ISSN 19954212, Polymer Science, Series D. Glues and Sealing Materials, 2011, Vol. 4, No. 4, pp. 267280.

Pleiades Publishing, Ltd., 2011.

Original Russian Text N.A. Keibal, S.N. Bondarenko, V.F. Kablov, 2011, published in Klei. Germetiki. Tekhnologii, 2011, No. 2, pp. 612, No. 3, pp. 1825.

Modification of Adhesive Compositions Based on Polychloroprene

with ElementContaining Adhesion Promoters
N. A. Keibal, S. N. Bondarenko, and V. F. Kablov
Volzhskii Polytechnical Institute, Branch of Volgograd State Technical University,
ul. Engelsa 42a, Volzhskii, Volgogradskaya oblast', 404121 Russia
email: keibal@km.ru
Received October 13, 2010

AbstractThe possibility of using nitrogencontaining compounds as highly efficient adhesion promoters

for adhesive compositions based on polychloroprene is studied. Common regularities of enhancing the adhe
sion strength of a glue bond for vulcanizates based on variable rubbers are revealed.
Keywords: polychloroprene adhesives, modification of polychloroprene adhesives, nitrogencontaining pro
moters of adhesion, resin gluing.
DOI: 10.1134/S199542121104006X

There are many adhesives based on polychloroprene

(PCA), which can operate in a wide temperature range
and are designed to join various materials. The basis of
most PCA is polychloroprene rubber or its combination
with different polymers. These adhesives are used to
glue metals, wood, concrete, plastics, and leather. The
classical formulation of the adhesive compositions
based on chloroprene rubber includes zinc and magne
sium oxides, 101K resin, and a solvent. The solvents
used in polychloroprene adhesives include dichloroet
hane, ethyl acetate, amyl acetate, benzene, toluene,
dioxane, terebenthene, nefras, and others. Moreover, as
a solvent for polychloroprene adhesives, instead of indi
vidual compounds (acetone, ethyl acetate, dichloroet
hane), one can use a rectified lowboiling fraction of
pentaneheptane gasoline fraction oxidate. The com
position of this solvent includes mostly acetone,
ketones, and C4C7 esters with a content of water and
monocarboxylic acids of less than 1% [1].
Di and polyphenols, hexamethylenetetramine,
and other products of the condensation of amines with
aldehydes, diphenylguanidine, and structuring sub
stances that contain polyisocyanates are used as accel
erators for selfcuring adhesives based on polychloro
prene. A 20% alcohol solution of potassium hydroxide
is a very active promoter; in its presence, the vulcani
zation process takes place at ambient temperature over
1 day.
From the technological and economic points of
view, the production of an adhesive composition must
be the simplest in instrumentation and highly effi
cient.
Ample opportunities to enhance the strength of
multilayer resin products come from applying adhe
sives with reactive functional groups. The number of

functional groups in an adhesive can be increased by

introducing additives that allow one to enhance the
adhesion to resins based on various rubbers.
A survey of technical and patent literature shows
that, nowadays, not only the creation of novel formu
lations for adhesive compositions based on polychlo
roprene, but also the development of technology for
modifying already known adhesive compositions is an
urgent task. Therefore, the creation of and search for
new adhesion promoters for adhesives based on poly
chloroprene in order to enhance their operational
properties is of current interest.
At present, it is known that, to improve the gluing
properties of polychloroprene compositions, they
must be diluted with modifying additives that consist
of different resins, e.g., indenecumarone or resol
phenol resins, or resins based on cyclopentadiene. It
was also established that the products of the cocon
densation of phenol, acetaldehyde, and acetonaph
thene, as well as resin polymerizate of methylsty
rene or copolymer of cyclopentadiene with unsatur
ated dicarboxylic acid or its anhydride can also be used
as resins [24]. An adhesive composition is also
known that includes Baipren polychloroprene resin,
filler, solvent, and water. The indicated composition
includes a mixture of polyvinyl chloride resin PSKh
LS and phenolformaldehyde resin 101K as a modi
fying agent [5].
The application of products of phthalic acid anhy
dride condensation with resorcinol as modifying
agents in adhesives based on chloroprene allows one to
use these compositions for viscose and cotton textile
materials [6]. Moreover, there are also known formu
lations of adhesive compositions based on chloroprene
rubber that contain pergut, thiuram, and thiurea as

267

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KEIBAL et al.

