CA1093745A - Polymerization process - Google Patents
Polymerization processInfo
- Publication number
- CA1093745A CA1093745A CA271,551A CA271551A CA1093745A CA 1093745 A CA1093745 A CA 1093745A CA 271551 A CA271551 A CA 271551A CA 1093745 A CA1093745 A CA 1093745A
- Authority
- CA
- Canada
- Prior art keywords
- process according
- compound
- amine
- lithium
- ether
- 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
Homopolymers of conjugated dienes and copolymers of conjugated ted dienes with vinyl aromatic compounds or with other conjugated dienes having improved properties and an alastomeric character are prepared by use of a catalytic composition which comprises (a) an organo-lithium initiator and (b) a tercatalyst system comprising (b1) a compound of barium or strontium or calcium, (b2) an organometallic compound of a metal of Group 2B or 3A of the Mendeleev Periodic Table of Elements and (b3) an alkali metal alcohol ate ether or amine.
Homopolymers of conjugated dienes and copolymers of conjugated ted dienes with vinyl aromatic compounds or with other conjugated dienes having improved properties and an alastomeric character are prepared by use of a catalytic composition which comprises (a) an organo-lithium initiator and (b) a tercatalyst system comprising (b1) a compound of barium or strontium or calcium, (b2) an organometallic compound of a metal of Group 2B or 3A of the Mendeleev Periodic Table of Elements and (b3) an alkali metal alcohol ate ether or amine.
Description
3~7~
The present invention relates -to an improved process for -the preparatlon of homopolymers of conjugated dienes or copolymers of conjugated dienes either with each other or with vinyl aromatic compounds, which polymer.~ have a low content of 1,2 linkages and a high content of trans-1,4 linkages, and which polymers have an elastomeric charac-ter.
In copending Canadian application No. 223,556 filed. June 4, 1375, Applicant has described a basic process of homopolymerizing conjugated dienes or copolymerizing conjugated dienes either wi-th other conjugated dienes or with vinyl aromatic compounds, for the preparation oE
homopolymers or copolymers which have simultaneously a high content of more than about 70% of trans~ linkages and a low content of less than about 5~ of 1,2 linkages, which comprises : reacting the monomers in a reaction medium in the presence of an added anionic catalytic composition comprising ~a) an organo-lithium initiator and (b) a cocatalyst system :
comprising (bl) a compound of barium or strontium and (b2) an organometall1c compound of a metal of Group 2~ or 3A of the Mendel.eev Periodi.c Table of Elements.
In copending Canadian app:Lication No. 255,17~
filed June 17,.1976, Applicant has disclosed that the above described basic process can be improved by replacing the two components of the cocatalys~t system with a single catalyst compound having, in each molecule, one atom of a metal of Group
The present invention relates -to an improved process for -the preparatlon of homopolymers of conjugated dienes or copolymers of conjugated dienes either with each other or with vinyl aromatic compounds, which polymer.~ have a low content of 1,2 linkages and a high content of trans-1,4 linkages, and which polymers have an elastomeric charac-ter.
In copending Canadian application No. 223,556 filed. June 4, 1375, Applicant has described a basic process of homopolymerizing conjugated dienes or copolymerizing conjugated dienes either wi-th other conjugated dienes or with vinyl aromatic compounds, for the preparation oE
homopolymers or copolymers which have simultaneously a high content of more than about 70% of trans~ linkages and a low content of less than about 5~ of 1,2 linkages, which comprises : reacting the monomers in a reaction medium in the presence of an added anionic catalytic composition comprising ~a) an organo-lithium initiator and (b) a cocatalyst system :
comprising (bl) a compound of barium or strontium and (b2) an organometall1c compound of a metal of Group 2~ or 3A of the Mendel.eev Periodi.c Table of Elements.
In copending Canadian app:Lication No. 255,17~
filed June 17,.1976, Applicant has disclosed that the above described basic process can be improved by replacing the two components of the cocatalys~t system with a single catalyst compound having, in each molecule, one atom of a metal of Group
2~ per either one atom of a metal of Group 2B or two atoms of a metal of Group 3~A, and having one of the following two formulas:
:
~ æ~
.
M2A/-M3ARlR2R3R4 / or M2A/ M (R )4 ~
in which M A iS a metal of Group 2A of the ~endeleev Periodic Table of Elements, such as barium, calcium, stro.nt.ium, or magnesium; M3A is a metal of Group 3A of the Mendeleev Periodic Table of Elements, such as baron, alumlnum, etc O;
M B is a metal of Group 2B of the ~endeleev Periodic Table of Elements, such as zinc and cadmium; Rl, R2 and R3 are alkyl or aralkyl radicals; and R4 is an alkyl radical or an aralkyl radical or the radical oR5 in which R5 is an alkyl radical or an aralkyl radical.
