CA1141881A - Process for producing carbo-chain homopolymers, block and random copolymers of conjugated dienes with vinylaromatic monomers - Google Patents

Abstract

ABSTRACT OF THE DISCLOSURE

A process for producing carbo-chain homopolymers, block-and random copolymers of conjugated dienes and vinylaromatic monomers comprising polymerization of dienes, vinyl- or di-vinylaromatic monomers or copolymerization thereof in a medium of a hydrocarbon solvent at a temperature ranging from -30 to +150°C in the presence of an organolithium catalyst of the formula R(Li)X, wherein R is a hydrocarbon radical or a diene polymer, x is an integer of from 1 to 4, and a modifying ad-ditive which is a compound comprising a product of interac-tion between a phenolamine resin and an alkali metal and hav-ing the general formula:
wherein n is an integer of from 1 to 10;
M is sodium or potassium;
R is an alkyl with 2 to 20 carbon atoms or an aryl-alkyl with 7 to 20 carbon atoms;

R1 is an alkyl with 1 to 6 carbon atoms, an arylalkyl with 7 to 9 carbon atoms or hydrogen;
this modifying additive is used in an amount of from 0.07 to 2.0 g/equiv. per one g/equiv. of active lithium.

Description

~R~)CESS FQR i'~O~UCI~G CAR~-C-~AI~ HOI-~.IOPO~.&~S, B~OCK- AN~ Rl~N~O~I COPOL~.~;~`RS 0~ CONJUGA~ED DI~I~r~S
'IT-~ VINYL-AROli~TIC -~lGNO~S

The present invention relates to ~rocesses ~or tne pro-duction of pol~mers, and more speci~ically, ~o a process for producin~ carbo-chain homopolymers, block- and random copo-lymers of conju~ated ~ienes with vinylaromatic monomers; the rcsulti~g polymers are employed as a material for the manu-facture o~ tyres, rubber-engineering articles, rubber ~oot-wear. Articles manufactured ~rom such polymers are not in~erior to article~ made of natural rubber in respect of their crac~-ing-resista~ce and heat-~ormation.
Carbo-chain block- and random copolymers can be used in the production of cables owing to their high dielectric pro-perties.
~ no~n in the art is a process ior producing carbo-chain homopolymers, bloc~- and random copolymers by polymerization of conju~ated dienes, vinyl- or divinylaromatic monomers or intercopolymerization thereof in an inert nydrocarbon so~ent medium at a temperature within the ran~e o~ from -30 to 150C
in the presence o~ a~ organolithium cacalyst and a modifying additive, i.e. a co~pound of the ~eneral formula ~~(O~il)n, where-in n is an integer of ~rom 1 to 3, ~q is potassiu~, sodium, rubidium or cesium; R is an aliphatic, aromatic or a cyclo-`.. `

aliphatic radical.
~ his prior art process has a disadva~tage residing inthat the organic compounds of alkali metals with a nu~ber of carbon atoms of at most 20 employed as the ~iodifying ad-ditive are but sparingly soluble in aliphatic, cycloaliphatic and aromatic hydrocarbons. In practice o~ this prosess it is necessary to disperse said insoluble products ~hich is acco~-panied by difficulties er.countered in storage an;l a precise metering of the resulting suspensions into the reaction medium.
By-products forMed wi~n the use o~ oxygerl-containin~ organic compounds of alkali metals with a number of carbon atoms below 20 are volatile and can contaminate the recycle solvent ~hus necessitating additional investments ~or its puri~ication. i~ur-thermore, tAe polymerizate is unstable and, to prevent destruc-tion o~ the resulting polymer upon recovery and drying tnereo~, stabilizing agents should be introduced thereinto. All tnis com-plicates the polymerization process technology.
Also known in the art is a process ~or producing carbo-chain random copolymers o~ conjup,ated dienes with vinylaroma-tic monomers in a hydrocarbon solvent.
The process is conducted at a temperature within the range o~ ~rom -30 to 150C in the presence o~ a catalyst com-prising a compound o~ the general ~ormula R(Li)X, wherein R
is a hydrocarbsn radical containing 1 to 20 carbon atoms, x is an integer of ~rom 1 to 4, and in the presence o~ an addi-tive comprisin~ an organometallic compound. Such compoundscan be those correspondin$ to ~ormulae: R'M, Rr(yM)n; R"(C-yrS)r and the like, wherein R' is a hydrocarbon radical v~ith 1 to 20 carbon atoms, R" is a hydrocarbon radical with 4 to 20 car-bon atoms, y is an atom of oxygen or sulphur; n is an inte-ger ol ~rom 1 to 3, and ~l is sodium, potassium, rubidium or cesium.
As a solvent ~or the copolymeriza-tion use is made of aliphatic, aromatic and cycloaliphatic hydrocarbons. As a re-sult, a solution o~ a copolymer is ootained, which is tAen added with an antioxidant. ~terwards, the desired product is recovered by conventional methods (cf. British Patent No. 1,029,445~.
~ his prior art process has disadvantages which may be exempli~ied by that the or~anic compounds o~ alkali metals corresponding to the above-given ~or~ulae are sparingly soluble in aliphatic, cycloaliphatic and aromatic hydrocarbons. In the practical implementation of this process it is necessary to ~orm suspensions o~ these insoluble products. Furthermore di~-~iculties are encountered in storage and a precise meterin~ o~
the dispersion prior to admission thereof into the reaction system, especially in per~ormin~ a continuous polymerization process.
The resulti~g polymerizate is unstable and, to prevent .

