Hindawi

International Journal of Polymer Science

Volume 2018, Article ID 4905304, 9 pages
https://doi.org/10.1155/2018/4905304

Research Article
Synthesis and Properties of Adhesive
Polymer-Methylmethacrylate Materials

Ulyana Khromiak ,1 Volodymyr Levytskyi,2 Kateryna Stepova,1 and Andry Tarnawsky1

1
Department of Environmental Safety, Lviv State University of Life Safety, 35 Kleparivska Str., Lviv 79000, Ukraine
2
Department of Chemical Technology of Plastics Processing, Lviv Polytechnic National University,
12 S. Bandery Str., Lviv 79013, Ukraine

Correspondence should be addressed to Ulyana Khromiak; [email protected]

Received 23 October 2017; Revised 2 February 2018; Accepted 21 February 2018; Published 27 March 2018

Academic Editor: Marta Fernández-Garcı́a

Copyright © 2018 Ulyana Khromiak et al. This is an open access article distributed under the Creative Commons Attribution
License, which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly
cited.

Kinetics of emulsion polymerization of hydrophilic vinyl monomers in the presence of polyvinylpyrrolidone and technological
principles of their synthesis are determined. Reasonable technological parameters in the synthesis of copolymers are determined.
Physicochemical properties of the synthesized copolymers (surface tension, the size of latex particles, and pH) are determined.
Synthesized graft copolymers were used to create high-adhesion polymer-monomer compositions. These compositions have high
reactivity at room temperature. It can be regulated by the nature of the polymer matrix and the introduction of comonomers
and fillers due to the influence of physicochemical factors on the process of polymer formation. The rate of polymerization and
the degree of monomer conversion largely depend on the nature of the polymer matrix. The highest polymerization rate and
the maximum degree of conversion are observed when using a copolymer of polyvinylpyrrolidone and polymethylmethacrylate.
Materials based on the developed compositions are characterized by a low residual monomer content and high operational
properties, such as surface hardness, Vicat softening temperature, and adhesive bond strength to supports of different nature.

1. Introduction in water and many aqueous organic media, high ability to

complex formation, and high sorption characteristics are
The contemporary development of science and technology used as modifiers [1, 2].
requires the creation of new polymer materials with a corre- Polyvinylpyrrolidone (PVP) and its copolymers belong to
sponding set of special properties: high adhesion to supports such polymers. Due to their specific properties, additional
of different nature, high physicomechanical, thermophysical, opportunities for improving modern technologies [3, 4],
and selective-sorption properties. These include low-toxic obtaining of new functionalized materials [5], and expanding
adhesive polymer-monomer compositions of medical and the branches of their use are opened.
general technical purposes. Monomer-polymer compositions are widely used in a
Among the methods for preparation of such materials variety of industries especially as a basis for preparing mate-
with the necessary properties the most interesting are those rials with enhanced adhesion properties. Among such mate-
based on the modification of known industrial polymers in rials, acrylates based adhesives occupy a special place [6].
polymerization processes. These methods make it possible to First of all, the increased interest in acrylates-containing glues
obtain polymer materials with the preferable set of techno- is caused by their high operational properties: cure speed,
logical and operational properties at rather low material and adhesion to a variety of materials, strength and durability of
energy costs. adhesive compounds, and their low toxicity [7]. In this regard,
The determining factor for most of the technologies these materials are widely used in a variety of industries,
based on the preparation of modified polymeric materials is namely, in medicine, dentistry, construction, engineering,
modifier. Polymers with high surface activity, good solubility automotive, and electrical and textile industries [8]. It should
2 International Journal of Polymer Science

