CA1061314A - Polymers or copolymers of modified steric composition obtained by the use of a new catalytic composition - Google Patents
Polymers or copolymers of modified steric composition obtained by the use of a new catalytic compositionInfo
- Publication number
- CA1061314A CA1061314A CA228,556A CA228556A CA1061314A CA 1061314 A CA1061314 A CA 1061314A CA 228556 A CA228556 A CA 228556A CA 1061314 A CA1061314 A CA 1061314A
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- Canada
- Prior art keywords
- organo
- lithium
- barium
- reaction
- compounds
- Prior art date
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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
Polymers of conjugated dienes and copolymers of con-jugated dienes with vinyl aromatic compounds or with other con-jugated diene a having a high content of trans-1,4 linkages and a low content of 1,2 or 3,4 linkages and an elastomeric character are prepared by use of a catalytic composition which comprises (a) an organo-lithium initiator and (b) a cocatalyst system comprising a compound of barium or strontium and an organometallic compound of a metal of Group IIB or IIIA of the Mendeleev periodic table of elements.
Polymers of conjugated dienes and copolymers of con-jugated dienes with vinyl aromatic compounds or with other con-jugated diene a having a high content of trans-1,4 linkages and a low content of 1,2 or 3,4 linkages and an elastomeric character are prepared by use of a catalytic composition which comprises (a) an organo-lithium initiator and (b) a cocatalyst system comprising a compound of barium or strontium and an organometallic compound of a metal of Group IIB or IIIA of the Mendeleev periodic table of elements.
Description
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 ... : .
....
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 : .,~., .
,., 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 ,.
:, . .. . .
,." ~, .
,.. .. ..
.~ . .
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 ' ; ::
.~ .
;-;~;, .. .... .
- 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.
, ,~................................................................... . .
` ~
~ 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 . .:,. .
(~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 ~:
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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 ?, :',.,~, ' ' `' :;', . .
... . .
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~`~
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: ~ .
, ~ ~1 N ~ CO ~ O
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C
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.' F~ . .. . . .. .. ...
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i~ h ~ ~ ~ ~ rl r-l u~
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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 . .
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a~ X
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. 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 .;!
~' ' '' `,',.
.~.-'' '~.:. . ' . ; , ...
.,. .~, .
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:
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,...................................................................... ,',':'`'. " '' co u~ ~
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. :
rl 0~ t ' :, Ic~ ~
l :
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.,.,,~, . . .
. ~ ' .
.
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' :
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.; . '.,:, .
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.. i . ,, . , ,~, . "
, -- . ~,~ . . .
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...
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;~:
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f~lf ~:
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' ~ 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 , .
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ff ~
.`;, ff~' ~- ~f' ~ -;f:~
`''"`' : :~
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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 ~ .. .
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-26- ~
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3~
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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 ~ ~ ~ ~ ~ ~ ~ ~ ~ ~
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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~ ~
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,',,-: : -': .: '-: ., -,., 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-;..,.,', ~ ... .
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: ;
:
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r ~ ~ ,~ h h h ~ ~t e~ ~~ 'æ O P~
:'`.~ ::
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'.;~, ,, 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 , , ,;"", ~ .
.~
',' ' , ' , ;''' ''' ~,,,,, ' "~' '.
:':,; - ' ' ' , -, . ,,: , .
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,, 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 ~.,' ,. .
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5 ~
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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 ~ . ,.
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.,, 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~ ~ :
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0 ~D ~ d- ~D ~tt~ ~ O O U~ ~ , N N 1-l C~ l NC~l N ~ N ~I rl ~,., h : .
'.''''' ~3~ '' . .
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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 : : : .
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,~ .., ~ . . ,, ~'~.' ............ I . .
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~ , .` ~' . .
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: ~ :
, -. .
:.~ 10 , ,",,, ", :. - , . .
. i l , i,l . '.: .
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¦ C~ 0 oo 01:) 00 CO ~ CO: ~ ~ t~ ~ ., s.l I . ! :
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.''. . '; ~rl . . .
