Note: Descriptions are shown in the official language in which they were submitted.
The present in~ention relates -to a process of preparing,
with the use of a new catalytic composition, po].ymers of conjugated
dienes or copolymers of conjugated dienes either with each other
. or with vinyl aromatic compounds having a low content o~ 1,2 or
.. - 3,4 linkages and a high content of trans-1,4 linkages while -
retaining an elastomeric character.
.~ A number of c~talytic composition~ are known which m~ke
it possible to prepare a solution in hydrocarbon media of diene ~-
polymers having a high degree of stereospecificity: high contents
o~ cis-1,4 (for instance, polybutadiene, polyisoprene) or of trans- :
1,4, or else of 192 or 3,4. The polymers of high content of trans
: 1,4 (more than 95%) ~hich ~re prepared in this manner have a ~ery
.: .
.~ ~trong tendency to crystallize at ordinary temperature~ '~hey be-
; have more like pla~-tic~ than like elastomers and for thi~ reason
. cannot be used as the main component of the mixture serving to
. manufacture elastic objects and in particular tires.
.. It i~ al~o well known that polymer~ of con~ugated dienes
": ..
~.:. and copolymer~ of conjugated dienes either ~ith e~ch other or with :.
. vinyl aromatic compounds prepared in hydrocarbon medium by means of
:. 20 lithium catalytic compo~itions do not have a high ~teric purity.
~ A~ a matter of fact, ~ith the lithium catalytic composi-tions the
polymer~ and copolymer~ obta.ined have, for visco~i-ties of the order
.; of 2 or 3, a content of 1,2 or 3,4 linkage~ of the diene portion
. . .~ ..
~;i which is always greater than 6% and a co~tent of trans-lj4 linkages
~hich i9 always less than 60%. Thus the contents are a9 follows: -
~,~r;- ~ For polybutadienes snd copolymers of butadiene .~
45~0 to 55% o~ tran~-1,4 `
7% to 12% of 1,2
40~o to 45% of ci~-1,4 `
_ For polyisoprene~ and copolymers of i~oprene
.~ 10% to 25% of tran~-194
. 6% to 10% o~ 3~4
70~o to 85% of cis-~,4
. ,;
~0~ 3 ~ ~ -
~or higher vi~cosities, equal to ~t least 6, one can note in
particular in the case of isoprene and it~ copolymers a ci~1,4
content increase up to 95% to the detriment of the contents of
trans-1,4 and of 1,2 or 3 9 4 .
With lithium catalytic compo~itions the proportions of
.: .
1,2 or ~,4 linkages as compared to the 1,4 linkage~ can be in-
ereased within the above limits by recourse to certain artifices,
~or in~tance, by modi~ying the polarity of the reaction medium
On the other hand, there are no methods for varying the
content of tran~-1,4 linkage B within a wide range while retaining
the content of 1,2 or 3,4 linkage~ at a very low level.
The object of the present invention i9 to remedy this
~tate of the art by providing a mean~ which makes it possible to
obtain diene polymers or copo~ymers ha~ing a high content of trans-
1,4 linkages in the diene portions of these oompoullds either o~er
the sntire length of the chain o~ the polymer or on-y over a por
tion o~ its length, a~ well as a very small content of 1,2 or 3,4
linkage~. `
Thus one object of the invention i~ to provide, on the
one hand9 a proces9 for polymerizing or copolymeri~ing conjugated
dienes with each other or with vinyl aromatio compounds leading to
th~ obtaining of product~ having a high content of trans-1,4
linkages and at the same time a low content of 1,2 or 3,4 linkage~
and, on the other hand, these products themselve~.
Another object o~ the invention i~ to provide a catalytic
composition and it~ process of preparation which makes it possible
to manu~acture polymers of conjugated dienes and copolymers of con-
, ,, ~
~ugated dienes either with each other or with vinyl aromatic
~^ compound~ which have a high content of trans-1l4 linkage~ and have
only a low content of 1,2 or 3,4 linkage~.
~, Accordlngly, the present invention provides a oatalytic
i~ composition for the polymerization of dienes or copolymerizatio~ of
; 2
''.'','''` :
... . ~ :.
. .: . . . . .
~ 3
diene~ with each other or with vinyl aro~atic compound~ ~hich
comprise~:
a) an organo-lithium initiator a~d
b) a cocatalyst system comprising a compound of bariu~
or strontium and an organometallic compound of a metal of Group
; IIB or IIIA o~ the Mendeleev periodic table of elements.
By "organo-lithium initiator" there i~ understood, ~irst
of all, any organometallic compound compri~ing one or more carbon-
lithium bonds, and ~econdly any ionic-radical adduct of lithium :
and certain polynuclear aromatic hydrocarbon~, and thirdly metallic
lithium itsel~, as well as finally the oligomer~ produced by the
:; addition o~ lithium to conjugated dienes or ~ub~tituted styrene3.
~ 8 repre~entative e~amples of the organo-lithium
in~tiator the fo~lowing compound~ may be mentioned:
The all~l organo-lithium~ ~uch as e~hyl-lithium, n-butyl-
lithium 9 isobutyl-lithium, sec.-butyl-lithium~ ter.-butyl-lithium 9
... .
i~opropyl-lithium, n-amyl-lithium, isoamyl-lithium; the alkenyl .`
organo-lithiums ~uch as allyl-lithium, propenyl~ thium, i~obutenyl- :
lithium; the "live" lithium polymers such as polybutadieny1-lithium,
po~yisoprenyl-lithium9 and poly~tyryl-lithium; the dilithium :
,1 ,. .
pQlymethylenes ~uch as 1,4-dilithium butane, 1,5-dilithium pentane, ..
.. .. . .
1,20-dilithium eicosane; the aryl organo-lithium~ ~uch as benzyl-
lithium, phenyl-lithium, l,l-diphenyl-methyl-lithium the poly-
lithiums resulting ~rom the reaction o~ metallic lithium with aryl- :
. sub~tituted ethylene compounds such ~ diphenylethylene, trans-
stilbene, tetra-phenylethylene; the radical ions such as lithium- :
naphthalene, lithium-anthracene~ lithium-chrysene~ lithium-
diphenyl a3 well ag the derivatives ~ubstituted by one or more
alkyls. ~ ~
With re3pect to the component~ of the cocatalyst sy~tem ;; ::.
there i8 under~tood by "compound o~ barium or ~trontium": the
hydride~ H2Ba and ~2Sr; the mono or poly~unctional organic acid
. ~ .
~, .
~ \
~ 3
salts of the formulas (R - C00)2Ba or Sr, R1 ~ (C00)2Ba or Sr in
~hich R and R1 are organic radicals, the first monovalent and the
second divalent, not having other function~ capable o~ inactivat-
ing the organo-lithium initiator, and the corresponding thio acids,
as well a~ the mono or polyfunctional alcoholates and the corres-
po~ding thiolates; the mono or polyfunctional phenates and the
oorresponding thiophenates9 the alcohol acid ~nd phenol acid salts
,. ~ . .
o~ barium or 3trontium and the corresponding thio product~; barium
or strontium~ -di~etonates such as the reaction products of barium
i~ 10 or strontium with ace-tylacetone, dibenzoylmethane, thenoyltri~luoro- .
..... .