modifiers [7, 8]. An adhesive based on polychloro

prene was developed that additionally contains an
alcohol, e.g., isopropanol, and a gluing resin, e.g.,
phenolformaldehyde modified with colophony. This
adhesive enables the formation of a joint in a single
stage and improves its thermal stability due to the
addition of a structuring agent that contains polyiso
cyanate, e.g., 1,4tetramethylenediisocyanate, as a
modifier [9].
An adhesive composition based on chloroprene rub
ber is also known that can be used in the tire and resin
technical industry; it includes chloroprene rubber, zinc
oxide, nefras, and ethyl acetate as solvents, and, addi
tionally, colophony and colloidal silicon acid, as well as
a modifying agent that consists of a molecular complex
of resorcinol with urotropine, stabilizer, and RUD
plasticizer. Applying this modifier enables one to
enhance the gluing ability and strength of contact
between the resin mixture based on chloroprene rubber
and resinfree cord based on rubbers of general assign
ment [10]. The adhesion properties of adhesive compo
sitions based on polychloroprene can be improved by
introducing compounds that contain different reactive
functional groups in their formulation.
During the production of aniline, vat waste that
consists of more than 80% aniline are formed in large
amounts. As a result of the performed investigations,
we have established that, upon the interaction of
ED20 epoxy resin, methacrylic acid glycidyl ester or
epichlorohydrin with vat fractions of aniline produc
tion, products that contain residual epoxide and
hydroxylic groups, as well as fragments of aromatic
amines, the presence of which was confirmed by
1H NMR data and IR spectral investigations, are
formed. It was revealed that the aforementioned prod
ucts can be used as adhesion promoters for adhesive
compositions based on polychloroprene.
As is known, the chlorine atom in polychloroprene
macromolecule (in units 3, 4 of the structure) can
readily pass to the allylic position, at which it possesses
enhanced reactivity and serves as an active point for
the polymer chain. A possible approach to modifying
the polychloroprene macromolecule using the devised
adhesion promoters presented below was confirmed
by the IR spectral investigations and data of the ele
mental analysis for the presence of nitrogen in multi
ply reprecipitated polychloropren:

~ CH2

HNR2
C ~ +
NR3
CH
CH2Cl

~ CH2 C ~
CH
CH2N+HR2Cl
~ CH2 C ~
CH
CH2N+R3Cl

Based on the presented scheme for modifying poly

chloroprene and an analysis of the literature data [11],
we suggested the model of the polymer with improved
properties. It was found that, to produce the composi
tions with enhanced adhesion parameters, it is neces
sary to have a set of certain functional groups in the
polymer macromolecule
ARBR'BR=A,
Cl

R''
{X1, X2, X3}

where A is the chain region providing the material

crystallization tendency (units of 1,4transisomer);
R' is a methylene or ethylene group; R" is an alkylene
group providing for increased mobility of Xgroup;
R= is an unsaturated radical (allylic), which imparts
flexibility to the molecule; B is the group responsible
for the mobility of the macromolecular chain; and
{X1, X2, X3} are the functional groups containing
nitrogen and halogen atoms and hydroxylic groups.
Highmolecular compounds, the nature of which is
in accordance with or close to this model, may be
related to the group of particular polymers of adhesion
assignment. To prove this model, experimental inves
tigations were carried out of the adhesive bonds of vul
canizates based on various rubbers. To join cured res
ins to one another and the metallic surface, the adhe
sive composition based on chloroprene rubber was
developed. It was established that, upon gluing, the
adhesion strength is significantly enhanced due to the
presence of modifier containing the interaction prod
ucts of ED20 epoxy diane resin with vat wastes of
aniline production in the composition based on an
88NT nairite adhesive [12].
In most cases, there is no directly proportional
dependence between the value of adhesion strength
and the content of functional groups in an adhesive.
This dependence, as a rule, has an extremal character.
While choosing an adhesion promoter for gluing of the
resins based on SKI3, it was established that the most
efficient promoting additive is KA40, which is
formed at an ED20 : KA ratio of 60 : 40. The intro
duction of this product in the amount of 1% of the
adhesive weight leads to the best results. Thus, the
shearing strength of the initial adhesive composes
0.61 MPa, while that for the adhesive with KA40 pro
moter comprises 0.99 MPa. As the amount of pro
moter in the adhesive composition increases, which
results in the enhancement of the concentration of
polar functional groups, the adhesion strength (having
reached a certain limit) ceases to increase or even
starts to reduce. The latter is apparently associated with
the reduction of the mobility of the adhesive macromol
ecule, an increase in their rigidity, and hindrances for
achieving the most favorable positions relative to the
active centers of the substrate surface [13, 14].
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269

Table 1. Effect of adhesion promoters based on ED20 epoxy resin and KA on adhesion properties of 88NT series adhesive
Shearing strength, MPa
Basis of gluing
vulcanizates
SKI3 rubber

SKEP40 rubber

Content of the adhe

sion promoter, %
Without a promoter
0.5
1.0
2.0
Without a promoter
0.25
0.5
1.0
2.0
3.0

adhesion promoters
KA30

KA40

0.63
0.79
0.71

0.96
0.99
0.78

1.00
1.03
1.14
0.98
0.96

0.99
1.00
1.05
1.09
1.03

While investigating the strength of joints for vulca

nizates based on SKEP40 ethylenepropylene rubber,
it was established that the most efficient promoter is
KA30, derived at an ED20 : KA ratio of 70 : 30, the
introduction of which in the amount of 1% relative to
the adhesive weight led to a 15% increase in the shear
ing strength (Table 1) [15].
The introduction of KA30 adhesion promoter into
88NT adhesive composition in the amount of 1%
favors the enhancement of the strength of adhesive
bond for vulcanizates based on SKN18 (Fig. 1). It
was revealed that the shearing strength of the initial
adhesive reaches 0.46 MPa, while that of the adhesive
with KA30 promoter reaches 0.80 MPa [15]. The
separate introduction of ED20 or KA into the adhe
sive compositions only insignificantly increases the
adhesion strength of adhesive joints of vulcanized res
ins. The effect of the developed promoters on the the
strength of adhesives strongly depends on the formula
tion of the gluing compositions themselves. The
changes in the adhesion parameters for 88SA and
88NP adhesives in the presence of the developed pro
moters are analogous to those observed upon gluing
vulcanizates using an 88NT series adhesive containing
the developed additives [1619].
The developed adhesion promoter, which contains
the interaction products of ED20 epoxy diane resin
and vat fractions of aniline, can also be used in the
adhesive composition based on chloroprene rubber,
which includes polychloroprene resin nairite KRNT,
butylphenolformaldehyde resin 101K, zinc oxide,
magnesium oxide, organic solvent (a mixture of ethyl
acetate and nefras), and diphenylguanidine as a plasti
cizer. This adhesive composition provides increased
strength in gluing vulcanized resins to one another and
upon their bonding to metallic surfaces [20].
Aniline resin, which contains the products of pro
cessing vat wastes of aniline production, has proven to
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KA50
0.61
0.75
0.82
0.73
0.99
1.04
1.08
1.07
0.99
0.97