the polymer destruction upon recovery and drying thereo~, a stabilizing agent must be added.
~ urthermore, in the case of using, as modifying addi-tives, oxygen- and sulphur-containing organic oompounds o~
alkali metals volatile organic by-products are liberated which can contaminate the recycle solvent, thus necessitating addi-tional expenses ~or purilication thereof.
Also k~own in the art, apart ~rom the above-discussed processes, is a process ~or producing carbo-chain random co-polymers o~ conjugated dienes with vinylaro~atic monomers (cf. British Patent No. 1,501,136) comprising copolymeriza-tion o~ conjugated dienes with vinylaromatic monomers in a hydrocarbon solvent medium at a temperature within the range o~ ~rom -30 to 150C in the presence o~ a catalyst, i.e. li-thium or a~ organolithium compound of the general formula R(~i)X, wherein R is a hydrocarbon radical, x i8 an integer o~ ~rom 1 to 4, in the presence o~ a modi~ying additive com-prising a reaction product o~ alkali metals Na, K, Rb, Cs or 4ydroxides thereof with conjugated diene homopolymers or co-polymers with terminal hydroxy groups having molecular weight o~ ~rom 500 to 5,000 or compounds o~ the general formula R~ , wherei~

Rl i~ (C~2~ m' [ (C~2)~ ~ ] m, -6- .

[ (C~2)n ~ ~ m~ wherein n is an integer o ~rom 1 to 5~ m is an integ~er o~ from 4 to 100, M is the alkali metals me~tioned hereinbefore, y is an integer o~ 1 to 10; said additives being taken in an amount ranging from 0.005 to 2.5 moles per one mole o~ active lithium.
This prior art process has a disadvantage residi~g in inst~bility o~ the polymerization product due to the ~act that the modi~ying additive employed does not prevent the polymer from oxidation.
It is an object o~ the present invention to provide a process for producing carbo-chain homopolymers, block- and random copolymers of conju~ated dienes with vinylaromatic monomers which would make it possible to overcome the above-mentioned disadvantage.
It is the main object o~ the present invention to pro-vide such a process ~or producing carbo-chain homopolymers, block- and random copolymers o~ conjugated dienes with vi~yl aromatic monomers which would make it possible to incr~as~
the desired product stability through the use o~ a mod~ying additive preventing oxidation o~ th~ polymer.
These and other objects are accomplished by that in a process ~or producing carbo-¢hain homopolymers, block- and random copolymers o~ conaugated dienes with vinyl~romatic mo-nomers or co,polymerization thereo~ in a medium o~ a hydrocar- -bon solvent at a temperature within the range o~ ~rom -30 ~i4U~i . , to 150C in the presence o~ an organolithium catalyst of '~he general ~ormula R(Li)X, wAerein R is a l~drocarbon radical or a dien~ polymer, x is an integer o~ from 1 to 4, and a modify-in~ additive, in accordance with the present invention, as the modi~ying additive use is made o~ a compound comprising a product of interaction of a phenol-amine resin and alkali metals and havin~ the general ~ormula:
OM OM

B R,~ CH2NY-C1~2 ~ I (I) ~ ~ R
wherein n is an integer o~ ~rom 1 to 10; M is sodium or potassium, R is an alkyl containing 2 to 20 carbon atoms or an arylalkyl co~taining 7 to 20 carbon atoms; Rl is an alkyl containing 1 to 6 carbon atoms, an arylalkyl contain-ing 7 to 9 carbon atoms or hydrogen which additive is taken in an amou~t o~ from 0.07 g/equiv. to 2.00 g/equiv. per one - - g/equiv. o~ active lithium.
¦ The term active lithium as applied to the use of the ! above-mentioned organo-lithium compound of the general ~or-mula R(~i)X denotes lithium directly associated with carbon and serving as the polymerization center.
- It is advisable to use, as the organolithium catalyst, n-butyllithium, sec.butyllithium, dilithiumpolydivinyl or polyisopropyllithium.
As a ~ydrocarbon solvent use can be made o~ aliphatic, cycloaliphatic, aromatic hydrocarbons and mixturas thereo~.
It is advisable to use, as the hydrocarbon so'vent, cyclo-hexane, toluene, isopentane, he~ane or he~ane-heptane ~rac-tion of petroleum.
The process according to the present invention is per-formed in the ~ollowing manner.
$he startin~ monomers which are polymerized in the pro-ce~s according to the present invention comprise conjugated dienes, vinyl- or divinylaromatic compound~ or mixtures of both. As the conjugated dienes use is made of dienes con-taining 4 to 12 carbon atoms per molecule, namely 1,3-but~-diene, isoprene, 1,3-pentadiene, 2,3-dimethyl-1,3-butadiene,