be noted that the use of (meth)acrylic adhesives is expanding kinetics of the polymerization and therefore the technological
in current conditions to solve many technological tasks [9]. features of the process and its productivity. This influence
The main components of (meth)acrylic adhesives are is caused by changes in the interphase characteristics of the
(meth)acrylic monomers or polymers, initiating systems, polymerization system, adsorption phenomena at the phase
hardeners, stabilizers, and modifiers. Methylmethacrylate boundary, and changes in the solubility of monomers in the
(MMA) is often used as the main monomer in the dispersion medium with the active participation of the emul-
(meth)acrylic adhesives. It provides high adhesive strength sifier. Emulsifiers have to meet a number of requirements
and is a good solvent for a number of polymers. When [13, 14]: high surface activity, ability to micellization, and
combined with oils MMA makes it possible to glue untreated nontoxicity.
surfaces. MMA has several disadvantages, in particular, Due to its properties and structure PVP can serve as an
high volatility, pungent odor, and fire risk. It is used in emulsifier in the processes of emulsion polymerization and
admixture with high boiling monomers such as hydroxyalkyl also be an effective polymer matrix, which actively partici-
methacrylate, glycidyl methacrylate, and methacrylates of pates directly in the polymerization processes. It should be
higher alcohols: tetrahydrofurfuryl-, diethylaminoethyl-, 2- noted that the influence of the emulsifier on the regularities
oxopropyl neopentyl-, and other glycolmethacrylates and of the emulsion polymerization of vinyl monomers primarily
styrene [10–12]. resulted in change in the interphase characteristics of the
The aim of the work is the development of functionalized polymerization system and the solubility of the monomers in
materials based on graft copolymers of polyvinylpyrrolidone the reaction medium. On the basis of the conducted studies,
for high-adhesion methyl methacrylate-copolymer composi- it has been established that PVP macromolecules exhibit
tions. high surface activity on the interphase surface of water-
vinyl monomer. This activity increases with a decrease in the
2. Materials and Methods polarity of the monomer in the VA-MMA-styrene series. This
is evidenced by the nature of the interphase tension isotherms
Copolymers were synthesized by emulsion polymerization of in the vinyl monomer-aqueous PVP solution system, the PVP
vinyl monomers in the presence of PVP, potassium persulfate, adsorption dependencies in the coordinates of the Langmuir
or hydrogen peroxide at 60–70∘ C and the ratio of monomer: equation, the maximum values of the Gibbs adsorption (𝐺𝑚 =
aqueous phase = 1 : 3. 2.14 ⋅ 10−6 mol/m2 ), and adsorption work (𝑊ad = 48.8 ⋅
The kinetics of the emulsion polymerization of the test 10−3 J/m2 ) for styrene. PVP has different effects on the total
compositions were studied by dilatometric method for mea- (true and colloidal) solubility of vinyl monomers in aqueous
suring the volume change of the reaction mixture during solution.
polymerization. Due to the increase of the PVP concentration up
IR studies were carried out on a spectrograph “Specord- to 0.2 mol/l monomer concentration, solubility of MMA
75IR” at room temperature. The spectra were recorded at increases from 0.15 to 0.22 mol/l, for VA it decreases from 0.33
the same intensity and the same scan rate between 400 and to 0.18, and for styrene it is almost unchangeable. Obviously it
4000 cm−1 . is a consequence of specific intermolecular interactions in the
The adhesive compositions were synthesized by the system that will affect the polymerization processes in these
polymerization of MMA or a mixture thereof with other systems.
monomers in the presence of synthesized copolymers at room High surface activity and solubilization ability of PVP
temperature. To determine the properties of the adhesive prove its high efficiency as an emulsifier in the processes
compositions, a number of studies were carried out. The of emulsion polymerization of vinyl monomers (KKM PVP,
conversion degree of the monomer was determined by the 0.09–0.11 mole/liter monomer concentration).
bromide-bromate method. The surface hardness and Vicat The effect of the monomer nature (MMA and styrene),
softening temperature of the samples were measured on the concentration factors, temperature, and stirring rate on the
Heppler consistometer. Adhesion was determined according kinetic regularities the of emulsion polymerization process
to ISO 527-5: 2009. of vinyl monomers in the presence of PVP was established.
Emulsion polymerization of vinyl monomers in the presence
3. Results and Discussion of PVP is characterized by a different rate depending on the
nature of the monomer (Figure 1).
3.1. Technological and Kinetic Features of Emulsion Polymer- Obviously the features of the emulsion polymerization
ization of Vinyl Monomers in the Presence of PVP. It has of vinyl monomers are caused by the dependence of the
been established that the enhanced initiating ability of the mechanism of particle formation from the solubility of the
series of (meth) acrylic monomers has graft copolymers of monomer in the aqueous solution of PVP: during the MMA
PVP. Copolymers were synthesized on the basis of PVP and polymerization the process may run in the aqueous solu-
vinyl monomers (MMA, vinyl acetate (VA), and styrene) tion with the formation of macroradicals by homogeneous
by emulsion polymerization. The emulsion polymerization nucleation, as well as in the micelles of the emulsifier (PVP),
of vinyl monomers is mostly carried out in the presence and continues in the polymer-monomeric particles, which
of emulsifiers that are surfactants of different nature [13– are formed from the emulsifier micelle or from aggregates of
15]. The nature of the emulsifier and its concentration in macromolecules released from the water phase. In the case
the reaction medium greatly influence the mechanism and of styrene, the polymerization process begins in the micelles
International Journal of Polymer Science 3