ED20

KA

0.64
0.70
0.67

0.81
0.78
0.69

0.98
1.05
1.02
1.00
0.95

1.02
1.06
1.04
1.02
1.00

be a rather efficient promoter of adhesion; it contains

aniline (no more than 15%), dinitroaniline, and resin
ous admixtures. The application of this resin in the
adhesive composition based on chloroprene rubber
enables one to obtain a strong adhesive bond between
vulcanized resins (Fig. 2) [21].
The possibility of applying the interaction products
of epichlorohydrin with vat fractions of aniline pro
duction as adhesion promoters for gluing composi
tions based on polychloroprene was shown by experi
mental studies. The composition of an adhesive based
on chloroprene rubber, butylphenolformaldehyde
resin 101K, water, zinc oxide, magnesium oxide, and
organic solvent (a mixture of ethyl acetate and nefras)
Shearing strength, MPa
0.9
0.8
0.7

0.6

0.5

4
2
5

0.4
0

0.5

1.0

1.5
2.0
2.5
Promoter content, %

Fig. 1. Effect of promoter content in the adhesive

composition on the adhesion properties of 88NT
adhesive upon gluing of vulcanizates based on
SKN18: (1) KA40 (ED20 : KA = 60 : 40); (2) KA;
(3) ED20; (4) KA30 (ED20 : KA = 70 : 30);
(5) KA50 (ED20 : KA = 50 : 50).

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KEIBAL et al.

a modifier [22]. The efficiency of these adhesion pro

moters in gluing resins based on SKI3 is presented in
Table 2.

Shearing strength, MPa

1.4
1.3
1.2
1.1
1
1.0
0.9
0.8
0.7
0.6
2
0.5
0.4
2
3
0
1
Promoter content, %

It was revealed that, in this case, the greatest effect

on the enhancement of gluing strength have modifying
additives derived at an EPCH : KA ratio of 70 : 30
(EG30) and 60 : 40 (EG40), the introduction of
which in the amount of 0.51.0% relative to the adhe
sive weight leads to the maximal value of adhesion
strength [23]. An analogous regularity was also revealed
upon gluing vulcanizates based on SKEP40 [24].

Fig. 2. Effect of AS promoter content in adhesive

composition on adhesion properties of 88NT adhesive
upon gluing of vulcanizates based on SKEP40 (1)
and SKN18 (2).

is known that contains epichlorohydrin or the interac

tion products of epichlorohydrin and vat fractions of
aniline production in variable ratios (EG modifier) as

The interaction products of methacrylyc acid gly

cidyl ester (MAGE) with vat products of aniline pro
duction are also of particular interest as modifying
agents for the adhesives of 88 series. Adhesive compo
sitions based on chloroprene rubber are known that
can be used in the resin industry upon gluing vulca
nized resins with each other. The adhesive composi
tions include polychloroprene rubber (nairite DP or
NT) or neoprene AS, butylphenolformaldehyde resin
101K, water, zinc oxide, magnesium oxide, organic
solvent (a mixture of ethyl acetate and nefras) and GK
modifier, which is the interaction product of meth

Table 2. Effect of adhesion promoters based on epichlorohydrin and vat wastes of aniline production on the adhesion prop
erties of 88 series adhesives
Shearing strength, MPa, of the adhesive joints of vulcanizates based on SKI3
Content of the adhesion
promoter, %

adhesion promoters
EG30

EG40

Without a promoter
0.25
0.5
1.0
2.0
3.0

1.11
1.13
1.00
0.98
0.79

0.87
1.04
1.10
1.03
0.95

Without a promoter
0.25
0.5
1.0
2.0
3.0

1.03
1.05
1.38
1.10
1.05

1.14
1.29
1.58
1.09
1.00

Without a promoter
0.25
0.5
1.0
2.0
3.0

1.20
1.47
1.25
1.17
1.03

0.98
1.19
1.23
1.12
0.87

EG50
88NT trademark adhesive
0.61
0.79
0.94
0.97
0.96
0.84
88SA trademark adhesive
1.02
1.04
1.07
1.22
1.18
1.10
88NP trademark adhesive
0.66
0.95
1.19
1.23
1.17
0.99
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EPCH

KA

0.82
1.02
0.98
0.93
0.88

0.75
0.82
0.78
0.68
0.65

1.35
1.18
1.13
1.10
1.07

1.25
1.19
1.16
1.12
1.03

0.89
1.14
1.21
1.20
1.09

0.85
0.81
0.94
1.13
1.10

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acrylic acid glycidyl ester with vat wastes of aniline

production. This gluing composition yields enhanced
gluing strength [25].
It was revealed that, upon gluing of resins based
SKI3 and SKEP40, the best results are achieved
using adhesion promoters obtained at a MAGE : KA
ratio of 50 : 50 and 70 : 30 (GK50 and GK30,
respectively), at which the strength of the adhesive
bond reaches the maximal values [26].
High values of adhesion strength upon gluing vul
canizates based on SKEP40 and promoted by chloro
prene adhesives of 88 series can be explained by the
considerable degree of swelling of these vulcanizates in
the used solvent mixture.
Type of rubber

Degree of swelling, %

SKI3
SKN18
SKEP40

51
52
72

* The degree of swelling was defined in a 1 :1 ethyl acetatenefras

solvents mixture for 24 h.