2-methyl-1,3-pentadiene, 2-phenyl-1,3-butadiene and 4,5-di-ethyl-1,3-octadiene. It is pre~erred to use-, as the conjug~at-ed diene, 1,3-butadiene and isoprene.
As the vinylaromatic compound (including divinylaroma-tic compounds) use can be made o~ compounds with 8 to 20 car-bon atoms containing at least one vinyl group bound to the car-bon atom o~ the aromatic ring, namely: styrene, 3,5-diethyl-styrene, ~,4,6-trimethylstyrene, 4-cycl~hexylstyrene, 4-phe-nylstyrene, 3,5-diphenylstyrene, vinylnapnthalene, 8-phenyl--l-~inylnaphthalene, divinylbenzene and the li~e. It is pre-~erable to use styrene and divinylbenzene.

~ ~

The aboYe-mentioncd starting monomers are subjecteà
to polymerization or copolymeri~ation therebetween in a me-dium OI a h~drocarbon solvent.
As the hydrocarbon solvent use can be made of alipha-tic, cycloaliphatic, aromatic hydrocar`oons and mixtures there-of such as isopentane, hexane, heptane, octane, hexane and hexane-heptane petroleum fractions, cyclohe~ane, methyl-cyclohexane, benzene, toluene, xylene, ethylbenzene, isopro-pylbe~zene, a mixture o~ cyclohexane with the hexane-heptane petroleum ~raction, a mixture o~ toluene with the hexane-heptane petroleum fraction and the like.
The process of polymerization of the monomers is con-ducted at a temperature within the range of from -30 to l~50 C, pre~erably from 20 to 100C. Inl~eneral, pressure during polymerization is maintained su~icient to keep the monom~ric materials in the liquid state.
The polymerization process is conducted in the presence o~ an organolithium catalyst and a modifying additive.
As the lithium-organic catalyst use i9 made of an orga-nolithium compound of the formula R(Li)X, wherein R is a hy-drocarbon radical or a diene polymer; x is an integer of ~rom 1 to 4; for e~ample, methyllithium, ethyllithium, n-butyl-lit~ium, naphthyllithium, tolyllithium, ~ec.butyllithium, tert.butyllithium, phe~yllithium, cyclohexyllithium, l,6-di-1`~41~81 lithiumnaphthalene, 1,3,5-trilithiumcyclohexane, 1,2,4,6-tetralithiumcyclohexane, dilithiumpolybutadienyl, dilithium-polyisophenyl, dilithiumpolystyryl and the like. The organo-lithium compound is taken preferably in an amount ranging from 0.2 to 50 mg/equiv. per 100 g of a mixture of the starting monomers depending on the molecular weight to be obtained.

As the modifying additive use is made of a reaction product of phenolamine resin with an alkali metal correspond-ing to the general formula:
OIM pM

Rl ~ CH2-NH-C~

wherein n is an integer of from 1 to 10; R is an alkyl with a number of carbon atoms of from 2 to 20 or an arylalkyl with a number of carbon atoms of from 7 to 20; Rl is an alkyl with a number of carbon atoms of from 1 to 6, or an arylalkyl with a number of carbon atoms of from 7 to 9, or hydrogen;
M is sodium or potassium.

The modifying additive as used in the process according to the present invention is soluble in aliphatic, cycloali-phatic, aromatic hydrocarbons; it can be stored for a long time in the absence of moisture and oxygen; it can be readily 1i4~1`