It has now been found that an improvement in the foregoing basic process consists in effecting the polymeri-zation or copolymerization in the presence of a catalytic composition comprising (a) an organo-lithium initiator and ~b) a tercatalyst system comprising.(bl) a compound of barium or strontium or calcium, (b2) an organometallic com-pound of a metal of Group 2B or 3A o:E the Mendeleev Periodic ~Table of Elements and ~b3) an alkali metal~alcoholate ether or amine and more particularly an alkali metal alcoholate ether or amine having one o~ the following two formulas:
R(OCH2OEI2~nOMlA or (R)2NCH2CH2OM1A
in which M1A represents an alkali metal, such as lithium, sodium~ or potassium, R is an alkyl radical; and n is a whole number.
The present improvement makes it possible to increase substantially the content of trans-1,4 linkages of homopolymers of conjugated dienes and copolymers of conjugated dienes either with other conjugated dienes or wi-th vinyl aromatic compounds, that is to say to obtain a conten~ of trans-1,4 linkages of the order of 80% to 90% in the case of polybutadiene or butadiene-styrene copolymers.
'
:
~ æ~
.
M2A/-M3ARlR2R3R4 / or M2A/ M (R )4 ~
in which M A iS a metal of Group 2A of the ~endeleev Periodic Table of Elements, such as barium, calcium, stro.nt.ium, or magnesium; M3A is a metal of Group 3A of the Mendeleev Periodic Table of Elements, such as baron, alumlnum, etc O;
M B is a metal of Group 2B of the ~endeleev Periodic Table of Elements, such as zinc and cadmium; Rl, R2 and R3 are alkyl or aralkyl radicals; and R4 is an alkyl radical or an aralkyl radical or the radical oR5 in which R5 is an alkyl radical or an aralkyl radical.
It has now been found that an improvement in the foregoing basic process consists in effecting the polymeri-zation or copolymerization in the presence of a catalytic composition comprising (a) an organo-lithium initiator and ~b) a tercatalyst system comprising.(bl) a compound of barium or strontium or calcium, (b2) an organometallic com-pound of a metal of Group 2B or 3A o:E the Mendeleev Periodic ~Table of Elements and ~b3) an alkali metal~alcoholate ether or amine and more particularly an alkali metal alcoholate ether or amine having one o~ the following two formulas:
R(OCH2OEI2~nOMlA or (R)2NCH2CH2OM1A
in which M1A represents an alkali metal, such as lithium, sodium~ or potassium, R is an alkyl radical; and n is a whole number.
The present improvement makes it possible to increase substantially the content of trans-1,4 linkages of homopolymers of conjugated dienes and copolymers of conjugated dienes either with other conjugated dienes or wi-th vinyl aromatic compounds, that is to say to obtain a conten~ of trans-1,4 linkages of the order of 80% to 90% in the case of polybutadiene or butadiene-styrene copolymers.
'
3~7~
The homopolymers and copolymers thus obtained have an elastomeric character which permits their use as the principal component of mixtures intended for the manufacture of pneumatic tires. Furthermore, the butadiene-styrene copolymers, containing the usual fillers for the manufacture of tires, have a "green strength" or resistance to elongation which is similar to that of natural rubber.
Furthermore, the present improvement provides particularly simple and broad possibilities of regulating the inherent viscosity of the homopolymers and copolymers. Thus it makes it po~sible to obtain homopolyemrs and copolymers having an inherent viscosity which is higher than that of the elastomers obtained by the above-mentioned basic process.
Finally, the present improved process makes it possible to obtain a rate of homopolymerization and of copolymerization which is higher than that obtained using the catalytic compositlon of the above-mentioned basic process.
One preferred embodiment of the present improved process consists in using the compound of barium or strontium or calcium with the organometallic compound of a metal of Group 2B or 3A of the Mendeleev Periodic Table of Elements in the form of a preformed mixture obtained by the mixing of the two components together at a temperature between about 20C
and about lo0QC. The preformed mixture, the organo-lithium initiator, and the alkali metal alcoholate ether or amine may be added to the monomers either separately and in any order or at the same time.
The homopolymerization or copolymerization may be carried out con~tinuously or batchwise elther in solution in an aliphatic, cycloaliphatic or aromatic hydrocarbon solvent or in bulk at a temperature between about 0C and about 100C.
~, , .
-- 3 ~
One advantageous embodiment consists in using the components of the catalytic composition in such quantities that the ratios are within the following limits:
1~ mole of an organometallic compound of a metal of Group 2B or 3A
mole of a compound of Bà or Sr or Ca 0 25C mole of a compound of Ba or Sr or Ca ~1 gram atom of lithium 1 mole of alkali metal alcoholate ether or amine ~ 4 mole of a compound of Ba or Sr or Ca As alkali metal alcoholate e-thers or amines, the lithium alcoholate ethers or amines are preferably ùsed and more particularly the compounds C2H5(0CH2CH2)20Li and (C2H5)2NCH2CH20Li.
As organometallic compounds of a metal of Group 2B
or 3A, the compounds (C2H5)2Zn, (C2H5)3Al, and (i-butyl)3Al are preferably employed.
As compounds of barium or strontium or calciumr the alcoholates or phenates are pr~fèrred and particularly - barium nonylphenate.
As the organo-lithium initiator, n-butyl lithium is preferred.