~ acetone, benzoyltri~luoro-acetone, ben~oyl-acetone; the organic
,.. .
i derivatives of barium or ~trontium ~uch as those of l,l-dipheny-
,, ,
lethylene, 1,2-acenaphthylene, tetraphenylbuta~s, ~-methyl-styrene
or el~e those su¢h a~ diphenyl barium or strontium, bis-cyclopenta-
~, ,
:j dienyl barium or strontium, the barium or strontium trialkyl~ilyls,
. barium or strontium triphenylsilyl; the mi~ed organic derivative~
~uch as phenyl-barium iodide, methyl-strontium iodide, barium or
~$rontium salts o~ secondar~ ~mines; ~etone metal~ suc~ as barium
or strontium ben~ophenone, barium or strontium cinnamone, and the
corresponding alkyl products a3 well as the ~ul~ided homologues;
the radical ions of barium and of strontium such as those of
n~phtha~ene, anthra~ene, chrysene, diphenyl, eto~
v~ As representative examples o~ the organometallic compound
~` of a metal of Group II~ or IIIA of the Mendeleev periodic table o~
~lement~ there may be mentioned: Di~lXyl zinc or cadmium compound~
such a~ diethyl zinc~ diethyl cadmium; halogenated or nonhalogenated
organo-aluminum compounds such as triethyl aluminum~ tri-isobutyl
.~ aluminum; diethyl aluminum chloride, ethyl aluminum di-¢hloride,
~;`; ethyl aluminum sesquichloride 7 methyl aluminum sesquichloride;
w` 30 dialkyl aluminum hydrides such ag dieth~l aluminum hydride,
dii~obut~l aluminum hydride; ~nd organoboron compound~.
~- The cocatalytic system may be formed in accordance with
- _4_
I
... .
the following two preferred variants:
- In accordance with the first variant 9 the different
component~ of the cocatalytic system are di~solved separately in
a separate hydrocarbon solvent, preferably identical to the one
which will be used subsequently upon the polymerization or
copolymerization reaction ~o as to be able to be introduced
~epar~tely into the reaction medium.
_ In accordance with the ~econd variant, the cocatalyst
8ygtem i9 "preformed" by mixing the barium or ~trontium compound
and the organometallic compound of a metal of Group IIB or IIIA
within a hydrocarbon solvent. These preformed cocatalyst system~
are characterized by the fact that they are more solub1e in the ;~
h~drocarbon solvents and by the fact that they retain their high
aotivity for long period~ of ti-me. Thl~ mixing between the two ;~
components of th~ cocatalyst sys-tem is accompanied, a~ a matter of
fact, by a total or partial solubilizing of the barium or strontium
compour.d and in particular of those which are normally insoluble in
hydrocarbon media ~uch a~ the hydrides, the acetylacetonates and
most of the alcoholates. The result i9 thus that the use of the
preformed cocatalytic s~stem i~ particularly easy-
In accordance with the first variant, the components o~ ;
the ¢ooatalytic 8y9tem dis~olved in the hydrocarbon solvent are in-
troduced separately into the reaotio~ medium, ei-ther at the start
of the reactio~ at the same time as the organo-lithium initiator in
order to ~orm the catalytic compo~ition "in situ", or during the ~-
course of the polymerization jointly in ~mall quantities or at a
single time, or else one after the other in any order. ~his ma~ner
of procedure i9 ~ustified primarily ~or barium or ~trontium com- ;
pounds whi~h are soluble in the ~olvents in question.
It will be understood that only a~ from ~he mome~t when
the entire cocatalytic system which ha~ been i~troduced into the
reaction medium has reacted with the organo-lithium lnitiator will
~, ; . .:
_5-
`: :
- i:
~ 3~
one benefit from the effect desired, namely the increa~e in the
content of trans-1,4 linkages and the decrea~e in the content of
1,2 or 3,4 linkages. '~he result i~ that when the entire cocatalytic
~y~tem i~ present from the very start of the reaction9 o~e obtains
products having a very high content of trans-194 linkage~ and a
very low content of 1?2 or 3,4 linkages over the entire length of
the polymer or copolymer. -
~ n the other hand, ~hen the component~ of the cocatalytic
~ystem are introduced during the reaction, either jointly in small
quantities or one after the other, one can prepare products having
~everal sequences and having di~ferent steric configuration~, the
addition of the cocatalytic sy~tem resul-ting in the formation of
~equence~ high in trans-1,4 linkages and low in 1,2 or 3,4 linkage~.
In ~ocordance with the ~econd variant, ~hen the
cocatalytic sy~tem i8 used in "preformed" form, one can add it to
the organo-lithium initiator either at the start of the reaction in
order to obtain a product having a content of trans-1,4 linkages
which i~ oonstant from one end to the other of the m~cromolecular
chains or during the reaction in one or more additions, depending
on whether it is desired to have a modification of steric con~igura-
tion only as from ~aid addition or whether it i8 desired to have
the modlfication o~ configuration progressively.
- ~he ca~alytic composition in accordance ~ith the in- -
vention has an activity which i9 spread over a wide range of con-
~entration~ of the catalyst and ratios of the componente of the
catalytic compo~ition.
Depending on the conditions under w~ich ~he reaction ~akes
place ~nature of solvent, the monomer or monomer~ pre~ent,
temperature, etc.) the molar ratios between each of the compsnent~
of the cocatalytic system and between one of the latter with either
the organo-lithium initiator or the "live" lithium polymer or
copolymer can be different in order to obtain given content~ of
-6
... : .
....
tran~-1,4 and 1,2. It will therefore be necessary to 2djust the~e
dif~erent molar ratio~ ~n accordance with the conditions under
which one is operating and the ~teric configura-tion~ desired In
this way, for instance, the contents can be regulated continuously
from 45% to 95~ of trans-1,4 a~d ~rom 12% to 3~ of 192 in the case
slof polybutadiene or copolymers having a ba~e of butadiene and from
25% to 45~ of trans-1,4 and 10% to 5% of 3,4 in the case o~ poly-
i~oprene or of copolymers having a ba~e of isoprene.
-The re~ult i~ that the optimum concentration for one
component of the cataly~t compo~ition depends on the concentration
o~ the other components of the cataly~t composition. However, one
can a~sign certain limit~ to the different molar ratios within
:..
which one will obtain optimum contents of tran~-1,4 linkages and
minimum content~ of 1,2 or 3,4 linkages.
'he said limits are:
mole R3 Me II~A or R2 Me IIB
0-2_ mole of compound of ~a ox~r _1
with
mole of compound of ~a or Sr
O.25' _ __ __ __ __ __ __ ___
~20 gram stom of ~i ~
J;, ` ' .
and preferably:
mole R3 Me IIIA or R2 Me IIB
0.5S
~ mole of compound of Ba or Sr
i, with
~h;
~ mole of compound of ~a or Sr
!~0.5~ ----- _-------__ ~-----_ ~- Sl.5
;~!','i;gram atom of Li
~with R3Me IIIA representing sn organometallic compound of a metal
... .
~ of Group IIIA and R2Me IIB repre~enting an organometallic compound
i,. ~ . ,; , . . .
of a metal of Group IIB.
; 30By gram atom of lithium there i9 understood the quantity
~ . . .
of active organo-lithium compound u~ed which represent~ the
difference between the total amount actually intro~uced and the
,:.. ,; :
minimum neces~ary to obtain a commencement of the polymeri~ation
: .,~., .
-7-
,.,
1~
(quantity 3erving, inter alia, to neutralize the residual
impurities of the reaction media).
The present invention provide~, in addition to a
catalytic composition and its method of preparation~ a process by
which the monomers are polymerized and copolymerized, leading to
products having a very high content of trans-1,4 ~inkages and a
low content of,l,2 or 3,4 linkages retaininy however an elastomeric
character. ~ ~:
In accordance with a first variant, a product having a
high content o~ trans-1,4 linkages and a low content of 1,2 or 314 ..
linkages over the entire length of the polymer or copolymer is :~.
,
obtained by introducing the cat~lytic compo3ition st the start of
the reaction. ..
~, . .
In accordance with another variant, the process leads to
polymers and copolymer~ having different or el~e progre~ive se- .-
quenoes and steric configurations depending on whether the
components of the catalytic compo~ition are added to the reaction
medium one or more times, jointly or separately.