dispensed and homogeneously distributed over the reaction me-dium. I~Ae modifying~ additive according to the present inven-tion acts as a regulator o~ penetration of diene mol~cules into the polymeric chain with the ~ormation of a predetermined microstructure; it also serves as an agent varying relative reactivity o~ diene, vinyl- and divinyl-aromatic hydrocar-bons, thus providing an opportunity for the production o~
either block- or random copolymers of dienes and vinylaroma-tic monomers.
The modi~ying additive is introduced at a rate o~ 0.07 to 2.0 g/equiv. per one g/eguiv. o~ active lithium serving as the polymerization centre.
The aminophenolic resins ~ormed after the decomposi-tion of the modi~ying additive are not volatile and, which is most important, prevent oxldation of the polymer upon re-covery and drying thereof.
The modifying additive according to the present inven-tion is introduced into the reaction mi~ture as a solution in a h~drocarbon solvent or a mineral oil.
On completlon of polymerization (conversion of from 50 to 99.9%), the reaction mixture is treated with an agent con-verting the modifying additive to the OH-form. As such a~ent use is made o~ water or acids.
~ he polymerization process can be per~ormed both conti-; -12-nuously and batc~-wise. ~he process is carried out in an appa-ratus provided with an impeller, a cooling-and-haating jacket, means for charging the starting components ~nd means ~or dis-charging the solution o~ a homo- or copolymer.
~ he apparatus is preliminary exempted ~rom moisture and oxygen. A hydrocarbon solvent, a diene and vinylarom~tic mono-mers, an organolithium compound and the modi~ying additive are ~ed into the apparatus in speci~ied proportions in the atmo-sphere o~ an inert gas (nitrogen, argon).
In the continuous embodiment o~ the process according to the present invention the solvent and monomers in the form o~ a preliminary prepared mixture or separately are ~ed into a battery consisting o~ several apparatus; the catalyst and modi~yin~ additi~e are continuously supplied thereto a~ well.
On completion o~ polymerization, an additional quantity o~ the antioxidant is added to the copolymer solution and the polymer i8 recovered ~rom the solution by conventional techn-i~ues (such as precipitation with alcohol, aqueous outgassing method or water-~ree outgassing method).
~ he process according to the present invention is tech-nologically simple and can be implemented on a commercial scale. Owing to the use o~ the novel modi~ying additive pre-venting oxidation o~ t~e polymer, the process according to the present invention makes it possible to enhance stability of the desired product as compared to the prior art processes.

~J

`` 1~4~, For a better understanding of the present i~vent on, some specific Examples are ~iven hereinbelow by way of il-lustration o~ the process according to the invention.
~ xample 1 Into a preliminarily evacuated and nitrogen-filled ap-paratus there are c~arged 3,200 g o~ cyclohe~ane, 110 ~ o~
styrene, 330 g of divinyl, 6.36 mg/equiv. of dilithiumpoly-divinyl and 0.84 mg/equiv. o~ a product of interaction bet-ween a phenolamine resin and sodium o$ formula (I) herein-before, vvherein n = 4, R is C8H17 and Rl i9 hydrogen. The reaction mass is heated to the temperature of 65C and kept under stirrin~ for 4 hours. On completion o~ the reaction, the polymer is deactivated by means o~ a solution of acetic acid (0.03~), recovered by means of isopropanol and the po-lymer is dried on hot rolls. The polymer yield is 420 g (95.5%). Intrinsic visco~ity is 1.19 dl/g (toluene, 25C).
The divinyl portion has the ~ollowing structure, %; 1,2 -- 12.1; cis - 1,4 - 45.9, trans-1,4 - 42. The content of block polystyrene is 5%. The block-copolym~r has the structure ' ype A-~-A, wherein B is a copolymer o~ butadiene and styrene, A is poly~tyrene.
E~ample 2 Into an apparatus preconditioned as in Example 1 herein-above ~here are charged 3,200 g o~ cyclohexane, 110 g o~

~i~1 styrene, 330 g o~ 1,3-butadiene, 5 mg/equiv. of sec.butyl-lithium and 1.8 mg~e~uiv. o~ a product o~ interaction bet-ween a phenolamine resin with sodium o~ ~ormula (I), where-in n = 1, R is C8H17 and Rl is C4 ~ . The reaction mass is heated to the temperature o~ 65C and maintained under stirring ~or 4 hours. On completion o~ the reaction the polymer is deactivated with water, recovered by means o~ alcohol and dried over hot rolls. In the oourse of the process samples are taken ~or di~erent degrees o~ conversion to de~ine the content of styrene. The data illustrating the content of combined styrene in the copolymer Por di~ferent conversions are given in the ~ollowing Table 1.
~able 1 Time lapse Monomer 25Content o~ styrene ~rom the be- conver- n in the copolymer, ginning o~ sion~O D %
polymeriza-tion,min ---- ----------------_--____ _ __ _ _ . ____ 5 20 1.5~0 21.~8 10- 40 1.5340 22.85 15 50 1.5350 24.01

3 80 1.535 24.01 120 100 1.5357 24.~2 .0 " 1~4~

The polymer yield is 440 g (100%). Intrinsic viscosity is 1.8 dl/g. The polymer contains no block styrene and has the ~ollowing structure of the diene portion,~:
cis-1,4-uni t9 ` 43.8 trans-1,4-units 31.2 1,2-u~it~ 18.

