CA1106543A - Method for polymerizing mono- and diolefine compounds - Google Patents
Method for polymerizing mono- and diolefine compoundsInfo
- Publication number
- CA1106543A CA1106543A CA290,496A CA290496A CA1106543A CA 1106543 A CA1106543 A CA 1106543A CA 290496 A CA290496 A CA 290496A CA 1106543 A CA1106543 A CA 1106543A
- Authority
- CA
- Canada
- Prior art keywords
- mono
- polymerization
- reaction
- pia
- carried out
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F36/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds
- C08F36/02—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds
- C08F36/04—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated
Abstract
ABSTRACT OF THE DISCLOSURE.-Mono-and diolefin compounds can be readily and efficiently polymerized with the aid of a catalyst system having an improved activity; said system being composed by an aluminum alkyl or aluminum hydride derivative associated to a compound of a transition metal and to a polyimino alane (PIA). Such a ternary system has proven to be much more efficient than the usual binary PIA-transition metal binary catalyst systems.
Description
S~3 This invention relates to an improved me-thod for the polymerization and the copolymerization of mono~o:Lefins and diolefins, which method employs a novel catalyst system permitting to obtain a hlgher yields of stereospecific polymers as compared with the known systems., ~t is known to polymerize unsa-turated compounds by means of binary catalysts composed by compounds of transition metals together with aluminum-alkyls or hydrides. More particularlyr the present Assignee is the owner of many patents and patent applications related to the polymerization of such compounds by means of systems based on derivatives of tra~sition metals in union with poly-imino-alanes (PIA).
Among many others, systems have been disclosed which are comprised of TiC14 and compounds resulting from the repetition of unions of the kind (H A1 NR) in which R
is a hydro-carbonaceous radical, compounds which are cha~
racterized by a molecular cage-Iike structure the steric configuration of which is a func-tion of the number of iminic units.
We have now surprisingly found that the addition of aluminum alkyl-, or hydride-, derivatives (A) to the binary system compri5ed of the compound of the transition metal (B) and poly-imino alane (Cl permits to prepare ternary catalysts for the polymerization of mono- and diolefine, which are much more active than the catalysts composed by the couples AB or BC. More particularly, A
is a compound of the formula Al R3_XHx in which R is a hydrocarbonaceous radical and x is a number ranging from 0 ~o 3.
The same Assignee hereof is the owner of the Canadian Patent Application No. 269.333, filed on 7.1.1977 relating to a method for the modification of the PIA, consisting in
Among many others, systems have been disclosed which are comprised of TiC14 and compounds resulting from the repetition of unions of the kind (H A1 NR) in which R
is a hydro-carbonaceous radical, compounds which are cha~
racterized by a molecular cage-Iike structure the steric configuration of which is a func-tion of the number of iminic units.
We have now surprisingly found that the addition of aluminum alkyl-, or hydride-, derivatives (A) to the binary system compri5ed of the compound of the transition metal (B) and poly-imino alane (Cl permits to prepare ternary catalysts for the polymerization of mono- and diolefine, which are much more active than the catalysts composed by the couples AB or BC. More particularly, A
is a compound of the formula Al R3_XHx in which R is a hydrocarbonaceous radical and x is a number ranging from 0 ~o 3.
The same Assignee hereof is the owner of the Canadian Patent Application No. 269.333, filed on 7.1.1977 relating to a method for the modification of the PIA, consisting in
-2- ' ~
causing PIA to react wlth aluminum alkyls with molar ratios between the iminic units ~1-I Al NR) and the aluminum alkyl comprised between l and 3.
The react.ion according to the above ci-ted can be reproduced by -the following pattern:
(H Al NR)n ~ ~ Al R'3 -> ~(R' Al NR)z ~H Al NR)n-Al R3_x Hx (l) (I) wherein n indicates the number of repeating iminic units, R
and R' are hydrocarbonaceous radicals, equal or different from each other, z is equal to the product y~, z varying .
Erom l to n and x having.the above indicated values. Compounds :
are obtained, derived from the parti.al or total replacement of the hydride hydrogens oE the PIA by alkyl groups with retention of the typical cage-like molecular structure, together with hydride derivatives of aluminum having the composition Al R3-x ~x As the quantity of al.uminum alkyl is increased, the reaction is conducive to the formation of derivatives (I) having an increasing number of alkyl radicals bound to aluminum until obtaining PIA derivatives in which all the hydride atoms have been replaced by alkyl radicals.
