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Emulsion Semi-Batch Terpolymerization

Process Using Hybrid Emulsifiers for
Synthesizing New Emulsion Pressure
Sensitive Adhesives (EPSAs)
a b c
Jaber Khanjani , Gholam Hossein Zohuri , Mehran Gholami ,
d c
Behrooz Shojaei & Reza Dalir
a
Iran Polymer and Petrochemical Institute , Tehran , Iran
b
Department of Chemistry, Faculty of Science , Ferdowsi University
of Mashhad , Mashhad , Iran
c
Samed Chemical Inds. Co. (Mashhad Adhesive) , Mashhad , Iran
d
Click for updates Polymer and Color Engineering Department , AmirKabir University
of Technology (Tehran Polytechnic) , Tehran , Iran
Accepted author version posted online: 05 Mar 2013.Published
online: 18 Oct 2013.

To cite this article: Jaber Khanjani , Gholam Hossein Zohuri , Mehran Gholami , Behrooz Shojaei
& Reza Dalir (2014) Emulsion Semi-Batch Terpolymerization Process Using Hybrid Emulsifiers for
Synthesizing New Emulsion Pressure Sensitive Adhesives (EPSAs), The Journal of Adhesion, 90:2,
174-194, DOI: 10.1080/00218464.2013.772052

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 The Journal of Adhesion, 90:174–194, 2014
Copyright # Taylor & Francis Group, LLC
ISSN: 0021-8464 print=1545-5823 online
DOI: 10.1080/00218464.2013.772052

Emulsion Semi-Batch Terpolymerization

Process Using Hybrid Emulsifiers for
Synthesizing New Emulsion Pressure
Sensitive Adhesives (EPSAs)

JABER KHANJANI1, GHOLAM HOSSEIN ZOHURI2,

MEHRAN GHOLAMI3, BEHROOZ SHOJAEI4, and REZA DALIR3
Downloaded by [North West University] at 23:00 20 December 2014

1
Iran Polymer and Petrochemical Institute, Tehran, Iran
2
Department of Chemistry, Faculty of Science, Ferdowsi University of Mashhad,
Mashhad, Iran
3
Samed Chemical Inds. Co. (Mashhad Adhesive), Mashhad, Iran
4
Polymer and Color Engineering Department, AmirKabir University of Technology
(Tehran Polytechnic), Tehran, Iran

In order to obtain a suitable formulation of designing direct

synthesis of acrylic latexes to be used as emulsion pressure sensitive
adhesives (EPSA), having high shear resistance together with high
peel strength and tack, free radical emulsion polymerization of
hard monomers, such as styrene (St), vinyl acetate monomer
(VAM), methyl methacrylate (MMA) and butyl methacrylate
(BMA), and soft monomers, butyl acrylate (BA) and 2-ethylhexyl
acrylate (2-EHA) along with multifunctional monomers, namely
acrylic acid (AA), were carried out. The effect of the type of hard
and soft acrylic monomers, the type and level of emulsifiers, and
the initiator concentration on the emulsion polymer stability and
final properties of the EPSA were investigated. The results obtained
showed an optimized composition. This composition led to a signifi-
cant increase in shear strength and peel strength to 909 kPa and
0.45 N=mm, respectively, while the synthesized PSA was still too
tacky, 5.5 cm, according to adhesion performance testing. For mak-
ing this successful balance of the conflicting adhesion properties of
PSA, a series of anionic and nonionic emulsifiers were investigated.
It was interestingly found out that the hybrid emulsifiers (anionic
coupling with nonionic) with the optimized compositions could

Received 23 September 2012; in final form 29 January 2013.

Address correspondence to Jaber Khanjani, Iran Polymer and Petrochemical Institute,
P.O. Box 14965=115, Tehran, Iran. E-mail: jaber.khanjani@gmail.com

174
 Emulsion Semi-Batch Terpolymerization Using Hybird Emulsifiers 175

enhance the stability of the emulsion system and improve the

properties of PSA compared with the mono-emulsifier. We also tried
to adjust the initiator concentration with the level of the optimized
hybrid emulsifier, polyoxyethylene alkyl phenyl ether (K30), dioctyl
sulfosuccinate (DOSS), and sodium vinyl sulfonate (SVS) with the
ratio 2:1:1, resulting in a highly preferred proportion of the 0.5 part
of the initiator versus 1.25 parts of the hybrid emulsifier in terms of
the total weight of the monomers.