~ xample 3 Into a preliminary evacuated and nitrogen-~illed appa-ratus there æe charged 3,200 g of cyclohexane, 110 g of styrene, 330 g o~ 1~3-butadiene, 5 mg/equiv. o~ n-butyl-lithium ana 0.35 mg/equiv. o~ a solution, in cyclohexane, o~
a product o~ interaction between a phenolamine resin with po-tassium o~ formula (I) hereinbefore, wherein n = 4, R is C8~l7~ Rl i9 hydrogen. The reaction mass is heated to the temperature of 65C and maintained under stirring for 4 hours.
On completion o~ the reaction the polymer is deactivated with a solution o~ acetic acid (0.03 mole), recovered with alcohol and dried o~er hot rolls. The polymer yield is 430 g (lOO~o).
Intrinsic viscosity is 1.45 dl/g. The structure o~ the divinyl portion i8 as ~ollows, ~ :

1,2-units 12.7 cis-1,4-units 42.8 trans-1,4-uQits 44.5.

--1~--,!

114~t381.

The polymer prepared by the procedure of _xample 3 is subjected to oxidation at the temperature o~ 130C in the atmosphere of oxygen. The latent period is 1~0 minutes. Tne control sample produced with the use o~ potassium buty ate starts to get oxidized without any latent period. The same 8ample prepared by the procedure of hxample 3 when su~jected to a thermal oxidation at the temperature of 130C in tne at-mosphere of oxygen ~or 30 minutes shows the '~alles plastici-ty retention index o~ 47.5%. The control sample with 1% of Neozone ~ shows the index o~ 42.~%.
Exsmple 4 Into an apparatus preconditioned in much the same man-ner as in Example 3 there are charged 3,200 g o~ cyclohe~ane.
110 g of styrene, 330 g o~ 1,3-butadiene, 5 mg/equiv.of sec.
butyllithium and 0.6 mg/equiv. o~ a solution, in cyclohexane, of a product of interaction between a phenolamine resin and potassium o~ formula (I), wherein n = 10, R is C8H17 and R
i9 hydrogen. ~he reaction mass is heated to the temperature o~ 65C and maintained under stirring for 4 hours. On comple-tion o~ the reaction the polymer is deactivated with water, recovered with alcohol and dried on hot rolls. In the course o~ the polymerization samples are taken ~or di~erent degrees o~ conversion to determine the content of styrene. The data ill~strating the content o~ combined styrene in the copolymer ~"J

.

1141~1 at di~ferent conversions are shown in ~able 2 hereinbelow.

Table 2 Time period from Conversion ` 2Content of styrene the beginning o~ o~ the mo- n 5in the copolymer, the polymeriza- nomers, % D %
tion, min ______ _ ________________ ______________________ ______________ 1.5357 24.8 1.5~60 25.17 1.5360 ~ 25.17 86 . 5 1 . 5360 25 . 17 120 100 1 . 5360 25 . 17 ~ he polymer yield i~ 440 g (100%). Intrinsic viscosity is 1.77 dl/g. The polymer contains no block styrene and has the ~ollowing structure o~ the divinyl portion, %:
ci~-1,4-units 39.3 - trans-l ,4-units 44. 7 1 ,2-units 16Ø

For physico-mechanical te~ts o~ the polymers produced in the ~oregoing Examples, rubber mixes are prepared accord-ing to the following ~ormulation, parts by weight:
polymer 100 carbon black 40.0 stearic acid 1.5 zinc oxide 5.0 commercial sulphur 2.0 altax 3.0 The mixes are vulcanized at the temperature of 14-3C
for 40~ 60 and 80 minutes. '~e data illustrating properties of the thus-produced vulcanizates are shown in Table 3.

Table 3 .
P o 1 y m e r o~ ~ x a m p 1 e C h a r a c t e r i 8 - -----------------------------------t i c s 1 2 3 4 _____________________________ _____________ _______________ Tensile strength, kg/cm2 215 272 245 270 Relative elongation, % 508 612 560 604 Residual elongation, % 20 16 20 16 . . .

~xa~ple 5 Into a reactor in the atmosphere o~ argon there are Charged 13~5 mg/equiv. o~ a solution, in hexane, of a pro-_19_ .~

~a duct of interaction between a phenolamine resin and potas-sium of ~ormula I, wherein n = 10, R is C~H17, Rl is C~3, and 13.44 mg/equiv. of a solution in cyclohexane of sec.bu-tyllithium. 73 ml o~ isoprene are added thereto at the tem-perature o~ ~5C. After ~ days at the temperature o~ 25C
the polymer is precipitated with isopropanol. There are ob-tained 4.7 g of the polymer; its i~trinsic viscosity is 2.53 dl/g; the content of units i9 as ~ollows, ~0:
cis-1,4-units trans-1,4-units - 74 ~,4-units 25.

