CA1042008A - Nickel bis-diorgano-orthophosphate catalyst compositions - Google Patents
Nickel bis-diorgano-orthophosphate catalyst compositionsInfo
- Publication number
- CA1042008A CA1042008A CA294,367A CA294367A CA1042008A CA 1042008 A CA1042008 A CA 1042008A CA 294367 A CA294367 A CA 294367A CA 1042008 A CA1042008 A CA 1042008A
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- carbon atoms
- orthophosphate
- catalyst
- diorgano
- nickel bis
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Abstract
Abstract This invention comprises use of nickel bis-diorgano-orthophosphates as catalysts used in conjunction with alkyl aluminum halides, and certain vanadium catalysts to produce high polymers of such monomers are achieved with significant residual aliphatio unsaturation.
Description
104;~00~
Nickel organophosphorus compounds have been used alone and with cocatalysts for the controlled polymerization of olefins as shown, for example, in United States Patent Nos.
3,432,518; 3,655,810 and 3,660,445.
The object of this invention is to provide new catalyst combinations for controlled oligomerization both alone and during high polymerization of olefins with other catalysts.
This invention employs novel compounds of the general formula Ni[OP(O) (R)2]2 in which each R is a non-aromatic hydrocarbon group free of aliphatic unsaturation, i.e. an alkyl or cycloalkyl group, con-taining one to eight, preferably two to four, carbon atoms or a non-aromatic hydrocarbon ether group free of aliphatic unsatur-ation, i.e. an alkoxyalkyl group, containing three to six carbon atoms or a chlorinated or brominated derivative of any of such groups. These compounds are disclosed in the parent application, Canadian Patent Application 213,706, filed Decemb-er 18, 1974.
This invention also comprises a combination catalyst for controlled olefin oligomerization consisting essentially of the reaction product of (A) a nickel bis-diorgano-ortho-phosphate of the general formula Ni[OP tO) (OR)2]2 in which each R is as defined above and (B) an alkyl aluminum halide of the general formula R'cAl Xd in which each R' is an alkyl group of one to six carbon atoms, each X is a halogen atom, preferably chlorine or bromine, each of c and d is 1 or 2 and the total of c and d is 3. The mol ratio of (A) to (B) can range from 1:1 to 1:20 but is preferably in the range of 1:8 to 1:12.
This invention comprises a combination catalyst for olefin polymerization consisting essentially of components (A) and (B) as described above in the ratio range described togeth-~04~0~
er with ~C) a vanadium bis-diorganoorthophosphate of the gener-- al formula V(O)[OP (0) (OR)2~2 in which each R is as defined above, mol ratio of (C) to (B) ranging from 1:4 to 1:10.
This invention further comprises the use of the above-described catalyst combinations in a method for olefin aligomerization or polymerization consisting essentially of (1) mixing the appropriate catalyst combination described above with (D) a mono- or di-olefin which can be any aliphatic, cycloaliphatic or aromatic hydrocarbon containing no more than about 8 carbon atoms, preferably an aliphatic hydrocarbon con-taining no more than about 4 carbon atoms and/or a styrene, either alone or with (E) a hydrocarbon solvent free of aliphat-ic unsaturation, i.e., an alkyl, cycloalkyl or aromatic ; hydrocarbon containing up to 14 carbon atoms, any aromatic hydrocarbon being optionally substituted with up to about four lower alkyl groups or other non-interfering substituents such as, for example, amines, oxygen-free anions of non-metallic in-organic acids such as chlorine atoms and bromine atoms and nitrile groups, at a temperature and pressure and for a time sufficient to cause reaction of (D) and (2) separating the resulting products. The total amount of catalyst combination is present in an amount of from about 0.0001 to 0.01 total mol per mol of (D)~ This system operates spontaneously as an exothermic reaction as soon as the components are mixed.
Generally, the system temperature can range from 0 to 250C., preferably 50 to 150C., and the system pressure can range from 1 to 500 psig., preferably 10 to 100 psig. The desired reaction can take up to 24 hours, but for the aliphatic olefins ; the reaction is generally almost instantaneous and is maintain-ed by a continuous addition of monomer or monomers with or without additional catalyst.
Examples of desired products employed in the present . ,
Nickel organophosphorus compounds have been used alone and with cocatalysts for the controlled polymerization of olefins as shown, for example, in United States Patent Nos.
3,432,518; 3,655,810 and 3,660,445.