The use of quantities of (H Al NR)n in excess over the aluminum alkyl in the reaction indicated above encourages the formation of simple hydride derivatives of aluminum, such as AlR2H, AlRH2, AlH3 andt more particularly the hydrogen-richer species.
The interaction of the latter species, or of the aluminum alkyls themselves with PIA moleculaes is responsible for the formation of species which, in union with the transition ~. :
65~3 metal, give rise to catalysts endowed with a stro~yer catalytic activity. This fact, which ulfils the requirements oE the present invention, has been ascertained by us on the basis of the following facts:
1. The results which have been obtained in poly-merization tests of isoprene with the ternary systems indicated above, in comparison.with the binary systems PIA-TiC14 and A1~3-TiCl~, indicate that the improved activity displayed by the tern-ary systems can be attributed to particular interaction compound of PIA with Al R3 or with AlR3 XHx. The results are plotted in FIGURE 1 in which the solid polymer yield is reported on the ordinates as a function of the molar ratio Al/Ti on the abscissae.
IN FIGURE 1 the curves are referred to A-TiC1 AlEt3, B-(H Al N-isoPr)6 ~ Ti C14, and C- ~H Al N-isoPr)6 ~ Al Et3.
The same result has heen obtained in the poly-merization of ethylene wi-th the ternary systems TiC13-PIA-AlR3 as compared with the binary systems TiC13-PIA, and TiC13-AlR3~ The results are tabulated in TABI,E 2.
2. An activating effect due to the replacement of the hydride hydrogens of the PIA by alkyl groups is to be excluded, inasmuch as the totally or partially alkylated PIAs have proven. to be much less active than the starting PIAs, or even inactive in the polymerization of isoprene in union with TiCl~.
causing PIA to react wlth aluminum alkyls with molar ratios between the iminic units ~1-I Al NR) and the aluminum alkyl comprised between l and 3.
The react.ion according to the above ci-ted can be reproduced by -the following pattern:
(H Al NR)n ~ ~ Al R'3 -> ~(R' Al NR)z ~H Al NR)n-Al R3_x Hx (l) (I) wherein n indicates the number of repeating iminic units, R
and R' are hydrocarbonaceous radicals, equal or different from each other, z is equal to the product y~, z varying .
Erom l to n and x having.the above indicated values. Compounds :
are obtained, derived from the parti.al or total replacement of the hydride hydrogens oE the PIA by alkyl groups with retention of the typical cage-like molecular structure, together with hydride derivatives of aluminum having the composition Al R3-x ~x As the quantity of al.uminum alkyl is increased, the reaction is conducive to the formation of derivatives (I) having an increasing number of alkyl radicals bound to aluminum until obtaining PIA derivatives in which all the hydride atoms have been replaced by alkyl radicals.
The use of quantities of (H Al NR)n in excess over the aluminum alkyl in the reaction indicated above encourages the formation of simple hydride derivatives of aluminum, such as AlR2H, AlRH2, AlH3 andt more particularly the hydrogen-richer species.
The interaction of the latter species, or of the aluminum alkyls themselves with PIA moleculaes is responsible for the formation of species which, in union with the transition ~. :
65~3 metal, give rise to catalysts endowed with a stro~yer catalytic activity. This fact, which ulfils the requirements oE the present invention, has been ascertained by us on the basis of the following facts:
1. The results which have been obtained in poly-merization tests of isoprene with the ternary systems indicated above, in comparison.with the binary systems PIA-TiC14 and A1~3-TiCl~, indicate that the improved activity displayed by the tern-ary systems can be attributed to particular interaction compound of PIA with Al R3 or with AlR3 XHx. The results are plotted in FIGURE 1 in which the solid polymer yield is reported on the ordinates as a function of the molar ratio Al/Ti on the abscissae.
IN FIGURE 1 the curves are referred to A-TiC1 AlEt3, B-(H Al N-isoPr)6 ~ Ti C14, and C- ~H Al N-isoPr)6 ~ Al Et3.
The same result has heen obtained in the poly-merization of ethylene wi-th the ternary systems TiC13-PIA-AlR3 as compared with the binary systems TiC13-PIA, and TiC13-AlR3~ The results are tabulated in TABI,E 2.
2. An activating effect due to the replacement of the hydride hydrogens of the PIA by alkyl groups is to be excluded, inasmuch as the totally or partially alkylated PIAs have proven. to be much less active than the starting PIAs, or even inactive in the polymerization of isoprene in union with TiCl~.
3. An improved polymerization activity towards isoprene has been observed, relative to the PIA,
- 4 .~ .