Several examples of the manner in which the presen-t improved process i 5 carried out are given below by way of ; ilIustration.
In all tests, the inhexent viscosities are estab-lished at 25C in a 1 g/l solution in toluene and the concen-trations of the components contained in the catalytic composition are expressed in micromols per 100 g of monomers.
The ~ontents of trans-1,4 linkages and 1,2 linkages are expressed with respect to the diene portion, while the content by weight of styrene in the copolymer is expressed wLth respect to the total amount of copolymer obtained.
The homopolymers and copolymers thus obtained have an elastomeric character which permits their use as the principal component of mixtures intended for the manufacture of pneumatic tires. Furthermore, the butadiene-styrene copolymers, containing the usual fillers for the manufacture of tires, have a "green strength" or resistance to elongation which is similar to that of natural rubber.
Furthermore, the present improvement provides particularly simple and broad possibilities of regulating the inherent viscosity of the homopolymers and copolymers. Thus it makes it po~sible to obtain homopolyemrs and copolymers having an inherent viscosity which is higher than that of the elastomers obtained by the above-mentioned basic process.
Finally, the present improved process makes it possible to obtain a rate of homopolymerization and of copolymerization which is higher than that obtained using the catalytic compositlon of the above-mentioned basic process.
One preferred embodiment of the present improved process consists in using the compound of barium or strontium or calcium with the organometallic compound of a metal of Group 2B or 3A of the Mendeleev Periodic Table of Elements in the form of a preformed mixture obtained by the mixing of the two components together at a temperature between about 20C
and about lo0QC. The preformed mixture, the organo-lithium initiator, and the alkali metal alcoholate ether or amine may be added to the monomers either separately and in any order or at the same time.
The homopolymerization or copolymerization may be carried out con~tinuously or batchwise elther in solution in an aliphatic, cycloaliphatic or aromatic hydrocarbon solvent or in bulk at a temperature between about 0C and about 100C.
~, , .
-- 3 ~
One advantageous embodiment consists in using the components of the catalytic composition in such quantities that the ratios are within the following limits:
1~ mole of an organometallic compound of a metal of Group 2B or 3A
mole of a compound of Bà or Sr or Ca 0 25C mole of a compound of Ba or Sr or Ca ~1 gram atom of lithium 1 mole of alkali metal alcoholate ether or amine ~ 4 mole of a compound of Ba or Sr or Ca As alkali metal alcoholate e-thers or amines, the lithium alcoholate ethers or amines are preferably ùsed and more particularly the compounds C2H5(0CH2CH2)20Li and (C2H5)2NCH2CH20Li.
As organometallic compounds of a metal of Group 2B
or 3A, the compounds (C2H5)2Zn, (C2H5)3Al, and (i-butyl)3Al are preferably employed.
As compounds of barium or strontium or calciumr the alcoholates or phenates are pr~fèrred and particularly - barium nonylphenate.
As the organo-lithium initiator, n-butyl lithium is preferred.
Several examples of the manner in which the presen-t improved process i 5 carried out are given below by way of ; ilIustration.
In all tests, the inhexent viscosities are estab-lished at 25C in a 1 g/l solution in toluene and the concen-trations of the components contained in the catalytic composition are expressed in micromols per 100 g of monomers.
The ~ontents of trans-1,4 linkages and 1,2 linkages are expressed with respect to the diene portion, while the content by weight of styrene in the copolymer is expressed wLth respect to the total amount of copolymer obtained.
- 4 -Example 1 This example presents by way of comparison a test based on the homopolymerization of butadiene by means of the catalytic composition used in the above-mentioned basic process and that used in the present improved process.
The following agents were used:
- solution of C2H~(OCH~CH2)2OLi in tolu~ne - solution of butyl lithium in hexane: (BuLi) - Solution A formed of the mixture heated at 800C
for 1 hour of 1 equivalent of barium nonylphenate with 4 equivalents of triethyl aluminum.
Two comparative tests were carried out.
Into a reactor, under the pressure of rectified nitrogen, there were lntroduced two liters of heptane, as solvent, and 272 g of butadiene and the temperature was increased to 80C. Solution A, butyl lithium and ; C~H5(OCH2CH2)2oLi were then added in succession.
When the conversion rate reached 70%, the reactions were stopped and the homopolymers recovered.
The results are se-t forth in Table I below.
TABLE I
Ca~ytic Composition hme Polybutadienes _ _ . . _ .
Inherent Trans-Solution A viscos- 1,4 1,2-Test Ba(OR)2 Al Et3 BuLi ~ 5( 2C 2)2 ity teCnnt(~) tennt (~
_ _ ........... _ , . . . , 1 300 1200 900 ~ 6 hrs. 200 78 5 ~: 2 300 1200 900 600 1 hr. 2.4 90 2 :
It will be noted that the improved process of the present invention employing the Catalytic Composition 2 makes it possible to obtain, on the one handr an appreciable increase :~ ~ (12~) in the content of tr~ns-1,4 linkages and, on the other : hand, homopolymers of higher inherent viscosity .in shorter periods of time~
~ - 5 -.