The object of this invention is to provide new catalyst combinations for controlled oligomerization both alone and during high polymerization of olefins with other catalysts.
This invention employs novel compounds of the general formula Ni[OP(O) (R)2]2 in which each R is a non-aromatic hydrocarbon group free of aliphatic unsaturation, i.e. an alkyl or cycloalkyl group, con-taining one to eight, preferably two to four, carbon atoms or a non-aromatic hydrocarbon ether group free of aliphatic unsatur-ation, i.e. an alkoxyalkyl group, containing three to six carbon atoms or a chlorinated or brominated derivative of any of such groups. These compounds are disclosed in the parent application, Canadian Patent Application 213,706, filed Decemb-er 18, 1974.
This invention also comprises a combination catalyst for controlled olefin oligomerization consisting essentially of the reaction product of (A) a nickel bis-diorgano-ortho-phosphate of the general formula Ni[OP tO) (OR)2]2 in which each R is as defined above and (B) an alkyl aluminum halide of the general formula R'cAl Xd in which each R' is an alkyl group of one to six carbon atoms, each X is a halogen atom, preferably chlorine or bromine, each of c and d is 1 or 2 and the total of c and d is 3. The mol ratio of (A) to (B) can range from 1:1 to 1:20 but is preferably in the range of 1:8 to 1:12.
This invention comprises a combination catalyst for olefin polymerization consisting essentially of components (A) and (B) as described above in the ratio range described togeth-~04~0~
er with ~C) a vanadium bis-diorganoorthophosphate of the gener-- al formula V(O)[OP (0) (OR)2~2 in which each R is as defined above, mol ratio of (C) to (B) ranging from 1:4 to 1:10.
This invention further comprises the use of the above-described catalyst combinations in a method for olefin aligomerization or polymerization consisting essentially of (1) mixing the appropriate catalyst combination described above with (D) a mono- or di-olefin which can be any aliphatic, cycloaliphatic or aromatic hydrocarbon containing no more than about 8 carbon atoms, preferably an aliphatic hydrocarbon con-taining no more than about 4 carbon atoms and/or a styrene, either alone or with (E) a hydrocarbon solvent free of aliphat-ic unsaturation, i.e., an alkyl, cycloalkyl or aromatic ; hydrocarbon containing up to 14 carbon atoms, any aromatic hydrocarbon being optionally substituted with up to about four lower alkyl groups or other non-interfering substituents such as, for example, amines, oxygen-free anions of non-metallic in-organic acids such as chlorine atoms and bromine atoms and nitrile groups, at a temperature and pressure and for a time sufficient to cause reaction of (D) and (2) separating the resulting products. The total amount of catalyst combination is present in an amount of from about 0.0001 to 0.01 total mol per mol of (D)~ This system operates spontaneously as an exothermic reaction as soon as the components are mixed.
Generally, the system temperature can range from 0 to 250C., preferably 50 to 150C., and the system pressure can range from 1 to 500 psig., preferably 10 to 100 psig. The desired reaction can take up to 24 hours, but for the aliphatic olefins ; the reaction is generally almost instantaneous and is maintain-ed by a continuous addition of monomer or monomers with or without additional catalyst.
Examples of desired products employed in the present . ,
- 2 -.
.
. . . .. . .
lQ~;~OOi invention include:
Nickel bis (dipropyl orthophosphate), nickel bis (di-n-octyl orthophosphate), nickel bis (di-4,4-dimethylhexyl orthophosphate), nickel bis (di-2-ethylhexyl orthophosphate), nickel bis (diethyl orthophosphate), nickel bis (diisobutyl or-thophosphate), nickel bis (monobutyl mono-tert-butyl ortho-phosphate), nickel bis (monopentyl mono-2-methylpentyl ortho-phosphate), nickel bis (di-3-methylhexyl orthophosphate), nickel bis (mono-2-ethyl-hexyl mono-3-methylhexyl orthophos-phate), nickel bis (di-2,3-dimethylhexyl orthophosphate), .-nickel bis (dicyclohexyl orthophosphate), nickel bis (dibutyl orthophosphate), nickel mono(diethyl orthophosphate) mono (di-isohexyl orthophosphate), nickel bis (di-3,3-dimethylpentyl orthophosphate), nickel mono (monoheptyl monohexyl orthophos-phate) mono(monoheptyl monooctyl orthophosphate), nickel bis -. (di-2,2,4-trimethylpentyl orthophosphate), nickel bis (di-2--` ethosyethyl orthophosphate), nickel bis (dicyclopentyl orthophosphate), nickel bis (di-2,2-dimethylbutyl orthophosphate), nickel mono(monopropyl monobutyl orthophosphate) mono(monoamyl monohexyl orthophosphate), nick-el bis (dicyclohexyl orthophosphate), nickel bis (dicyclobutyl orthophosphate), nickel bis (di-3-chloropropyl orthophosphate), nickel bis (bis-2,3-dibromopropyl - orthophosphate) and nickel bis (di-2-chloroethyl orthophosphate).