The increase in the area of the vulcanizate surface

available for adhesive action upon swelling favors an
increase in the adhesion strength of the gluing joint.
Moreover, the adhesive molecules can penetrate the
swollen layers of the gluing material.
In the case of gluing resins based on SKN18, it was
established that the suggested adhesion promoters can
be used to enhance the strength of the gluing joint
(Table 3) [27].
Upon gluing standard vulcanized resins based on
chloroprene rubber using adhesives of the 88 series,
which contain small amounts of the indicated adhe
sion promoters, the strength of gluing surpasses the
strength of the resin. As a rule, breaking has a cohesion
character (by resin), even at small amounts of the pro
moter (about 0.050.5 % relative to the weight of the
adhesive). Apparently, this is connected with the fact
that the strength of the adhesive joint can reach the
level of the cohesion strength of the main material or
be even somewhat higher due to the appearance of a
complex stress state (effect of the contact strengthen
ing). Moreover, this may be connected with the diffu
sion of the adhesive macromolecules or its regions
deep into the substrate surface, i.e., thesocalled phe
nomenon of the coalescence of bodies, which leads
to an increase in the width of the adhesive joint from 5
to 15 m [28, 29].
Hence, the aforementioned aminocontaining
compounds serve as efficient adhesion promoters for
adhesive compositions of the 88 series based on poly
chloroprene, which is likely to be connected with their
chemical interaction with the filmforming polymer
macromolecule [30].
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Table 3. Effect of type of adhesion promoters and their

content in composition on adhesion properties of 88 series
adhesives

Promoter Promoter
type
content, %

Without a promoter
KA30
1.0
KA50
2.0
GK30
2.0
GK40
0.5
1.0
EG40
0.5
EG50
0.5
2.0
AS
0.5
1.0

Shearing strength, MPa, of the

adhesive joints of vulcanizates
based on SKN18
adhesive trademark
88NT

88SA

88NP

0.46
0.80
0.65
0.96
0.76
0.82
1.20
1.09
1.10
1.04
0.89

0.95
1.02
0.99
0.98
1.03
1.00
1.18
1.24
1.38
1.04
1.27

0.97
1.06
1.17
1.01
1.03
1.08
1.08
1.35
1.05
1.31
1.50

The depth to which an adhesive penetrates vulcani

zates based on SKI3 and SKEP40 upon gluing was
defined using local electronprobe microscopic analy
sis. The procedure is based on constructing profiles of
the distribution of the elements (Cl) only involved in
the composition of an adhesive composition in the
direction perpendicular to the gluing plane (Fig. 3).
As a result of the performed investigations, it was
established that, in the case of the introduction of the
adhesion promoter into an adhesive composition, the
depth of the penetration of the adhesive into the vul
canizate based on SKI3 increases by twofold. Analo
gous results were obtained for vulcanizates based on
SKEP40 [3133]. Figure 4 shows electronmicros
copy micrographs of the transverse sections of the vul
canizate samples with an adhesive bond. It can be seen
from Fig. 4 that the bond of nonmodified adhesive has
rather welldefined boundaries, whereas the bond
boundaries of the modified adhesive are vague. The
more intense color of the bond of nonmodified adhe
sive is explained by the composition contrast of the
image, in which Clcontaining regions look brighter
because the concentration of chlorine is higher. The
paler color of the bond of modified adhesive testifies
the diffusion of chlorine deep in the vulcanizate. The
broadening of the adhesive joint width may also be
connected with the mutual diffusion of polymers. It
should be noted that the great depth of the diffusion
layer is related to the intersolubility of the modified
macromolecules of polychloroprene and macromole
cules of vulcanizates. Intersolubility is confirmed by
the absence of the exfoliation phases in solutions of

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KEIBAL et al.
Imp./s
Cl

S
Zn

Vulcanizate spectrum
1

9
keV

Mg
Ca
1

Adhesive spectrum
4

Zn
7

9
keV

Fig. 3. Spectra of the materials of adhesive joint with element content.

()

10 m (b)

10 m

Fig. 4. SEM images of transverse sections of adhesive compositions for samples of vulcanizates based on SKI3 with
initial (a) and modified (b) adhesive.