~v~
wi-th products (II) obtained hy subsequent chlorination of PIA and treatment with LiAlH~.
In agreement with the reactions 2 and 3 such treatments correspond to the Eormation o~
complexes of PIA with AlH3.
(H Al NR)6 ~ H Cl C(Cl Al NR) (H Al NR)5 J (2) ~ ( Cl Al Nr) (H Al NR)5 J + Li ~l H4 (H Al NR)6.Al H3+
LiCl 13) (II) FIGUR~ 2 refers to the activity increase as observed for the product IX with respect to the starting PIA: the FIGURE reports the solid polymer yield plot, in ordinates, as a function ~
~ . .
,~, .
oE the A1/Ti ratio ol~the abscissae.
In saicl FIGUR~ 2 tile cur~es are reEerre~, respec-tively, to A - (ll Al N-isoPr)6.AlH3 ~ TiCl~
B - (ll Al N isoPr)6 ~ TiC~4 The polymeriza-tion runs can be carried out at a temperature ranging from -50~ to ~250C and preferably in the range from +10C -to 200C and under a pressure ranging from -the vapor pressure of the monomer when the lat-ter is li~uid, to 200 atmospheres, the interval from 1 to 20 a-tmospheres being preferred, possibly in the presence of a solvent selected from among -the aliphatic, aromatic or cycloaliphatic hydrocarbons.
The interval of -the molar ratio A1/Me (in which Al indicates the sum of the aluminums of the iminic units and of the aluminums of the simple hydride or alkyl derivatives, and Me is the transition metal), which ratio, as is known, has an influence on the polymerization velocity and the yield of solid polymer, can be varied from 0.1 to 500, the preferable interval being varied consistently with -the nature of the monomer which is intended to be polymerized.
Figure 3, wherein the yield oE solid polvmer is reported on the ordinate as a function of khe Al/Ti molar ratio on the abscissa, shows the results ob-tained in the polym-erization of isoprene with a ternary sys-tem (curve A) in compar-ison with a binary systern (curve B).
The present invention will be now further under-tood by reference -to the Eollowing non restrictive examples.
EXAMPLES 1 ~ 15 FIGURE 1, in which the yield of solid polymer, on the ordinates, is plotted as a function oE the ratio A1/Ti (abscissae) comprises the results as obtained with the ternary "'~
system (H Al N-iso-C3H7)6 - Al(C2ll5)3 TiC14, correspondi.ngly, in par-ticular, to the molar ratio Al (C2ll5)3 :_1 (H Al N-iso C3H7)6 ~ 0.02 in comparison with the resul-ts which have ob-tained with binary systems (H Al N-isoC3H7)~ - Ti Cl4, and ( 2 5)3 ~
The polymeriza-tion runs have been carried ou-t according to the following procedure :
A pop bottle which had previously been heated . and cooled under a nitrogen stream is chargecl, the nitrogen atmosphere being maintained, with anhydrous n-hep-tane (mls 90), TiCl4 (0.64 millimol) and then Al(C2H5)3 or PIA, by adding, or not, ~ -------- 7 ~ .
- 5a -~6~43 Al (C2H5)3 in the amount indicated, consistently with the desired Al.lTi ratio. A brown preci.pitate is formed.
The reaction mixture is aged by shaking it for lO
minutes at room temperature and 20 grams of isoprene are added thereto. ~he bottle is sealed and st:irred durlng 2 hours in a thermos-tatic bath at 30C. After that such a time has elapsed, the polymerization is discontinued by adding 20 mls of methanol in which an antioxidant has been dissolved.
, The reaction mixture is poured in an excess of methanol and the solid polymer is dried at 50C under vacuum, and weighed.
The polymer struc-ture is determined by infxared analysis and the intrinsic viscosity at 30C in toluene is measured.
TABLE l reports the structure and the intrinsic viscosity of polyisoprenes as obtained with the abo~e specified ternary catalyst system.
EXAMPLES l6 - 35 FIGURE 2, in which the solid polymer yield is reported on the ordinates as a function of the Al~Ti ratio on the abscissae, comprises the results obtained in the polymeriza-tion of isoprene with the (H Al N-isoC31I7)6. AlH3 - TiCl4 system as compared with those obtained with the (H Al N-.
iSoc3H7)6-Ticl4 system These results confirm the improved activi-ty of the species which result from the complex~forming of (H Al N-iso C3H7)6 with simple alane derivatives.
