, which process comprises reacting ethylene with said at least one comonomer in a liquid aliphatic hydrocarbon reaction medium comprising a liquid alphaolefin in the presence of a catalyst composition comprising:
(a) a vanadium-containing compound;
(b) an organoaluminum compound; and (c) a promoter having the structure:
wherein:
n is 1, 2, 3 or 4;
X, X1 and X2 are halogen;
A is oxygen, sulfur or halogen;
R1 is hydrogen; halogen; C1-C16 alkyl; or -COOR4 wherein R4 is C1-C18 alkyl, C3-C18 alkenyl, C5-C6 cycloalkyl, C7-C9 aralkyl or C6-C10aryl;
R2 is hydrogen, halogen or C1-C16 alkyl;
with the provisos that:
when n is 1 and A is halogen, there is no R3;
when n is 1 and A is oxygen or sulfur, R3 is hydrogen, C1-C18 alkyl, C6-C10 aryl, C7-C9 alkylaryl, C7-C9 arylalkyl, C3-C6 alkenyl, C1-C18 haloalkyl, C6-C10 haloaryl, C7-C9 haloalkylaryl or C7-Cg haloarylalkyl;
when n is 2, A is oxygen or sulfur, and R3 is C2-C12 alkylene, C4-C6 oxydialkylene, or C4-C6 thiodial-kylene; and when n is 3 or 4, A is oxygen or sulfur, and R3 is a Cn-C12 alkyl radical having the valence n;
wherein the molar ratio of said promoter to the vanadium in said vanadium-containing compound is about 6:1 or greater;
with the proviso that when said comonomer consists of mono-alphaolefin, the molar ratio in the reactor of ethylene to comonomer is about 3:1 or less.
(a) a vanadium-containing compound;
(b) an organoaluminum compound; and (c) a promoter having the structure:
wherein:
n is 1, 2, 3 or 4;
X, X1 and X2 are halogen;
A is oxygen, sulfur or halogen;
R1 is hydrogen; halogen; C1-C16 alkyl; or -COOR4 wherein R4 is C1-C18 alkyl, C3-C18 alkenyl, C5-C6 cycloalkyl, C7-C9 aralkyl or C6-C10aryl;
R2 is hydrogen, halogen or C1-C16 alkyl;
with the provisos that:
when n is 1 and A is halogen, there is no R3;
when n is 1 and A is oxygen or sulfur, R3 is hydrogen, C1-C18 alkyl, C6-C10 aryl, C7-C9 alkylaryl, C7-C9 arylalkyl, C3-C6 alkenyl, C1-C18 haloalkyl, C6-C10 haloaryl, C7-C9 haloalkylaryl or C7-Cg haloarylalkyl;
when n is 2, A is oxygen or sulfur, and R3 is C2-C12 alkylene, C4-C6 oxydialkylene, or C4-C6 thiodial-kylene; and when n is 3 or 4, A is oxygen or sulfur, and R3 is a Cn-C12 alkyl radical having the valence n;
wherein the molar ratio of said promoter to the vanadium in said vanadium-containing compound is about 6:1 or greater;
with the proviso that when said comonomer consists of mono-alphaolefin, the molar ratio in the reactor of ethylene to comonomer is about 3:1 or less.
2. The process of claim 1 wherein the molar ratio of promoter to vanadium is between about 6:1 and about 150:1.
3. The process of claim 2 wherein the molar ratio of promoter to vanadium is between about 8:1 and about 120:1.
4. The process of claim 3 wherein the molar ratio of promoter to vanadium is between about 12:1 and about 100:1.
5. The process of claim 4 wherein the molar ratio of promoter to vanadium is between about 24:1 and about 80:1.
6. The process of claim 1 wherein the liquid aliphatic hydrocarbon reaction medium comprises pro-pylene.
7. The process of claim 1 wherein the liquid aliphatic hydrocarbon reaction medium comprises a liquid alphaolefin and a C3-C10 aliphatic hydrocarbon which is inert to the polymerization reaction.
8. The process of claim 7 wherein the liquid alphaolefin comprises propylene.
9. The process of claim 8 wherein the liquid aliphatic hydrocarbon reaction medium is comprised of between about 20 and about 80 weight percent propylene.