()

100 m (b)

100 m

Fig. 5. SEM images of the films of compositions

based on polychloroprene adhesive of 88SA trade
mark: (a) initial adhesive; (b) modified adhesive.

polychloroprene and rubbers under investigation in a

1 : 9 ratio.
Moreover, the modification reduces the degree of
crystallinity at the expense of the disturbance of the

regularity of macromolecules of the grafted modifier

molecules. While studying the changes in structure of
adhesion films after modification, it was established
that the surface of the adhesive film bearing adhesion
promoters is characterized by more texturized struc
ture. This is supported by the micrographs presented
in Figs. 5 and 6.
The more developed structure of the adhesive film
favors an increase in the contact area between the
adhesive and substrate. This occurs due to the better
cohesion of the textured adhesive film with the rough
surface of vulcanizates, which increases the strength of
the adhesive joint. The mentioned phenomena are
adequately described by the mechanical theory of
adhesion.
Based on the results obtained, we have developed a
model for the formation of an adhesive joint that takes
into account the diffusion layer that is formed by the
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modified fragments and polychloroprene macromole

cules. The strength of an adhesive bond of the resins
based on various rubbers, such as SKI3, SKMS30AR
KM15, and their mixtures, can be achieved by the
introduction of nitroneclass modifiers into the compo
sitions of adhesives based on polychloroprene [34].
Chloroprene adhesives find widespread application
in footwear production. Thus, in the leatherfootwear
industry, fastsetting adhesives based on chloroprene
rubber nairite NT are used; these adhesives are cured
at room temperature [35]. To enhance the adhesion of
nairite adhesives, colophony, indenecumarone, and
glyphthalic resins are introduced [36]. An adhesive
composition was developed that includes polychloro
prene; magnesium oxide; zinc oxide; polyisocyanate;
and an organic solvent, which is distinct in that, in
order to increase the bonding strength and longevity of
the adhesive joint, it includes a modifying additive,
i.e., magnesiumchelated ptertbutylphenolformal
dehyde resin, and N,Ndithiodimorpholine [37].
To join a plasticate, in particular polyvinylchloride,
an adhesive composition was developed based on
polychloroprene and is now used in the footwear
industry. The peculiarity of the adhesive composition
formulation consisted of modifying a filmforming
polymer via grafting an adhesion additive, methyl
methacrylate, on a polychloroprene using the radical
polymerization process [38].
Another adhesive composition used in the footwear
industry contains chloroprene rubber, namely, tetrame
thylthiuramdisulfide; an amine accelerator of vulcani
zation, i.e., urotropine or diphenylguanidine; a resin
additive, i.e., colophony or ptertbutylphenolformal
dehyde resin (or their mixture); a modifier that contains
a curing agent, i.e., the interaction product of 1cyan
oguanidine with formaldehyde taken in a 2 : 1 ratio; and
organic solvents. The application of the abovemen
tioned modifier allows one to increase the adhesion
strength, thermal stability, and water resistance upon
gluing the materials for producing footwear with an
increased moisture and grease content [39].
The possibility of increasing the adhesion strength
of gluing compositions of the 88 series based on poly
chloroprene via modifications with nitrogencontain
ing compounds was studied based on the example of
compounds such as Nnitrosodiphenylamin, ortho
phenylenediamine, and paraoxydiphenylamine,
which are currently used in industry as curing agents;
vulcanization inhibitors; and antioxidants, respec
tively [4046]. The interaction of the polychloroprene
macromolecule with the indicated compounds is con
firmed by IR Fourier spectral investigations. The
above compounds appeared to be efficient adhesion
promoters for adhesives of the 88 brand upon gluing
vulcanizates based on various rubbers.
It was experimentally determined that the intro
duction of nitrogencontaining adhesion promoters
into the adhesive compositions based on polychloro
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()

273

(b)

Fig. 6. Micrographs of films of compositions based

on 88SA polychloroprene adhesive: (a) initial adhe
sive; (b) modified adhesive. 1500.
m
2.0
1.0
0

m
400
300
200
100
m
0
20
10 20
10
30
20 0 10
30 0 10 20 m
m
m

Fig. 7. SEM images of the surface of polychloro

prene films: (a) initial; (b) modified.

prene in insignificant amounts (about 0.13.0% of the

adhesive weight) allows one to achieve a significant
increase in the adhesion strength of a gluing joint of
vulcanizates based on different rubbers upon gluing
them together [72]. Thus, for example, the introduc
tion of Nnitrosodiphenylamine into 88NT adhesive
in the amount of 0.10.3% yields a 2.7fold increase
in the gluing strength for SKI and KhK, a 1.7fold
increase in the strength for SKEPT, and a threefold
increase in the strength for SKN (Table 4).
Upon modifying the 88SA adhesive using the
aforementioned nitrogencontaining compounds, one
can observe analogous dependences in resin gluing. As
a result of modifications with nitrogencontaining
compounds, polychloroprene macromolecules proba
bly acquire surfactant properties. As this takes place,
increases in the density of molecule packing at the
substrate surface, which leads to an increase in the
adhesion strength due to the fact that the nonpolar
part of the macromolecule remains in the gluing layer,
while the polar part is adsorbed on the surface and
attempts to diffuse deeply into the substrate [48].
According to the results of scanning electron
microscopy, the modified polychloroprene film has a
more developed surface (Fig. 7); i.e., the number and
sizes of jags increase and their appearance is likely
connected with the formation of novel supramolecular
structures that result from the increase in the flexibility
and mobility of modified polychloroprene macromol
ecules. The crests of microirregularities at the film sur
face most likely represent regions of macromolecules

274

KEIBAL et al.

