CA1121100A - Method for the polymerization of compounds having a system of conjugated double bonds - Google Patents
Method for the polymerization of compounds having a system of conjugated double bondsInfo
- Publication number
- CA1121100A CA1121100A CA000295139A CA295139A CA1121100A CA 1121100 A CA1121100 A CA 1121100A CA 000295139 A CA000295139 A CA 000295139A CA 295139 A CA295139 A CA 295139A CA 1121100 A CA1121100 A CA 1121100A
- Authority
- CA
- Canada
- Prior art keywords
- polymerization
- aralkyl
- aryl
- double bonds
- compounds
- 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
- 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 :
The present invention is directed to a method for poly-merizating a compound containing at least one non-aromatic system of conjugated carbon-carbon double bonds, which rom-prises contacting the monomer with, as sole catalyst, a com-pound produced by the reaction in an ethereal solvent of equimolar quantities of sodium and an ethylenic compound having the formula :
The present invention is directed to a method for poly-merizating a compound containing at least one non-aromatic system of conjugated carbon-carbon double bonds, which rom-prises contacting the monomer with, as sole catalyst, a com-pound produced by the reaction in an ethereal solvent of equimolar quantities of sodium and an ethylenic compound having the formula :
Description
This lnvention re~late~ to a rne~hod for poly-merizing a compound containing at least one non-aromatic system of conjuc3ated carbon-carbon double bonds, which comprises con-tacting the mo~omer with, as sole catalyst, a compound produced by the xeaction in an ethereal solvent of equinolar quantities of sodium and an ethylenic compound having the formula Rl ~ / R4 C = C
R / \ R3 wherein each of Rl, R2, R3 and R4, which can be the same or dif~
ferent, is a hydrogen atom or an alkyl, aryl, aralkyl or alkaryl radical, with the proviso that at least one of Rl, R2, R3 and R i5 selected from aryl, aralkyl and alkaryl radicals or an alkyl radical.
It is known from US Patent Speciication 3.177.190 to use a catalyst system composed by organic derivatlves of lith-ium (lithium-isoprenyl) or by adducts o such derivatives with cycloaliphatic or aromatic molecules (such as Li-isobutyl, and the dilithiumstilbene-dimethylbutadiene adduat) to pxepare polymers having reactive termlnal yroups.
It is likewise known (Die Makromolekulare Chemie, 92 (1966), pages 180-197) that is is possible to employ composi-tions of the kind referred to hereinabove in the polymerization of a few monovinyl monomers, such as acrylonitrile, styrene, methylmetacrylate, in which electron-attractlng groups are con-tained.
We have now found, and this is the subject matter of this invention, that it is possible to polymerize -- 2 -- ...
L~ ~
compounds which contain at least one system o conjugatea double bonds in the presence of a catalys-t system composed by the prod-uct of interaction of an alkali metal with organic substrates as defined hereinabove. This fact is actually surprising, since it is contrary to the expectations to which the above scientific papers would lead and more particularly it is against the first paper cited above ln which the a~kali metal is employed in the form o~ an alkyl or alkenyl derivative.
A particularly advantageous embodiment of the present invention is a methvd as outlined above in which the alkali metal is sodlum, which is not too expensive and readily available as compared with the other alkali metals, and the organic compound is selected from among stilbene, tetraphenyl-ethylene, l,l-diphenylethylene, 1,1,2-triphenylethylene and so forth.
It is obvious, anyhow, that the extension to the other alkali metals is obviously feasible and that anyone skilled in the art will meet with no dlficulty in selecting the catalyst couple which is the most suitable ~7ithout ~hereby de~
parting from the scope of the present invention.
The interaction reaction between Na and the organic compound takes place between -78C and ~70C~ prefer-ably at a ternperature from 0C to ~30C in polar solvents and preferably in THFj methyl-THF, dioxane, diethyl ether, dimethyl ether, dibutyl ether, diethylene glycol-diethyl ether, diethylene glycol-dimethyl ether or admixtures of any two or more thereof.