The process in accordance with the invention i9 particu-
20 larly suitable for the polymerization o~ diene~ and the copolymeri-
zation of dienes.and vinyl aromatic compounds.
As representative ex~mples of dienes, mention mag be made
of con~ugatea diene~ ~uch ~9 l,~-butadiene, i~oprene, 293-dimethyl-
1,3-butadieneJ l~-pentadiene9 2-methyl-1,3 pent~diene, and 2,4- .
hexadiene. `.. '~'~r
As repreeentative examples of vinyl aromatic compounds .
; mention may be made of styrene, ortho-, meta-~ and para-methyl ~ty-
`.~ rene or the commercial mix-ture "vinyl-toluene", the di- and poly-
methyl styrenes, p-tert-butylstyrene the vinylnaphthalenes; the :~
~: 30 metho~y styrenes, the halostyrenes, ~inylme~ len~, vinyldurol,
and divinylbenzene.
. Produot.~. having a ~i~h.. content ~ tr~ns 1,~ linkages pre- :pared in accordance with -this new process on basis of the new
-8-
,.
:, . .. . .
,." ~, .
,.. .. ..
.~ . .
catalytic composition have the characteristic of being ela~tomer~
and there~ore of lending themselve~ to being placed in the form of
a mixture in order to produce rubber~, contrary to the other
polymers of very high tran~ 1,4 purlty prepared up to now by mea~s
of different catalytic compositions, ~hich are pla~tic ~nd brittle
at ordinary temperature because cry~talline.
The mixtures in nonvulca~i~ed state produced with the
products obtained by the carrying out of the process due to their
high content of trans-1,4 have characteristic~ such as improved ~` ;
~ . .
green strsngth, very high breaking force and elongation at rupture
and better dimensional stability.
~he~e mi~tures of improved properties are then capable of
.
leadlng to better rubber~ which can be used in particular for the
manu~acture of tire~.
,,jl , ~, . . ..
; ~he ~ollow~ng nonlimitative e2amples are given solely in
order to illustrate the i~vention,
EXA~PIE 1
Butadiene/Styrene Copolymerization by Means o~ the
Catalytic Compo~ition n-Butyl ~ithium/Cinnamone-Barium/~riethyl
~luminum
Preparation of the Coc~t~ e~
Since the cinnamone-barium comple~ is ~oluble in toluene, ;`
it ~as po~sible to ~tudy the specific influence of each of the
components of the oocatalyst ~ystem, the ratio Ba/Al not being
;; fixed for reasons of ~olubility in the reaction medium.
~ he cinnamone-barium co~plex is prepared in a 250 cc.
-, ~teinie bottle in an~atmo~phere of rectified nitrogen9 by dissolv- ~
^. ing 0.1 mole of cinnamone ~195-diphenyl-1,4 pentadiene - 3-one) in i -
'~ 50 cc. of tetrahydrofurane in which 1.5 g. of finely dividedi~ 30 metallic barium are present i~ suspension. After this mi~ture ha~
;; been agitated for about 20 hour~ at room temper~ture, a red ~olution
i9 obtained, which :i9 îiltered. ~his ~olution is evapor~ted under
~.,. j .
9 ,,:
~,''. ' .
.. ..... .
~06~3~ `
vacuum. The brownish-red deposit obtained, a~ter being wa~hed
twice with heptane, i~ di~solved in toluene, ~-till under an
atmosphere of rectlfied nitrogen, so as to obtain an 0.025 M
solution of barium,
~t l e~
'~o ~erie~ of copolymeri~ation experimen-ts are carried
out by introducin~ into 250 cc. Steinie bot1tle~; as catalytic
composition:
vsrisble amount~ of from 0 to 200 x lO 6 moles of
triethyl aluminum
50 2 lO 6 mole~ of active n-butyl-lithium, as clefined
above.
In the ~irst series, no barium compound i~ used.
50 x 10 6 moles of cinnamone-barium are introduced into ea¢h of
the bottle~ o~ the seoond ~erie~.
~ he copolymerization i8 carried out in the pre~ence o~
cyclohexane (123 g. per 250 c¢. Steinie bottle) with 9.225 g. of
: butadiene and 3.075 g. of styre~e per bottle,
j;~ The reaction fla~ks are placed in a thermo~tatically
controlled tsnk maintained at 70a. where they are agitated for a
variable period o~ time 90 a~ to obtain ~amples corre~ponding to
increa~ing percentages of conversion.
~ he re~ult~ obtained at 50~o con~ersion are ~et ~orth in
~able~ IA and IB belo~:
~, . , ,:
~ '' " ` ' `'i '
; ::
.~ .
;-;~;,
10-
.. .... .
- I
, ~ , .~ ' . ' ~ ' ' .,
: - -
.
. .. .
1`-
l`~
~1 C`J -i O ' ,',.'
1'.'.. :
,~ F h i. :
;. ! . 1 :-
3 ~ ~
f, , , . ,~
''1 .. '' ' , ~;" ''
~a
o~ 1 .
o O o ~ ~
h ~
: " . '
~,................................................................... , I .. .
.,"~ , . , . i ' .
:;:, :
`:, ' ~ ~. . .
13~ ~
' , I ~ ~ ~, ,, ,, o .,
,. . .
~.,'
., ~
: . "
a
~` ~ h ~ m IS~
~" ~
) . '`'
"' ~
~ ' :~ '
:j''~ ` 'i , ': '
:';;. ",:: ,: ,`
:' ;` ~ U~ .`~ , `,
P~l ~
N ll~ 0 ~ ~
""i~,, a~ "``
.' ~s ~~
.
~ ~
:,~........ O ~ q~ O O O IS~ O O . ~:
, o o ~-1 U~ O ~) 1~ ' ',
n ~ u~ o
h h O u~ o ~ o o
~''" 4) ~ ~ C~ ~
.',.`.~ ~ q~
.,~,,''`'' ~o ~lo~ ~, :
~ .'
.~ .. . .
.. ,":" .
. . ,.,
. ~....
3L~6~3~
. ,
When examining these re~ult~ one notes the influence of
each of the compounds introduced on the ~teric configuration of the
polymers obtained (% of trans-1,4 and ~o of 1,2) and subsidiarily on
~ ,. .
the reaction kinetics, the inherent viscosity reached and the
method of incorporating the ~tyrene.
With respect to the influence on the steric configura~
tion and in particular on the conten-ts of ~rans-1,4 and of 1~29 it
i8 noted that the expected effect i9 obtained only ~hen the three
components of the catalytic compo~ition are present together in the i -
reaction medium; if one or the other is absent, a steric configura-
tion i8 obtained ~hich i~ rather clo~e to the one obtained with
: .. . .
n-butyl-lithium used by itself.
; EXAMPLE 2
Polymerization of Butadiene by Mean~ of n-Butyl ~ithium
and a "Pre~ormed" Cocatalytic Sy~tem: Barium Acetylaoetonate/
Trialkyl Aluminum
Pre~aration of Cooatal~st System:
The barium acetylacetonate i9 prepared directlg by -
reacbion of acetylacetone and barium hydroxide in anhydrous -~
I~'' , . . . .
methanol medium.
The product prepared i8 in~oluble in hydrocarbons. A
soluble cocatalytic sy~tem i9 obtained by mixing the barium
ac~tylacetonate and the trialkyl aluminum in the presence of a
;il hydrocarbon solvent under a rectified-nitrogen atmosphere for 15
minutes at room temperature.
: ,
Three cocatalytic ~ystems are prepared:
~YS~EM A~
, .
5 32 millimoles of barium acetylacetonate having been
placed in suspension in 170 g. of normal heptane, 23.4 millimoles
. . 30 of commercial triethyl alu~inum of a concentration of 0.92 M are
added After agitation, a clear ~olution of 2.9 x 10 2 M barium
and 11.3 x 10 2 M aluminum i9 obtained.