~xample 6 ; Into a preliminary evacuated and nitrogen-~illed appa-ratus there are charged 3,000 g o~ a mixture o~ cyclohexane with hexane-heptane ~raction in the weight ratio o~ 75:25 respectively, 550 g o~ divinyl, 7.7 mg/equiv. oi n-butyl-lithium and 5.8 mg/equiv. o~ a solution in toluene o~ a pro-duct of interaction between a phenolamine resin a~d sodium in ~ormula I, wherein n = 5, R is C8H17, Rl is hydrogen-The reaction mass is heated to a temperature of 40 to 45C
and maintained ior 5 hours under stirring. On completion of the process the polymer is deactivated w~th isoprop~nol, washed and dried on hot rolls. The polymer yi01d is lOO~o. It has the ~ol}owing unit structure, %: l,2-units 56.3; cis-~141~8i 1,4-units 18.5, trans-1,4-units 25.2. ~ooney vi~cosity is 7&.
E~ample 7 Into a preliminary evacuated and nitrogen-filled appa-ratus there are charged 3,000 g o~ a mixture of cyclohexane witn hexane-heptane ~raction as in hxample 6 hereinbefore, 500 g of divinyl, 6.5 mg/equiv. of n-butyllithium and 11.6 mg/equiv. o~ a solution in toluene o~ a product of interac-tion between a phenolamine resin and sodium o~ ~ormula~I)where-in n = 10, R is C8E17, Rl is hydrogen. '~he reaction mass is heated to a temperature o~ ~rom 35 to 40C and maintained ~or 5 hour~ under stirring. On completion of the process the po-lymer is deactivated with isopropanol, washed and dried on hot rolls. '~he polymer yield is 100%. It has the following unit structure: 1,2-units 32%, cis-1,4-units 37.7%, trans--1,4-units 30.3%. Mooney viscosity is 22.

~xample 8 Into a preliminary evacuated and nitrogen-~illed appa-ratus there are ¢harged 3,000 g of heptane-hexane fraction of gasoline wit~ tne boiling interval o~ ~rom ~4 to 92 C, 500 g of divinyl, 12 mg/equiv. of dilithiumpolydivinyl, 11.~ mg/equiv. o~ a solution, in toluene, o~ a product OI in-teractio~ between phenolamine resin and sodium of ~ormula(Il wherein n = 5, R is C8H17, Rl is hydrogen. '~he reaction mass is heated to a temperature o~ 30 to 35C and maintained for _, ~41~, 8 hours under ~tirring. On completion of the process the po-lymer is deactivated by isopropanol, washed and dried on not rolls. The polymer yield i8 100%. Mooney visco~ity is 21. The content o~ 1,2-units i9 44~, trans-1,4-unitJ i9 24.5~.
EXample 9 Into a preliminary evacuated and nitrogen-~illed appa-ratus there are charged 3,200 g o~ cyclohexane, 1~0 g o~
vinylnaphthalene~ 310 g o~ piperylene, 5 mg/equiv. of li-thium in the ~orm o~ 1,2,4,6-tetralithiumcyclohexane and 10 mg/equiv. o~ potas~ium in the ~orm o~ a solution, in cy-clohex~ne, o~ a product o~ interaction o~ phenolamine resin and potassium of ~ormulalI), wherein n = 10, R is C20~41, Rl i9 C6Hl~- The reaction mass is heated to the temperature o~
65C and maintained ~or 3 hours under ~tirring. On completion o~ the reaction, the polymer i~ deactivated~vith water and dried in an air drier. ~he yield oi the polymer is 430 g (100%). Intrin~ic visco~ity is 1.8 dl/g (toluene, 25C).
~ample 10 Into a preliminary evacuated and nitro~en-~illed appa-ratus there are charged 6,000 g o~ a mixture o~ cyclohe~ane with hexane-heptane ~raotion in a manner similar to that o~
~Xample 6 hereinbefore, 1,100 g o~ divinyl and 22 m~/equiv.
o~ n-butyllithium, 8.35 mg/aquiv. of divinylbenzene and 15.75 mg/equiv~ o~ a product o~ interaction between a phenolamine resin and sodium o~ formula~IJ, wherein n = 10, R is C2~5, Rl is hydrogen. The re~ction mass is heated to 40-42C and maintained at this temperature for 4 hours under stirring.
On completion o~ the process, the polymer is deactivated with isopropanol, washed and dried on hot rolls. The polymer yield is 100%, the strueture of the divi~yl portion is as followss trans-1,4-unlts 22~o~ 1,2-units 54%. Mooney viscosity i9 67.5-Example 11 Into a reactor there are charged 7,800 g of cyclohexane,920 g ol vinyltoluene, 1 litre o~ a solution of polyisopre-nyllithium with a molecular weight o~ about 350 and tne to-tal content o~ active lithium of 0.5 mg/equiY.; 1 litre of a 0.5N solution o~ a product of interaction between a phenol-amine resin and sodium(l35 g)o~ ~ormula(I~ wherein n = 4, R is C8H17, Rl is an alkylaryl C9~11. The reaction mass is maiutained ~or two hours at the temperature o~ 50C, the polymer is recovered by steam distillation and dried in va-cuum to give 1,130 g (100%~ o~ a ~loc~-copolymer with the molecular wPight o~ 2,000 and the ~tructure o~ the AB t~pe, wherei~ A is polyisoprene, B is polyvinyltoluene; the con-tent of phenolamine resin is 12%.
~ample 12 Into a prelimihary evacuated and nitrogen-filled appa-1~4~8B1 ratus there are charged 3,000 g of hexane-heptane fraction with the boiling range of from 64 to 92C, 500 g o~ trans-piperylene, lV mgfequiv. of lithium in the form of dili ~hiu~-polydivinyl (0.35 N solution in the hexane-heptan~ fraction) and 6 mg/equiv. of potassium in the form of a solution, in to-luene, of a product o~ interaction o~ a phenolamine resin and pota9~ium of ~ormula(I~ wherein n = 5, R is C8H17, Rl is h~dro-gen. The reaction mass is heated to tne temperature of 80C
and maintained for 6 hours at this temperature under stirring.
On completion o~ the r~action, the polymer is deactivated ~ith isopropanol, washed and dried on hot rolls. The polymer yield is 450 g (95%). Intrinsic viscosity (toluene, 25C) is 2.1 ~l/g.
The ~tructure of the polymer i~ as ~ollows, %:
trans-l, 4-1,2-units 65,0 ~,4-units 3.3 1~2-units 18.9.

