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Patent 1141881 Summary

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(12) Patent: (11) CA 1141881
(21) Application Number: 1141881
(54) English Title: PROCESS FOR PRODUCING CARBO-CHAIN HOMOPOLYMERS, BLOCK AND RANDOM COPOLYMERS OF CONJUGATED DIENES WITH VINYLAROMATIC MONOMERS
(54) French Title: PROCEDE D'OBTENTION D'HOMOPOLYMERES A CHAINE CARBONEE, DE COPOLYMERES SEQUENCES ET IRREGULIERS DE DIENES CONJUGUEES A DES MONOMERES VINYLAROMATIQUES
Status: Term Expired - Post Grant
Bibliographic Data
(51) International Patent Classification (IPC):
  • C08F 2/38 (2006.01)
  • C08F 12/06 (2006.01)
  • C08F 36/04 (2006.01)
  • C08L 61/34 (2006.01)
(72) Inventors :
  • JUDIN, VIKTOR P. (USSR)
  • SHATALOV, VALENTIN P. (USSR)
  • KOVTUNENKO, LEONID V. (USSR)
  • SHALGANOVA, VALERIA G. (USSR)
  • KASHKINA, NADEZHDA K. (USSR)
  • MISTJUKOVA, LIDIA N. (USSR)
  • SEMENOVA, NEONILA M. (USSR)
  • KORBANOVA, ZINAIDA N. (USSR)
  • MITIN, IVAN P. (USSR)
  • MOISEEV, VLADIMIR V. (USSR)
  • KOSOVTSEV, VLADIMIR V. (USSR)
(73) Owners :
  • JUDIN, VIKTOR P.
  • SHATALOV, VALENTIN P.
  • KOVTUNENKO, LEONID V.
  • SHALGANOVA, VALERIA G.
  • KASHKINA, NADEZHDA K.
  • MISTJUKOVA, LIDIA N.
  • SEMENOVA, NEONILA M.
  • KORBANOVA, ZINAIDA N.
  • MITIN, IVAN P.
  • MOISEEV, VLADIMIR V.
  • KOSOVTSEV, VLADIMIR V.
(71) Applicants :
  • JUDIN, VIKTOR P.
  • SHATALOV, VALENTIN P.
  • KOVTUNENKO, LEONID V.
  • SHALGANOVA, VALERIA G.
  • KASHKINA, NADEZHDA K.
  • MISTJUKOVA, LIDIA N.
  • SEMENOVA, NEONILA M.
  • KORBANOVA, ZINAIDA N.
  • MITIN, IVAN P.
  • MOISEEV, VLADIMIR V.
  • KOSOVTSEV, VLADIMIR V.
(74) Agent: MARKS & CLERK
(74) Associate agent:
(45) Issued: 1983-02-22
(22) Filed Date: 1979-07-27
Availability of licence: N/A
Dedicated to the Public: N/A
(25) Language of filing: English

Patent Cooperation Treaty (PCT): No

(30) Application Priority Data: None

Abstracts

English 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:
<IMG>
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.


Claims

Note: Claims are shown in the official language in which they were submitted.


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:
<IMG>
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
29

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.

Description

Note: Descriptions are shown in the official language in which they were submitted.


~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
--5--
.

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-
-10--

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
-- 11 --

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~
-14-

~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
-15-
.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
-17-
~"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-
-18-

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-
-20-

~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
-21-
_,

~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
-22-

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-
-23-

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)
-24-

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
-25-

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
-26-

~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-
-27-

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.
-28-

Representative Drawing

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Administrative Status

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Event History

Description Date
Inactive: Expired (old Act Patent) latest possible expiry date 2000-02-22
Grant by Issuance 1983-02-22

Abandonment History

There is no abandonment history.

Owners on Record

Note: Records showing the ownership history in alphabetical order.

Current Owners on Record
JUDIN, VIKTOR P.
SHATALOV, VALENTIN P.
KOVTUNENKO, LEONID V.
SHALGANOVA, VALERIA G.
KASHKINA, NADEZHDA K.
MISTJUKOVA, LIDIA N.
SEMENOVA, NEONILA M.
KORBANOVA, ZINAIDA N.
MITIN, IVAN P.
MOISEEV, VLADIMIR V.
KOSOVTSEV, VLADIMIR V.
Past Owners on Record
IVAN P. MITIN
LEONID V. KOVTUNENKO
LIDIA N. MISTJUKOVA
NADEZHDA K. KASHKINA
NEONILA M. SEMENOVA
VALENTIN P. SHATALOV
VALERIA G. SHALGANOVA
VIKTOR P. JUDIN
VLADIMIR V. KOSOVTSEV
VLADIMIR V. MOISEEV
ZINAIDA N. KORBANOVA
Past Owners that do not appear in the "Owners on Record" listing will appear in other documentation within the application.
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Document
Description 
Date
(yyyy-mm-dd) 
Number of pages   Size of Image (KB) 
Cover Page 1994-01-04 1 15
Abstract 1994-01-04 2 28
Drawings 1994-01-04 1 5
Claims 1994-01-04 2 52
Descriptions 1994-01-04 26 804