. I h ~t O O O O O o O O 1~ ~ C~J O
a) o o o o o o o o a~ oo a~ o . ~I r~l ~I rl r~ ~ rl . rl ,., . .
,',,,~,',, p~ . ' ,.',:~s 'l ~r~l . ~ ~
Na:~ O ~d- ~ l . ~ r~ r~ t~O O ~ s ~_ U~
.~,j~,,,,,"~ . . . ' ~ ' ' j t~ ~ . D
',''''S'''. I ~~r;
~.,'''' ' O ~ ~ ~1 C~ CC
~` d~r3 0 ~-1 ~ ~-1 r~ tU
a:~ ~ ~:~
h rf ~ .
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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 ''' " '' '' 1,. . :
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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, 1 ' ,:
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v~
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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~V~3~
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 '' ' ; ~ " '' ' , ' ' . '', ' ' : :~
`
. .:
.
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.
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.. . . .
~ 30 i :
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~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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.~ 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 ... : .
....
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 : .,~., .
,., 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 ,.
:, . .. . .
,." ~, .
,.. .. ..
.~ . .
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 ' ; ::
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.
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:,~........ O ~ q~ O O O IS~ O O . ~:
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~ .' .~ .. . .
.. ,":" .
. . ,., . ~....
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.
, ,~................................................................... . .
` ~
~ 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 . .:,. .
(~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 .. . . .
: ., .. . . . .. .
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;
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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;':~!
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.
.
~'' 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:
;
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; ,: i .;!
~' ' '' `,',.
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.
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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 .
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,, ~ ,, '.~ ' :
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, , 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 ~?~
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ff ~
.`;, ff~' ~- ~f' ~ -;f:~
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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: `
.... , , .: . : .
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r~ ~ ~D O 00 C`~ CO t-~ ~ tO (51 C~ ..
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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 ~ ., .
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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.
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~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. , ~ . .. .~
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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, ,~ "
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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
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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, 1 ' ,:
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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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~V~3~
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 '' ' ; ~ " '' ' , ' ' . '', ' ' : :~
`
. .:
.
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.
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~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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Claims (14)
1, A process of polymerizing conjugated dienes or copolymerizing conjugated dienes with other conjugated dienes or with vinyl aromatic compounds to form elastomeric products having simultaneously a high content of trans-1,4 linkages and a low content of 1,2 or 3,4 linkages which comprises reacting the mono-mers in a reaction medium in the presence of an added catalytic composition comprising (a) an organo-lithium initiator and (b) a cocatalyst system comprising a compound of barium or strontium and an organometallic compound of a metal of Group IIB or IIIA of the Mendeleev periodic table of elements.
2. The process according to claim 1 wherein the cocatalyst system is preformed and added to the reaction medium at the same time as the organo-lithium initiator at the start of the reaction.
3. The process according to claim 1 wherein the cocatalyst system is preformed and added in one or more batches to the reaction medium during the course of the reaction which has been previously initiated by the organo-lithium initiator.
4. The process according to claim 1 wherein the components of the cocatalyst system are added to the reaction medium in one of the following ways:
a) separately at the start of the reaction in one or more batches at the same time as the organo-lithium initiator, b) one after the other in any order during the reaction which has been previously initiated by an organo-lithium initiator, or c) jointly in one or more batches during the reaction which has been initiated previously by an organo-lithium initiator.
a) separately at the start of the reaction in one or more batches at the same time as the organo-lithium initiator, b) one after the other in any order during the reaction which has been previously initiated by an organo-lithium initiator, or c) jointly in one or more batches during the reaction which has been initiated previously by an organo-lithium initiator.
5. The process according to claim 1 wherein butadiene is used as the conjugated diene and styrene is used as the vinyl aromatic compound and the catalytic composition comprises n-butyl-lithium, a barium phenate, and a trialkyl aluminum
6. The process according to claim 1 wherein the cata-lytic composition is added to the reaction medium in such a manner as to continuously regulate the content of trans-1,4 linkages be-tween a) 45% and 95%, the content of 1,2 linkages being between 12% and 3% in the case of polybutadiene and copolymers having a base of butadiene, b) 25% and 45%, the content of 3,4 linkages being be-tween 10% and 5% in the case of polyisoprene and copolymers having a base of isoprene.