'7~i Example 2 This example relates to the preparation of copolymers of butadiene and styrene.
Two tests were carried out in a reactor wlder the pressure of rectified nitrogen. Two liters of heptane, styrene and butadiene were introduced in such quantities that the ratio by weight of monomers to heptane was 1:5~ The temperature was increased to 80C whereupon ~here was added the catalytic composition formed of the Solution A defined in Example 1, butyl lithium and C2H5(ocH2cH2)2oLi-When the conversion rate reached 80%, the reactions were stopped and the copolymers recovered.
The results are set forth in Table II below.
.
` ~\
37~
~ o a) ~ 0~o o ~r O ~ h~ H ~1 O ~ ~
C~ In _... ,. .. _ . _._.. _ ... __ u~ I a)--h ~ ~ o~O t~
a ~ ~ O
O I
~ ~n O
C~ ~ ` ~ C~O CO 0 ~'~ 0~-_.. _ ~
.IJ~
~ ~rl CO
h O ~I cn U N r l __ .~.... . ~
~ a) ~) ~ o~O o~
~I N
H t~
_ ~
rl ~ D7 k h h ,s~ o H
H . - ~
~ 0~, E~ ~
C) ~ o o . ~ o o O O ,~ .~
rl In . , ~ N _______ ~; ',~
U . ~ ~ O O
~) ~ , ~i ~ ~9 :0 ~ 1~
.~ ~ ~
(~ ~ ~
o ~
n : ~ o o 0~ ~ ~r : ,~ : ~
: ~ m ; :
~ ~ ~ 2 ,, .
:~ ~
3t7~
On test pieces of these two copolymers and natural rubber (NR) filled with 50 parts of HAF carbon black per 100 parts of elastomer but not vulcanized, force-elongation measurements wexe carried out at 25C, forming the "green strength" measurement. The force-elongation measurements were carried out on "dumbbell" test pieces of 2.5 mm in thick-ness using an "Instron" electric dynamometer 24 hours after molding and with a rate of traction of 10 cm/minute. The results obtained are shown in the graph of the drawing, the ordinate of which represents the force exerted in g/mm2 while the abscissa represents the elongation ~in %). It is noted that the copolymers obtained have a resistance to elongation similar to that of natural rubber (NR).
Example 3 A Solution A was used formed of the mixture preformed at 80C for 1 hour of 1 equivalent of barium nonylphenate and . 4 equivalents of triethyl aluminum.
Into a reactor under the pressure of rectified nitrogen there was continuously introduced a mixture of toluene, butadiene, and styrene in such amounts that the weight ratio of monomers to solvent was equal to 1:4 and the ratio of butadiene to styrene was 4.
~ olution A, butyl lithium and C2H5(oCH2CE~2~2OLi were also introduced continuously in such amounts that the molar ratio of Ba:BuLi was equal to 1:3 and the ratio of Ba:alcohola~e was equal to 2:5. The rate of flow was regulated in such a manner that there were 600 x 10 6 gram atoms o~ Ba in the reactor for 100 grams of monomer, and the dwell,`time was 1 hour. The copolymerization was carried out 30~ at 80C. :~
The percentage o~:conversion reached was 65%. The copol~mer formed was continuously recovered at the outlet of . .
~37'~
the reactor. It contained 11% by weight of styrene and had an inherent viscosity of 1.9. The content of 1,2 linkages was 4%
and the content of trans-1,4 linkages was 80%.
Example 4 A catalytic composition formed of the Solution A
defined in the preceding example, butyl lithium and (C2H5)2NCH2CH2oLi was used. Into a 250 ml S-teinie bottle under the pressure of rectified nitrogen there were introduced 100 ml of heptane as solvent and 13.6 g of butadiene. The càtalytic composition was then added and the bottle was placed in a bath main-tainied thermostatically at 80C in which it is agitated.
A-t the end of the reaction, when the conversion rate reached 80%, the polybutadiene was recovered in accordance with a customary method. The results are set forth in Table III below.
- T~3LE III
Catalytic Cbmposition Reaction Polybutadiene ___ me ~ Trans- r~
Solution A Inherent 1,4 1,2-3a(0R)2 Al E-t3 BuLi (C2H5)2N CH2CH20Li visc~s- teconnt(%) toonn ~ . . ~ ~ . I
100 400 300 200 45 min. 1.0 90 3 Example 5 A catalytic composition was used formed of the Solution A defined in Example 1, butyl lithium and C2H5(OCH2CH2)2ONa and a -test was carried out by repeating the method o~ operation of Example 4. The results obtained are s~t forth in Table IV below.
,~
. :
-~' _ 9 _ TABLE IV
¦ Ca~ytic Composition t~lePolybutadiene _ _ Trans-Solution A Inherent 1,4 1,2-_ _ Ba(OR)2 Al Et3 B ~ C2H5(~12~I2)2Na v scos- con- tent(%) . _ ~ .. _ 200 800 600 200 2 hrs. 0.9 82 4 Example 6 A catalytic system was used consisting of the Solution A defined in Example 3, BuLi and C2H5(oCH2CH2)3oLi and a test was carried out by repeating the method of operation set forth in Example 5. The results obtained are set forth in Table V
below~
T~BLE V
Catalytic Cbmpositlon Reactionl Polybutadiene _ ~ 'Trans-Solut: on A Inh~rent 1,4 1,2-Ba(OR), Al Et3 BuLi 2 5tOcH2cH2)3oLl V19005- c~nbent cDntent 240 180 120 1 hr. l 2.03 85 3 30 min.¦
.