KEYWORDS Adhesion; Cohesion; Emulsion polymerization;

Hard monomer; Hybrid emulsifier; Latex and dispersion; Peel;
Pressure sensitive adhesives; Soft monomer; Tack
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1. INTRODUCTION

Pressure sensitive adhesives (PSAs) are viscoelastic materials that can adhere
to solid surfaces in a short time with the aid of light pressure [1]. PSAs are
widely used at the industrial scale as labels, tapes, and protective films [2].
From the basic research point of view, the tack property of such adhesives
is a very interesting behavior. Indeed, for the viscoelastic materials to have
the property of tack, adhesion must be developed during the bonding step
and cohesion during debonding step. To balance these conflicting properties,
PSAs are generally based on complex formulations, including a polymer base
that gives cohesion [2]. Nevertheless, there is another way of giving these
properties to PSAs which is direct synthesis of them by polymerization pro-
cesses. Although PSAs can be obtained by different polymerization processes
such as solution, emulsion, hot-melt, and radiation curing, most of the acrylic
PSAs are solvent-based PSAs due to desirable adhesion properties, resistance
to water, solvents and plasticizer, and aging performance [1]. Recently, restric-
tive regulations regarding the removal of volatile organic contents have
caused the PSAs prepared by emulsion polymerization to be more commonly
used instead of their solvent-borne counterparts [3]. However, the EPSAs have
other advantages, including low cost, inflammability, high molecular weight,
high solid content, and ease of application, in addition to their environmental
safety [3]. Among the various rubbers available, acrylic-based EPSAs are
commonly used due to inherent tack, optical clarity, good resistance toward
oxidation, UV radiation, and relatively low cost [4]. Commercially, EPSA are
prepared with soft monomers such as BA and 2-EHA as the main monomers
because of their low plateau modulus and good weather ability [5–7]. The
performance of EPSA is judged mainly on three major properties: peel, shear
strength, and tack of the final product [8].
In spite of advantages of EPSA, the solvent-borne acrylic PSAs have
been marginally preferred over the emulsion PSAs in high-performance
 176 J. Khanjani et al.

applications due to their superior adhesive performance at high tempera-

tures. The former have much higher shear strength, together with higher peel
and tack properties, than the latter for the aforementioned applications. This
is due to the continuous network morphology formed by the chain entangle-
ments in the solvent-borne adhesives when the solvent has evaporated [9].
By contrast, the microgels in the latex particles of the water-borne adhesives
retain their discrete morphology in the adhesive film [7]. This morphology
decreases the shear strength of the emulsion adhesive because of the poor
interconnections between the microgels and the linear polymers in the film
[10,11].
Further investigations on EPSAs have shown that, in most of cases, to
improve their room temperature shear and peel strength at normal rates with
the increase of EPSA cohesion energy, it is necessary to raise the glass tran-
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sition temperature (Tg) of homopolymers or copolymers of BA and 2-EHA by

copolymerizing with other monomers [12,13]. The polymer should contain at
least one hard monomer having a Tg greater than 0
C [14].
Increasing shear strength of EPSA has generally been accomplished by
crosslinking the PSA, although considerable care must be exercised so that
high levels of tack and adhesion are retained. There are two major crosslink-
ing mechanisms for acrylic adhesives: free radical copolymerization of multi-
functional ethylenically unsaturated groups with the other monomers such as
acrylic acid and use of UV crosslinkers [15]. With the aim to better understand
tack phenomenon, it is often decided to initially lower the complexity of the
system, for example, by direct molecular synthesis of EPSA, thus resulting in
the addition of AA in the emulsion system according to the first method
aforementioned and for the other components of the emulsion system, too.
Besides, the emulsion copolymerization and terpolymerization system
approach has a profound effect on the final properties of acrylic EPSA. As
the use of acrylic EPSA has increased significantly, various methods for fab-
ricating EPSAs have been proposed [16]. The batch process is carried out by
adding all the reactants at the beginning and allowing the reaction to proceed
to completion with agitation [17,18]. The higher quantity of the monomer
droplets associated with the batch process can also give a decrease in col-
loidal stability, with an excessive amount of coagulum formed during the
reaction, whereas the semicontinuous batch process can be used as a seeding
technique, i.e., a small particle size seed latex is charged to the reactor as a
preformed latex or is formed in situ in the first stage of a two-stage polymer-
ization. This is the so-called core-shell emulsion copolymerization, which has
long been used in industry to combine the desirable properties of the core
and the shell properties [19]. Generally, both in the industry and laboratory,
a semi-batch polymerization process has been used for EPSA production.
This process which is used in this study for synthesis of acrylic PSAs is carried
out by making a pre-emulsion of monomers, charging them to a reactor,
which is heated and purged with nitrogen, continually feeding an emulsified
 Emulsion Semi-Batch Terpolymerization Using Hybird Emulsifiers 177