7. A catalytic composition for the polymerization and copolymerization of olefins which comprises:
a) an organo-lithium initiator, and b) a cocatalyst system comprising a compound of barium or strontium and an organometallic compound of a metal of Group IIB or IIIA of the Mendeleev periodic table of elements.
a) an organo-lithium initiator, and b) a cocatalyst system comprising a compound of barium or strontium and an organometallic compound of a metal of Group IIB or IIIA of the Mendeleev periodic table of elements.
8. The catalytic composition according to claim 7 where-in the organo-lithium initiator is selected from the group consist-ing of alkyl organo-lithium compounds; alkenyl organo-lithium compounds;"live" lithium polymers; aryl organo-lithium compounds;
dilithium polymethylene compounds; polylithium compounds resulting from the reaction of metallic lithium with aryl-substituted ethylene compounds; and ionic-radical adducts of lithium and polynuclear aromatic hydrocarbons.
dilithium polymethylene compounds; polylithium compounds resulting from the reaction of metallic lithium with aryl-substituted ethylene compounds; and ionic-radical adducts of lithium and polynuclear aromatic hydrocarbons.
9. The catalytic composition according to claim 7 where-in the compound of barium or strontium is selected from the group consisting of the hydrides; the monofunctional and polyfunctional organic acid and thio acid salts bearing no other functions capable of inactivating the organo-lithium initiator; the monofunctional and polyfunctional alcoholates and thiolates; the monofunctional and polyfunctional phenates and thiophenates; the alcohol acid and phenol acid salts of barium and strontium as well as the correspond-ing thio products; the .beta.-diketonates of barium and strontium; the organic derivatives of barium and strontium; mixed organic deriva-tives of barium and strontium; ketone metals and the corresponding alkyl products and sulfided homologues; and the radical ions.
10. The catalytic composition according to claim 7 where-in the organometallic compound of a metal of Group IIB or IIIA of the Mendeleev periodic table of elements selected from the group consisting of dialkyl zinc and cadmium compounds; halogenated and non halogenated organo-aluminum compounds; organoboron compounds;
and dialkyl aluminum hydrides.
and dialkyl aluminum hydrides.
11. The catalytic composition according to claim 7 where-in the components are present in such quantities that the ratios are within the following limits:
with with R3 Me IIIA representing an organometallic compound of a metal of Group IIIA and R2 Me IIB representing an organometallic compound of a metal of Group IIB.
with with R3 Me IIIA representing an organometallic compound of a metal of Group IIIA and R2 Me IIB representing an organometallic compound of a metal of Group IIB.
12. The catalytic composition according to claim 11 wherein the components are present in such quantities that the ratios are within the following limits:
with with R3 Me IIIA representing an organometallic compound of a metal of Group IIIA and R2 Me IIB representing an organo-metallic compound of a metal of Group IIB.
with with R3 Me IIIA representing an organometallic compound of a metal of Group IIIA and R2 Me IIB representing an organo-metallic compound of a metal of Group IIB.
13. The process of preparing the catalytic composi-tion defined by claim 7 which comprises preforming the cocata-lyst system by mixing together the components thereof which have been previously placed in solution or suspension in a hydrocarbon solvent and combining the preformed cocatalyst with the organo-lithium initiator.