The alkyl aluminum halides employed are primarily the compounds R' Al X2, R'2 Al X and mixtures thereof including the mixtures of the formula R'3A12X3 usually referred to as the sesquihalides. Each R' can be, for example, a methyl, ethyl, propyl, iso-propyl, n-butyl, sec-butyl, tert-butyl, pentyl or hexyl group. Each X can be fluorine, chlorine, bromine or iodine. Examples of suitable alkyl aluminum halides include .
:
.
.
., ~a~oos diethylaluminum chloride, n-butylaluminum dibromide, ethyl aluminum sesquichloride, methyl aluminum sesquichloride, ethyl aluminum sesquibromide, ethyl aluminum sesquifluoride and the like.
The catalyst combination of (A) and (B) is further augmented with an additional cocatalyst (C) one or more vana-dium bis-diorgano-orthophosphates of the formula V(0) OP (0) (OR)2 2 as described above. Examples of such compounds (C) correspond directly to the examples of the corresponding nickel compounds set forth above except that a vanadium atom with an oxygen atom is substituted for the nickel atom in each compound. Such catalyst combinations of (A), (B) and (C) combine the oligomerizing properties of the novel nickel compounds with the known high polymerization properties of the , .
vanadium compound. When component (C) is included, it should be present in a mol ratio to component (B) in the range of 1:4 to 1:10.
The catalyst composition of (A), (B) and (C) are sim-ply prepared by mixing the components. The components can be mixed prior to addition to the polymerization reaction system or can be added simultaneously or separately to such reaction system. The desired reaction generally takes place immediately, but in any case it is known that the desired reac-tion takes place in no more than two hours.
The combination catalyst system is used in the method comprising (1) mixing the appropriate combination catalyst des-cribed above with (D) one or more mono- or di-olefins which can be any aliphatic, cycloaliphatic or aromatic hydrocarbons containing no more than about 8 carbon atoms, preferably styrene, and/or one or more aliphatic hydrocarbons containing ; no more than about 4 carbon atoms, alone or with (E) a hydrocar-bon solvent free of aliphatic unsaturation selected from the -:
- ~
-- . ;: . . '~
. . .
.. . -~Q4~00~ -class aromatic hydrocarbon being optionally substituted with up to about four lower alkyl groups or other non-interfering substituents such as amines, anions of non-metallic inorganic acids and nitrile groups, at a temperature and pressure and for a time sufficient to cause the reaction of (D) and (2) separat-ing the resulting product.
Examples of suitable olefins (D) include ethylene, propylene, isobutylene, butene-l, cis-butene-2, trans-butene-2, pentene-l, hexene-l, cyclopentene, cyclohexene, cyclo-heptene, 4-methylcyclooctene, 2-methylbutene-1, styrene, buta-diene, isoprene, 3-vinylcyclohexene and the acyclic and cyclic terpenes. Substitution or inclusion of non-interfering groups . " ~ .
as in acrylonitrile, methyl vinyl ether, vinyl chloride and chloroprene is not intended to put such olefins outside the scope of suitable olefins (D). The preferred olefins are styrene and aliphatic olefins of 2 to 4 carbon atoms.
For these polymerization reactions the reacting mono-mer or monomers may act as a solvent for the system.
Alternatively, an inert solvent (E) can be employed. While ` 20 simple paraffin oils, cycloaliphatic hydrocarbons and aromatic - hydrocarbons can be used, the halogeno-alkanes are preferred, particularly methylene chloride, chloroform, carbon tetrachlo-ride and ethylene chloride.
The mol ratio of total catalysts to (D) can be as little as 0.0001:1 as taught in the prior art but preferably ` ranges from 0.001:1 to 0.01 to 1.
For the polymerization of olefins (D) no solvent com-ponent (E) need be present, but a small amount of component (E) may accelerate the polymerization reaction. In such cases the mol ratio of (E) to (D) should be less than 0.01:1, preferably no more than about 0.001:1.