mixture of monomers to the reactor, and adding the initiator to the reactor in
a stepped or ramped feed [20].
A balanced combination of tack, peel strength, and shear resistance is of
primary concern in PSA production. To achieve this purpose, a PSA is usually
a copolymer of an inherently tacky polymer (used to provide adhesion) with
a higher Tg polymer used to increase modulus. Considering the literature of
PSAs, it can be clearly seen that different efforts are made in the way of
adjusting conflicting adhesion parameters of them. Brooks et al. investigated
different factors affecting the performance of Butyl Acrylate (BA)=Vinyl
Acetate (VAc) methacrylic acid-based PSAs [21]. They reported a strong influ-
ence of methacrylic acid and the buffer (NaOH) on the final PSA properties.
The major part of the study was devoted to the properties of PSAs obtained
by blending different BA and VAc latexes.
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Relationships between peel strength and composition of random

BA=VAc solution-based copolymers were also reported by Chalykh et al.
where various substrates were used to assess the strength of the joint in
T-peel tests [22]. The influence of molecular parameters on the performance
of BA=AA emulsion- and solution-based copolymers was investigated by
Tobing and Klein [19]. They concluded that solvent-based PSAs tend to
outperform emulsion-based ones due to the presence of the continuous
network formed after the evaporation of the solvent. On the other hand,
the emulsion-based PSAs exhibited discrete microgels that were connected
by entanglements. Regardless of the polymerization procedure used, the
PSAs showed an increase in shear holding power as the gel content
increased. In another study, a range of BA=VAc polymers were synthesized
by Jovanovic and Dube in order to screen the system for application as a PSA
[8]. The influence of eight polymerization variables (i.e., BA=VAc ratio,
weight fraction of AA, type and weight fraction of stabilizer, weight fraction
of initiator and CTA, polymerization temperature, and solids content) on
final product properties of BA=VAc emulsion-based polymers was investi-
gated. Xu et al. focused on investigation of the semi-continuous emulsion
polymerization of BA and AA with different contents of MMA monomer
between 0 and 30% on the basis of the second-growth acrylic monomers’
weight. The effects of the addition of MMA on the gel fraction, entanglement
molecular weight (Me), and soluble molecular weight of poly (BA-co-MMA-
co-AA) were studied. Adhesive properties were related to the adhesive per-
formance, such as loop tack, peel force, and shear resistance [22]. In another
study, Lili and Dube attempt to improve the performance of post-treated
latex-based PSA films. First, a series of lattices that meet Tobing and Klein’s
criteria were produced. Next, the resulting PSA films were heated to study
which latex polymer properties would lead to post-heated PSA films with
better performance [23]. While the majority of the patent literature mentions
different formulations of acrylic monomers and different methods for syn-
thesis of acrylic resins, studies reporting the actual performance of such PSAs
 178 J. Khanjani et al.

relating to parameters affecting latex particles and thus adhesive film stability
and mechanical strength, especially hard and soft monomers optimized
composition, emulsifier content, initiator ratio, altogether in order to make
a formulation in direct synthesis for higher tack properties, are rare. In this
study, acrylic emulsion latexes were prepared by semi-batch emulsion
polymerization. A series of emulsifiers (anionic, nonionic, or hybrid) were
used to copolymerize and even terpolymerize MMA, BMA, VAM, St,
2-EHA, BA, and AA. The effects of the emulsifier types, the proportion of
hybrid emulsifiers, the content of emulsifiers, concentration of initiator,
and soft monomer=hard monomer composition on the stability of the
emulsion polymers synthesized and adhesion performance of final products
were investigated.
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2. EXPERIMENTAL