13
, ,~................................................................... . .
` ~
~ 3
: . SYSTEM B:
: ~o ~ ~5 millimole 8 of barium acetylacetonate ~uspended
in 170 g. of toluene there are added 26.3 millimole~ of commercial
triethyl aluminum of a concentration oY 0.92 M After agitation
there i3 obtained a clear solution of a concentration of
3.2 x 10 2 M b~rium and 11.6 x 10 2 M alumi.num
SYST~ C~
To ~.58 millimoles of barium acetylacetonate suspended .~ ;~
,;~ in 170 g. of heptane there are added 25.1 millimoles o~ commercialtri-isobutyl aluminum of a concentration of 0.79 M Upon agitatlon
there is obtained a clear solution of a concentration of
; 2.4 x 10 2 M barium and 11.8 x 10 2 M aluminum.
.,, ~
Pol.ymerization
These three cocatalytic. systems are u~ed in combination
with n-butyl-llthium to polymerize butadiene dissol~ed in heptane
(fir~t series of experimentc) or in toluene (~econd series of
experiments).
These series of experiments are carried out in 250 cc.
. Steinie bottles clo~ed by a rubber stopper through whieh the
.` 20 different ingredients necessary for the polymerization are intro-
.. duced. Into these bottles, under the pressure of rectified nitro-
~l gen (about 1 bar~ there are introduced 123 g. of solvent (heptane
or toluene) and then 12.3 g. of butadiene followed by one of the
. ~
:. preceding cocatalytic system~ and finall~ the n-butyl-lithium, l'he
~, .
bottle~ are then placed in a tank which i9 maintained constant by
. thermo~tat at 60C and are ~gitated therein ~or three hours~
:.
.~ At the end of these three hours, the polymeri~ation~ are
stopped by introducing into ~aid tank 0.25 cc. of ~ ~olution of
~. methanol in toluene of 60 gD/liter. A phenolic antioxidant is ~l~o
30 introduced (Agerite Gel~rol manufactured`by Vanderbilt) ~2cc. of a
` 246 g3/liter solution)~
~ ~he polymers are then recovered by coagulation by means
. .:,. .
14--
(~3 Trademark.
. . .
~,:, ' . '
. . . .
,,.: ~ ;.,
3~
of a methanol-acetone mixture and dried under vacuum in an oven
(80Co ~ 0~2 bar - 15 hours). -
~he percentage~ of conversion of butadiene into poly- .`
butadiene which have been obtained, the inherent visco~itieis
e~tablished at 25C. in 1 g./liter solution in toluene and the ~
~teric configurations are determined on the sample~ thus obtained. .:
~ he re~ults obtained are ~ummari~ed in Tables IIA and
IIB below: - .
. . .
.
.. 10
~ . ,
,, , I .. . . .
: .,
.. . . . .. .
~,, . .
,,,' . ':.
~ ., . , - , : -
~, ~ , . . . .
',; . ,. ' ,
,................. ~ . ' :
;
,, 1, ' . , ' .
i ~l ' : '
, ~ ,,,
i, ' .
`'~, ' ' . .
t., ~ , .
,,;~' '~ ,. . .
;' ' . ' ' ~
i;'~,'
.~;',;~ '
~'';~ ~ ' ' ' ' ' ' '
~' ,;;~ , ' '
'''.''~ ' ' . '
''1,';.'
"I!d' ~ 5
.. ... . .
.,,;" "~
.,.:
,J-.~
.~ ' `'
3~
~: . N ~:
, a~ ~ ~ d ~ ~ ~ ,"~ ,
',,
,' ,~ ',
,~ . ~I t-- t~t~ N t<~
.~ .. ,
~, , .,.. . :
"~ g
, I O ~ rl a~ ~ ~ o ~ h
,' ~ O
';, H ~1 ~ .
~' . ~ ~ I
~:~ h c) O ;.
R ~1 O o u) u~ ~1 ~ It~ ~I R
' $ ~
"
o ~
o~ ~Sl ~¢1 0 ~I 0 ~~
~ ,. atla ~ o ~1 o rl O a) :
:. o 1: h ~ 3 0~{3 ~ ~1 .~ ~.
~ O
.,.,,, l ,1 1 0 1 o I o o ~ o :
" i I O O O ~1 0 ~1 0 r~
:': It~ r~
~ ~ ~ d H ~ r~ d h
~........... I IOa ~
"~ .
... .
- : , . . :
," ` l`
~0~31~
~,.
.. .
.,'. , .`: - .
,~ rl
,' :,,'
-,1 .
h r-l ~ N O ~ a )
~"
s~
~) I 1'~' '
:j,, , . ~
~:~,i O el~ O O
~, O N ~ If~
c I
", ~31 *
h ~ ~ 0 ~ r- O
D h El 13 a a
a a ~ `;
I o I o I
o ~ o ~
Q) ~I C~ ~I O rl O r~ O ~ O
a) ~t
d ~ h ~ r l ~ r-l ~ r I ~5 ~
~ ~ ~ ~ h
',.i.'~ O O F ~ ~ V * ,~
~" ,
E_~ 3 ~ 4
Polymerization of ~utadiene by Means o~ n~utyl ~ithium
and a "Preformed" Cocatalytic Sy~tem: Dibenzoylmethane
Barium/Triethyl Aluminum
Pre~ar~tion_of Cocatal2~t S~tem `~
~he dibenzoylmethane barium chelate is prepared airectly
from dibenzoylmethane and barium hydroxide, in anhydrous methanol
'`t medium. . -
~he product prepared i~ insoluble in hydrocarbons. The
lQ cocatalytio ~y~tem is prepared by mixing 5.2 millimoles o~ ;
~ dibe~zoylmethane barium and 26 millimole~ of commercial triethyl
" aluminum of a concentration of 0.84 M in an atmosphere of rectified
nitrogen su~pended in 123 g. of heptane. ~his mixture i~ brought
to 60C. for one half hour while agitating ~o that the chelate
dissolves. There i9 then obtained a yellow solution which remains
clear after it has returned to room temperature. It has a
' concentration of about 3 ~ 10 2 M barium and 15 x 10 2 ~ aluminum
Polymeri~ation
This cocatalytic system i~ used in combination with `~
~! 20 n-butyl 11thium to polymerize butadie~e in ~olution in heptane.
~ he polymerization conditions are the same ~s those de-
~cribed previously ~Steinie bottles of 250 cc., 123 g. o~ heptane
and 12.3 g. of butadlene~ 3 hours at 60C.).
Re~ults Obta~ned
:.,~.~ . .. .
i;':~!
." ,. . ..
, .~,. . .
,.~. !.~ ' ;
! ' :. "
; ~ ' . :
` ',` " ' ~,
,.'" . ' i
'~ 30
?,
:',.,~, ' ' `'
:;', . .
... . .
-18-
,~, , .
~`~
~L0~131'~ ~ :
.. ` . ,. ,-
O O
. r1 N C~J ~ ~J N C~i C~J C~l ~ :: ,
., .'~
.~: .
: ~ .
, ~ ~1 N ~ CO ~ O
,,"~,, F ~ .
C
:':-, O ~ C~
.' F~ . .. . . .. .. ...
;. ~ !` .
,." ~ '1 `', ' ~" , '
O ~r~
i~ h ~ ~ ~ ~ rl r-l u~
,;',, ~i ;',
, V . , .
'I' ., H
H ~ , : .
O O O O O O O O O .:.. '.
~i ~i o o lo o loo lo lo o
t~ u~ N ' ~ .
r l N N et C~l ~ ~ r--
~;: `'' ''"
, ,~ . I . .