100 12
(2)
10
80 (1)
8

V (mol/ l·s)
60 (1)

1470
A (%)

1440
40

1200
4

1160
Intensity
(1 ) (2)
20
(2 ) 2

1500
1460

1220
0 0

1180
1 2 3 4 5 6 7 8 8.5
 · 10−3 (s) (3)

1300
1450

1140
Figure 1: Degree and rate of emulsion polymerization of vinyl

1500
monomers in the presence of PVP: (1), (1󸀠 ) – 0; (2), (2󸀠 ) – V. (1),
(2)VV0. (1󸀠 ), (2󸀠 ) styrene. 𝐶mon. = 0.99 mol/l; 𝐶in. = 2.81⋅10−3 mol/l;
𝐶PVP = 0,09 mol/l; 𝑀PVP = 28000; 𝑇 = 323 K.
1700 1500 1300 1100
] (＝Ｇ−1 )
of the emulsifier and continues in the polymer-monomer Figure 2: IR spectra of PVP-gr-PMMA copolymers depending on
particles formed from them. In addition, polymerization the ratio of components in the synthesis and the drying temperature
of styrene can occur in micelles and in microdrops of a of the copolymer: MMA : PVP in the synthesis of the copolymer,
monomer, which is specific for nonionic emulsifiers (like mol/mol monomer concentration: (1), (2) 3 : 1; (3) 1 : 1. 𝑇𝑑 , 𝐾: (1)
PVP). 313; (2), (3) 343.
The polymerization reaction rates for the monomer and
initiator are 1.9 and 0.75, respectively, for MMA and 1.6 and
0.55 for styrene. the size of latex particles. The size of the latex particles also
It was found that the polymerization rate of all the depends on the nature of the monomer and, depending on
investigated vinyl monomers increases with increase in ratio the mixing rate, is described by the following:
of the monomeric and aqueous phases, the concentration
of the initiator, and the temperature. Dependence of the for styrene: 𝑟PVP-gr-PS
MMA polymerization rate on the particle size in the range
of 70–200 nm is described by the following: = −2 ⋅ 10−4 ⋅ 𝑉mix.
3 2
+ 0.0927 ⋅ 𝑉mix. − 15.758 ⋅ 𝑉mix.

𝑉pol.VV0 = 1 ⋅ 10−4 ⋅ 𝑟2 − 0.055 ⋅ 𝑟 + 5.603. (1) + 988.58,

(2)
for VV0: 𝑟PVP-gr-PVVA
As a result of polymerization, graft copolymers of PVP are
formed in the investigated systems. This is evidenced by the = −9 ⋅ 10−5 ⋅ 𝑉mix.
3 2
+ 0.0517 ⋅ 𝑉mix. − 9.6168 ⋅ 𝑉mix.
physicochemical and IR spectroscopic studies. The IR spectra
of synthesized methylmethacrylic copolymers (Figure 2) + 666.24.
have characteristic bands that are related to both the PVP
links (1300 cm−1 , 1450 cm−1 , 1470 cm−1 , and 1500 cm−1 ) and In our opinion, an increase in the particle radius and,
PMMA (1140 cm−1 , 1160 cm−1 , 1180 cm−1 , 1200 cm−1 , and correspondingly, a decrease in their total quantity, with an
1220 cm−1 ). increase in the initial concentration of the monomer, can be
The degree and effectiveness of grafting depend signifi- attributed to the increase in the viscosity of the polymeriza-
cantly on the conditions of the process, in particular the PVP tion system, which leads to a decrease in the mobility of the
concentration in the aqueous medium and the temperature radicals formed during the decomposition of the potassium
of the process. persulfate and, as a consequence, a decrease in the initial
It has been established that the properties of latexes quantity of polymer-monomer particles. Also, it should be
obtained by emulsion polymerization (surface tension, pH, noted that, according to the classical theory of emulsion
and particle radius) depend on the conditions of the process: polymerization, when the conversion rate reaches 10–15%, the
the ratio of the monomeric and aqueous phases, the tempera- rate increases due to a termination constant decrease. This
ture, the concentration of the monomer and initiator, and the leads to an increase of particles size of synthesized latex and
amount of PVP. As the concentration of the initiator increases changes in their structure and properties.
and the temperature of the process decreases, the size of the Synthesized PVP copolymers have sufficiently high sorp-
latex particles and the pH decrease (Figure 3). tion properties that can be controlled by polymerization
The ratio between the components of the polymerization conditions, primarily by the process temperature and the con-
system and the mixing rate also has a significant effect on centration of the initiator. As the polymerization temperature
4 International Journal of Polymer Science