The product of this reaction can be used as such in the polymerization mixture, possibly together with other sol-vents, in order to obtain particular effects on the molecular B
weight and/or on-~el~crostructure.
Such a polymeriæation is preerably carxled ou~
at a temperature comprised be~ween -50C and -~lOO~C, under a pressure which can be varied from atmospherical pres5ure to the pressure which is proper o the monomer-solvent system.
i More particularly, the polymerization solvent can be selected from among the polar compounds and the mixtures of allphatic; or cycloaliphatic., or aromatic compounds with such polar compounds.
The monomers which can be polymerized according to the method of this invention are those which contain at least one system of conjugated double honds, such as butadiene, p~-el~e piperylene, C - C
4 5 fraction and, lastly, mixtures of monomers . - ~
.. . .. ., _ ~ _ . . ..
.. _ .. ..... .. . _ . .. ..
.___ . .
B
of the diolefinconjugated type.
As cornpared with khe conventiorlal polymerization methods and more par-ticularly with Na naphthalene, the method according to the present invention permits -to achieve a few undeniable advantages such as:
a) an improved stability of khe catalyst in time (the Na-stilbene system is stable for a few days at room temperature) and at temperatures up to 60C - 70C.
b) Higher polymer yields with the same quantity of alkali metal contained in the initiator, the other pol~nerization parameters belng equal (a mol percent of catalyst relative to the monomer, variable from 0.1% to 5% is generally sufficient)~
c) Shorter polymerization times for obtaining a complete converslon (from 10 minutes to one hour, the other parameters being equ~
d) A wider versatility of the catalyst system in regula-ting the molecular weight (according to the type of solvent which is used,) there are obtained oligomer~
with a mol~ wt. Erorn 500 to 2,000 iE one worlc~ in toluene or polyme~rs having a high rnolecular weight, ~OC
(~ tx ~ 0.5) if one works in THF - Intermed:iate viscosity values are obtained by operating with mixtures of the two solvents.
e) Possibility of controlling the microstructure of the pol~ner obtained and moré particularly the possibility of obtaining high contents of 1,2- in the case of -the polybutadiene, and high 3,4- in the case of polyisoprenes. The vinyl-addition contents can be varied, however, according to the nature of the solvent and consistently with the in-tended practical uses.
., A) q~e pol~merization catalyst is prepared by reacting 10 mill:imols of stilbene with a stuichiometrical quantit,y Oe Na and sand in 70 mls of THF and by keeping the reac-tion mixture stirred at 25C for 5 hours. The mixture is then filtered and titrated. The yield relative to the reacted Na is 95%.
B) 2 mls of the anhydrous solution in THF (0.2 millimol of catalyst) prepared as specified in A) are placed in a bottle stoppered with a crown-cap, which bottles has been de-aerated and nitrogen-purged a-t a tempera-ture of 25C. There are added 18 mls of anhydrous toIuene, the bottle is stoppered and there are introduced by injection 2.8 grams of butadiene (50 milli-mols).
After 30 minutes, the polymerization mixture is treated with a 1/1 solution of water and methanol in a separatory funnel, the supernatant layer is recovered and evaporated to dryness.
rrhere are obtained 2.8 grams (yield = 100%) of a polymer having a liquid consistency (mol.wt. 800) the micro-structure oE which is as follows:
1, 2- : 84.7% , 1,~- : 15.3% , l,~-cis : 0%
.
In a bottle equipped with a crown-cap stopper,which has been de-aerated and purged by nitrogen, there are placed
R / \ R3 wherein each of Rl, R2, R3 and R4, which can be the same or dif~
ferent, is a hydrogen atom or an alkyl, aryl, aralkyl or alkaryl radical, with the proviso that at least one of Rl, R2, R3 and R i5 selected from aryl, aralkyl and alkaryl radicals or an alkyl radical.
It is known from US Patent Speciication 3.177.190 to use a catalyst system composed by organic derivatlves of lith-ium (lithium-isoprenyl) or by adducts o such derivatives with cycloaliphatic or aromatic molecules (such as Li-isobutyl, and the dilithiumstilbene-dimethylbutadiene adduat) to pxepare polymers having reactive termlnal yroups.