~I r~
a~ X
P ~
'~:`,:,,, I o I O I O I O ~ '
~i t ,l '' ,, --I ,.. ..
. o o g o 8
, ~ tO N ~1 1 1 ~ C~l ~D ~ I I I I
, 00 ~
.
.
~''
1~)ti~3~
~; EXAMPIæ _4 j;
Copolymeriæation of Butadiene and Styrene by Mean~ of
n-~utyl ~ithium and the "Preformed" Cocatalytic Sy~tem of Example
.
The ~ame dibenzoylmethane barium trie-thyl aluminum
cocatalytic ~ystem i~ u~ed
The copolymerization is carried out in 250 cc. Steinie
bottles as previously, under the ~ame e~perimental conditions.
. Into each o~ the reaction fla~ks there are introduced:
,.
123 g. o~ heptane
-:
,,. ~.
. 1? . 3 g . of monomers: 9.225 g. o~ butadiene and 3 075 g
. of styrene (namely 25% of the charge)
.... .
,~:
. 65 x 10 6 mole~ of active n-Bu~i .
, ~
60 x 10-6 mole~ of cocatalytic oomplex, c~loulated a~
barium (and therefore accompanied by 300 2 10 6 mole~ of Al)
, ..
i; At 80C., the re~ults obtained, a~ a ~unotion of the time
i. of the reaction, are a8 follows:
;
.,." , ~ ,
. ' ~ , ', ' ,
r.. , 20
.,, `.
; ,: i
.;!
~' ' ''
`,',.
.~.-
''
'~.:. . ' . ; ,
...
.,. .~, .
~', j , :
;,,,j .
" . ' ,
,
... . ..
.,. ~.
.. i. i .
;
~., ~ ; , .
:
~1~6~3~4~ : "
,
.
~ '
.
,, .`:
. ~ . ,.
o ., `
..~ ,.
~ ,o
gD f~ ''':
t ~ ~ .
.. , o ~ ,1 . `
., O ~ , ~ ~ ~ '
. E ~ co ~
.,~ . . . .
.. ~ . ` .
~, i .
.,.,. ;.,.
!,'
.1 !.
,...................................................................... ,',':'`'. " ''
co u~ ~
r~ l :',' ,`
. I
O ,
~' ,.
~,,,y '~o
~., h . .
. :
rl 0~ t ' :,
Ic~ ~
l :
,.",'i., . ':'
"
~3~ n
':
.,.,,~, . . .
. ~ ' .
.
3 ~ ~
he final copolymer obtained after the end OI 18 hours
had an inherent viscosity of' 1.1.
., .
EXAMP~E 5
- Butadiene-Styrene Copolymerization by Me~ns of the Cata-
lytic Composition n-Butyl ~ithium/Barium ~o.nylphenate/Triethyl
Aluminum or Diethyl Zinc
. e~aration of the Cocatal~st_S~stem
The barium nonylphenate i~ prepared by contac-ting nonyl-
phenol (0.02 mole) ~nd bariumi hydro~ide (0.01 mole o~ Ba(0~)2) in
,, 10 the presence of 100 cc. of toluene. The mixture i~ agitated in the
s hot (60 ~ 80C.) until the barium hydroxide ha3 entirely disappear-
ed. About ~alE the solvent i9 evaporated in vaouum ~o as to carry
over all o~E the ~ater formed and the co~centrated solution is then ~:
made up to 100 cc. by means of freah toluene. In this way there i8 ;.;
~,, obtained a solution of anhydrous bariumi nonylphenate in toluene of .-
a concentration of about 1/10 M. : ~;
,
' Copol~merization
Butadie~e and ~tyrene are copolymRrized in 250 cc. Steinie
bottles~ into which there are introduced:
heptane 123 g~
butadiene ~.225 g.
~tyrene 3.075 g.
n-butyl-lithium 50 x 10 6 moles (calculated as
acti~e product) ~.
barium nonylphenate 50 x 10 moles
In order to complete the catalytic compo~ition there are
' added: - - ,
either 100 x 10 6 moles of triethyl aluminum or . : :
~, 100 x 10 6 mo~e~ of diethyl zinc.
, In the case of the control test, nei-ther of these two,,, . i
.~ 30 compound~ i~ added,
, ~he copolymerization i~ carried out at 70C, :Eor ~ariable
.~,. . .
. .-22- ~ .
~,....
~ 36~
period~ of time set forth in Table V in ~rhich the re~ultrs obtained
are entered .
I' :
I.,i .
.; . '.,:, .
..... ..
,. . . .
.~ , ,: . .
.. i . ,,
. , ,~, . "
, -- . ~,~ . . .
~, ~", ~. ,'
~: !` ~
~ , :
~ '~ , .
' '. , ' .
~. . . ....
~7 -23
~ " . .
...
~O~f~
;~:
~ ~ ~ o fff~ ~ ~ ~ ~ `
f~lf ~:
~: ~f
f 'f ~,rf ~ f~-~f' 'N'~ ~ ~ f'~
' ~ i
,-~f ~,'f ~~fY~ f ~f5,'f ~L' 'OC' ''X ~ l '
. ql o~ I
,, ~ ,, '.~ ' :
,`." ff Lr~fXf ~C'' Cf ~' ~ ff3`ff Cf ~r `'' '
1.: .
'f ',,', ':
, , a~ ~ ff~ O O O O ~ O O O O flr~ O O O O .'
~:, ;.1 ff~f f~f ~ 'f 'X ~ ''~'f .~ ~ 'f '~
~ ... l .r~ ~ ~ 1 f~ff'f frff fr.'f ~I ~?~
.~.. ;,. " ~fV 0 , .
.t .. f~_~ ffr,tf : :', .
' U f~ d. ",
ff_ O O "
ff ~
.`;, ff~'
~- ~f' ~ -
;f:~
`''"`' : :~
'~,',, ' ~;
3~
EXAI~PL~. 6
Copolymerization of ~utadiene-Styrene and Copolymers
. having Two Different Sequences with Steric Configuration o~ ~heir ;;
. Own . :
i,~ .. . .
~his copolymer i8 obtai~ed by adding, during the poly- ;
merization, one of the three components of the catalytic compo~
, , .
. .tion, triethyl aluminum in the present ca~e, the n-butyl-lithium
; and the barium compound being added together upon the start o~ the
.~ react~on.
`: 10 ~ntO a 250 cc Steinie bottle there are added~ in all: cases under an atmosphere of rectified nitrogen, 12~ g. of heptane
9.225 g. of butadiene, 3.075 g. of styrene, 50 x 10 6 mole3 of
active n-b~tyl lithium, 50 x 10 6 moles of barium nonylphenate pre-
pared as in the preceding example.
! i ~
The mixture i9 allowed to copolymerize for one and a half
hour~ at 70C.
~he percentage conver~ion reached is 54%. The copolymer
~c~ contains 16% styrene and shows the ~ollowing steric configuration:
5~% trans-1,4 and lO~o 1,2 (in its polybutadiene portion)0 ~.
Whereupon 100 x 10 6 mole~ of triethyl aluminum are added
per Steinie bottle whereupon the polymerization i~ allowed to pro- .~-
ceed at 70C. for an hour and a half~ ~he final copolymer contains
14% ~tyrene. Moreover, on the a~erage 61% of the butadiene links
.~ are in trans-1,4 ~orm and 8% in 1,2. ~he overall percentage of
i~ con~er~ion i~ 76%. i`
.~ Thi~ means that the re~ultant copolymer has t~o 3equences,
namely~
. - the first, representin~ 71~ of the tot~l copolymer,
. contalns on the one hand 16% styrene and 53% trans-1,4% and on the ~.
other h~nd 10~ 192 for the steric configuration of the polybutadiene
portion9
the ~econd, representing 29% of the total copolymer,
,"
~ -25-
.~;
. .
