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-
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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-