..
:
' :
" ~ .
--- 1,0 --
The following agents were used:
- solution of C2H~(OCH~CH2)2OLi in tolu~ne - solution of butyl lithium in hexane: (BuLi) - Solution A formed of the mixture heated at 800C
for 1 hour of 1 equivalent of barium nonylphenate with 4 equivalents of triethyl aluminum.
Two comparative tests were carried out.
Into a reactor, under the pressure of rectified nitrogen, there were lntroduced two liters of heptane, as solvent, and 272 g of butadiene and the temperature was increased to 80C. Solution A, butyl lithium and ; C~H5(OCH2CH2)2oLi were then added in succession.
When the conversion rate reached 70%, the reactions were stopped and the homopolymers recovered.
The results are se-t forth in Table I below.
TABLE I
Ca~ytic Composition hme Polybutadienes _ _ . . _ .
Inherent Trans-Solution A viscos- 1,4 1,2-Test Ba(OR)2 Al Et3 BuLi ~ 5( 2C 2)2 ity teCnnt(~) tennt (~
_ _ ........... _ , . . . , 1 300 1200 900 ~ 6 hrs. 200 78 5 ~: 2 300 1200 900 600 1 hr. 2.4 90 2 :
It will be noted that the improved process of the present invention employing the Catalytic Composition 2 makes it possible to obtain, on the one handr an appreciable increase :~ ~ (12~) in the content of tr~ns-1,4 linkages and, on the other : hand, homopolymers of higher inherent viscosity .in shorter periods of time~
~ - 5 -.
'7~i Example 2 This example relates to the preparation of copolymers of butadiene and styrene.
Two tests were carried out in a reactor wlder the pressure of rectified nitrogen. Two liters of heptane, styrene and butadiene were introduced in such quantities that the ratio by weight of monomers to heptane was 1:5~ The temperature was increased to 80C whereupon ~here was added the catalytic composition formed of the Solution A defined in Example 1, butyl lithium and C2H5(ocH2cH2)2oLi-When the conversion rate reached 80%, the reactions were stopped and the copolymers recovered.
The results are set forth in Table II below.
.
` ~\
37~
~ o a) ~ 0~o o ~r O ~ h~ H ~1 O ~ ~
C~ In _... ,. .. _ . _._.. _ ... __ u~ I a)--h ~ ~ o~O t~
a ~ ~ O
O I
~ ~n O
C~ ~ ` ~ C~O CO 0 ~'~ 0~-_.. _ ~
.IJ~
~ ~rl CO
h O ~I cn U N r l __ .~.... . ~
~ a) ~) ~ o~O o~
~I N
H t~
_ ~
rl ~ D7 k h h ,s~ o H
H . - ~
~ 0~, E~ ~
C) ~ o o . ~ o o O O ,~ .~
rl In . , ~ N _______ ~; ',~
U . ~ ~ O O
~) ~ , ~i ~ ~9 :0 ~ 1~
.~ ~ ~
(~ ~ ~
o ~
n : ~ o o 0~ ~ ~r : ,~ : ~
: ~ m ; :
~ ~ ~ 2 ,, .
:~ ~
3t7~
On test pieces of these two copolymers and natural rubber (NR) filled with 50 parts of HAF carbon black per 100 parts of elastomer but not vulcanized, force-elongation measurements wexe carried out at 25C, forming the "green strength" measurement. The force-elongation measurements were carried out on "dumbbell" test pieces of 2.5 mm in thick-ness using an "Instron" electric dynamometer 24 hours after molding and with a rate of traction of 10 cm/minute. The results obtained are shown in the graph of the drawing, the ordinate of which represents the force exerted in g/mm2 while the abscissa represents the elongation ~in %). It is noted that the copolymers obtained have a resistance to elongation similar to that of natural rubber (NR).
Example 3 A Solution A was used formed of the mixture preformed at 80C for 1 hour of 1 equivalent of barium nonylphenate and . 4 equivalents of triethyl aluminum.
Into a reactor under the pressure of rectified nitrogen there was continuously introduced a mixture of toluene, butadiene, and styrene in such amounts that the weight ratio of monomers to solvent was equal to 1:4 and the ratio of butadiene to styrene was 4.
~ olution A, butyl lithium and C2H5(oCH2CE~2~2OLi were also introduced continuously in such amounts that the molar ratio of Ba:BuLi was equal to 1:3 and the ratio of Ba:alcohola~e was equal to 2:5. The rate of flow was regulated in such a manner that there were 600 x 10 6 gram atoms o~ Ba in the reactor for 100 grams of monomer, and the dwell,`time was 1 hour. The copolymerization was carried out 30~ at 80C. :~
The percentage o~:conversion reached was 65%. The copol~mer formed was continuously recovered at the outlet of . .