It is likewise known (Die Makromolekulare Chemie, 92 (1966), pages 180-197) that is is possible to employ composi-tions of the kind referred to hereinabove in the polymerization of a few monovinyl monomers, such as acrylonitrile, styrene, methylmetacrylate, in which electron-attractlng groups are con-tained.
We have now found, and this is the subject matter of this invention, that it is possible to polymerize -- 2 -- ...
L~ ~
compounds which contain at least one system o conjugatea double bonds in the presence of a catalys-t system composed by the prod-uct of interaction of an alkali metal with organic substrates as defined hereinabove. This fact is actually surprising, since it is contrary to the expectations to which the above scientific papers would lead and more particularly it is against the first paper cited above ln which the a~kali metal is employed in the form o~ an alkyl or alkenyl derivative.
A particularly advantageous embodiment of the present invention is a methvd as outlined above in which the alkali metal is sodlum, which is not too expensive and readily available as compared with the other alkali metals, and the organic compound is selected from among stilbene, tetraphenyl-ethylene, l,l-diphenylethylene, 1,1,2-triphenylethylene and so forth.
It is obvious, anyhow, that the extension to the other alkali metals is obviously feasible and that anyone skilled in the art will meet with no dlficulty in selecting the catalyst couple which is the most suitable ~7ithout ~hereby de~
parting from the scope of the present invention.
The interaction reaction between Na and the organic compound takes place between -78C and ~70C~ prefer-ably at a ternperature from 0C to ~30C in polar solvents and preferably in THFj methyl-THF, dioxane, diethyl ether, dimethyl ether, dibutyl ether, diethylene glycol-diethyl ether, diethylene glycol-dimethyl ether or admixtures of any two or more thereof.
The product of this reaction can be used as such in the polymerization mixture, possibly together with other sol-vents, in order to obtain particular effects on the molecular B
weight and/or on-~el~crostructure.
Such a polymeriæation is preerably carxled ou~
at a temperature comprised be~ween -50C and -~lOO~C, under a pressure which can be varied from atmospherical pres5ure to the pressure which is proper o the monomer-solvent system.
i More particularly, the polymerization solvent can be selected from among the polar compounds and the mixtures of allphatic; or cycloaliphatic., or aromatic compounds with such polar compounds.
The monomers which can be polymerized according to the method of this invention are those which contain at least one system of conjugated double honds, such as butadiene, p~-el~e piperylene, C - C
4 5 fraction and, lastly, mixtures of monomers . - ~
.. . .. ., _ ~ _ . . ..
.. _ .. ..... .. . _ . .. ..
.___ . .
B
of the diolefinconjugated type.
As cornpared with khe conventiorlal polymerization methods and more par-ticularly with Na naphthalene, the method according to the present invention permits -to achieve a few undeniable advantages such as:
a) an improved stability of khe catalyst in time (the Na-stilbene system is stable for a few days at room temperature) and at temperatures up to 60C - 70C.
b) Higher polymer yields with the same quantity of alkali metal contained in the initiator, the other pol~nerization parameters belng equal (a mol percent of catalyst relative to the monomer, variable from 0.1% to 5% is generally sufficient)~
c) Shorter polymerization times for obtaining a complete converslon (from 10 minutes to one hour, the other parameters being equ~
d) A wider versatility of the catalyst system in regula-ting the molecular weight (according to the type of solvent which is used,) there are obtained oligomer~
with a mol~ wt. Erorn 500 to 2,000 iE one worlc~ in toluene or polyme~rs having a high rnolecular weight, ~OC
(~ tx ~ 0.5) if one works in THF - Intermed:iate viscosity values are obtained by operating with mixtures of the two solvents.
e) Possibility of controlling the microstructure of the pol~ner obtained and moré particularly the possibility of obtaining high contents of 1,2- in the case of -the polybutadiene, and high 3,4- in the case of polyisoprenes. The vinyl-addition contents can be varied, however, according to the nature of the solvent and consistently with the in-tended practical uses.