The compound has been obtained with ~he following procedure. By working in a nitrQgen atmosphere, to a solution of (H Al N-isoC3H7)6 (9-5 millimols) in diethyl ether (60 mls) there is added slowly a solution (mls 13.5) of ~Cl (9.5 milli-mols) in diethyl ether. The reaction corresponds to the average substitution of an atom of hydride hydrogen by a chlorine atom according to the reac-tion pattern ~2) ~see ~L~at6S~3 S. Cucinella et al, JA Organometal. Chem.., 108, 13 (1976).
The product thus ob-~ained ~57.10 3 gram-atoms oE aluminum?, in diethyl ether ~100 mls) has been supplemented by a solution of LiAlH4 (9.5 millimols) in diethyl ether (12 mls).
According to the reaction pat-tern (3) a compound II is formed, which has been separated by evaporating the solution upon separation of LiCl by filteri.ng it off and dried under vacuum (10 3 millimeters oE mercury cluring 8 hours at room temperature~. ~
The chemical analysis indicates for the product which : .
has thus been obtained:
Al : N : HaCt ~ 1 : 0.87 : 1.25 :
The polymerization tests have been carried out according to the procedure of EXAMPLES 1 to 15. Also in the case of the System II-TiC14 the as-obtained polymer has a high .
contents of 1,4-cis and high values oE ~ n J- ~: -. For example, the polymer obtained for an.~l~Ti of 1.15 has the following pro~erties : 1,4-cis : 95.8% i 1,4-tra~s 1.3% ; 1,2-unsaturations : 0% ; 3,4-unsaturations 2.9% ;
~ n J toluene = 5-20-_ FIGURE 3, in wh1ch the yield of solid polymer, ordinates, is reported as a function of the Al/Ti ra-tio, abscissae, comprises the results obtained in the polymerization of isoprene with the ternary system IH Al ~-isoC3H7)6- Al H
~isoC4Hg)2 - TiC14 ~curve A) in comparison with the binary system (H Al N-isoC3H7)6 TiC14 ~curve B).
The polymerization tests have been carried ou-t according to the procedure of Examples 1 to 27. The poly-isoprene which has been obtained with the ternary system hasa high contents of 1,4-cis unsa-turations and high values of . For example, the polymer which has been obtained ~3 wi-th an ~l/Ti = 1.20 has the Eollowin~ proper-ties:
l,4~cis : 95~6~ ' 1,4-trans : 0% ; 1,2 unsat. = 0.5% ;
3,4-unsat. = 3.8~ i total unsaturations O 102 ;
n ~ 30C = ~.6.
toluene A 5 liter autoclave equipped with stirrer, has been dried and deaerated by heating~it under vacuum and Eilled up to ambient pressure with hydrogen and charged b~ siphoning-10 in with 1,6000 mls of anhydrous nor.heptane. The temperature is raised to 90C, whereafter there are charge 300 mls of nor. heptane to which there have been added, in the order given, TiC13 - AlPIA - Al Et3 in the quantities of TiC13
~v~
wi-th products (II) obtained hy subsequent chlorination of PIA and treatment with LiAlH~.
In agreement with the reactions 2 and 3 such treatments correspond to the Eormation o~
complexes of PIA with AlH3.
(H Al NR)6 ~ H Cl C(Cl Al NR) (H Al NR)5 J (2) ~ ( Cl Al Nr) (H Al NR)5 J + Li ~l H4 (H Al NR)6.Al H3+
LiCl 13) (II) FIGUR~ 2 refers to the activity increase as observed for the product IX with respect to the starting PIA: the FIGURE reports the solid polymer yield plot, in ordinates, as a function ~
~ . .
,~, .
oE the A1/Ti ratio ol~the abscissae.
In saicl FIGUR~ 2 tile cur~es are reEerre~, respec-tively, to A - (ll Al N-isoPr)6.AlH3 ~ TiCl~
B - (ll Al N isoPr)6 ~ TiC~4 The polymeriza-tion runs can be carried out at a temperature ranging from -50~ to ~250C and preferably in the range from +10C -to 200C and under a pressure ranging from -the vapor pressure of the monomer when the lat-ter is li~uid, to 200 atmospheres, the interval from 1 to 20 a-tmospheres being preferred, possibly in the presence of a solvent selected from among -the aliphatic, aromatic or cycloaliphatic hydrocarbons.
The interval of -the molar ratio A1/Me (in which Al indicates the sum of the aluminums of the iminic units and of the aluminums of the simple hydride or alkyl derivatives, and Me is the transition metal), which ratio, as is known, has an influence on the polymerization velocity and the yield of solid polymer, can be varied from 0.1 to 500, the preferable interval being varied consistently with -the nature of the monomer which is intended to be polymerized.