~37'~
the reactor. It contained 11% by weight of styrene and had an inherent viscosity of 1.9. The content of 1,2 linkages was 4%
and the content of trans-1,4 linkages was 80%.
Example 4 A catalytic composition formed of the Solution A
defined in the preceding example, butyl lithium and (C2H5)2NCH2CH2oLi was used. Into a 250 ml S-teinie bottle under the pressure of rectified nitrogen there were introduced 100 ml of heptane as solvent and 13.6 g of butadiene. The càtalytic composition was then added and the bottle was placed in a bath main-tainied thermostatically at 80C in which it is agitated.
A-t the end of the reaction, when the conversion rate reached 80%, the polybutadiene was recovered in accordance with a customary method. The results are set forth in Table III below.
- T~3LE III
Catalytic Cbmposition Reaction Polybutadiene ___ me ~ Trans- r~
Solution A Inherent 1,4 1,2-3a(0R)2 Al E-t3 BuLi (C2H5)2N CH2CH20Li visc~s- teconnt(%) toonn ~ . . ~ ~ . I
100 400 300 200 45 min. 1.0 90 3 Example 5 A catalytic composition was used formed of the Solution A defined in Example 1, butyl lithium and C2H5(OCH2CH2)2ONa and a -test was carried out by repeating the method o~ operation of Example 4. The results obtained are s~t forth in Table IV below.
,~
. :
-~' _ 9 _ TABLE IV
¦ Ca~ytic Composition t~lePolybutadiene _ _ Trans-Solution A Inherent 1,4 1,2-_ _ Ba(OR)2 Al Et3 B ~ C2H5(~12~I2)2Na v scos- con- tent(%) . _ ~ .. _ 200 800 600 200 2 hrs. 0.9 82 4 Example 6 A catalytic system was used consisting of the Solution A defined in Example 3, BuLi and C2H5(oCH2CH2)3oLi and a test was carried out by repeating the method of operation set forth in Example 5. The results obtained are set forth in Table V
below~
T~BLE V
Catalytic Cbmpositlon Reactionl Polybutadiene _ ~ 'Trans-Solut: on A Inh~rent 1,4 1,2-Ba(OR), Al Et3 BuLi 2 5tOcH2cH2)3oLl V19005- c~nbent cDntent 240 180 120 1 hr. l 2.03 85 3 30 min.¦
.
..
:
' :
" ~ .
--- 1,0 --
Claims (7)
1. A process of homopolymerizing conjugated dienes or copolymerizing conjugated dienes with other conjugated dienes or with vinyl aromatic compounds to form elastomeric products which comprises reacting the monomers in the presence of a catalytic composision comprising (a) an organo-lithium initiator and (b) a tercatalyst system comprising (bl) a compound of barium or strontium or calcium, (b2) an organometallic compound of a metal of Group 2B or 3A of the Mendeleev Periodic Table of Elements and (b3) an alkali metal alcoholate ether or amine.
2. The process according to claim 1 wherein the compound of barium or strontium or calcium is mixed with the organo-metallic compound of a metal of Group 2B or 3A of the Mendeleev Periodic Table of Elements at a temperature between about 20°C
and about 100°C for about l hour to form a preformed mixture.
and about 100°C for about l hour to form a preformed mixture.
3. The process according to claim 1 wherein the components of the catalytic composition are present in such quantities that the ratios are within the following limits:
4. The process according to claim 1 wherein the alkali metal alcoholate ether or amine has one of the following two formulas:
R(OCH2CH2)nOM1A' or (R)2NCH2CH2OM1A
in which MlA represents an alkali metal; R is an alkyl radical;
and n is a whole number.
R(OCH2CH2)nOM1A' or (R)2NCH2CH2OM1A
in which MlA represents an alkali metal; R is an alkyl radical;
and n is a whole number.
5. The process according to claim 1 cherein butadiene is used as the conjugated diene, styrene is used as the vinyl aromatic compound and the catalytic composition comprises n-butyl lithium, a barium phenate, a trialkyl aluminum, and a lithium alcoholate ether or amine.