., A) q~e pol~merization catalyst is prepared by reacting 10 mill:imols of stilbene with a stuichiometrical quantit,y Oe Na and sand in 70 mls of THF and by keeping the reac-tion mixture stirred at 25C for 5 hours. The mixture is then filtered and titrated. The yield relative to the reacted Na is 95%.
B) 2 mls of the anhydrous solution in THF (0.2 millimol of catalyst) prepared as specified in A) are placed in a bottle stoppered with a crown-cap, which bottles has been de-aerated and nitrogen-purged a-t a tempera-ture of 25C. There are added 18 mls of anhydrous toIuene, the bottle is stoppered and there are introduced by injection 2.8 grams of butadiene (50 milli-mols).
After 30 minutes, the polymerization mixture is treated with a 1/1 solution of water and methanol in a separatory funnel, the supernatant layer is recovered and evaporated to dryness.
rrhere are obtained 2.8 grams (yield = 100%) of a polymer having a liquid consistency (mol.wt. 800) the micro-structure oE which is as follows:
1, 2- : 84.7% , 1,~- : 15.3% , l,~-cis : 0%
.
In a bottle equipped with a crown-cap stopper,which has been de-aerated and purged by nitrogen, there are placed
2 mls of a solution of catalyst in THF (O.2 millimol of catalyst) prepared as in Example 1 (A~.
rrhere are added 2 mls of THF and 16 mls toluene, the bottle is sealed and there are introduced by injection 2.8 grams of butadiene (50 millimols). After 30 minutes the polymerization mixture is trea-ted with a 1/1 solution of methanol and water in a separatory funnel, the toluene layer 10~
is recovered and evaporated to dryness.
There are obtained 2.8 grarns (yield = 100%) of a pol~ner having a r~2 73Oolcene = 0.26 and the following microstructure :
1~2-: 85% i 1~4-: 15% ~ 1,4-CiS: 0%.
A pol~nerization reac-tor, which has been previously deaerated and scavenged with nitrogen is charged, a-t -40C~
with . ~ -~~
t 0.2 millimol (calcu~ated relative to Na) of' a solut,lon composed by the product of interactlon obtalnecl by reaction for 4 hour.g at -40C of Na and s-tilbene in THF. THF is added until reachiny a total volume of 20 mls and there are added 2.8 grams of butadiene (50 millimols).
After 2 hours the polymerization mixture is treated with CH30H and a polymer is obtained having a ~ ]toluene = l.l and a microstructure as follows :
1,2- : 87% ; 1,4-cis : 0~ ; 1,4-trans = 13~ .
The yield of solid polymer is 80~.
.
A de-aerated, nitrogen-scavenged polymerization bottle having a crown~cap stopper is charged at a temperature of 25~C with 0.2 millimol of the product of interaction of Na and stilbene, prepared as in Example 1 (A).
There are added 18 mls toluene and 5 mls iso-prene (50 millimols). The bottle is sealed and stirred. After 2 hours, coagulation of the polymer with methanol is carried out.
There are obtained 2.9 grams of a polymer ~yield = 85%) havlng a / ~ 7t 1 ~ 0.12 and the ~ollowing micro-structure :
rrhere are added 2 mls of THF and 16 mls toluene, the bottle is sealed and there are introduced by injection 2.8 grams of butadiene (50 millimols). After 30 minutes the polymerization mixture is trea-ted with a 1/1 solution of methanol and water in a separatory funnel, the toluene layer 10~
is recovered and evaporated to dryness.
There are obtained 2.8 grarns (yield = 100%) of a pol~ner having a r~2 73Oolcene = 0.26 and the following microstructure :
1~2-: 85% i 1~4-: 15% ~ 1,4-CiS: 0%.
A pol~nerization reac-tor, which has been previously deaerated and scavenged with nitrogen is charged, a-t -40C~
with . ~ -~~
t 0.2 millimol (calcu~ated relative to Na) of' a solut,lon composed by the product of interactlon obtalnecl by reaction for 4 hour.g at -40C of Na and s-tilbene in THF. THF is added until reachiny a total volume of 20 mls and there are added 2.8 grams of butadiene (50 millimols).