2.1. Materials
n- Butyl acrylate (n-BA) and 2-ethylhexyl acrylate (2-EHA) were purchased
from BASF Chemical Company (Ludwigshafen, Germany). MMA, BMA, St,
and VAM all were purchased from Shazand Petrochemical Co (Arak, Iran)
and were distilled in vacuum and stored at 0–5
C before use. Sodium vinyl
sulfonate (SVS) as an active anionic emulsifier, dioctyl sulfosoccinate (DOSS)
as an anionic emulsifier, and nonylphenol ethoylate (KENON 30) as nonionic
emulsifier were purchased from Kimyagaran Emrooz Chemical Industries Co
(Arak, Iran). Ammonium persulfate (APS, 99%; Aldrich, Lancaster, UK) was
used as free radical initiator as supplied. The inhibitor was removed from
AA, as a multifunctional monomer creating active sites for crosslinking in
the structure of the EPSA, (AA, 99%; Aldrich) just before use by passing
through a column of activated aluminum oxide. Deionized water was used
throughout the study.

2.2. Latex Preparation

PSAs were prepared as approximately 50% solid content latexes by semi-
batch polymerization. Water (40 g) and ammonium persulfate (0.1 g) as a
polymerization initiator were fed to a 1 L glass reactor equipped with a stirrer,
a temperature controller, and a reflax condenser. The mixture was heated to
80
C. Thereto was added 100 parts(g) of the monomer mixture shown in
Table 1, 60 parts of water, 5 parts of KENON 30 as an emulsifier (except
for BA-St copolymer thereto 2.5 parts KENON 30 and 2.5 parts DOSS
was used). The resulting mixture was stirred and emulsified to prepare a
pre-emulsion.
The total amount of pre-emulsion was continuously fed to the glass
reactor with the speed 1.6 mL=min for the first hour and 0.71 mL=min for
 Emulsion Semi-Batch Terpolymerization Using Hybird Emulsifiers 179

TABLE 1 Copolymer Composition (parts wt%) in Terms of the Total Weight of the Monomers

PSA1 PSA2 PSA3 PSA4 PSA5 PSA6 PSA7 PSA8 PSA9 PSA10 PSA11 PSA12 PSA13

BA 99 89 79 69 89 79 69 89 79 69 89 79 69
MMA – 10 20 30 – – – – – – – – –
BMA – – – – 10 20 30 – – – – – –
Vac – – – – – – – 10 20 30 – – –
St – – – – – – – – – – 10 20 30
AA 1 1 1 1 1 1 1 1 1 1 1 1 1
KENON30 5 5 5 5 5 5 5 5 5 5 5 5 5
APS 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1
Water 100 100 100

the next 3 hours while affecting emulsion polymerization with stirring at

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250 rpm under nitrogen flow. After that, stirring was continued at 85
C for
a further hour to complete the polymerization. The latex was cooled to room
temperature and filtered through a 53-mm sieve. The residual monomer was
measured using gas chromatograph=mass spectrometer (GC=Mass) and was
less than 0.1% on the basis of the wet latex weight unless otherwise men-
tioned. According to the results which will be demonstrated based on the
adhesion performance of the copolymers, BA=VAc=BMA=AA terpolymers
with different levels of VAc and BMA were synthesized with the same poly-
merization process as the one used for copolymerization. The terpolymer
composition of the PSA is shown in Table 2.

2.3. Polymer Compositions

Polymer compositions were calculated based on the residual monomer
determined using gas chromatography. A gas chromatograph (Hewlett-
Packard 5710A, New York, USA) equipped with a flame-ionization detector
(FID) and a glass column OW 351 (chromatographic specialists) was used.
Injector and detector temperatures were 200 and 250
C, respectively, while
the column temperature was programmed as follows: an isothermal step at
80
C for 4 min was followed by heating to 180
C with a heating rate of

TABLE 2 Terpolymer Composition (parts wt%) in Terms of the Total

Weight of the Monomers

PSA14 PSA15 PSA16

BA 69 69 69
VAc 25 20 15
BMA 5 10 15
AA 1 1 1
KENON30 5 5 5
APS 0.1 0.1 0.1
Water 100 100 100
 180 J. Khanjani et al.

8
C=min. The final step was isothermal at 180
C for 20 min. Helium
(35 mL=min) and hydrogen (30 mL=min) were supplied to the detector.
Styrene was used as an internal standard. The injection volume was 1 mL.