14. The process of preparing the catalytic compo-sition defined by claim 13 which comprises preforming the cocatalyst system by mixing together the components thereof which have been previously placed in solution or suspension in the same solvent as the one used in the polymerization reaction.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FR7419475A FR2273822A1 (en) | 1974-06-05 | 1974-06-05 | POLYMERS OR COPOLYMERS WITH MODIFIED STERIC COMPOSITION OBTAINED BY IMPLEMENTATION OF A NEW CATALYTIC COMPOSITION |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1061314A true CA1061314A (en) | 1979-08-28 |
Family
ID=9139681
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA228,556A Expired CA1061314A (en) | 1974-06-05 | 1975-06-04 | Polymers or copolymers of modified steric composition obtained by the use of a new catalytic composition |
Country Status (21)
| Country | Link |
|---|---|
| JP (1) | JPS5123589A (en) |
| AR (1) | AR213389A1 (en) |
| AT (1) | AT341212B (en) |
| BE (1) | BE829806A (en) |
| BR (1) | BR7503483A (en) |
| CA (1) | CA1061314A (en) |
| CH (1) | CH603706A5 (en) |
| DE (2) | DE2524849C2 (en) |
| EG (1) | EG12270A (en) |
| ES (1) | ES438160A1 (en) |
| FI (1) | FI59109C (en) |
| FR (1) | FR2273822A1 (en) |
| GB (1) | GB1516861A (en) |
| IE (1) | IE41546B1 (en) |
| IT (1) | IT1041376B (en) |
| LU (1) | LU72633A1 (en) |
| NL (1) | NL154525B (en) |
| NO (1) | NO145341C (en) |
| RO (1) | RO70318A (en) |
| SE (1) | SE407068B (en) |
| ZA (1) | ZA753634B (en) |
Families Citing this family (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2340958A2 (en) * | 1974-06-05 | 1977-09-09 | Michelin & Cie | PROCESS FOR POLYMERIZATION OR COPOLYMERIZATION OF CONJUGATE AND POLYMERIC DIENES THUS OBTAINED |
| US4297240A (en) | 1980-02-25 | 1981-10-27 | The General Tire & Rubber Company | Solution polymerization |
| US4302568A (en) | 1980-02-25 | 1981-11-24 | The General Tire & Rubber Co. | 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 |
| ES2020484A6 (en) * | 1990-06-29 | 1991-08-01 | Repsol Quimica Sa | Method of preparing homopolymers of conjugate dienes and copolymers of conjugate dienes with other dienes or vinyl aromatic compounds |
| FR2722503A1 (en) | 1994-07-15 | 1996-01-19 | Michelin & Cie | FUNCTIONAL DIENE POLYMERS, PROCESS FOR THEIR PREPARATION AND THEIR USE IN ELASTOMERIC SILICA-FILLED COMPOSITIONS FOR USE IN TIRE ENVELOPES |
| FR2722505B1 (en) | 1994-07-15 | 1996-09-27 | Michelin & Cie | SILICA-FILLED ELASTOMERIC COMPOSITIONS FOR USE IN TIRE TIRES |
| FR2744127A1 (en) | 1996-01-26 | 1997-08-01 | Michelin & Cie | RUBBER COMPOSITION BASED ON A DIENE POLYMER HAVING A SILANOL FUNCTION AND COMPRISING AN ORGANOSILANE DERIVATIVE |
| WO2003037946A2 (en) | 2001-10-31 | 2003-05-08 | Societe De Technologie Michelin | Method of preparing block copolymers for tyre tread compositions and the copolymers thus prepared |
| 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 |
| FR2951186B1 (en) | 2009-10-12 | 2012-01-06 | Michelin Soc Tech | RUBBER COMPOSITION BASED ON GLYCEROL AND A FUNCTIONALIZED ELASTOMER AND TIRE TREAD FOR PNEUMATIC |
| FR2992649B1 (en) | 2012-07-02 | 2015-06-19 | Michelin & Cie | PROCESS FOR CONTINUOUS SYNTHESIS OF DIENE ELASTOMER |