110 3.5

100 (2)
3.4

90
3.3 (2)

80
r (nm)

3.2

pH
70
(1)
(1) 3.1
60

50 3

40 2.9
0.4 0.6 0.8 1 1.2 1.4 0.4 0.6 0.8 1 1.2 1.4
CＣＨ. (%) CＣＨ. (%)
(a) (b)

Figure 3: Influence of synthesis conditions on the properties of copolymer latexes: (a) 𝑟; (b) aX. (1) 323 K; (2) 333 K.

increases and the initiator concentration decreases, the sorp- 100 (1)
(2)
tion capacity of the copolymers decreases. Sorption ability (3)
of finely dispersed graft copolymers of polyvinylpyrrolidone
80
and polystyrene (PVP-gr-PS) is greater, compared to the (4)
graft copolymer of polyvinylpyrrolidone and polymethyl- (5)
methacrylate (PVP-gr-PMMA). With respect to heparin, it 60
is 3.0 ⋅ 105 and 3.1 ⋅ 104 units/m2 , respectively, with respect
A (%)

to iodine 36 and 32 mol/g. It can be used in the preparation 40

of sorption materials for antiseptics, therapeutic insulating
films, and thrombus-resistant products.
20
3.2. Discussion of the Results of the Investigation of the Tech-
nological and Physicochemical Basis for the Development of
0
Methyl Methacrylate-Copolymer Compositions and Materials 0 50 100 150 200
Based on Them. The emulsion polymerized graft copolymers  (min)
of PVP were used as a polymer matrix for the preparation of
MMA-copolymer compositions cured by block polymeriza- Figure 4: Kinetic curves of polymerization of MMA compositions
tion. depending on the nature and conditions of PM synthesis: (1),
The results of kinetic studies of MMA polymerization in (2), (4) PVP-gr-PMMA; (3) PVP-gr-PS; (5) PMMA. The ratio of
the presence of finely dispersed PVP copolymers depending MMA : PVP in the synthesis of PM, mole/mole monomer concen-
on the nature of the polymer matrix (PM) and the conditions tration: (1)–(3) 3 : 1; (4) 1 : 1. Td. PM, K: (1), (3), (5) 313; (2), (4) 343.
for its synthesis are shown in Figure 4.
The rate of polymerization and the degree of monomer
conversion largely depend on the nature of the polymer greater affinity of the monomeric and polymeric phases. It
matrix (Figure 4). Polymerization of MMA occurs at a high should be noted that the drying temperature of the polymer
rate and, depending on the nature of the polymer matrix, matrix also affects its activity. The copolymers dried under
the monomer conversion rate of 70–90% is achieved in 10–15 milder conditions (313 K) show greater activity.
minutes. The highest polymerization rate and the maximum In our opinion, the high polymerization rate of methyl
degree of conversion are observed when using the PVP-gr- methacrylate can be explained by intermolecular interactions
PMMA copolymer. between the components of the reaction medium, which may
It was found that the activity of the polymer matrix lead to the formation of a charge transfer complex (CTC)
also depends on the conditions of its synthesis. A polymer between a double bond of a monomer and a carbamate
matrix synthesized with a smaller amount of PVP exhibits group of PVP and higher affinity between the monomeric
significantly more activity during block polymerization of and polymeric phases. Interactions of this nature lead to
MMA. This, along with other factors, is a consequence of the a redistribution of electronic density on a dual bond of
International Journal of Polymer Science 5