Table 4. Effect of content and type of nitrogencontaining adhesion promoters on the adhesion properties of 88NT trade
mark adhesive
Modifier type

Shearing strength, MPa, of the adhesive joints of vulcanizates

Modifier con
tent, wt %

SKI3

SKEPT40

SKN18

Neoprene

0
0.1
0.3
0.5
1.0
2.0
0.5
1.0
2.0
3.0
0.5
1
2
3

0.61
1.27
1.65
0.85
0.77
0.80
0.71
1.10
0.98
0.76
1.02
1.29
0.92
1.07

0.99
2.17
1.44
1.67
1.07
1.16
1.15
0.86
1.27
1.43
0.91
1.52
1.21
1.38

0.46
1.12
1.41
1.07
0.92
0.97
1.01
1.31
1.12
1.21
0.96
1.56
1.18
1.27

0.73
2.18
1.56
1.95
1.44
1.56
1.20
1.50
1.28
2.55
0.97
1.48
1.29
1.37

Nnitrosodiphenylamine

paraOxydiphenylamine

orthoPhenylenediamine

Table 5. Effect of TCPP content on adhesion properties of 88NT adhesive

Modifier type
Trichloropropyl
phosphate

Trichloroethyl
phosphate

Modifier con
tent, wt %
0
0.1
0.3
0.5
1.0
2.0
0.05
0.1
0.5
1.0
3.0

Shearing strength, MPa, of the adhesive joints of vulcanizates

Combustibility*
SKI3

SKEPT40

SKN18

Neoprene

0.61
0.72
0.82
0.78
0.51
0.47
0.95
0.93
0.86
0.84
0.78

0.99
1.4
1.17
1.43
0.79
0.66
1.31
1.83
1.12
1.00
0.98

0.46
0.88
1.12
0.95
0.63
0.46
0.83
1.12
1.36
0.88
0.65

0.73
1.10
1.62
0.97
0.89
0.84
1.32
1.6
1.24
1.17
1.00

II
II
I
I
I
II
II
II
I
I

* According to OST 9009479.

that bear functional groups, which are known to serve

as active sites for the interaction of the adhesive with
the substrate surface.
Hence, the explored nitrogencontaining com
pounds are effective promoters of adhesion for gluing
compositions of the 88 series, the introduction of
which in small amounts facilitates the enhancement of
the strength of gluing bond of resins with each other by
two to three times on average [48, 49]. The enhance
ment of the adhesion strength and reduction of the
combustibility of gluing compositions based on poly
chloropreneare are possible via modifications with

phosphoruscontaining compounds (trichloroeth

ylphosphate (TCEP) and trichloropropylphosphate
(TCPP), which are notorious fire retardants. The per
formed investigations revealed that the above com
pounds increase the adhesion strength of a gluing bond
and favor the reduction in the degree of combustibility
of gluing films (Table 5) [47, 50, 51].
Apparently, the reason for the improved the
strength of the vulcanizate gluing bond is the increase
in the depth of the diffusion of polychloroprene mac
romolecule segments into the internal layers of the
gluing samples after interactions with phosphorus
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275

Adhesive

Adhesive

Resin
Resin

10 m

()

10 m

(b)

Fig. 8. SEM images of the transverse sections of the samples: (a) initial adhesive; (b) adhesive modified with TCEP.
Light vague bands (X) are regions with abnormally high chlorine concentration.

containing adhesion promoters, which is confirmed by

the local electron probe and Xray microanalyses data
based on a comparison of the characteristic Xray
spectra of the sample under investigation with the
standards of the known composition. While studying
the joined vulcanizates based on SKEPT40 using
local electron probe microanalysis, the following fea
tures were revealed. In the diffusion region, there are
segments with an abnormally enhanced content of
chlorine (Fig. 8). The depth of chlorine diffusion in
the modified samples increases to 23 m, whereas for
the nonmodified sample, it comprises 13 m.
One of the principles of the diffusion theory of
adhesion postulated as early as in 1960s states that the
penetration process is only accomplished by macro
molecules, the terminal groups of which are situated at
the sample surface, i.e., the diffusion is accomplished
by the displacement of the terminal segments [49].
Scanning electron microscopy revealed that the
modified gluing film made from polychloroprene is
the more developed surface, which may be explained
by the increase in the number of functional groups that
impart additional flexibility and mobility to the mac
romolecules of the filmforming polymer (Fig. 9).

Hence, the introduction of phosphoruscontaining

compounds into adhesive compositions allows one to
enhance the flexibility of polychloroprene macromol
ecules, which leads to an increase in the diffusion
depth of its separate regions and, thus, facilitates the
enhancement of the adhesive bond between resins
[5254].
At present, phosphorusboroncontaining oligo
mer (PBO) is known as a highly efficient inhibitor of the
flaming of cellulose and film materials, as well as syn
thetic fibers [55]. It was revealed that the above com
pound also serves as an efficient adhesion promoter for
adhesives of the 88 series upon gluing resins based on
various rubbers [56]. It was empirically established that
the introduction of PBO in amounts of about 0.5
5.0 wt % to the adhesive compositions based on poly
chloroprene allows to reach the essential enhance
ment of the adhesion strength (in 0.53.0 times on
average) of the vulcanizate gluing bond of different
rubbers upon gluing with each other (Table 6).
The structure of the film based on polychloroprene
bearing PBO is presented in Fig. 10.
Various fillers of mineral and organic nature may
significantly affect both the process of adhesion con
m
400
300
200
100

m
1.2
0.8
0.4
0
12
10

8
6
4
2
0

m 12

10

0
m

Fig. 9. SEM image of film based on polychloroprene

modified with TCEP.
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m

Fig. 10. SEM image of film based on polychloro

prene modified with PBO.
2011

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Table 6. Effect of PBO content on adhesion properties of 88

series adhesive
Modifier
content, wt %

Shearing strength, MPa, of the adhesive

joints of vulcanizates
SKEPT40 Neoprene AS
88SA trademark adhesive
0.70
1.02
1.12
1.10
1.29
1.30
1.17
1.22
1.07
1.15
88NT trademark adhesive
0.99
0.73
1.08
0.80
1.27
0.98
1.23
0.92