10, The process o claim 9 wherein the liquid aliphatic hydrocarbon reaction medium comprises between about 25 and about 60 weight percent propylene.
11. The process of claim 1 wherein ethylene is copolymerized with at least one copolymerizable mono-alphaolefin and at least one nonconjugated polyene.
12. The process of claim 11 wherein said copolymerizable mono-alphaolefin comprises at least one member selected from the group consisting of propylene, 1-butene, 1-pentene, 1-hexene, 3-methyl-1-pentene, 1-heptene, 1-octene and 1-decene.
13. The process of claim 12 wherein said copolymerizable mono-alphaolefin is propylene.
14. The process of claim 13 wherein the nonconjugated polyene comprises at least one member selected from the group consisting of 5-ethylidene-2-norbornene, 1,4-hexadiene and dicyclopentadiene.
15. The process of claim 1 wherein hydrogen gas is an added reactant.
16. The process of claim 1 wherein the promoter possesses a structure wherein:
n is 1 or 2;
X, X1 and X2 are chlorine;
A is oxygen;
R1 is hydrogen, chlorine, C1-C8 alkyl, or COOR4 wherein R4 is C1-C8 alkyl, cycloalkyl, benzyl or phenyl;
R2 is hydrogen, chlorlne or C1-C8 alkyl;
with the provisos that:
when n is 1, R3 is C1-C12 alkyl, phenyl, tolyl, benzyl, allyl, C1-C2 haloalkyl or halophenyl and when n is 2, R3 is C2-C6 alkylene, oxydiethylene or thiodiethylene.
n is 1 or 2;
X, X1 and X2 are chlorine;
A is oxygen;
R1 is hydrogen, chlorine, C1-C8 alkyl, or COOR4 wherein R4 is C1-C8 alkyl, cycloalkyl, benzyl or phenyl;
R2 is hydrogen, chlorlne or C1-C8 alkyl;
with the provisos that:
when n is 1, R3 is C1-C12 alkyl, phenyl, tolyl, benzyl, allyl, C1-C2 haloalkyl or halophenyl and when n is 2, R3 is C2-C6 alkylene, oxydiethylene or thiodiethylene.
17. The process of claim 1 wherein the promoter is selected from the group consisting of butyl 4,4,4-tri-chlorobut-2-enoate, methyl 2-methyl-4,4,4-trichlorobut-2-enoate, ethyl 4,4,4-trichlorobut-2-enoate, 2-ethylhexyl 4,4,4-trichlorobut-2-enoate and butyl perchlorocrotonate.
18. The process of claim 17 wherein the promoter is butyl 4,4,4-trichlorobut-2-enoate.
19. The process of claim 17 wherein the promoter is butyl perchlorocrotonate.
20. The process of claim 1 wherein between about 1 x 10-8 and about 3 x 10-1 mole of vanadium per liter of total reaction medium is present.
21. The process of claim 20 wherein between about 1 x 10-7 and 1 x 10-2 mole of vanadlum per liter of total reaction medium is present.
22. The process of claim 21 wherein between about 1 x 10-6 and 5 x 10-3 mole of vanadium per liter of total reaction medium is present.
23. A process for the production of a copolymer of ethylene with at least one comonomer selected from the group consisting of (i) at least one copolymerizable monoalphaolefin selected from the group consisting of propylene, 1-butene and 1-pentene; and (ii) at least one nonconjugated polyene selected from the group consisting of 5-ethylidene-2-norbornene, dicyclopentadiene and 1,4-hexadiene;
in a liquid aliphatic hydrocarbon reaction medium comprising at least one liquid alphaolefin selected from the group consisting of propylene, 1-butene and 1-pentene;
in the presence of a catalyst composition comprising:
(a) a vanadium-containing compound;
(b) an organoaluminum compound; and (c) a promoter selected from the group consisting of butyl 4,4,4-trichlorobut-2-enoate, methyl 2-methyl-4,4,4-trichlorobut-2-enoate, ethyl 4,4,4-trichlorobut-2-enoate, 2-ethylhexyl 4,4,4-trichlorobut-2-enoate and butyl perchlorocrotonate;
wherein the molar ratio of said promoter to the vanadium in said vanadium-containing compound is about 6:1 or greater;
with the proviso that when said comonomer consists of a monoalphaolefin, the molar ratio in the reactor of ethylene to comonomer is about 3:1 or less.