100 (1)
(2)
(3)
(4)
80
(5)

(6)
(1) 60

1250

A (%)
1480
1420
Intensity

(2) 40
1640

560
20

590
1275

0
1490
1435
1670

0 50 100 150 200

 (min)

Figure 6: Kinetic curves of MMA polymerization in the presence

2000 1800 1600 1400 1200 1000 800 600 400 of PVP-gr-PMMA depending on nature and content of comonomer
and filler. Comonomer: (2) HEMA, (3) GMA, and (4) VP. Filler:
] (＝Ｇ−1 )
(5) Al2 O3 , and (6) SiO2 . Comonomer content: 20% (mas.). Filler
Figure 5: IR spectra of copolymer PVP-gr-PS (1) and MMA, a content: 10% (mas).
copolymer composition on based on it (2).

weight of the polymeric component, the shape and size

monomer and, consequently, to a decrease in the total of the particles, and the monomer : polymer ratio. As it
activation energy of the polymerization process. was established on the basis of kinetic studies, when the
The results of IR-spectroscopy studies prove the inter- monomer : copolymer ratio changes from 1 : 1.5 to 1 : 3, time
molecular interactions with carbamate groups of PVP in the of gel formation decreases about 10 times. The optimal ratio
polymerization system and the morphology of synthesized between the monomeric and the polymeric phases for the
copolymers and monomer-polymeric materials (Figure 5). investigated systems is 1 : 2.
It should be noted that, for the pure PVP, the characteris- The addition of various fillers, namely, silicon (IV)
tic absorption bands are 560, 1300, 1415, 1480, and 1735 cm−1 . oxide and aluminum oxide, leads to a decrease in the
As we see, for copolymer PVP-gr-PS and methylmethacrylate polymerization rate of the MMA and the limiting degree of
copolymer composition, these bands are shifted. polymerization.
This displacement is especially apparent for carbamate Depending on the nature of the polymer matrix and
groups of the pyrrolidone ring and the methylene groups of the monomeric phase, the ratio between phases and the
the macrochain (Table 1). presence of filler during polymerization under the investi-
Obviously, these groups take an active part in the gated conditions, a number of stages can be distinguished
intermolecular interactions between the components of the in terms of physicochemical properties: sandy, sticky, dough-
system. In this case, the activating effect of the polymer like, viscous, and fully cured.
matrix on the polymerization process of vinyl monomers is Duration of each of these stages for different systems
seen. It gives the opportunity to develop compositions that based on the PVP-gr-PMMA copolymer is shown in Figure 7.
can polymerize under mild conditions without the use of The sandy stage begins immediately after mixing the
traditional initiators of radical polymerization. components, and, depending on the temperature, it can last
It is established that the kinetic regularities of the from 30 s to 5 min. In this case, only the swelling of the
polymerization process are affected by the comonomer and finely divided polymer in the monomer begins. It occurs
mineral filler (Al2 O3 , SiO2 ) (Figure 6). on the surface of the powder particles and depends on
The addition of comonomers such as 2-hydroxyethyl- their dimensions. In this regard, the polymerization system
enemethacrylate (HEMA), glycidylmethacrylate (GMA), and has no plasticity and the material contains a large amount
vinylpyrrolidone (VP) to MMA leads to a decrease in the of unbound monomer. For some systems there is no sand
polymerization rate, regardless of the nature of the polymer stage. The sticky stage is characterized by the appearance
matrix (PVP-gr-PMMA and PVP-gr-PS). It should be noted of yarns, sticky mass properties, and great ductility and
that the ratio between the monomer and the polymer fines flowability, with the material having high adhesion. The
has a significant effect on the polymerization process. The dough-like stage is characterized by high plasticity, low
monomer quantity should be as small as possible but enough fluidity, and lack of tackiness. At this stage, the reaction
for complete swelling of the polymer. The swelling rate mass can be formed into different products. The rate of
of the fine powder and the formation of a homogeneous transition of the system from the plastic stage to the dough-
mass essentially depends on the temperature, the molecular like one for all polymer matrices is practically the same
 6