Figure 3, wherein the yield oE solid polvmer is reported on the ordinate as a function of khe Al/Ti molar ratio on the abscissa, shows the results ob-tained in the polym-erization of isoprene with a ternary sys-tem (curve A) in compar-ison with a binary systern (curve B).
The present invention will be now further under-tood by reference -to the Eollowing non restrictive examples.
EXAMPLES 1 ~ 15 FIGURE 1, in which the yield of solid polymer, on the ordinates, is plotted as a function oE the ratio A1/Ti (abscissae) comprises the results as obtained with the ternary "'~
system (H Al N-iso-C3H7)6 - Al(C2ll5)3 TiC14, correspondi.ngly, in par-ticular, to the molar ratio Al (C2ll5)3 :_1 (H Al N-iso C3H7)6 ~ 0.02 in comparison with the resul-ts which have ob-tained with binary systems (H Al N-isoC3H7)~ - Ti Cl4, and ( 2 5)3 ~
The polymeriza-tion runs have been carried ou-t according to the following procedure :
A pop bottle which had previously been heated . and cooled under a nitrogen stream is chargecl, the nitrogen atmosphere being maintained, with anhydrous n-hep-tane (mls 90), TiCl4 (0.64 millimol) and then Al(C2H5)3 or PIA, by adding, or not, ~ -------- 7 ~ .
- 5a -~6~43 Al (C2H5)3 in the amount indicated, consistently with the desired Al.lTi ratio. A brown preci.pitate is formed.
The reaction mixture is aged by shaking it for lO
minutes at room temperature and 20 grams of isoprene are added thereto. ~he bottle is sealed and st:irred durlng 2 hours in a thermos-tatic bath at 30C. After that such a time has elapsed, the polymerization is discontinued by adding 20 mls of methanol in which an antioxidant has been dissolved.
, The reaction mixture is poured in an excess of methanol and the solid polymer is dried at 50C under vacuum, and weighed.
The polymer struc-ture is determined by infxared analysis and the intrinsic viscosity at 30C in toluene is measured.
TABLE l reports the structure and the intrinsic viscosity of polyisoprenes as obtained with the abo~e specified ternary catalyst system.
EXAMPLES l6 - 35 FIGURE 2, in which the solid polymer yield is reported on the ordinates as a function of the Al~Ti ratio on the abscissae, comprises the results obtained in the polymeriza-tion of isoprene with the (H Al N-isoC31I7)6. AlH3 - TiCl4 system as compared with those obtained with the (H Al N-.
iSoc3H7)6-Ticl4 system These results confirm the improved activi-ty of the species which result from the complex~forming of (H Al N-iso C3H7)6 with simple alane derivatives.
The compound has been obtained with ~he following procedure. By working in a nitrQgen atmosphere, to a solution of (H Al N-isoC3H7)6 (9-5 millimols) in diethyl ether (60 mls) there is added slowly a solution (mls 13.5) of ~Cl (9.5 milli-mols) in diethyl ether. The reaction corresponds to the average substitution of an atom of hydride hydrogen by a chlorine atom according to the reac-tion pattern ~2) ~see ~L~at6S~3 S. Cucinella et al, JA Organometal. Chem.., 108, 13 (1976).
The product thus ob-~ained ~57.10 3 gram-atoms oE aluminum?, in diethyl ether ~100 mls) has been supplemented by a solution of LiAlH4 (9.5 millimols) in diethyl ether (12 mls).
According to the reaction pat-tern (3) a compound II is formed, which has been separated by evaporating the solution upon separation of LiCl by filteri.ng it off and dried under vacuum (10 3 millimeters oE mercury cluring 8 hours at room temperature~. ~
The chemical analysis indicates for the product which : .
has thus been obtained:
Al : N : HaCt ~ 1 : 0.87 : 1.25 :
The polymerization tests have been carried out according to the procedure of EXAMPLES 1 to 15. Also in the case of the System II-TiC14 the as-obtained polymer has a high .
contents of 1,4-cis and high values oE ~ n J- ~: -. For example, the polymer obtained for an.~l~Ti of 1.15 has the following pro~erties : 1,4-cis : 95.8% i 1,4-tra~s 1.3% ; 1,2-unsaturations : 0% ; 3,4-unsaturations 2.9% ;
~ n J toluene = 5-20-_ FIGURE 3, in wh1ch the yield of solid polymer, ordinates, is reported as a function of the Al/Ti ra-tio, abscissae, comprises the results obtained in the polymerization of isoprene with the ternary system IH Al ~-isoC3H7)6- Al H
~isoC4Hg)2 - TiC14 ~curve A) in comparison with the binary system (H Al N-isoC3H7)6 TiC14 ~curve B).