The temperatures required for polymerization reac-104200E~
tions with the catalyst combinations of this invention are not particularly critical with the catalyst combinations of this invention. Some heat may be necessary to initiate reaction such as heating to at least 30C. The maximum temperature which can be employed is dependent on the melting points, boil-ing points and decomposition points of the catalytic components, the reaction component (D) and the products as well - as the desired control over rate of reaction. For practical purposes, the maximum temperature is about 200C. and the pre-ferred temperature range is 40C to 100C.
Ambient pressures are satisfactory generally ranging from atmospheric pressure to no more than about 50 atmospheres, preferably no more than 100 psig.
Under these conditions of temperature and pressure the polymerization reactions can be operated batchwise for from five minutes to four hours or more or these reactions can be run continually. The separation of the desired product is well within the skill of the art being primarily a problem of fractional distillation.
Typically, for polymerization a reaction vessel is purged with some monomer (D) if gaseous or an inert gas such as nitrogen. Then enough of the alkyl aluminum halide (B) is added to dry the vessel. An inert solvent such as heptane may be added. The desired amount of components (A) and (B) and (C), if any, are added, preferably in (A) to (B) mol ratios of 1:8 to 1:12 and (B) to (C) mol ratios of 4:1 to 10:1, with monomer (D) at ambient pressure at a sufficient rate to allow continuous reaction but not at such an excessive rate as to kill the reaction. The product is then distilled off if oligomer or extracted if high polymer. Although prior addition of cocatalyst (B) favors rapid initiation and more rapid reaction of monomer (D) in the presence of the initial excess of this ;
``.' 10~00~
component (B), concurrent addition of (B) with (A), with or without (C), favors formation of higher molecular weight oligo-mer products. Generally, this latter method is preferred for the catalyst combination of (A), (B) and (C).
The following example is illustrative of the best presently-known methods of practising this invention and are - not intended to limit this invention the scope of which is delineated in the appended claims. Unless otherwise stated, all quantitative measurements are by weight.
Example Gopolymerization of Ethylene and Propyl-e-ne A stirred two liter autoclave with controlled cooling coils was purged and then pressurized to 30 psig with ethylene gas. Hydrogen gas was then ~dded until the pressure rose to 34 psig. Subsequently, 1300 ml. of dry, pure n-heptane was added - followed by 320 ml. of liquid propylene. A reservoir containing an equimolar mixture of ethylene and propylene was coupled to the autoclave, and the mixture was introduced at a rate sufficient to maintain a pressure of 60 psig throughout - 20 the copolymerization reaction to give a total of 3.5 moles of .
: monomer.
A combination catalyst was prepared by dissolving 0.31 gram of vanadium bis-diethylorthophosphate (0.00083 mole) and 0.19 gram of nickel bis-dibutylorthophosphate (0.00040 - mole) in 30 ml. of benzene. The cocatalyst was 2.4 grams of ethyl aluminum sesquichloride (0.020 mole as calculated above) dissolved in 30 ml. of n-heptane.
The combination catalyst and cocatalyst solutions were added concurrently and continuously to the reaction mixture for a period of 80 minutes after initiation, the temperatures being maintained in the range of 20 to 30C. Upon completion of the reaction and removal of solvent 123 grams of .-.
.'"' ~' ;` 104;~0~
clear polymer gum product was isolated.
The above preparation was then repeated omitting the nickel bis-dibutylorthophosphate to produce another polymer gum product. -Both products were examined and found to be ethylene-... ~;
propylene copolymers. However, the proton magnetic resonance (60 Mhz NMR) spectra of the products showed that the first product contained olefinic bond structures which were absent in the second polymer product. This finding was verified by the - 10 infrared spectra of cast films of the products, the first product having significant absorption around 900 cm. -1. Vap-or bromination of the film of nickel-catalyzed polymer appreci-, ably increased absorption around 1600 cm. 1, indicating ., .
bromine replacement of the olefinic hydrogens without anysignificant saturation of the olefinic bond structures.
Oxidation of the films on glass in air at 200F. for several hours resulted in curing of the nickel-catalyzed film ; to less gummy texture than the other polymer. Adhesion of the .
nickel catalyzed polymer to glass was appreciably greater than the other polymer.
' , .
" ' ~''' ' .
:. :
'', .
.. ~
': :
.