Table 1: Characteristic absorption bands for PVP-gr-PS (1) and MMA-copolymer composition based on PVP-gr-PS (2).
Characteristic absorption bands, cm−1
for PVP for PS
Composition 560 1300 1415 1480 1735 696 750 1590
C=\; NX
C–N; CX2 – CH2 –ring CN–ring C=\ CH–aromatic ring C=C
Amide VI
(1) 560 1250 1420 1480 1640 700 750 1580
(2) 590 1275 1435 1490 1670 700 750 1590
International Journal of Polymer Science
International Journal of Polymer Science 7

into the composition leads to an increase in the strength of the

10
adhesive compound of polymethylmethacrylate materials.
The content of the filler has a significant influence on
8 the surface hardness and Vicat softening temperature. The
introduction of SiO2 and the heat treatment at 333 K lead
6 to an increase in the surface hardness (193 MPa) and Vicat
 (min)

softening temperature (126∘ b). Obviously, it happens due to

4 the changes in the submolecular structure of the material
caused by chemical and physical factors. Changes in the sub-
molecular structure of the materials caused by heat treatment
2
and the filler confirm the results of the thermomechanical
analysis shown in Figure 9.
0 (b)
The decrease of the deformation value in a wide tem-
1 (a)
2 perature range for thermally treated samples and samples
3
4 containing the filler is obviously a consequence of increasing
Figure 7: Stages of polymerization of VV0-PVP-gr-PMMA the density of the fluctuation network of the polymeric
compositions depending on comonomer nature: (1) without component.
comonomer; (b) HEMA. Comonomer content: 20% (mas.). 1: sandy It should be noted that the developed materials have a
stage; 2: sticky stage; 3: dough-like stage; 4: viscous stage. high enough adhesive strength, regardless of the nature of
the substrate. The greatest value of the adhesive strength is
observed for PMMA materials, which is caused by their par-
tial swelling due to the MMA diffusion from the monomer-
and increases with the increase in their dispersion. The
polymer composition. The introduction of comonomers with
viscous stage is characterized by the preservation of a given
polar groups into the composition leads to an increase in the
shape of the material, even with a short-term mechanical
adhesive strength of methyl methacrylate materials.
action, and precedes the complete curing of the material. The
duration of these stages determines the area of use of the However, process shrinkage (0.1–1.0%), water absorp-
developed compositions: either for glutinous materials, for tion (0.8–1.2%), thermomechanical properties, and chemical
compounds, or for putty. The presence of this or that stage stability in acidic and alkaline media are also dependent
can be regulated by mixing times and by the ratio of the on the conditions of synthesis of the polymer matrix and
monomer and polymer phases. All these stages are the result the nature of the comonomer and filler. The materials that
of such chemical and physicochemical processes between contain comonomers such as HEMA and VP, as well as
the polymeric and monomeric phases as wetting, swelling, copolymers with a large number of PVP units, exhibit
dissolution, and polymerization. These stages differ in the increased water absorption. Obviously, it may be attributed
different degree of swelling of the polymer matrix, different by the fact that due to the presence of carbamate groups PVP
ductility, fluidity, tackiness, and residual monomer content. has an increased capacity for water sorption, and the presence
The technological recommendations were developed of hydrophilic HEMA in the monomer phase increases
depending on the further use of the compositions. For glues water absorption due to increased nonuniform structure.
the mixing time should not be more than 2–2.5 minutes, At the same time, heat treatment as a result of changes in
for putties 3-4 minutes, and for compounds 5-6 minutes. To the supramolecular structure leads to a decrease in water
prevent the formation of air voids in the composition, it is absorption. The calculated diffusion coefficients (7.0 ⋅ ⋅ ⋅ 7.6 ⋅
necessary to add the monomer phase to the fine polymer 10−7 sm2 /s), sorption coefficients (1.9 ⋅ ⋅ ⋅ 2.3⋅10−2 g/sm3 ), and
powder in small portions. permeability (17.1 ⋅ ⋅ ⋅ 17.5 ⋅ 10−9 g⋅sm/(sm2 ⋅s)) of chemical
The obtained modified materials on the basis of the reagent (NaOH, H2 SO4 ) in the sample indicate a sufficiently
developed MMA-copolymer compositions have rather high high chemical stability of the developed materials in acidic
operational properties, such as surface hardness, Vicat soft- and alkaline media.
ening temperature, and adhesive bond strength to supports
of different nature (Figure 8). 4. Conclusions
It is established that the surface hardness and Vicat
softening temperature depend on the nature and conditions Monomer-polymer compositions based on MMA and graft
of synthesis of the polymer matrix and also on the nature copolymers PVP-gr-PMMA or PVP-gr-PS have a high reac-
of the comonomer. The addition of bifunctional GMA to tivity at room temperature. It can be regulated by the nature
the composition results in a significant increase in surface of the polymer matrix and the introduction of comonomers
hardness and heat resistance. It may be caused by the and fillers due to the influence of physicochemical factors on
formation of more structured materials. Vinylpyrrolidone the polymerization process.
increases these values, apparently as a result of the formation Materials based on the developed compositions have low
of a more uniform structure due to the better swelling of the content of the residual monomer and sufficiently high oper-
copolymer that contains the PVP units in the monomeric ational properties such as surface hardness, heat resistance,
phase. The introduction of comonomers with polar groups and adhesion to supports of different nature.
8 International Journal of Polymer Science