The polymerization tests have been carried ou-t according to the procedure of Examples 1 to 27. The poly-isoprene which has been obtained with the ternary system hasa high contents of 1,4-cis unsa-turations and high values of . For example, the polymer which has been obtained ~3 wi-th an ~l/Ti = 1.20 has the Eollowin~ proper-ties:
l,4~cis : 95~6~ ' 1,4-trans : 0% ; 1,2 unsat. = 0.5% ;
3,4-unsat. = 3.8~ i total unsaturations O 102 ;
n ~ 30C = ~.6.
toluene A 5 liter autoclave equipped with stirrer, has been dried and deaerated by heating~it under vacuum and Eilled up to ambient pressure with hydrogen and charged b~ siphoning-10 in with 1,6000 mls of anhydrous nor.heptane. The temperature is raised to 90C, whereafter there are charge 300 mls of nor. heptane to which there have been added, in the order given, TiC13 - AlPIA - Al Et3 in the quantities of TiC13
5 millimols, (Al.PIA + Al.~lE-t3) 15 millimols, with a variable lAlEt3 : AlpI~ . On completion of the addition of the catalyst hydrogen is charged until attaining a gauge pxessure of 1.5 kilograms per sq. centimeter, then ethylene until attaining a total pressure of 2.5 kilograms/sq. centimeter, which is maintained constant with an æthylene stream adjusted 20 with a pressure-stat. The absorption of ethylene was checked ~;
continously with a flow-meter. After two hours of polymeri-zation run the autoclave has been cooled, the gas vented and the suspension dumped and centrifuged, and the polymer was dried in an oven vacuum at 60C and finally weighed.
The results which have been obtained are collected in TABLE 2 which shows the improved activity of the species which contains AlEt3 more particularly with the 6 to 8~ molar, both relative to the species having no AlEt3 and to that resulting from the complex-formation of (H Al N-isoPr)6 with simple alane derivatives in agreement with the reaction patterns 2 and 3 (EXAMPLES 28-43).
;~ ' , 3 . ~ ¦
3: ~ V
I ~ I
' ; (q ~ O O O ~ ~ -~ o w~ 4 ~ ~ o o O
~ . I i ~
~ . ¦ ~ ¦ I ¢
¦ e 16 ~ ~s~
i ¦ ~ e ~
1 ;
Il !~z
continously with a flow-meter. After two hours of polymeri-zation run the autoclave has been cooled, the gas vented and the suspension dumped and centrifuged, and the polymer was dried in an oven vacuum at 60C and finally weighed.
The results which have been obtained are collected in TABLE 2 which shows the improved activity of the species which contains AlEt3 more particularly with the 6 to 8~ molar, both relative to the species having no AlEt3 and to that resulting from the complex-formation of (H Al N-isoPr)6 with simple alane derivatives in agreement with the reaction patterns 2 and 3 (EXAMPLES 28-43).
;~ ' , 3 . ~ ¦
3: ~ V
I ~ I
' ; (q ~ O O O ~ ~ -~ o w~ 4 ~ ~ o o O
~ . I i ~
~ . ¦ ~ ¦ I ¢
¦ e 16 ~ ~s~
i ¦ ~ e ~
1 ;
Il !~z
Claims (6)
1. A method for the polymerization of mono- and diolefin compounds comprising the steps of contacting the compound(s) concerned with a catalyst system characterized in that the catalyst system is composed by the combination of :
a) an alkyl aluminum or hydride derivative of the formula AlR3-xHx in which R is a hydrocarbonaceous radical and x is a number variable from 0 to 3 ;
b) a compound of a transition metal ;
c) a poly-imino alane.
a) an alkyl aluminum or hydride derivative of the formula AlR3-xHx in which R is a hydrocarbonaceous radical and x is a number variable from 0 to 3 ;
b) a compound of a transition metal ;
c) a poly-imino alane.
2. A method for the polymerization of mono- and diolefin compounds according to claim 1, characterized in that the reaction is carried out at a temperature ranging from -50°C to + 250°C.
3. A method for the polymerization of mono- and diolefin compounds according to claim 2, characterized in that the reaction is carried out at a temperature variable from 10°C to 50°C for the diolefins and from 50° to 150°C for the mono-olefins.