After 2 hours the polymerization mixture is treated with CH30H and a polymer is obtained having a ~ ]toluene = l.l and a microstructure as follows :
1,2- : 87% ; 1,4-cis : 0~ ; 1,4-trans = 13~ .
The yield of solid polymer is 80~.
.
A de-aerated, nitrogen-scavenged polymerization bottle having a crown~cap stopper is charged at a temperature of 25~C with 0.2 millimol of the product of interaction of Na and stilbene, prepared as in Example 1 (A).
There are added 18 mls toluene and 5 mls iso-prene (50 millimols). The bottle is sealed and stirred. After 2 hours, coagulation of the polymer with methanol is carried out.
There are obtained 2.9 grams of a polymer ~yield = 85%) havlng a / ~ 7t 1 ~ 0.12 and the ~ollowing micro-structure :
3,4- : 85% ; 1,2~ : 15%.
A de-aerated. nitrogen-scavenged polymerization bottle having a crown-cap stopper is charged at a temperature of 25% with 30 milligrams (0.2 millim~l relative to Na) of the interaction product of Na and stiIbene (1 : l) in dioxane. There are added 10 mls of diethylenegly-col~methyl ether and, by injection, 2.8 grams of butadiene.
At,er 15 muns. the polym~r is coagulated with methanol.
mere ar,e obtained 2.8 grams of polymer tyield = 100%) having a = 0.5 and the following microstructure :
1,2- : ~5~ ; 1,4-trans : 15~ .
E~ F 6 A) The Na-tetraphenylet,hylene adduct is prepared by reac-ting D-n~J
10 millimols oE tetraphenylethylene with stoichiornetrica]
quan-tities of Na sand ln 80 mls oE aTIhydrous THF and ,stirring at 25C for 4 hours. The solution is filtered and then ti~
trated~ The yield relative to the reacted Na is 94%. ~ote:
the reaction can be carried out also at -78C with yields which are comparable to the above, the reaction time being the same.
B) One millimol of catalyst solution prepared as in A) is placed in a bot-tle having a crown-cap stopper with a total volume of 20 mls of THF. The bottle is sealed and 2.8 grams of butadie~e (50 millimols) are introduced therein by injection.
Aftér two hours the polymerization mixture is coagulated with methanol. There are obtained 2.8 grams of polybutadiene (yield = 100%) haviny a /~ tolu~n~ = 0 9 and -the follow-ing microstructure:
1,2- = 90% , 1,4-trans : 10% ' 1,4-cis : 0%.
. .
By adopting a high-vacuum technique the Na-stilb~ne catalyst is prepared in a reactor by reacting in situ 18 mil:Ligrams o~ Na (0.'75 rnill:irrlol) and 64 milligrams of stilbene (0.35 millimol) in 60 mls of THF during one hour at a tempera~
ture of 25C. There are introduced 2.4 grams of butadiene (45 millimols) and polymerization is caused to occur during 30 minutes. The mixture is cooled to -78C and there are added 2.2 grams of styrene (21 millimols). The solution is allowed to stand at room temperature for 10 hours. The mixture is coagulated from methanol and 4.3 grams of polymer are obtained (yield 100% of raw polymer). Extraction is carried out for 24 hours with acetone. A polymer is obtained which contains 30% of styrene, expressed in millimols.
A de-aerated. nitrogen-scavenged polymerization bottle having a crown-cap stopper is charged at a temperature of 25% with 30 milligrams (0.2 millim~l relative to Na) of the interaction product of Na and stiIbene (1 : l) in dioxane. There are added 10 mls of diethylenegly-col~methyl ether and, by injection, 2.8 grams of butadiene.
At,er 15 muns. the polym~r is coagulated with methanol.
mere ar,e obtained 2.8 grams of polymer tyield = 100%) having a = 0.5 and the following microstructure :
1,2- : ~5~ ; 1,4-trans : 15~ .