0
1.0
2.0
3.0
5.0
0
1.0
2.0
3.0

SKI3
1.00
1.10
1.30
1.12
1.00
0.61
0.69
1.01
1.13

tact formation and the properties of the gluing joint.

The application of fillers in gluing joints allows to con
trol thixotropic properties of the indicated composi
tions, favors better filling of the splits between the glu
ing surfaces with the adhesive what affords the econ
omy of gluing materials.
Nowadays, it is established that carbon whites of
BS50 and BS100 trademarks play a double role in
the formulations of gluing compositions based on
polychloroprene, namely, a filler and modifying agent,
which increases the adhesion of gluing compositions
to resins.
Silica filler Rosil175 represents finedispersed
precipitated silicon dioxide. It is known that at present
Rosil175 is widely used in resin mixtures to increase
the cohesion strength. We have found that the intro
duction of the mentioned compound into the gluing
compositions based on polychloroprene allows to sub

stantially increase their adhesion strength upon resin

gluing (Table 7).
While investigating the effect of the combined
introduction of Rosil175 and PBO (in different
equimolar ratios) on the adhesion of adhesives based
on polychloroprene, the enhancement of adhesion
strength of the gluing bond of resins based on different
rubbers is observed.
To increase atmosphere, water, and chemical
resistance of the adhesive compositions based on poly
chloroprene, an efficient method is the chemical
modification of a polymeric base via grafting of meth
ylmethacrylate using the processes of radical polymer
ization in solution. The developed composition can be
used as an alternative for the adhesive based on poly
urethane to join plastics based on PVC as well as to
create solution protectivesealing compositions [57].
Novel, promising modifiers of polyfunctional
action are the compounds of nitrone series. Nitrones
upon interaction with macromolecular compounds
form grafted stable radicals able to participate in phys
icochemical processes that occur both upon forma
tion of polymeric material and upon its exploitation,
thereby, affecting a whole complex of the product
properties. The efficiency of nitrone action is proven
in adhesives based of various elastomers as well as
chlororubbers [58, 59].
Moreover, quinoline esters were suggested and
studied as efficient adhesion promoters for the adhe
sives of both cold and hot curing based on variable
elastomers. They are bifunctional compounds and act
not only as a highefficiency adhesion promoter, but
also as a high activity vulcanizing agent that increases
the strength of an adhesive film. One of the additional
arguments in favor of the choice of this class of com
pounds is their solubility in solvents that are used in
the production of elastomeric adhesives. As the adhe
sion promoters were studied quinoline esters EKh1
(TU (Specifications) 844153873) and EKh10
(TU (Specifications) 844157278), differing in the

Table 7. Effect of Rosil175 modifier content on the adhesion properties of 88 series adhesives
Modifier
content, wt %

Shearing strength, MPa, of the adhesive joints of vulcanizates

SKEPT40

0
0.5
1
2

0.7
1.15
1.13
1.16

0
1
2
3

0.99
1.06
0.84
1.01

KhK

SKI3

SKN18

1.0
1.32
1.31
1.06

0.75
0.93
0.81
1.0

0.61
0.9
1.43
1.01

0.46
0.73
0.78
0.89

88SA trademark adhesive

1.02
1.36
1.62
1.35
88NT trademark adhesive
0.73
1.46
0.77
1.83
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Table 8. Effect of modifier content on adhesion properties of 88 series adhesives

Shearing strength, MPa, of the adhesive joints of vulcanizates
Modifier type and content, wt %
SKI3

SKEPT40

88SA trademark adhesive

0.42
0.73
0.44
1.10
0.72
1.00
0.52
0.90
0.43
0.79
0.45
0.79
0.44
0.77
88NT trademark adhesive
0.49
0.75
0.63
1.21
0.77
1.30
0.70
0.73
0.64
0.57
0.42
1.12
0.72
1.05
0.59
1.05
0.58
0.83

Without a modifier
TEA
0.5
1.0
1.5
PEPA
0.5
1.0
1.5
Without a modifier
TEA
0.5
1.0
1.5
2.0
PEPA
0.5
1.0
1.5
2.0

substituents and presenting the interaction products of

sterically hindered phenols with quinonedioximes.
Upon thermal imapct, one of the products of decom
position of these esters is pdinitrobenzene (PDNB),
known as an efficient adhesion promoter for the adhe
sives based on chlororubbers [60, 61].
A possibility to modify the adhesives based on
KhNK and KhSKI, designed to glue the resins made
of both polar and nonpolar rubbers, with quinol esters
was considered. Quinol esters posses high promoting
action toward adhesives of different types of KhK and
somewhat surpass PDNB in the efficiency. The con
tent of adhesion promoters composed 5 wt % per
100 wt % of the polymer. Upon the introduction of
EKh1 and EKh10 into the adhesives of chloronairite
CN modified with SKMVP15 rubber (1 : 0.5), the
substantial enhancement of the strength and thermal
stability of the adhesion bonds between SKI3 resin
and steel also occurs.
Upon the modification of the adhesives of 88 series
based on polychloroprene with aminocontaining
compounds, i.e., triethanolamine (TEA) and polyeth
ylenepolyamine (PEPA), the following regularities
were revealed.
The introduction of the indicated adhesion pro
moters based on polychloroprene into the composi
tion in insignificant amounts (about 0.52% of the
adhesive weight) allows one to significantly enhance
the adhesion strength (by 3050%) of the gluing bond
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SKN18