4. A method for the polymerization of mono- and diolefin compounds according to claim 1, characterized in that the reaction is carried out under a pressure ranging from the vapor pressure of the monomer and 100 atmospheres.
5. A method for the polymerization of mono- and diolefin compounds according to claim 4, characterized in that the reaction is carried out under a pressure variable from 1 to 50 atmospheres.
6. A method according to claim 1, characterized in that the reaction is carried out in the presence of a solvent selected from among the aliphatic, aromatic and cycloaliphatic hydrocarbons.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| IT29602/76A IT1064496B (en) | 1976-11-22 | 1976-11-22 | PROCESS FOR THE POLYMERIZATION OF MONO AND DIOLEFINIC COMPOUNDS |
| IT29602A/76 | 1976-11-22 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1106543A true CA1106543A (en) | 1981-08-04 |
Family
ID=11228082
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA290,496A Expired CA1106543A (en) | 1976-11-22 | 1977-11-09 | Method for polymerizing mono- and diolefine compounds |
Country Status (20)
| Country | Link |
|---|---|
| JP (1) | JPS6055526B2 (en) |
| AU (1) | AU510549B2 (en) |
| BE (1) | BE861062A (en) |
| CA (1) | CA1106543A (en) |
| CH (1) | CH629507A5 (en) |
| CS (1) | CS203177B2 (en) |
| DD (1) | DD133334A5 (en) |
| DE (1) | DE2751919C2 (en) |
| DK (1) | DK149127C (en) |
| FR (1) | FR2371464A1 (en) |
| GB (1) | GB1587659A (en) |
| HU (1) | HU176874B (en) |
| IL (1) | IL53366A (en) |
| IT (1) | IT1064496B (en) |
| LU (1) | LU78555A1 (en) |
| NL (1) | NL180012C (en) |
| NO (1) | NO149924C (en) |
| SE (1) | SE440362B (en) |
| YU (1) | YU39055B (en) |
| ZA (1) | ZA776811B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS62127088U (en) * | 1986-02-05 | 1987-08-12 | ||
| BE1007698A3 (en) * | 1993-11-04 | 1995-10-03 | Solvay | Catalyst system used for the polymerization of alpha-olefin polymerization and method for this. |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1423016A (en) * | 1972-12-20 | 1976-01-28 | Snam Progetti | Mono-olefin-conjugated diene copolymerisation using a ternary catalyst system |
| FR2237911A1 (en) * | 1973-07-04 | 1975-02-14 | Okktinskoe Mauchno Proizv | High yield ethylene(-propylene)polymer prepn. - using titanium chloride and polyalkylalumoxane reactn. prod. as catalyst system |
| IT1019677B (en) * | 1974-07-01 | 1977-11-30 | Snam Progetti | POLYMER COMPOUNDS OF ALUMINUM OF POLYIMINIC NATURE PROCEDURE FOR THEIR PREPARATION AND THEIR USE AS COMPONENTS OF CATALYTIC SYSTEMS FOR THE POLY MERIZATION OF UNSATURATED COMPOUNDS |
-
1976
- 1976-11-22 IT IT29602/76A patent/IT1064496B/en active
-
1977
- 1977-11-09 AU AU30478/77A patent/AU510549B2/en not_active Expired
- 1977-11-09 CA CA290,496A patent/CA1106543A/en not_active Expired
- 1977-11-13 IL IL53366A patent/IL53366A/en unknown
- 1977-11-15 ZA ZA00776811A patent/ZA776811B/en unknown
- 1977-11-18 CH CH1415177A patent/CH629507A5/en not_active IP Right Cessation
- 1977-11-18 NO NO773949A patent/NO149924C/en unknown
- 1977-11-21 FR FR7734946A patent/FR2371464A1/en active Granted
- 1977-11-21 CS CS777645A patent/CS203177B2/en unknown
- 1977-11-21 DK DK516077A patent/DK149127C/en not_active IP Right Cessation
- 1977-11-21 JP JP52139027A patent/JPS6055526B2/en not_active Expired
- 1977-11-21 GB GB48445/77A patent/GB1587659A/en not_active Expired
- 1977-11-21 DE DE2751919A patent/DE2751919C2/en not_active Expired
- 1977-11-21 YU YU02770/77A patent/YU39055B/en unknown
- 1977-11-21 SE SE7713140A patent/SE440362B/en not_active IP Right Cessation
- 1977-11-21 LU LU78555A patent/LU78555A1/xx unknown
- 1977-11-22 NL NLAANVRAGE7712876,A patent/NL180012C/en not_active IP Right Cessation
- 1977-11-22 DD DD7700202190A patent/DD133334A5/en unknown
- 1977-11-22 BE BE182820A patent/BE861062A/en not_active IP Right Cessation