200 150

150
100
F (MPa)

Tv (∘ C)
100

50
50

0 0
1 2 3 4 1 2 3 4
(a) (b)

40

30
！ (MPa)

20

(С)
10
(В)

0
(А)
1 2
3 4
(c)

Figure 8: Surface hardness (1), Vicat softening temperature (b), and the strength of adhesive bonding (c) VV0-PVP-gr-PMMA
compositions depending on comonomer nature: 1, without comonomer; 2, VP; 3, GMA; 4, HEMA. Nature of support material: (0) steel/steel;
(j) ceramics/ceramics; (b) steel/PMMA.

100 The developed materials can be used in various industries

as compounds and adhesives and also in dentistry as com-
80 ponents of filling materials, toning lacquers, and protective
coatings.
60
Conflicts of Interest
 (%)

40 The authors declare that they have no conflicts of interest.

20
References
(1)
(2)
[1] L. M. Al-Harbi, S. A. Kosa, M. K. Baloch, Q. A. Bhatti, and E.-
(3) S. E.-B. H. El-Mossalamy, “Adsorption of Polyvinylpyrrolidone
0
0 50 100 150 200 over the Silica Surface: As Affected by Pretreatment of Adsor-
bent and Molar Mass of Polymer Adsorbate,” International
T (∘ C)
Journal of Polymer Science, vol. 2016, Article ID 2417292, 2016.
Figure 9: Thermomechanical curves of materials based on MMA- [2] J. W. Sikora, V. Levytskyi, V. Moravskyi, and H. Gerlach,
PVP-gr-PMMA compositions: (1), (3) not heat-treated, (2) heat- “Twin screw extrusion with Expancel foaming agent,” Journal
treated at 333 K; (3) with SiO2 . Filler content: 10 wt.%. of Polymer Engineering, vol. 33, no. 6, pp. 501–508, 2013.
International Journal of Polymer Science 9

[3] V. E. Levyts’kyi, A. S. Masyuk, D. S. Samoilyuk, L. M.