. . . .. . .
lQ~;~OOi invention include:
Nickel bis (dipropyl orthophosphate), nickel bis (di-n-octyl orthophosphate), nickel bis (di-4,4-dimethylhexyl orthophosphate), nickel bis (di-2-ethylhexyl orthophosphate), nickel bis (diethyl orthophosphate), nickel bis (diisobutyl or-thophosphate), nickel bis (monobutyl mono-tert-butyl ortho-phosphate), nickel bis (monopentyl mono-2-methylpentyl ortho-phosphate), nickel bis (di-3-methylhexyl orthophosphate), nickel bis (mono-2-ethyl-hexyl mono-3-methylhexyl orthophos-phate), nickel bis (di-2,3-dimethylhexyl orthophosphate), .-nickel bis (dicyclohexyl orthophosphate), nickel bis (dibutyl orthophosphate), nickel mono(diethyl orthophosphate) mono (di-isohexyl orthophosphate), nickel bis (di-3,3-dimethylpentyl orthophosphate), nickel mono (monoheptyl monohexyl orthophos-phate) mono(monoheptyl monooctyl orthophosphate), nickel bis -. (di-2,2,4-trimethylpentyl orthophosphate), nickel bis (di-2--` ethosyethyl orthophosphate), nickel bis (dicyclopentyl orthophosphate), nickel bis (di-2,2-dimethylbutyl orthophosphate), nickel mono(monopropyl monobutyl orthophosphate) mono(monoamyl monohexyl orthophosphate), nick-el bis (dicyclohexyl orthophosphate), nickel bis (dicyclobutyl orthophosphate), nickel bis (di-3-chloropropyl orthophosphate), nickel bis (bis-2,3-dibromopropyl - orthophosphate) and nickel bis (di-2-chloroethyl orthophosphate).
The alkyl aluminum halides employed are primarily the compounds R' Al X2, R'2 Al X and mixtures thereof including the mixtures of the formula R'3A12X3 usually referred to as the sesquihalides. Each R' can be, for example, a methyl, ethyl, propyl, iso-propyl, n-butyl, sec-butyl, tert-butyl, pentyl or hexyl group. Each X can be fluorine, chlorine, bromine or iodine. Examples of suitable alkyl aluminum halides include .
:
.
.
., ~a~oos diethylaluminum chloride, n-butylaluminum dibromide, ethyl aluminum sesquichloride, methyl aluminum sesquichloride, ethyl aluminum sesquibromide, ethyl aluminum sesquifluoride and the like.
The catalyst combination of (A) and (B) is further augmented with an additional cocatalyst (C) one or more vana-dium bis-diorgano-orthophosphates of the formula V(0) OP (0) (OR)2 2 as described above. Examples of such compounds (C) correspond directly to the examples of the corresponding nickel compounds set forth above except that a vanadium atom with an oxygen atom is substituted for the nickel atom in each compound. Such catalyst combinations of (A), (B) and (C) combine the oligomerizing properties of the novel nickel compounds with the known high polymerization properties of the , .
vanadium compound. When component (C) is included, it should be present in a mol ratio to component (B) in the range of 1:4 to 1:10.
The catalyst composition of (A), (B) and (C) are sim-ply prepared by mixing the components. The components can be mixed prior to addition to the polymerization reaction system or can be added simultaneously or separately to such reaction system. The desired reaction generally takes place immediately, but in any case it is known that the desired reac-tion takes place in no more than two hours.
The combination catalyst system is used in the method comprising (1) mixing the appropriate combination catalyst des-cribed above with (D) one or more mono- or di-olefins which can be any aliphatic, cycloaliphatic or aromatic hydrocarbons containing no more than about 8 carbon atoms, preferably styrene, and/or one or more aliphatic hydrocarbons containing ; no more than about 4 carbon atoms, alone or with (E) a hydrocar-bon solvent free of aliphatic unsaturation selected from the -:
- ~
-- . ;: . . '~
. . .
.. . -~Q4~00~ -class aromatic hydrocarbon being optionally substituted with up to about four lower alkyl groups or other non-interfering substituents such as amines, anions of non-metallic inorganic acids and nitrile groups, at a temperature and pressure and for a time sufficient to cause the reaction of (D) and (2) separat-ing the resulting product.