6. The process according to claim 5 wherein the lithium alcoholate ether is C2H5(0CH2CH2)20Li.
7. The process according to claim 5 wherein the lithium alcoholate amine is (C2H5)2NCH2CH20Li.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FR7604115A FR2340958A2 (en) | 1974-06-05 | 1976-02-12 | PROCESS FOR POLYMERIZATION OR COPOLYMERIZATION OF CONJUGATE AND POLYMERIC DIENES THUS OBTAINED |
| FR76-04115 | 1976-02-12 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1093745A true CA1093745A (en) | 1981-01-13 |
Family
ID=9169132
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA271,551A Expired CA1093745A (en) | 1976-02-12 | 1977-02-11 | Polymerization process |
Country Status (8)
| Country | Link |
|---|---|
| US (1) | US4129705A (en) |
| JP (1) | JPS5298077A (en) |
| AU (1) | AU516472B2 (en) |
| BR (1) | BR7700888A (en) |
| CA (1) | CA1093745A (en) |
| ES (1) | ES455730A2 (en) |
| IT (1) | IT1118065B (en) |
| ZA (1) | ZA77819B (en) |
Families Citing this family (33)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6026406B2 (en) | 1978-09-13 | 1985-06-24 | 旭化成株式会社 | Method for producing conjugated diene polymer |
| US4297240A (en) * | 1980-02-25 | 1981-10-27 | The General Tire & Rubber Company | Solution polymerization |
| FR2480291A1 (en) * | 1980-04-09 | 1981-10-16 | Michelin & Cie | PROCESS FOR THE PREPARATION OF CONJUGATED DIENE POLYMERS OR CONJUGATED DIENE COPOLYMERS EITHER BETWEEN THEM, OR WITH A VINYLAROMATIC COMPOUND |
| FR2480288A1 (en) * | 1980-04-09 | 1981-10-16 | Michelin & Cie | PROCESS FOR THE PREPARATION OF POLYMERS OF CONJUGATED DENES OR OF CONJUGATED COPOLYMERS EITHER BETWEEN THEM, OR WITH A VINYLAROMATIC COMPOUND |
| JPS57159807A (en) * | 1981-03-27 | 1982-10-02 | Asahi Chem Ind Co Ltd | Production of conjugated diene polymer |
| US4401800A (en) * | 1982-06-14 | 1983-08-30 | The Firestone Tire & Rubber Company | Lithium alkoxide diamines as modifiers for polymerization of dienes using lithium-based initiators |
| FR2567135B1 (en) * | 1984-07-03 | 1989-01-13 | Asahi Chemical Ind | POLYMER OR COPOLYMER OF BUTADIENE AND PROCESS FOR PREPARATION |
| JPH0662808B2 (en) * | 1985-03-29 | 1994-08-17 | 日本ゼオン株式会社 | Anti-vibration rubber |
| JP2730163B2 (en) * | 1989-04-07 | 1998-03-25 | 日本合成ゴム株式会社 | Method for producing high trans low vinyl conjugated diene polymer |
| JP2811484B2 (en) * | 1989-12-20 | 1998-10-15 | 日本ゼオン株式会社 | Rubber composition |
| GB8929024D0 (en) * | 1989-12-22 | 1990-02-28 | Ici Plc | Processes |
| JP2859951B2 (en) * | 1990-01-16 | 1999-02-24 | 日本ゼオン株式会社 | Manufacturing method of toner |
| EP0609010B1 (en) * | 1993-01-29 | 2000-03-15 | Bridgestone Corporation | A process for producing a diolefin polymer or copolymer and a rubber composition containing such a diolefin polymer or copolymer |
| US5753579A (en) * | 1995-12-26 | 1998-05-19 | The Goodyear Tire & Rubber Company | Trans microstructure directing initiator system |
| EP0877034A1 (en) * | 1997-05-05 | 1998-11-11 | The Goodyear Tire & Rubber Company | Random trans SBR with low vinyl microstructure |
| DE19806775A1 (en) * | 1998-02-18 | 1999-08-19 | Basf Ag | (Co)polymerization of vinyl aromatic monomer and diene to prepare styrene homopolymers |
| US6177603B1 (en) | 1998-06-12 | 2001-01-23 | Bridgestone Corporation | Organo zinc and rare earth catalyst system in the polymerization of conjugated dienes |
| US6359088B1 (en) * | 1998-10-01 | 2002-03-19 | The Goodyear Tire & Rubber Company | Calcium-based catalyst system |
| EP1018521A1 (en) * | 1999-01-06 | 2000-07-12 | Société de Technologie Michelin | Process for preparation of diene polymers having amino groups, the polymers, rubber compositions and treads thereof |
| FR2854635B1 (en) * | 2003-05-07 | 2006-07-14 | Michelin Soc Tech | PROCESS FOR THE PREPARATION OF BLOCK COPOLYMERS FOR PNEUMATIC BEARING BAND COMPOSITIONS AND COPOLYMERS |
| FR2854636B1 (en) * | 2003-05-07 | 2006-07-14 | Michelin Soc Tech | PROCESS FOR THE PREPARATION OF BLOCK COPOLYMERS FOR PNEUMATIC BEARING BAND COMPOSITIONS AND COPOLYMERS |
| JP5543338B2 (en) | 2007-06-07 | 2014-07-09 | アルベマール・コーポレーシヨン | Adducts, or adducts and oligomers, or adducts and oligomers and low molecular weight polymers, and their preparation |
| US8993684B2 (en) | 2008-06-06 | 2015-03-31 | Albemarle Corporation | Low molecular weight brominated polymers, processes for their manufacture and their use in thermoplastic formulations |
| EP2370383A2 (en) * | 2008-12-02 | 2011-10-05 | Albemarle Corporation | Toluene and styrene derived telomer distributions and brominated flame retardants produced therefrom |