Bilyi, and T. V. Humenets’kyi, “Morphology and Properties of
Polymer–Silicate Composites,” Journal of Materials Science, vol.
52, no. 1, pp. 17–24, 2016.
[4] V. Levytskyi, A. Masyuk, D. Katruk, and M. Bratychak, “Reg-
ularities of obtaining, morphology and properties of metal-
containing polymer-silicate materials and polyester composites
on their basis,” Chemistry and Chemical Technology, vol. 10, no.
1, pp. 35–40, 2016.
[5] V. Skorokhoda, Y. Melnyk, V. Shalata, T. Skorokhoda, and S.
Suberliak, “An investigation of obtaining patterns, structure
and diffusion properties of biomedical purpose hydrogel mem-
branes,” EasternEuropean Journal of Enterprise Technologies, vol.
1, no. 6-85, pp. 50–55, 2017.
[6] S. P. Davtyan, A. O. Tonoyan, A. Z. Varderesyan, and S. C.
Müller, “Frontal copolymerization in the presence of nano-
particles,” European Polymer Journal, vol. 57, pp. 182–186, 2014.
[7] N. M. B. Smeets, “Amphiphilic hyperbranched polymers from
the copolymerization of a vinyl and divinyl monomer: The
potential of catalytic chain transfer polymerization,” European
Polymer Journal, vol. 49, no. 9, pp. 2528–2544, 2013.
[8] A. M. Oliveira, K. L. Guimarães, and N. N. P. Cerize, “The role
of functional monomers on producing nanostructured lattices
obtained by surfactant-free emulsion polymerization - A novel
approach,” European Polymer Journal, vol. 71, article no. 7015,
pp. 268–278, 2015.
[9] P. Klemarczyk and J. Guthrie, “Advances in anaerobic and
cyanoacrylate adhesives,” Advances in Structural Adhesive Bond-
ing, pp. 96–131, 2010.
[10] H. Kilambi, S. K. Reddy, L. Schneidewind, J. W. Stansbury, and
C. N. Bowman, “Copolymerization and dark polymerization
studies for photopolymerization of novel acrylic monomers,”
Polymer Journal, vol. 48, no. 7, pp. 2014–2021, 2007.
[11] L. Liu, W. Feng, X. Lü, and W.-K. Wong, “First example
of near-infrared (NIR) luminescent Yb4(Salen)4-containing
metallopolymer through radical copolymerization with MMA
(methyl methacrylate),” Inorganic Chemistry Communications,
vol. 75, pp. 29–32, 2017.
[12] S. Pal, B. Banoth, G. Rahithya, A. Dhawan, and P. De,
“Copolyperoxides of 2-(acetoacetoxy)ethyl methacrylate with
methyl methacrylate and styrene; Synthesis, characterization,
thermal analysis, and reactivity ratios,” Polymer (United King-
dom), vol. 53, no. 13, pp. 2583–2590, 2012.
[13] H. Lutz, H.-P. Weitzel, and W. Huster, “Aqueous Emulsion
Polymers,” Polymer Science: A Comprehensive Reference, 10
Volume Set, vol. 10, pp. 479–518, 2012.
[14] X. Liu, Z. Wu, F. Zhou, D. Li, and H. Chen,
“Poly(vinylpyrrolidone-b-styrene) block copolymers tethered
surfaces for protein adsorption and cell adhesion regulation,”
Colloids and Surfaces B: Biointerfaces, vol. 79, no. 2, pp. 452–459,
2010.
[15] K. Shen, D. Qi, Y. Li, X. Zhao, and Y. Li, “Controlled emul-
sion polymerization of styrene and methylmethacrylate in the
presence of amphiphilic tertiary amine N-oxides,” Colloids and
Surfaces A: Physicochemical and Engineering Aspects, vol. 482,
pp. 728–733, 2015.
 Nanomaterial
Nanomaterials
Journal of

The Scientific Journal of International Journal of

World Journal
Hindawi Publishing Corporation
Applied Chemistry
Hindawi Hindawi
Scientifica
Hindawi
Polymer Science
Hindawi
http://www.hindawi.com
www.hindawi.com Volume 2018
2013 www.hindawi.com Volume 2018 www.hindawi.com Volume 2018 www.hindawi.com Volume 2018 www.hindawi.com Volume 2018

Advances in Advances in
Chemistry
Hindawi
Physical Chemistry
Hindawi
www.hindawi.com Volume 2018 www.hindawi.com Volume 2018

Submit your manuscripts at

www.hindawi.com

International Journal of Advances in

Analytical Chemistry Condensed Matter Physics
Hindawi Hindawi
www.hindawi.com Volume 2018 www.hindawi.com Volume 2018

Engineering
Journal of
Journal of International Journal of Advances in Journal of
Chemistry
Hindawi
Biomaterials
Hindawi
High Energy Physics
Hindawi Hindawi
Nanotechnology
Hindawi
www.hindawi.com Volume 2018 www.hindawi.com Volume 2018 www.hindawi.com Volume 2018 www.hindawi.com Volume 2018 www.hindawi.com Volume 2018

International Journal of Journal of BioMed Advances in Advances in

Corrosion
Hindawi
Materials
Hindawi
Research International
Hindawi
Tribology
Hindawi
Materials Science and Engineering
Hindawi
www.hindawi.com Volume 2018 www.hindawi.com Volume 2018 www.hindawi.com Volume 2018 www.hindawi.com Volume 2018 www.hindawi.com Volume 2018