- 1977-12-21 HU HU77SA3076A patent/HU176874B/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| IL53366A (en) | 1981-03-31 |
| NO773949L (en) | 1978-05-23 |
| NL7712876A (en) | 1978-05-24 |
| NL180012B (en) | 1986-07-16 |
| IT1064496B (en) | 1985-02-18 |
| IL53366A0 (en) | 1978-01-31 |
| CH629507A5 (en) | 1982-04-30 |
| BE861062A (en) | 1978-05-22 |
| YU277077A (en) | 1982-06-30 |
| GB1587659A (en) | 1981-04-08 |
| DK149127B (en) | 1986-02-03 |
| NL180012C (en) | 1986-12-16 |
| LU78555A1 (en) | 1978-04-13 |
| NO149924B (en) | 1984-04-09 |
| FR2371464A1 (en) | 1978-06-16 |
| ZA776811B (en) | 1978-09-27 |
| AU510549B2 (en) | 1980-07-03 |
| DE2751919A1 (en) | 1978-05-24 |
| AU3047877A (en) | 1979-06-28 |
| JPS5365382A (en) | 1978-06-10 |
| HU176874B (en) | 1981-05-28 |
| DK516077A (en) | 1978-05-23 |
| FR2371464B1 (en) | 1980-05-16 |
| SE440362B (en) | 1985-07-29 |
| DD133334A5 (en) | 1978-12-27 |
| DE2751919C2 (en) | 1982-11-25 |
| JPS6055526B2 (en) | 1985-12-05 |
| DK149127C (en) | 1986-07-14 |
| NO149924C (en) | 1984-08-01 |
| SE7713140L (en) | 1978-05-23 |
| YU39055B (en) | 1984-02-29 |
| CS203177B2 (en) | 1981-02-27 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US3787384A (en) | Catalysts and process for the polymerization of olefins | |
| Hsieh et al. | Polymerization of butadiene and isoprene with lanthanide catalysts; characterization and properties of homopolymers and copolymers | |
| US2924593A (en) | Polymerization of ethylene using as a catalyst the product formed by mixing a bis(cyclopentadienyl) zirconium salt with an alkyl metallic compound | |
| KR20110139318A (en) | Catalytic systems made of a complex of rare earths for stereospecific polymerisation of conjugated dienes | |
| KR20120031186A (en) | Catalytic system for conjugated diene polymerisation, polymerisation method and functional polymer obtained | |
| US4699962A (en) | Olefin polymerization | |
| US3899474A (en) | Process for manufacturing hydrogenated polymers from conjugated diolefins | |
| US3068180A (en) | Polymerization of diolefins with a co or ni halide-aluminum alkyl compound catalyst | |
| US5109085A (en) | Olefin polymerization process | |
| US3525729A (en) | Process for production of polymers with controlled saturation | |
| CA1106543A (en) | Method for polymerizing mono- and diolefine compounds | |
| US5958820A (en) | Gas-phase polymerisation of conjugated dienes in the presence of rare earth allyl compounds | |
| JPH10330428A (en) | Production of polybutadiene | |
| US4203867A (en) | Transition metal composition and production thereof | |
| US4524195A (en) | Process and catalyst for olefin polymerization | |
| US4791086A (en) | Olefin polymerization | |
| CA1144299A (en) | Polymerization process for cis-1,4-polybutadiene using aliphatic solvents and an aromatic polymerization regulator | |
| US3640987A (en) | Process for manufacturing titanium trichloride the catalysts obtained therefrom and their uses in the polymerization of polymerizable monomers | |
| CN107602737B (en) | Application of chromium-series metal organic framework material in olefin polymerization | |
| US4169927A (en) | Process for the polymerization of ethylene | |
| US3172881A (en) | Titanium haude-organometal-organq- metal iodide catalyst for produc- tion of cis i,x-polybutadiene | |
| US4314045A (en) | Polymerization process for cis-1,4-polybutadiene using aliphatic solvents and an aromatic polymerization regulator | |
| US3462405A (en) | Preparation of polymerization catalyst | |
| CN113402637B (en) | Rare earth catalyst, preparation method thereof, rare earth catalyst composition containing rare earth catalyst and application of rare earth catalyst composition | |
| US3577396A (en) | Polymerization of conjugated dienes by means of a nickel fluoroborate hydrate/organometallic compound catalyst system |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| MKEX | Expiry |