2.4. Gel Content Determination

The gel content of the acrylic PSA copolymers and terpolymers was mea-
sured via the solvent-extraction method. Three samples (0.25 g) of dried film
were added to 25 mL of THF and stirred at 300 rpm at room temperature for
48 h. The samples were then centrifuged at 6000 rpm for 1 h. The sediment
gel phase was separated from the sol phase and dried in a vacuum oven
at 25
C for 24 hours. The gel fraction was determined gravimetrically.
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2.5. Viscosity Measurement

The viscosity of the PSA copolymer latex products was evaluated with a digital
rotational viscometer (RV DV-2, Brookfield, USA). The viscometer operates by
the principle of rotation of a cylinder or disc (spindle 1), which is submerged
in the latex to be analyzed, measuring the resistance of the substance at a pre-
set speed. The resultant resistance or torque is the measurement of the flow
viscosity. The measurements were carried out at 25
C at 50 rpm.

2.6. Measurement of the Glass-Transition Temperature (Tg)

Theoretically, the glass transition was determined by the following equation [20]:
X
1=Tg ¼ wi=Tgi; ð1Þ

where Tg is the glass transition temperature of a copolymer indicated by absol-

ute temperature, Tgi is the glass transition temperature of a homopolymer of a
monomer compenent, indicated by absolute temperature, and wi is the weight
fraction of a component in a copolymer.
Experimentally, the Tg values of the acrylate copolymers and terpoly-
mers were determined with a Metter-Toledo (Schwerzenbath, Switzerland)
DSC 822 system differential scanning calorimeter. An empty, crimped alumi-
num pan was used as a reference. Approximately 10 mg was placed into a
preweighed aluminum pan and heated to 150
C to eliminate any thermal his-
tory. The next step involved cooling the sample from 150 to 80
C followed
by a 2-min isothermal step. The second heating from 80 to 150
C was used
for the determination of the Tg. All heating and cooling steps were per-
formed at a rate of 10
C=min. An empty aluminum pan was used as reference
and for determination of the baseline that was subtracted from the samples.
The Tg was taken as the inflection point. A thermogram of the sample PSA4 is
represented in Fig. 1 and the method of Tg determination is shown.
 Emulsion Semi-Batch Terpolymerization Using Hybird Emulsifiers 181

FIGURE 1 DSC thermogram of PSA4.

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2.7. Adhesive Performance Tests

2.7.1. TACK
A film of the sample PSA with a thickness of 200 mm was coated on a poly-
vinyl chloride sheet and was preserved at room temperature until it was dried
after 24 hours. Tackiness of the PSA synthesized was determined in accord-
ance with the ASTM D3120 method. Then, a ball on the top of the roll ball
was placed and released to roll on the inclined surface and pass the surface
of the PSA film. The distance the roll passes through the film is a scale of
the tackiness measured in centimeters. The less the roll passes in terms of
centimeters the tackier the PSA is.

2.7.2. PEEL STRENGTH

Peel strength of the PSA film was measured according to the ASTM 3330
method using a tensile apparatus ZWICK, Z020 (Ulm, Germany) with load
cell 20 kN at a test speed of 5 mm=s. A tape of the sample PSA with a width
of 2.5 cm and a length of 30 cm was prepared and then glued on a not
less than 1.1 mm [0.043 in.] thickness 302 or 304 stainless steel sheet with
bright annealed finish. The surface roughness height was 50  25 nm [2.0 
1.0 min.] arithmetical average deviations from a mean line. Then, a steel roller
85  2.5 mm [3.25  0.1 in.] in diameter and 45  1.5 mm [1.75  0.5 in.] in
width, covered with rubber approximately 6 mm [0.25 in.] in thickness,
having a Shore scale durometer hardness of 80, moved five times by hand
at the rate of 10  0.4 mm=s [24  0.5 in.=min] at surface of the tape. The
folded end of the tape at a 90
angle was doubled back and 25 mm [1 in.]
of the tape was peeled from the panel. The panel into a fixture clamped to
the moving jaw of the adhesion tester is placed so that it will maintain a
peeling angle at 90
during the peeling of the next 75 mm [3 in.] of tape
and the free end of the tape into the other jaw. The moving jaw is operated
at speed of 5 mm=s.
 182 J. Khanjani et al.