.
. , . ,. . , . , ; :
~~ ~ 0~1 3 ~
contains on the one hand 9% ~tyrene and on the other hand 79%
trans-1,4 and 4~ of 1,2~ for the polybutadiene portion.
- EXArnPIE 1
:
Polymerization of Butadiene b~ Means of n-Butyl ~ithium
and a "Preformed" Cocatalytic System: Barium Alcoholate/Organo-
Aluminu~, ohlorinated or ~onchlorinated `~
Preparation of the Cocntal~st S~stem
; Various barium alcoholates and variou~ organo-aluminum
compounds are used to preform dif~erent cocatalytic 3y~tems under
; 10 the following general conditions:
~ bout 2 g. of barium alcoholate are introduced into
250 cc. Steinie flasks under an atmosphere of rectified nitrogen.
... .
100 co. of heptane are added and then an amount of alkyl or chloro-
alkyl aluminum 89 indicated in the following tablec 'rhe flasks are ~;
then plaoed in a tank ~rhich i8 maintained by thermostat at 60C. ln
~ which they are agitated for si~ hour~. The barium alcoholate which
ti may still not have diægolved is then filtered o~f under an atmo-
~l sphere of rectified nitrogen and the amount of barium in ~olution
i9 determined.
In Table VIIA below there are given for each of the
. , ,
alcoholates and organo-aluminum~ u~ed the quantities o~ product
introduced (for 100 oc. of heptane~), the concentration of barium
(in moles/liter) obtained after di~olving and filtration, a~ well
;~ a~ the yield of dissolved barium ~ith reference to the quantity of
barium alcoholate introduced, and the reference to the cocatal~tic ~;~
. ~, .. .
'J' ~y~tem thu~ prepared: `
.... , , .: . : .
.. . .
~` 30
~ .. .
'O jl, j
.~;, ; . .
IJ~ ~ ~
-26- ~
" ~ : .
3~
" . ~,
,.. .
!7 ~ H ~ P~ ~ 1 :~ X O P-1
'; ' ~ CO~ ~ C~C`J ~ C~IC`J C~l~ . ...
r~ ~ ~D O 00 C`~ CO t-~ ~ tO (51 C~ ..
~ ~ ~ r^l N ~ ~ rl N ~1 . ~D 1~ N N . ..
~.', . ' ~1~ ' '' . . ~
~ h ~
,' ,0 I .~ .' ~'
~'1 '0 rl N N N N N I N~N~ NIoN10~1" O O N
~.,/, g,~ ~ ~ ~ ~ ~ ~ ~ ~ ~ P~ 1~ ~4 "~ ~
~;` C) d~ c5~ C~ Lh t~ rl ~ C~ a~ ~g i.
~ii rl rl t~- ~t ri I--i ri O N ri O N r~i O ~ ~ N
I
a . .
:, p O ¦ O O O ~1 ,~ N ,~ 1
3 ~I I PC ~C ~ ~ ~ ~ ~ ~ ~ ~ ~ ~
-:-' E-l ~ ~ 1 In 00 0 ~ ~ t~ ~ O N ~1 N ~D O ~D
O .; ~ J ~ N ~1 '`ND r~ N rl N ~ C~ l
~,~, . ."".,',' .
1 ~ ~ ~ ~ ~ . ~ ~C ~ ~ ~ ~ ~ ~ M :
'h ~ ~o o u~ ~o ~ ~ 0~0 N ~1 ~ t~CO
t~ o Cl~ c~) co o~ a~ cooo
. . ',
~ h~ h ~ J h~ ~
~~.,, ,' ,'
r-l ~ .' ~ . ,'.. , ~.
~ ~ ' ~ . ~ r~
h ~Fq ~ F~ ~ Fq ~ ,~
~' .
,,'~,.' , ,
.~., . ::
.~.;. .
~ ~.
3~
.
., ,.
; . ~? CY 1:~; U~ H
; ,.',
' rl ¦ ~t ~ u~ ~ . ~
~ ,.,:
.
,.. ~ '~"
~,!y~
., l ~.;,
rl C~J N C~ l ~;
,, . ~ $ O O O O !,.
; '' ~
d,~ ~ ~ ~ ~ ` : :
o o ~U~ ~U~ .~
rl rl OD C)~ ~ ~ ,~ ~
~ ~ 7 ~ ~o ~; -
to ~:
m
. :; .
. 1 ; ~ ,
H ~ ~i t I t I I 0
: ~ H 13 ~ O O O O I : . . .
. ;~ ~ 0 ~ rt ~l ~t ~t ~ ` .
tO ~t ~ ~C ~ ~
:": ~ ~ ~ C~ O ~1 N
` ,;` ` E-l h ~ ~ r-- r
N rl ~ ,
',,',' '':~,'' "
.,, . . ~.~
ol o rl ~ O . ' '' .
`' ``cq .~ ~ ~1 ~ ~ ~4 :'" ': '
t h l ~ O~o ~ :
';';.::~,a ~ t-CO 0~~ , '.
~ `'~
' ,~ - ~,
."", ~ ~ I P~ ~ Ei Si ~ ~i': .
s ."~
'i" h rl t~ ~ ~1 ~ rl ~rl
,"~' - o ~ ~ ~ ,
~,r~ I)
~ J..
a~ ~0~
.. ~ O .~ ~
' ~ ~ h o h h ~ 1
c~rl ~ o `
~ ~ ~ C~
. . ,~
,',,-: : -
': .: '-
: ., -
,., i
'::,; i : ,
:. ' .... ` . . ~ .,. ~ ` ` . ; . : `:
3~
,,
With these cocatalytic systems3 butadiene i9 polymerized
unaer the following condition~
. Into a 250 cc. Steinie bottle there are introduced: !~
,~ . heptane 123 g.
. butadiene 12.3 g.
l,~ cocatalytic system 50 x 10 6 moles of barium
r^ active n-butyl lithium: quantlty indicated i~ the 5~
'~ ~ollowing table 1~.
,.1 The pol~merizatio~ reaction i9 carried out with agitation
,~ 10 for 14 hours at 70C.
,:. . i
The results obtained ~ith the different cocatalytic 'I :
systems are set ~orth in ~able VIIB: l
~ ., .
?' i ~.. ,., i- .
.'` ¦!
,,.~ , .
, 1 ' '
,, ~." .
;'~'. 1'
~',~, ~.... .
"; i
5i
" ' 1~:
' i.................................................................... .. .
..,.,
.- -29-
;..,.,',
~ ... .
''i':''" '' '"'"'' :
: ;
:
.. ~1
. h
~ I . '.
~ ~1~ ~t C-- ~ ~D ~1 ~ 0~ N ~
.~ ~ O ~ ~ l O O ~ ~ '. ' .
. , .,'::
, ; ~1 ` ,', .
h ~ ~ ~ ~ d CO O G:)
O
H ¦ ~ $
- . . ..
Lt~
1 o ~ o ,~,~ ,3 o
t". . ~
''` 6q ~.
. ','.
... .. .
. .: , .:
.~. ~,_1 ,
. ~ rl rl
O c~
,~`'' , . ~ t ~
~-l ~ o
~. ~ t F; ~ F
r ~ ~ ,~ h h h
~ ~t e~ ~~ 'æ O P~
:'`.~ ::
~, ' ~'- .
'.;~, ,,
s ~v~
EXAMPL~ ~
Polymerization of Bu~adiene by Means of n-Butyl ~ithium
and a "Preformed" Cocatalytic System: Strontium Alcoholate/Organo
Aluminum Compound, Chlorinated or Not
Conditions identical to those of t;he preceding examp~es
- (except agitation for 7 hour~ at 70C, instead of 6 hour~ at 60C.),
The quantities indicated also correspond -to 100 cc. of
heptane.