| JO3423B1 (en) * | 2008-12-02 | 2019-10-20 | Albemarle Corp | Brominated Flame Retardants And Precursors Therefor |
| EP2361269A1 (en) * | 2008-12-02 | 2011-08-31 | Albemarle Corporation | Branched and star-branched styrene polymers, telomers, and adducts, their synthesis, their bromination, and their uses |
| EP2373697A1 (en) * | 2008-12-02 | 2011-10-12 | Albemarle Corporation | Bromination of telomer mixtures derived from toluene and styrene |
| JO3059B1 (en) | 2009-05-01 | 2017-03-15 | Albemarle Corp | Bromination of low molecular weight aromatic polymer compositions |
| KR20120088535A (en) | 2009-05-01 | 2012-08-08 | 알베마를 코포레이션 | Pelletized low molecular weight brominated aromatic polymer compositions |
| IT1404141B1 (en) | 2010-11-26 | 2013-11-15 | Pirelli | HIGH-PERFORMANCE TIRE |
| MX2017012768A (en) | 2015-04-24 | 2018-06-04 | Pirelli | High-performance tyre. |
| US10557022B2 (en) | 2015-04-24 | 2020-02-11 | Pirelli Tyre S.P.A. | High-performance tire |
| CN107921817B (en) | 2015-07-31 | 2020-02-28 | 倍耐力轮胎股份公司 | High-performance tyre |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3607851A (en) * | 1969-04-24 | 1971-09-21 | Firestone Tire & Rubber Co | Polymerization of conjugated diolefins |
| US3716495A (en) * | 1970-09-02 | 1973-02-13 | Phillips Petroleum Co | Polymerization initiator composition and use thereof |
-
1977
- 1977-01-13 US US05/758,941 patent/US4129705A/en not_active Expired - Lifetime
- 1977-02-08 ES ES455730A patent/ES455730A2/en not_active Expired
- 1977-02-08 JP JP1218577A patent/JPS5298077A/en active Granted
- 1977-02-11 CA CA271,551A patent/CA1093745A/en not_active Expired
- 1977-02-11 AU AU22238/77A patent/AU516472B2/en not_active Expired
- 1977-02-11 ZA ZA770819A patent/ZA77819B/en unknown
- 1977-02-11 IT IT67322/77A patent/IT1118065B/en active
- 1977-02-11 BR BR7700888A patent/BR7700888A/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| ES455730A2 (en) | 1978-01-16 |
| JPS5734843B2 (en) | 1982-07-26 |
| BR7700888A (en) | 1977-10-18 |
| AU516472B2 (en) | 1981-06-04 |
| AU2223877A (en) | 1978-08-17 |
| IT1118065B (en) | 1986-02-24 |
| ZA77819B (en) | 1977-12-28 |
| JPS5298077A (en) | 1977-08-17 |
| US4129705A (en) | 1978-12-12 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CA1093745A (en) | Polymerization process | |
| US5686371A (en) | Conjugated diene polymerisation | |
| Hsieh et al. | Polymerization of butadiene and isoprene with lanthanide catalysts; characterization and properties of homopolymers and copolymers | |
| US3280084A (en) | Reducing cold flow in conjugated diene polymers with a polyvinyl aromatic compound | |
| EP0076535B1 (en) | Process for polymerising conjugate diolefins, and means suitable for this purpose | |
| US4080492A (en) | Butadiene polymerization process | |
| KR860000675B1 (en) | Random styken-butadiene copolymers | |
| JPS6213363B2 (en) | ||
| EP0207558B1 (en) | Improved process for the polymerization of copolymerization of butadiene | |
| EP0331400B1 (en) | Catalyst composition for polymerization of conjugated diene and process for producing conjugated diene polymer | |
| US3303225A (en) | Production of polymetallated 1-acetylenes | |
| US4020255A (en) | Continuous insitu catalyst addition for polybutadiene polymerization | |
| US4079176A (en) | Polymerization process | |
| US5063190A (en) | Anionic initiator system for polymerizing monomers | |
| CA1192534A (en) | Catalyst containing a phosphine oxide modifier and process for production of polymers having increased 1,2-microstructure | |
| US3755269A (en) | Production of mercaptan-terminated polymers | |
| US4139490A (en) | Dehydrocarbyl magnesium and an alkali metal compound catalyst composition for polymerizing conjugated dienes | |
| EP0061902B1 (en) | Process for producing conjugated diene polymer | |
| US5216181A (en) | Liquid telechelic polymers having high 1,4-diene structure | |
| US4430487A (en) | Shortstop for synthetic cis-1,4-polyisoprene | |
| US5326838A (en) | Method of preparing homopolymers of conjugate dienes and copolymers of conjugate dienes with other dienes or vinyl aromatic compounds | |
| WO2018016980A1 (en) | Random copolymers of vinyl aromatic compounds and conjugated dimers and method for preparing the same | |
| CA1145883A (en) | Process for preparing bimodal or multimodal polymers of conjugated dienes | |
| US3972863A (en) | Method for preparing copolymers from conjugated dienes and monovinylaromatic compounds with random distribution of monomer units | |
| EP0344888B1 (en) | Liquid telechelic polymers having high 1,4-diene structure |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| MKEX | Expiry |