2.7.3. SHEAR STRENGTH

Shear strength of the PSA film was measured according to the ASTM D3654
method using tensile apparatus ZWICK, Z020 (Ulm, Germany) with load cell
20 kN at test speed of 5 mm=s. A tape of the sample PSA with a width of
1.2 cm and a length of 10 cm was prepared and then 1.2 cm of that was glued
on a not less than 1.1 mm [0.043 in.] thickness 302 or 304 stainless steel sheet
with bright annealed finish. The surface roughness height was 50  25 nm
[2.0  1.0 min.] arithmetical average deviations from a mean line. Then, a steel
roller 85  2.5 mm [3.25  0.1 in.] in diameter and 45  1.5 mm [1.75  0.5 in.]
in width, covered with rubber approximately 6 mm [0.25 in.] in thickness,
having a Shore scale durometer hardness of 80, moved five times by hand
at the rate of 10  0.4 mm=s [24  0.5 in. =min] at surface of the tape. It is
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common to test at least five specimens of a particular tape. Test specimens

should be taken from several rolls of a tape and, whenever possible, among
several production runs of a tape. Strong conclusions about a specific pro-
perty of a tape cannot be based on test results of a single unit (roll) of pro-
duct. So, this simple fact is considered during shearing tests. The free end of
the tape at a 180
angle was placed into a fixture clamped to the moving jaw
of the adhesion tester so that it will maintain a peeling angle at 180
during
the shearing and the other end of the panel into the other jaw. Then, the tape
was sheared using the tensile apparatus at speed of 5 mm=s.

2.8. Overall Conversion Measurement

Overall conversions were calculated from a mass balance of the reagents in
the polymerization with the gel content measured at each sampling time.

mass of polymer formed

Overall percentage conversion ð%Þ ¼  100 ð2Þ
total mass of monomer

3. RESULTS AND DISCUSSION

As discussed before, for controlling adhesion properties of PSAs and making

a balance collection of major adhesion properties of EPSA, namely, tack,
peel, and shear strength, it is compulsory to raise the glass transition tem-
perature of homopolymers or copolymers of soft monomers. In this study,
at the first stage, BA=St=AA, BA=BMA=AA, BA=MMA=AA, and BA=VAc=AA
copolymers were synthesized according to the aforementioned procedure.
The aim was to investigate on the effects of such hard monomers on the peel
and shear properties of PSAs synthesized (Table 3).
According to the figures reported in Table 3, copolymerization of n-BA
with other hard monomers except for styrene successfully increased the
shear strength of PSAs synthesized herein as they are able to create hard
 Emulsion Semi-Batch Terpolymerization Using Hybird Emulsifiers 183

TABLE 3 Final Properties of the Copolymers Synthesized

Sample Gel Viscosity Tg Tg Tack Peel Shear Conversion

no content (cPs) (DSC) (equation 1) (cm) (N=mm) (kPa) %

PSA1 49 70 52
c 54
c 2.7 0.15 122 98

PSA2 49 52 47
c 46
c 3.0 0.12 145 97
PSA3 49 15 33
c 35
c 5.5 0.07 155 97
PSA4 50 13 20
c 17
c 25.0 0.05 175 96
PSA5 50 68 48
c 46
c 3.1 0.21 139 98
PSA6 51 48 38
c 39
c 3.9 0.13 198 97
PSA7 50 44 32
c 31
c 4.8 0.11 200 98
PSA8 51 69 46
c 47
c 12.0 0.19 136 94
PSA9 51 43 40
c 41
c 10.0 0.20 177 93
PSA10 50 35 33
c 34
c 6.0 0.10 164 92
PSA11 49 2500 45
c 441
c 5.0 0.10 96 95
33
c 34
c
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PSA12 50 4500 9.0 0.08 111 93

PSA13 37 3800 22
c 23
c – 0.03 – 72

segments in their copolymer structure. The reaction between functional

groups of the polymer chains and the crosslinking reaction in the PSA films
represent approaches to enhancing the shear resistance. Nevertheless, these
copolymerizations could increase the shear resistance of the EPSA films at the
expense of lower peel and tack adhesive properties. Considering the results
obtained, PSA5 and PSA12 have shown a significant increase in peel and
shear strength without substantial trade-off in terms of tack properties. As
a result, VAc and BMA were selected as the most suitable hard monomers
to be terpolymerized with n-BA in order to increase shear resistance of
PSA while there has been approximately no change in tack and peel strength.
Further investigations for controlling tack properties of PSAs by direct
synthesis was followed by optimizing the ratio of VAc and BMA as hard
monomers versus soft monomers. With regard to the results shown in
Table 4, there has been a considerable increase in shear and peel strength
of PSA14 while being still too tacky in which 25 parts VAc and three parts
BMA were terpolymerized as hard monomers with n-BA.