., 10 , , ,;"",
~ .
.~
',' ' , ' , ;'''
'''
~,,,,, ' "~' '.
:':,; - ' ' ' , -
,
. ,,: , .
.... ,:,
''':' '' ' ', ~ '
,: , ,
~ ,
~;
.. ;: ..
, . .
.. ~ ,
r` `~
'
. .
: ' ~
':'',' ~ ' ' :
~I P ~
,, tr, 1~01 ' ' .,:;','
C $ ` I '~
J ~ C
~ ~' ', , , ' ' .,
~J, '
,`~' ' '
,_\j
1 0 ~31
,....
~ '~
;
~he ~ame condition~ as in the preceding example except .
- polgmeri~ation îor 6 hours at 70C" with 50 x 10 6 -
moles of strontium alcoholate per reaction flas~s. ,
~ . .. .~
?
,, . ,(
~, .. ..
.. . '
,~ :' "'' 10 ~.,'
,. .
,, ''.' '''
,, :! ' . .
, '. .'.
`.~ .; .
b
! " : . .
.,
:~"; ,'
~, . ~,
" . '
. ., .:
.
r~
~:
?~ ~ " , . ~
, ~
~"ii'
. '.
... ~ .
.,...
!, , I~
.," 1.
-'~3- 1
., . , . ~ , , .
: ! ' . ' '
~,' ' .
.,,. ".' ' ~ .
1~,' ' ;' ' .
.. ~ ~ ;' .'
;~ . ' ~
;i, ~ 0~
. '`,~ .
J, ~ O O O O ;~.' '
.~ '~ '' .''; ,' . .
.'
.. h~ ~:n O O
., I ~ ~ O O ..
,; .~, . ~
N ~ ~D C~
,,~',' :. '
~: 1 ' ` "
''';~' i . ;', '.:'
~''~ , .
.,. ~ ~ .
.","' P ~ , .
a~ ..
,",~
i:~ D ~
.','.'", , ~ .
5 ~
.,.. , ~ .
E~
Polymerization of Butadiene b~ Means of n~utyl ~ithium
~nd a "Preformed" Cocatalytic Sy~tem: ~arium Hydride/Organo- ;
Aluminum Compound, Chlorinated or Not
Preparation of the Cocatal~ic S~tems
The conditions of preparation are identical to tho~e of
Example 7 (6 hour~ at 60C.), the two gram~ of barium alcoholate
being replaced bg three grams of barium hydride, .~.
Two series of cocatalytic ~ystems were prepared, one ln
heptane (100 ccO per Steinie fla~k) snd the other in toluene (20 cc,
per flask3, ,-
, ~ .
.~ In ~ables IXA and IXB below, there are given ~or each of
the two series the ~uantitie~ of products used per Steinie bottle,
. ~
~ the ~inal ooncentration of barium in the ~olution obtained after
.. 1 filtration as well a~ the yield of barium a~ pre~lou~:L~ and the
reference to the preparation,
,~ "
, . :
. i ;
.~, ~;.
.... .
~ 20
~ . ,.
.,~ . '
~' ,
:
:-" ' ' `
:;
~;
.' ' .'
,: ~ . ' ,
': "
,
.`.,." ' ~
.' ' .
( ' i
' '.'.
5-
:,................ .
,;,,
''.: ' ' -: .. ' '
~a~3~ r
H H 1-l ~ P H ~ H H p ~ ~ PC H
~¦ H H H ~ t~ ~ P~ '~
,'`~ . . .
, . .'.', `
. C~l t~ ~ ~ ~ O
''~' a>~ ~ c~ ~i d ~ O 1:~ 0 O ri U~
r~l~ ,: .
;'i . . . :. .
~:,' O h . , . .
. . . .
','"':,
~ ~ C~J N N N ~~ C~l
~~lrl wrtrl r~101~ rl~l~~
.,, 0 ~ ~ ~ ~ ~ . U~ u~ ~ w ' .~ '
,~""i ~ pl ~ C\~ C::~ rl r~l rl ~1 ~D . .. ,. , ~', .
¢1 ~-i N ~_1 O et ~D O O O O O O I , : .
. ~ ;'~ '.
: : l ` :~
~3 ~ o~ o ~o~o~o lololo lololo :~:
~ ' o N~ ~1~1rl rl rlrl rl r-l f~ ~ :
~4 ~ ~ ~ ~ ',
C~
0 ~D ~ d- ~D ~tt~ ~ O O U~ ~ ,
N N 1-l C~ l NC~l N ~ N ~I rl
~,., h : .
'.''''' ~3~ '' . .
. . ~
t-~ ~: ~ ~ ~ 1~ ~ t<~ t~ : . . '
. O ~10~olo 10~olo 10~olo 10~olo ~
~ ~ ~ r~ ~ : ':
0 ~i~ ~ ~t ~ ~ ~ ~ ~
. ~ I E~t--`.O N O . .,. . o N ~t ~J
~ ¦ Q o ~ OD N 1~ r-- tl~D O 2 ~ ~
;',i;;' ' ' l : : : .
: .
,~ .., ~ . . ,,
~'~.' ............ I . .
,;`''','". ~I 1 ~ ~ ~ r~ rl ~ ' ' '
n C ,q l Q Q Q
ii~` . ...
~,'.`,, - `' .
L3
~ ,
.` ~' . .
1',~' ''
~¦ H ~ ~ H i H ~ ~ i ~ H ~ ¦ .
:~ ~ . ~ . 1,~
., ~d ~00 rl u~ 00 rf .
'; ~ri i Lf~ ~ rl ~ t~ ~ O C\l N ~ ~ rl r~l rl t~ ~ 0 rl ~ ~ 1 `
~' ~ , ~
, ~ w h .
. C~JoN~o~o N~o~C`~Jro~l,of C~l O O O O O i
g ~rl r-l r~l rl ~ S~ ~ rl
C ~ ~ ~i ~ ~ ~ ~
ri ~ t~ C~J C~; i N t~ 1-l ri N rl ~F r~ ~ .
~ . . l ,
010~0 10100 101010 101010 : ~:.
';';''' Fl;i .~r'i ~Fi ~r -1 rri ~ r r~ r~ 1
~ M M ~i ~4 K
F a~¦ O t--~ ~ ~1!- a~ c~ N O U~ ~
N C~; ri 1~ CO~; a)i r~ ' C~l rJ ~1
.
~} O ei Ei ~I rl o O O o rl ,~ ~l 0,
i ~ ~ ~ K ~ ~ ~ ~ i
O ~ C~' ~ CO ~i C~ ~ ~D O CC N
~r~ ,~ 0~ C~ rf ~ ln
''','`,''''~
.;'.` I ~d rl~
R 3 ol ~1 rl N V
~?~ F~3 I W I F~
.,~," I
.
~ `:
Same conditions as in E:~ample 7:
- polymerizatio~ at 70G, ~or 24 hours in heptane
medium
- , ..
- quantity of BaH2 per 250 cc. reaction flas~
50 x 10 6 mole 9 . . .
,~
.' ~he re ~ult~ obtaine d, ~ s a function of the ~uantitie ~ of , ~
n-butyl-lithium used~ are set forth i~ ~able I~:C: ~ :
, -
. .
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EXhMPIE 10
.
;. ,
. Polymerization of Eutadie~e by Means o~ the Catalyst
:~ Composition n-Butyl-Lithium/Barium Naphthenate/Diethyl Zinc
'.
t ~ . -
The barium naphthenate, prepared from commercial ;~
:;: naphthenic acid b~ neutraliz~tion with caustic soda in aqueou~
medium and precipitation by barium chloride i9 a salt soluble in
., ,
toluene medium. There i~ therefore u~ed an 0.113 mole/liter
~olution in barium o~ barium naphthenate in toluene.