Example 13 Into a preliminary evacuated and nitrogen-~illed appa-ratu~ there are charged 3,000 g of hexane-heptane fraction with the boilin~ rangc o~ ~rom 64 to 92C, 220 g o~ butadiene, 220 g o~ pipe~ylene (consiRting o~ 93.0% by weight of trans-~orm and 7% by weigh~ of cis-~orm), 5 mg~equiv. o~ n-butyl-lithium (a~ a 0.5 N solution in the hex~ne-heptane fraction) f~l4~

and 2.~ ,~t~equiv. of po~assiulll as a sol~ion, i~ tolue~.e, oi a pro~uct ol in~craction between a phe~olâmine resin à~
potassiuM o~! ~ormula~ , wherein ~ = 5, R is C~17, ~1 is ..y-dro~en. The reac~ion mass is heated to the te~nper.lture of 3~GC
alld maintained at this temperat~e for 4 hours un~er stirrin~.
On com~letion o~ the polymerization process, the po~ mer thus-produced is deac-tivated with isopropanol, washed ~n~ dried on hot rolls. 'l'he polymer yield is 400 g (95~0). Intrinsic vis-cosity of the polymer is 2.4 dl/g (toluene, 25C). Karrer plasticity is 0.40.
~xamplo 14 In-to a preliminary evacuated and nitro~en-filled appa-ratus there are charged 600 g of isopentane, 450 g o, sty-rene~ the mi~ture is cooled to the temperature o~ -30C and added with 10 mg/equiv. of n-butyllitnium (as a 0.5N solu-tion in he~ane-heptane fraction) and 0.7 mg/equiv. of soaium as a solution, in toluene, o~ a product of interaction of a phe-nolamine resin and sodium of formula~I~ wherein n = 5, R is C ~ , R is hydrogen. ~he reaction mass is maintained at the temperature of -~0C under stirring for 2 hours. ~n completion of the polymerization process, the resulting polymer is deacti-vated wit.i isopropanol. The suspe~sion of polystyrene in iso-pentane is poured onto a filtex. The p~lystyrene crumb separated from iso~entane is dried in a vacuum cabinet at t~e tempera-ture ol 50~. ~he polymer yield is 450 g (10070).
L~a~ple 15 Into a preliminary evacuated and nitro~en-~ille~ a~pa-ratu~ ther~ arc charged ~,000 g o~ toluene, 220 g Oî styrene, 10 mg/equiv. o~ n-butyllithium as a 0.5N solution in hexane-hepta~e ~raction ~nd 4 mgJequiv. oi' sodium as a solution, in toluene~ of a product OL interaction of a phenolamine res n and sodium o~ for~Jula I, wherein n =5, R is C8H17, Rl is h~dro-gen. ;~he reaction mass is heated to the temperature ol 150C
and maintained at this temperature under stirring ~or 30 mi-nutes. On completion o~' the polymerization process, the reac-tion mass is cooled, deactivated wit~ isopropanol, the polymer is washed with isopropanol and dried on hot rolls. The polymer yield is 340 ~.
~ ample 1~
Into a preliminary evacuated and nitrogen-~illed appa-ratus ~her~ are cAarged 800 g of hexane-heptane fraction with t2e boiling range o~ from 64 to 92C, 420 g of styrene, 1 g of divinylbenzene, 10 mg/equiv. of n-butyllithium (as a 0.5N
solution in the hexane-heptane ~raction), and 2 m~/equiY. of sodium as a solution, in toluene, of a product o~ interaction between a phenolamine resin ~nd so~ium o~ formula~I~ wherein ~g~