| JP2014040554A (en) * | 2012-08-23 | 2014-03-06 | Asahi Kasei Chemicals Corp | Butadiene and method of producing the same |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR1476322A (en) * | 1965-04-20 | 1967-04-07 | Shell Int Research | Solution polymerization process of dienes with lithium-hydrocarbyls or metallic lithium as catalysts |
| GB1271265A (en) * | 1968-06-08 | 1972-04-19 | Bridgestone Tire Co Ltd | Method of preparing conjugated diene polymers using catalysts based on organolithium compounds |
| US3664989A (en) * | 1969-10-27 | 1972-05-23 | Gennady Nikolaevich Petrov | Methods for the preparation of synthetic polymers |
| US3808186A (en) * | 1972-05-09 | 1974-04-30 | V Shatalov | Method for preparing trans-1,4-polydienes |
-
1974
- 1974-06-05 FR FR7419475A patent/FR2273822A1/en active Granted
-
1975
- 1975-06-03 ES ES438160A patent/ES438160A1/en not_active Expired
- 1975-06-03 IT IT68409/75A patent/IT1041376B/en active
- 1975-06-03 LU LU72633A patent/LU72633A1/xx unknown
- 1975-06-03 BR BR4460/75D patent/BR7503483A/en unknown
- 1975-06-03 BE BE156974A patent/BE829806A/en not_active IP Right Cessation
- 1975-06-03 RO RO7582416A patent/RO70318A/en unknown
- 1975-06-04 GB GB24148/75A patent/GB1516861A/en not_active Expired
- 1975-06-04 FI FI751645A patent/FI59109C/en not_active IP Right Cessation
- 1975-06-04 EG EG320/75A patent/EG12270A/en active
- 1975-06-04 DE DE2524849A patent/DE2524849C2/en not_active Expired
- 1975-06-04 CA CA228,556A patent/CA1061314A/en not_active Expired
- 1975-06-04 SE SE7506393A patent/SE407068B/en not_active IP Right Cessation
- 1975-06-04 NO NO751968A patent/NO145341C/en unknown
- 1975-06-04 DE DE2560562A patent/DE2560562C2/en not_active Expired
- 1975-06-05 JP JP50068107A patent/JPS5123589A/en active Granted
- 1975-06-05 CH CH727775A patent/CH603706A5/xx not_active IP Right Cessation
- 1975-06-05 ZA ZA00753634A patent/ZA753634B/en unknown
- 1975-06-05 AT AT428975A patent/AT341212B/en not_active IP Right Cessation
- 1975-06-05 IE IE1262/75A patent/IE41546B1/en unknown
- 1975-06-05 NL NL757506686A patent/NL154525B/en not_active IP Right Cessation
- 1975-06-05 AR AR259090A patent/AR213389A1/en active
Also Published As
| Publication number | Publication date |
|---|---|
| NO145341B (en) | 1981-11-23 |
| FI751645A (en) | 1975-12-06 |
| JPS5123589A (en) | 1976-02-25 |
| SE7506393L (en) | 1975-12-06 |
| RO70318A (en) | 1982-09-09 |
| CH603706A5 (en) | 1978-08-31 |
| AR213389A1 (en) | 1979-01-31 |
| ATA428975A (en) | 1977-05-15 |
| AT341212B (en) | 1978-01-25 |
| FI59109C (en) | 1981-06-10 |
| IE41546L (en) | 1975-12-05 |
| DE2524849C2 (en) | 1984-08-09 |
| JPS5230543B2 (en) | 1977-08-09 |
| FR2273822A1 (en) | 1976-01-02 |
| LU72633A1 (en) | 1976-03-17 |
| SE407068B (en) | 1979-03-12 |
| FR2273822B1 (en) | 1977-08-12 |
| EG12270A (en) | 1979-12-31 |
| GB1516861A (en) | 1978-07-05 |
| ES438160A1 (en) | 1977-05-01 |
| AU8184575A (en) | 1976-12-09 |
| BE829806A (en) | 1975-12-03 |
| ZA753634B (en) | 1976-05-26 |
| FI59109B (en) | 1981-02-27 |
| IT1041376B (en) | 1980-01-10 |
| NL154525B (en) | 1977-09-15 |
| NO751968L (en) | 1975-12-08 |
| DE2524849A1 (en) | 1975-12-11 |
| BR7503483A (en) | 1976-05-25 |
| NL7506686A (en) | 1975-12-09 |
| NO145341C (en) | 1982-03-03 |
| IE41546B1 (en) | 1980-01-30 |
| DE2560562C2 (en) | 1986-11-06 |
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