E~ F 6 A) The Na-tetraphenylet,hylene adduct is prepared by reac-ting D-n~J
10 millimols oE tetraphenylethylene with stoichiornetrica]
quan-tities of Na sand ln 80 mls oE aTIhydrous THF and ,stirring at 25C for 4 hours. The solution is filtered and then ti~
trated~ The yield relative to the reacted Na is 94%. ~ote:
the reaction can be carried out also at -78C with yields which are comparable to the above, the reaction time being the same.
B) One millimol of catalyst solution prepared as in A) is placed in a bot-tle having a crown-cap stopper with a total volume of 20 mls of THF. The bottle is sealed and 2.8 grams of butadie~e (50 millimols) are introduced therein by injection.
Aftér two hours the polymerization mixture is coagulated with methanol. There are obtained 2.8 grams of polybutadiene (yield = 100%) haviny a /~ tolu~n~ = 0 9 and -the follow-ing microstructure:
1,2- = 90% , 1,4-trans : 10% ' 1,4-cis : 0%.
. .
By adopting a high-vacuum technique the Na-stilb~ne catalyst is prepared in a reactor by reacting in situ 18 mil:Ligrams o~ Na (0.'75 rnill:irrlol) and 64 milligrams of stilbene (0.35 millimol) in 60 mls of THF during one hour at a tempera~
ture of 25C. There are introduced 2.4 grams of butadiene (45 millimols) and polymerization is caused to occur during 30 minutes. The mixture is cooled to -78C and there are added 2.2 grams of styrene (21 millimols). The solution is allowed to stand at room temperature for 10 hours. The mixture is coagulated from methanol and 4.3 grams of polymer are obtained (yield 100% of raw polymer). Extraction is carried out for 24 hours with acetone. A polymer is obtained which contains 30% of styrene, expressed in millimols.
Claims (10)
1. A method for polymerizing a compound con-taining at least one non-aromatic system of conjugated carbon-carbon double bonds, which comprises contacting the monomer with, as sole catalyst, a compound produced by the reaction in an ethereal solvent of equimolar quantities of sodium and an ethylenic compound having the formula:
wherein each of R1, R2, R3 and R4, which can be the same or dif-ferent, is a hydrogen atom or an alkyl, aryl, aralkyl or alkaryl radical, with the proviso that at least one of R1, R2, R3 and R4 is selected from aryl, aralkyl and alkaryl radicals.
wherein each of R1, R2, R3 and R4, which can be the same or dif-ferent, is a hydrogen atom or an alkyl, aryl, aralkyl or alkaryl radical, with the proviso that at least one of R1, R2, R3 and R4 is selected from aryl, aralkyl and alkaryl radicals.
2. A method according to claim 1, wherein at least two of R1, R2, R3 and R4 are selected from aryl, aralkyl and alkaryl radicals.
3. A method according to claim 1 or 2, wherein the ethylenic compound is stilbene, tetraphenylethylene, 1,1-diphenylethylene or 1,1,2-triphenylethylene.
4, A method according to claim 1, wherein the interaction between the sodium and the ethylenic compound takes place at a temperature in the range from -78°C to +70°C.
5. A method according to claim 4, wherein the temperature of the interaction is in the range from 0°C to +30°C.
6. A method according to claim 1, 2 or 4, wherein the interaction between the sodium and the ethylenic compound takes place in the presence of a solvent selected from tetrahydrofuran (THF), methyltetrahydrofuran, dioxane, diethyl ether, dimethyl ether, dibutyl ether, diethylene glycol-diethyl ether, diethylene glycol-dimethyl ether, or admixtures of any two or more thereof.
7. A method according to claim 1, wherein the polymerization is carried out at a temperature in the range from -50°C to +100°C.
8. A method according to claim 1, wherein the polymerization is carried out under a pressure of at least atmospheric pressure.
9. A method according to claim 1, 7 or 8, wherein the polymerization is carried out in the presence of a solvent selected from polar compounds or mixtures of aliphatic, cycloaliphatic or aromatic compounds with polar compounds.