n = 5, lt is C~rll7, ~1 is hydro~en. '~he reaction mass ls n ated uilaer stirril~ to the ~amp~rature of 100C and mair,tain~d at this tempcraturc ~or 2 hours. On compl~tion o~ thtA poly~ riza-tion process, the re~ction mass is cooled and deactivatcd ;ii~h isopropanol. l'he ~uspension o~ polystyrene in the hexane-heptane ~raction is poured onto a filter. The polystyrene crumb sepa-rated lrool ~h~ hexane-heptane rraction is dried in a vacuum--drying cabine-t at the temperature ol 60C. l`he polymer ~ield is 420 g (~OOYo).
~xample 17 Into a preliminary evacuated and argon-filled a~paratus there are c~arged 80 g o~ isopentane, 20 g o~ divinylbAenzene, 0.001 hl o~ n-outyllit~ium and 0.0001 g-atom o~ so~ium as a solution, in cyclohexane, of a produc~ o~ interaction bet-ween a ~henolamine resin and sodium o~ ~ormula~I)wherein n = 5, R is C8H17, Rl is hydrogen. ~he reaction mass is maintained under stirring at the temperature o~ 20C. On completion o~
the reaction, the reaction mass is treated wit~ isopropanol.
The polymer yield is equal to 10.1 g (50%).
~xample 18 Into a preliminary evacuated and argon-~illed apparatus there are charged 2 g o~ divinylbenzene, 2~ g o~ divi~yl-naphthalene, 160 g o~ hexane ~raction, 0.002 ~ o~ n~butyl-lithium and 0.000~ g-atom ol potassium as a solution in cyclo-he~anone, o~ a ~roduct o~ interaction betwe~n a pherlGlamiile resin an~ ~otassium of ~ormula(Il, wnerein n = 5, R is C~ 7, Rl is hydro~en. The reaction mass is maintained for 4 hours at t~e temi)erature o~ -30C. Then the reaction mass is treated with isopropanol. The yield of t~le polymer is 4 g.
~xample 19 Into a preliminary evacuated and nitrogen-~illed appa-ratus there are charged 3,000 g of' he~anc-heptane fraction ~iitA
the boilin~ range of from 64 to 92C, 300 g oi isoprene, 200 g o, tr~ns-piperylene, 6 mg/equiv. of n-butyllithium (as a 0.5;~
solution in the hexane-heptane fraction) and 3.5 mg/e~uiv. o~
potassium in the ~orm of' a solution, in toluene, o~ a product of interaction between a phenolamine resin and potassium o~
~ormula~I,), wherein n = 5, R is C8H17, Rl is hydrogen. The reaction mass is heated to the temperature o~ 80C under stirr-ing and maintained at this temperature for 4 nours. On comple-tion of' the polymerization process, the resulting polymer is deactivated by ~eans of' isopropanol, washed and dried on not rolls. ~he yield of the polymer is equal to 480 g (95~0). Intrin-sic viscosity o~ the polymer (as determined in toluene at the temperature of' 25C) is 2.65 dl/g.

Claims (3)

THE EMBODIMENTS OF THE INVENTION IN WHICH AN EXCLUSIVE PROPERTY
OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:

1. process for producing carbo-chain homopolymers, block- and random copolymers of conjugated dienes with vinyl-aromatic monomers comprising polymerization of monomers se-lected from the group consisting of dienes, vinylaromatic monomers and divinylaromatic monomers, or copolymerization thereof in a medium of a hydrocarbon solvent at a temperature ranging from -30 to +150°C in the presence of an organo-lituium catalyst of the general formula R(Li)x, wherein R is selected from the group consisting of a hydrocarbon radical and a diene polymer; x is selected from the group of integers, of from 1 to 4; and a modifying additive comprising a product of interaction between a phenolamine resin and an alkali me-tal and having the general formula:
wherein n is selected from the group of integers of from 1 to 10; is is selected from the group consisting of sodium and potassium; R is selected from the group consisting of an al-kyl with a number of carbon atoms of from 2 to 20 and an aryl-alkyl with a number of carbon atoms of from 7 to 20; R1 is selected from the group consisting of an alkyl with a number of carbon atoms of from 1 to 6, and an arylalkyl with a numb-er of carbon atoms of from 7 to 9, and a hydrogen; said modi-fying additive being taken in an amount of from 0.07 g/equiv.
per one g/equiv. of active lithium of said organolithium ca-talyst.

2. A process as claimed in Claim 1, wherein as the or-ganolitnium catalyst a catalyst is used which is selected from the group consisting of n-butyllithium, sec.butyllithium, dilithiumpolydivinyl and polyisoprenyllithium.

3. A process as claimed in Claim 1, wherein as the hydro-carbon solvent a solvent is employed which is selected from the group consisting of cyclohexane, toluene, isopentane, he-xane petroleum fraction and hexane-heptane petroleum fraction.