Examples of suitable olefins (D) include ethylene, propylene, isobutylene, butene-l, cis-butene-2, trans-butene-2, pentene-l, hexene-l, cyclopentene, cyclohexene, cyclo-heptene, 4-methylcyclooctene, 2-methylbutene-1, styrene, buta-diene, isoprene, 3-vinylcyclohexene and the acyclic and cyclic terpenes. Substitution or inclusion of non-interfering groups . " ~ .
as in acrylonitrile, methyl vinyl ether, vinyl chloride and chloroprene is not intended to put such olefins outside the scope of suitable olefins (D). The preferred olefins are styrene and aliphatic olefins of 2 to 4 carbon atoms.
For these polymerization reactions the reacting mono-mer or monomers may act as a solvent for the system.
Alternatively, an inert solvent (E) can be employed. While ` 20 simple paraffin oils, cycloaliphatic hydrocarbons and aromatic - hydrocarbons can be used, the halogeno-alkanes are preferred, particularly methylene chloride, chloroform, carbon tetrachlo-ride and ethylene chloride.
The mol ratio of total catalysts to (D) can be as little as 0.0001:1 as taught in the prior art but preferably ` ranges from 0.001:1 to 0.01 to 1.
For the polymerization of olefins (D) no solvent com-ponent (E) need be present, but a small amount of component (E) may accelerate the polymerization reaction. In such cases the mol ratio of (E) to (D) should be less than 0.01:1, preferably no more than about 0.001:1.
The temperatures required for polymerization reac-104200E~
tions with the catalyst combinations of this invention are not particularly critical with the catalyst combinations of this invention. Some heat may be necessary to initiate reaction such as heating to at least 30C. The maximum temperature which can be employed is dependent on the melting points, boil-ing points and decomposition points of the catalytic components, the reaction component (D) and the products as well - as the desired control over rate of reaction. For practical purposes, the maximum temperature is about 200C. and the pre-ferred temperature range is 40C to 100C.
Ambient pressures are satisfactory generally ranging from atmospheric pressure to no more than about 50 atmospheres, preferably no more than 100 psig.
Under these conditions of temperature and pressure the polymerization reactions can be operated batchwise for from five minutes to four hours or more or these reactions can be run continually. The separation of the desired product is well within the skill of the art being primarily a problem of fractional distillation.
Typically, for polymerization a reaction vessel is purged with some monomer (D) if gaseous or an inert gas such as nitrogen. Then enough of the alkyl aluminum halide (B) is added to dry the vessel. An inert solvent such as heptane may be added. The desired amount of components (A) and (B) and (C), if any, are added, preferably in (A) to (B) mol ratios of 1:8 to 1:12 and (B) to (C) mol ratios of 4:1 to 10:1, with monomer (D) at ambient pressure at a sufficient rate to allow continuous reaction but not at such an excessive rate as to kill the reaction. The product is then distilled off if oligomer or extracted if high polymer. Although prior addition of cocatalyst (B) favors rapid initiation and more rapid reaction of monomer (D) in the presence of the initial excess of this ;
``.' 10~00~
component (B), concurrent addition of (B) with (A), with or without (C), favors formation of higher molecular weight oligo-mer products. Generally, this latter method is preferred for the catalyst combination of (A), (B) and (C).
The following example is illustrative of the best presently-known methods of practising this invention and are - not intended to limit this invention the scope of which is delineated in the appended claims. Unless otherwise stated, all quantitative measurements are by weight.
Example Gopolymerization of Ethylene and Propyl-e-ne A stirred two liter autoclave with controlled cooling coils was purged and then pressurized to 30 psig with ethylene gas. Hydrogen gas was then ~dded until the pressure rose to 34 psig. Subsequently, 1300 ml. of dry, pure n-heptane was added - followed by 320 ml. of liquid propylene. A reservoir containing an equimolar mixture of ethylene and propylene was coupled to the autoclave, and the mixture was introduced at a rate sufficient to maintain a pressure of 60 psig throughout - 20 the copolymerization reaction to give a total of 3.5 moles of .
: monomer.
A combination catalyst was prepared by dissolving 0.31 gram of vanadium bis-diethylorthophosphate (0.00083 mole) and 0.19 gram of nickel bis-dibutylorthophosphate (0.00040 - mole) in 30 ml. of benzene. The cocatalyst was 2.4 grams of ethyl aluminum sesquichloride (0.020 mole as calculated above) dissolved in 30 ml. of n-heptane.
The combination catalyst and cocatalyst solutions were added concurrently and continuously to the reaction mixture for a period of 80 minutes after initiation, the temperatures being maintained in the range of 20 to 30C. Upon completion of the reaction and removal of solvent 123 grams of .-.