10. A method according to claim 1, wherein the monomer to be polymerized is butadiene, isoprene, piperylene, a C4 - C5 fraction of compounds containing at least one system of conjugated carbon-carbon double bonds or a mixture of two or more thereof.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| IT19385A/77 | 1977-01-18 | ||
| IT19385/77A IT1076233B (en) | 1977-01-18 | 1977-01-18 | PROCEDURE FOR THE POLYMERIZATION OF COMPOUNDS HAVING A SYSTEM OF DOUBLE CONJUGATE LINKS |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1121100A true CA1121100A (en) | 1982-03-30 |
Family
ID=11157237
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000295139A Expired CA1121100A (en) | 1977-01-18 | 1978-01-17 | Method for the polymerization of compounds having a system of conjugated double bonds |
Country Status (15)
| Country | Link |
|---|---|
| JP (1) | JPS5390390A (en) |
| AT (1) | AT359284B (en) |
| BE (1) | BE863038A (en) |
| CA (1) | CA1121100A (en) |
| DE (1) | DE2802044A1 (en) |
| DK (1) | DK24178A (en) |
| ES (1) | ES466392A1 (en) |
| FR (1) | FR2377423A1 (en) |
| GB (1) | GB1591066A (en) |
| IE (1) | IE46141B1 (en) |
| IT (1) | IT1076233B (en) |
| NL (1) | NL7800623A (en) |
| NO (1) | NO780152L (en) |
| SE (1) | SE7800505L (en) |
| ZA (1) | ZA7826B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3932178A1 (en) * | 1989-09-27 | 1991-04-04 | Savalica Bulgaro | Lock for bicycle front wheel - has holder on front wheel fork with rotary swivelling holding lever engaging bicycle frame |
-
1977
- 1977-01-18 IT IT19385/77A patent/IT1076233B/en active
-
1978
- 1978-01-04 ZA ZA00780026A patent/ZA7826B/en unknown
- 1978-01-13 AT AT25978A patent/AT359284B/en not_active IP Right Cessation
- 1978-01-16 SE SE7800505A patent/SE7800505L/en unknown
- 1978-01-16 FR FR7801119A patent/FR2377423A1/en active Granted
- 1978-01-16 NO NO780152A patent/NO780152L/en unknown
- 1978-01-17 GB GB1861/78A patent/GB1591066A/en not_active Expired
- 1978-01-17 DK DK24178A patent/DK24178A/en not_active Application Discontinuation
- 1978-01-17 CA CA000295139A patent/CA1121100A/en not_active Expired
- 1978-01-17 ES ES466392A patent/ES466392A1/en not_active Expired
- 1978-01-18 IE IE113/78A patent/IE46141B1/en unknown
- 1978-01-18 DE DE19782802044 patent/DE2802044A1/en not_active Withdrawn
- 1978-01-18 NL NL7800623A patent/NL7800623A/en not_active Application Discontinuation
- 1978-01-18 JP JP342178A patent/JPS5390390A/en active Pending
- 1978-01-18 BE BE184421A patent/BE863038A/en not_active IP Right Cessation
Also Published As
| Publication number | Publication date |
|---|---|
| BE863038A (en) | 1978-07-18 |
| IT1076233B (en) | 1985-04-27 |
| ES466392A1 (en) | 1978-10-01 |
| DK24178A (en) | 1978-07-19 |
| FR2377423A1 (en) | 1978-08-11 |
| ATA25978A (en) | 1980-03-15 |
| JPS5390390A (en) | 1978-08-09 |
| DE2802044A1 (en) | 1978-07-20 |
| FR2377423B1 (en) | 1980-09-12 |
| SE7800505L (en) | 1978-07-19 |
| GB1591066A (en) | 1981-06-10 |
| NL7800623A (en) | 1978-07-20 |
| AT359284B (en) | 1980-10-27 |
| ZA7826B (en) | 1978-11-29 |
| IE780113L (en) | 1978-07-18 |
| NO780152L (en) | 1978-07-19 |
| IE46141B1 (en) | 1983-03-09 |
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