KhK

0.81
0.83
0.85
0.89
0.76
0.77
0.62

0.61
0.73
0.75
0.69
0.46
0.38
0.27

0.75
0.76
0.75
0.53
0.44
1.03
0.72
0.53
0.50

0.43
0.76
0.80
0.77
0.72
0.47
0.66
0.62
0.56

between resins based on different rubbers (Table 8). At

present, phosphorusboroncontaining methacrylate
(PBM) is known as an inhibitor of burning for syn
thetic fibers, as well as for film materials based on
polyvinyl alcohol [62].
Since there are functional groups in this compound
that are able to enter the chemical interactions with
polychloroprene, it was of particular interest to study
the effect of PBM on the adhesion properties of adhe
sives of the 88 series. The derived data are presented in
Table 9.
An investigation of the strength of the gluing joint
of resins formed by a modified gluing composition
showed that, in general, the increase in the PBM con
tent in the adhesive composition to 0.5% leads to the
growth of the shearing strength, while the higher con
tent of PBM yields a reduction in the strength of the
bond between the gluing film and substrate.
As is known, nowadays, linoleum is one of the most
popular finishing materials for floor in the construc
tion and repair of buildings and facilities. The effect of
modifying adhesive of the 88 series on the strength of
the gluing bond of linoleum was studied experimen
tally (Table 10). TEA, PEPA, PBM, and Rosil175
were used as modifying additives, which were studied
previously as efficient adhesion promoters for gluing
resins.
It was established that the best results can be
obtained using the suggested compounds in the

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KEIBAL et al.

Table 9. Effect of PBM modifier content on adhesion properties of 88 series adhesives

Shearing strength, MPa, of the adhesive joints of vulcanizates
Modifier content, wt %
SKI3

SKEPT40

SKN18

KhK

88SA adhesive
Initial adhesive

0.42

0.81

0.61

0.73

0.1

0.67

0.81

0.61

0.77

0.3

0.68

0.81

0.63

0.77

0.5

0.70

0.82

0.64

0.78

1.0

0.71

0.82

0.70

0.78

1.5

0.66

0.60

0.60

0.74

2.0

0.54

0.47

0.49

0.89

88NT adhesive
Initial adhesive

0.49

0.75

0.75

0.43

0.1

0.82

0.52

0.85

1.26

0.3

0.89

0.57

0.86

1.44

0.5

1.05

0.88

0.98

1.86

1.0

0.77

0.78

0.69

1.35

1.5

0.72

0.73

0.63

1.34

2.0

0.62

0.61

0.58

0.84

Table 10. Effect of modification of 88 series adhesive on strength of linoleum gluing bond
Shearing strength, MPa
Adhesive

Modifier content, wt %

Modifier
TEA

88NT

88SA

PEPA

PBM

Rosil175

0.60

0.5

0.62

0.64

0.64

0.74

1.0

0.66

0.70

0.66

0.83

1.5

0.62

0.62

0.63

0.75

0.35

0.5

0.42

0.42

0.47

0.40

1.0

0.46

0.57

0.64

0.50

1.5

0.43

0.50

0.58

0.47

amount of 1% relative to the weight of the adhesive

composition. As this takes place, the value of the adhe
sive joint strength surpasses that of the material itself,
i.e., the disruption has a cohesion character (by lino
leum).

Polychloroprene adhesive compositions are also

widely used in the automobile industry, in particular,
Luch 2013 chloroprene adhesive is used to join the
Avtolin floor covering (based on PVC) with the ply
wood floor in Volzhanin buses.
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Shearing strength, MPa
0.60

PBM + TEA
PBO + TEA

0.55
0.50
0.45
0.40
0.35
0.30
0

1.0
1.5
0.5
Modifier content, %

2.0

Fig. 11. Change of adhesion strength of Luch 2013

adhesive depending on type and content of modify
ing agent.

The possibility of modifying the above adhesive

with elementcontaining compounds, i.e., the inter
action products of PBM with TEA, as well as PBO
with TEA (Fig. 11), was considered. It is clear from
Fig. 11 that the best values of the parameters are
achieved at a modifier content of 1 wt %. For example,
the strength of gluing in the case of modifying agent
PBO + TEA increases by 1.7 times and, for PBM +
TEA modifier, it increases by 1.5 times compared to
the initial data. The investigations allowed us to pre
dict the possibility of applying the indicated adhesion
promoters to modify the Luch 2013 adhesive compo
sition. Hence, the application of elementcontaining
compounds as adhesion promoters for adhesive com
positions based on polychloroprene allows one to
obtain gluing compositions with enhanced adhesion
parameters for elastic materials.
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POLYMER SCIENCE

Series D

Vol. 4

No. 4

2011