.'"' ~' ;` 104;~0~
clear polymer gum product was isolated.
The above preparation was then repeated omitting the nickel bis-dibutylorthophosphate to produce another polymer gum product. -Both products were examined and found to be ethylene-... ~;
propylene copolymers. However, the proton magnetic resonance (60 Mhz NMR) spectra of the products showed that the first product contained olefinic bond structures which were absent in the second polymer product. This finding was verified by the - 10 infrared spectra of cast films of the products, the first product having significant absorption around 900 cm. -1. Vap-or bromination of the film of nickel-catalyzed polymer appreci-, ably increased absorption around 1600 cm. 1, indicating ., .
bromine replacement of the olefinic hydrogens without anysignificant saturation of the olefinic bond structures.
Oxidation of the films on glass in air at 200F. for several hours resulted in curing of the nickel-catalyzed film ; to less gummy texture than the other polymer. Adhesion of the .
nickel catalyzed polymer to glass was appreciably greater than the other polymer.
' , .
" ' ~''' ' .
:. :
'', .
.. ~
': :
Claims (4)
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. A combination catalyst for olefin polymerization consisting essentially of the reaction product of (A) a nickel bis-diorgano-orthophosphate of the general formula Ni[OP (O) (OR)2]2 in which each R is selected from the class consisting of non-aromatic hydrocarbon groups free of aliphatic unsaturation and containing one to eight carbon atoms, non-aromatic hydrocarbon ether groups free of aliphatic un-saturation and containing three to six carbon atoms, and chlor-inated and brominated derivatives thereof, (B) an alkyl alumin-um halide of the general formula R'c Al Xd in which each R' is an alkyl group of one to six carbon atoms, each X is a halogen atom, each of c and d is 1 or 2 and the total of c and d is 3, the mol ratio of (A) to (B) ranging from 1:1 to 1:20 and (C) a vanadium bis-diorgano-orthophosphate of the general formula V
(O) [OP (O) (OR)2]2 in which each R is as defined above, the mol ratio of (C) to (B) ranging from 1:4 to 1:10.
(O) [OP (O) (OR)2]2 in which each R is as defined above, the mol ratio of (C) to (B) ranging from 1:4 to 1:10.
2. A composition in accordance with claim 1 wherein each R is an alkyl group of two to four carbon atoms and each X
is chlorine or bromine.
is chlorine or bromine.
3. A method for olefin polymerization consisting es-sentially of (1) mixing the catalyst of claim 1 with (D) an olefinic hydrocarbon containing no more than about 8 carbon atoms and, optionally, (E) a hydrocarbon solvent free of aliphatic unsaturation and containing up to 14 carbon atoms, any aromatic hydrocarbon being optionally substituted with up to about four non-interfering substituents, the mol ratio of total catalyst to component (D) ranging from 0.0001:1 to 0.01:1, at a temperature and pressure and for a time sufficient to cause reaction of (D) and (2) separating the resulting products.
4. A method in accordance with claim 3 wherein component (D) is selected from the class consisting of ali-phatic hydrocarbons containing two to four carbon atoms and styrene.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US41639073A | 1973-11-16 | 1973-11-16 | |
| CA213,706A CA1037963A (en) | 1973-11-16 | 1974-11-14 | Nickel bis-diorgano-orthophosphates, their preparation and use |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1042008A true CA1042008A (en) | 1978-11-07 |
Family
ID=25667751
Family Applications (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA294,367A Expired CA1042008A (en) | 1973-11-16 | 1978-01-05 | Nickel bis-diorgano-orthophosphate catalyst compositions |
| CA294,366A Expired CA1042009A (en) | 1973-11-16 | 1978-01-05 | Nickel bis-diorgano-orthophosphate catalyst compositions |
Family Applications After (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA294,366A Expired CA1042009A (en) | 1973-11-16 | 1978-01-05 | Nickel bis-diorgano-orthophosphate catalyst compositions |
Country Status (1)
| Country | Link |
|---|---|
| CA (2) | CA1042008A (en) |
-
1978
- 1978-01-05 CA CA294,367A patent/CA1042008A/en not_active Expired
- 1978-01-05 CA CA294,366A patent/CA1042009A/en not_active Expired
Also Published As
| Publication number | Publication date |
|---|---|
| CA1042009A (en) | 1978-11-07 |
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