~f
i 10 Pol~meriz~tion
But~diene i~ polymeriæed under the ~ame conditions a~
~~ previou~ly in 250 cc. Steinie bottles~ 12.3 g. of butadiene for .:~
123 ~. of heptane with 50 x 10 6 mole~ o~ bariuim naphthenate and
¦ 50 ~ 10 6 mole9 of ~ctive n-butyl-lithium per fla~k, for 6 hour~
at 70C.
~ r~he result~, ba~ed on the quantities of diethyl zinc
;! introduced, are ~et forth in r~able XD
, ~,~ , , ,~ .
~ 20
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E MP~E 11
Polymerization of I~oprene by Mean~ of the Ca~aly~t
- ~ompo~ition n-Butyl-Lithium/Barium ~onylphenate/Triethyl Aluminum
.> or Diethyl Zinc
. . .
. .
~ he solution of barium nonylphenate in toluene i9 pre-
pared in the sa~e manner as in E~a~ple. 5.
. ~he isoprene (12.3 g.) is polymerized in 250 cc, Steinie -
7'"' bottle~ ~n heptane medium (123 g.) for 6 hours at 70C~ with, per
.. reaction ~lask:
50 x 10 6 mole~ of active n-BuI~
~;~; 0 or 50 x 10 6 moles of barium nonylphenate
; 0, 100, or 200 x 10 6 moles of triethyl aluminum or
diethyl ~inc.
.. . ..
'~' In ~able ~I the lnfluenoe of the com~inSation of these
.~,,,;~.j ., .
~ different additi~es is compared,
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EXA~.~IE 12 - .
,, ~ ' , .
; I~oprene/Styrene Copolymeri~ation by Mean~ of the Same
Catalgst Composition as in Example 11
O~e operate~ under the same polymerization conditions in
250 cc. Steinie bottles~ i~ heptane medium (123 g.~ ~ith 9,24 g. of
... i~oprene a~d 3,08 g. of ~tyrene (25% referred to the isoprene). .
Copolymerization is effected for two hour~ at 70C, i~ the presence .
of 50 x 10-6 mole3 of acti~e n-~u~
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EXAMPIE 13
3utadiene/Vinyl Toluene Copolymerization by hleans of the
Catalyst Compo3ition n Butyl-~ithium/Barium ~onylphenate/'~riethyl
Aluminum
',.. ~ .
In 250 cc. fl~aks there are copolymerized: .
; 9.24 g, of butadiene . :
3.08 g. of vinyl toluene (commercial mi~ture of 2/3
~` metamethyl ~tyrene and 1/3 paramethyl styrene)
. ~ .
123 g. of heptane
50 2 10-6 moles of active n-~u~i
50 ~ 10 6 moles of b~rium nonylphenate
200 x 10 6 moles of triethyl aluminum for three hours at
. 70~.
l The result~ obtained are a~ ~ollow~:
conversion rate obtained: 64%
n = 0.97
.,. ~; .
~ 9~o ~inyl toluene present in the copolymer 82% trans-1,4
x linkagea and 34i 1,2 linkages in the polybutadiene phase.
,........................................................................... .
~, EXAMP~E 14
., ~. .
Butadiene/'rert-butylstyrene Copolymerization by Means of
'' 20 the Same Catalyst Composition as in Example 13
, l Per 250 cc. Steinie flask there are
lntroduced:
9.24 g. of butadiene
. ~
~: 3 7 08 g. of tert-butylstyrene (95~o psra, 5% ortho)
.. 123 g. o~ hept~ne
... .
.i 50 x 10 ~ moles of active n-~Bu~i
. 50 x 10 6 mole~ of barium nonylphenate
.i 200 ~ 10 6 mole3 of triethyl aluminum~
-. copolymerization i9 effected for 5 1/2 hours at 70C.
.~ 30
46
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; ~ " '' ' , ' ' . '', ' ' : :~
`
. .:
.
The re~ult~ obtained are as follows:
` n _ 1,12
:,
7~ tert- butylstyrene present in the copolymer
;~ 85~ trans-1,4 linkages and 3~ 1,2 linkages
. .
~ EXAMP ~
, . .
. Mechanical Propertie~ o~ a Mixture f~r Rubber Having a
.~ Base of Butadiene/Styrene Copolymer with a High Content of
~ ran~-1,4 and Low Content of 1~2
.:. 1, PreParation of the Copol~mer
. ~ ~he catalytic composition of Example 3 or 4 1~ used:
. ~. .
, n-butyl-lithium
.. . preformed cocatalytic sy~tem: dibenzoglmethane
,... ; barium/tricthyl aluminum,
,i ,.
. The polymerization is carried out in a 10 liter reactor
. ~ . .
';.. ~ in an atmosphere of rectified nitrogen with:
, Solvent: heptane: 5040 g.
,. .,: .
~: ; Monomers: butadiene: 378 g.
... . . .
styrene: 126 g. :.
;.`.,. Initiator: active n-butyl-lithium: 1,64 x 10 3 moles
; 20 Cocatalytic sy~tem: barium: 1.64 x 10 3 moles
,`i aluminum 8.2 ~ 10-3 moles
.. ~' ' for two.hours at 80C,
'" `r: The percentage conversion obtained i9 75% and the vi~co- ..
,- ~,.. .
. sity reached i9 1.4.
.' : A tri-chain grafting i9 then effected by introducing into
..... ..
': the medium which is still active 1,64 x 10 3 moles of diphenyl
,~;, . carbonate in accordance with Mlchelin ~rench Patent No. 2,053,786 .;.
.. `, published on April 16, 1971. Reaction is allowed to continue for
. . 20 minutes at a temperature of 80C. Methanol is then introduced
~,~ 30 to stop the reaction as well as an antioxidant (0.,55~ by weight
.~........... referred to the rubber) and the elastomer (about 38Q g.)
~:,. is recovered by steam distillation of the
`~ : 47
"~;, .
: , ..
301vent and drying under vacuum.
; The final viscosity sfter grafting has become 1.9. ~he
Mooney vi~cosity (1 ~ 3 at 100C.) i9 then 45. ;;
The-resultant copolymer has the following steric
configuration:
75~ trans-1,4)
) the same for the butadiene portion
5% 1,2
The content of incorporated styrene is 8~.
10 -2. Rubber-Makin~ ~ixture
~he elastomer described above i3 used to make a mixture
havi~g the following formula:
J elastomer 100
stearic acid 2
ZnO 3
, ~ntioxidant (4010 NA)
!; carbon black HAF 50
~ Philblack O *
:, *
processing oil Sundex 8125 5
, 20 (aromatic)
. , *
, Santocure
~ulfur 1.6
The same mix is prepared with a commercial butadiene-
.. styrene copolymer (SBR 1500) as control. Stress strain measure- :
ments are carried out on test pieces of these non-vulcanized mixe~
.
(measurement of the green strength).
The results obtained are as follov~:
* Tradcmark.
:.;
.. . . .
~ 30
i
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~.," . . ~
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,
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,:
N N I ~
, :. .` . - ':
3~
~he mixture prepared with the elastomer in f~ccordance
~ith the invention ha3 a better mechanical ~trength theni the con-
. trol mixture.
The two mixture~ are then vulcani.zed for 60 minute~ at
144C. The mechan~'cal properties obtained are set forth in
s Table XVB.
,
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,.. . . . .
It is no-ted tha-t -the elastomer in accordance wi-th the
,;;- invention, that i~ to ssy the SBR, with ~ high content of trans-1,4
'~ and a low content of 1,2, actually has the properties o~ a rubber
and even of a good rubber if one considers -the level of hysteresis
~' losse~ reached.
.... .
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