in a liquid aliphatic hydrocarbon reaction medium comprising at least one liquid alphaolefin selected from the group consisting of propylene, 1-butene and 1-pentene;
in the presence of a catalyst composition comprising:
(a) a vanadium-containing compound;
(b) an organoaluminum compound; and (c) a promoter selected from the group consisting of butyl 4,4,4-trichlorobut-2-enoate, methyl 2-methyl-4,4,4-trichlorobut-2-enoate, ethyl 4,4,4-trichlorobut-2-enoate, 2-ethylhexyl 4,4,4-trichlorobut-2-enoate and butyl perchlorocrotonate;
wherein the molar ratio of said promoter to the vanadium in said vanadium-containing compound is about 6:1 or greater;
with the proviso that when said comonomer consists of a monoalphaolefin, the molar ratio in the reactor of ethylene to comonomer is about 3:1 or less.
24. The process of claim 23 wherein the molar ratio of promoter to vanadium is between about 6:1 and about 150:1.
25, The process of claim 24 wherein the molar ratio of promoter to vanadium is between about 8:1 and about 120:1.
26. The process of claim 25 wherein the molar ratio of promoter to vanadium is between about 12:1 and about 100:1.
27. The process of claim 26 wherein the molar ratio of promoter to vanadium is between about 24:1 and about 80:1.
28. The process of claim 23 wherein the liquid alphaolefin comprises propylene.
29. The process of claim 23 wherein ethylene is copolymerized with at least one copolymerizable mono-alphaolefin and at least one nonconjugated polyene.
30. The process of claim 29 wherein said copolymerizable mono-alphaolefin is propylene.
31. The process of claim 23 wherein hydrogen gas is an added reactant.
32. The process of claim 23 wherein the promoter is butyl 4,4,4-trichlorobut-2-enoate.
33. The process of claim 23 wherein the promoter is butyl perchlorocrotonate.
34. The process of claim 23 wherein between about 1 x 10-8 and about 3 x 10-1 mole of vanadium per liter of total reaction medium is present.
35. The process of claim 34 wherein between about 1 x 10-7 and 1 x 10-2 mole of vanadium per liter of total reaction medium is present.
36. The process of claim 35 wherein between about 1 x 10-6 and 5 x 10-3 mole of vanadium per liter of total reaction medium is present.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US75084185A | 1985-07-01 | 1985-07-01 | |
| US750,841 | 1985-07-01 |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0680976A1 (en) * | 1994-05-05 | 1995-11-08 | Hüls Aktiengesellschaft | Process for producing ethylene copolymers |
| US6180554B1 (en) | 1998-06-24 | 2001-01-30 | Bayer Aktiengesellschaft | Catalyst system for the production of olefin (co)polymers |
| CN112725054A (en) * | 2019-10-28 | 2021-04-30 | 南京中科康润新材料科技有限公司 | Process method for directly synthesizing high-performance high-viscosity base oil by polymerizing low-carbon olefins |
-
1986
- 1986-06-03 CA CA000510667A patent/CA1272847A/en not_active Expired - Fee Related
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0680976A1 (en) * | 1994-05-05 | 1995-11-08 | Hüls Aktiengesellschaft | Process for producing ethylene copolymers |
| US5502125A (en) * | 1994-05-05 | 1996-03-26 | Huels Aktiengesellschaft | Process for preparing ethylene copolymers |
| US6180554B1 (en) | 1998-06-24 | 2001-01-30 | Bayer Aktiengesellschaft | Catalyst system for the production of olefin (co)polymers |
| CN112725054A (en) * | 2019-10-28 | 2021-04-30 | 南京中科康润新材料科技有限公司 | Process method for directly synthesizing high-performance high-viscosity base oil by polymerizing low-carbon olefins |
| CN112725054B (en) * | 2019-10-28 | 2023-10-20 | 南京中科康润新材料科技有限公司 | Process method for directly synthesizing high-performance high-viscosity base oil by polymerization of low-carbon olefin |
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