3.1. Effect of Emulsifiers

The effect of different kinds of emulsifiers on the properties of emulsion
latexes was investigated and the results are summarized in Table 5. Hybrid

TABLE 4 Final Properties of the Terpolymers Synthesized

Sample Gel Viscosity Tg Tg Tack Peel Shear Conversion

no content (cPs) (DSC) (equation 1) (cm) (N=mm) (kPa) %

PSA14 49 60 30
c 33.3
c 4.33 0.28 210 98

PSA15 50 254 32
c 33
c 4.36 0.18 161 94
PSA16 50 63 28
c 32.6
c 4.94 0.19 237 92
 184 J. Khanjani et al.

TABLE 5 The Effect of different Kinds of Emulsifiers on the Properties of Emulsion Latexes

Stabilities Stabilities
Emulsifiers Ratio Emulsion appearance Sample no polymerization shelf life

DOSS=K30 2:1 Fine blue PSA17 Good Poor

DOSS=K30 1:1 Fine blue PSA18 Good Poor
DOSS=K30 1:2 Milk white PSA19 Good Good
SVS=K30 2:1 Visible particles PSA20 Poor Good
SVS=K30 1:1 Visible particles PSA21 Poor Poor
SVS=K30 1:2 Visible particles PSA22 Poor Poor
K30= DOSS= SVS 2:1:1 Milk white PSA23 Good Good

emulsifiers of DOSS=KENON30, SVS=KENON30, and DOSS=SVS=KENON30

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with different levels of DOSS as an anionic emulsifier, SVS as an active anio-

nic emulsifier which can participate in the polymerization process in addition
to stabilizing monomers in micelle and mechanical properties enhancement
of microgels in the film structure of PSAs, and KENON30 as nonionic
emulsifier were studied.
As shown in Table 5, the hybrid emulsifiers of DOSS=KENON30 and
DOSS=KENON30=SVS with the ratios mentioned provided superior polymer-
ization stability, fine emulsion, and good shelf time stability. Compared with
other hybrid emulsifiers formulated for synthesizing different PSAs, the
performance of other emulsifiers are not fully satisfied. If anionic emulsifiers,
SVS and DOSS, are used separately, the polymerization system is unstable. As
for SVS, which is an active anionic emulsifier, the results proved that presum-
ably for designing a stable emulsion polymerization system using SVS, there
should be a limitation of its amount in a hybrid emulsifier; it should not be
more than 0.75% of the total weight of monomers present in polymerization.
Otherwise, the emulsion latex synthesized is unstable with visible large par-
ticles which are probably caused by homogenous emulsion polymerization
that occurred outside the micelles. Anionic emulsifiers are sensitive to pH
values and electrolyte ions so that it is difficult to control stability during
the polymerization process. Meanwhile, when the anionic emulsifier is used,
the surfaces of latexes are charged. Therefore, a force between the surface of
the latexes and the ion of emulsifier can be generated which results in a static
tension. Therefore, the negative charge on the surface of emulsion latexes
makes the free radicals enter into emulsion latexes with difficulties, which
leads to a slower reaction velocity and a lower conversion. Although using
a nonionic emulsifier such as KENON30 can decrease the static tension by
forming the hydrolyzed protective shield on the surface of latexes, the
particle size of the nonionic emulsifier is so large that the emulsion latexes
tend to sediment because of the gravity, which makes the shelf stability of
emulsion latexes unsatisfying. As a result, in order to make a stable
pre-emulsion to accomplish the polymerizatyion process successfully and
 Emulsion Semi-Batch Terpolymerization Using Hybird Emulsifiers 185

TABLE 6 The Effect of Hybrid Emulsifiers on Tack, Peel and Shear Strength of PSAs

Sample no Viscosity (cPs) Tack (cm) Peel (N=mm) Shear(kPa) Conversion %

PSA17 1540 3.0 0.29 175 96

PSA18 102 2.3 0.35 144 94
PSA19 198 4.0 0.11 154 94
PSA20 30 2.8 0.37 316 92
PSA21 35 2.9 0.16 153 95
PSA22 42 3.0 0.15 187 97
PSA23 80 2.5 0.35 248 98

get a fine stable emulsion latex with good shelf stability, we decided to use a
hybrid of KENON30, anionic emulsifier, SVS, an active anionic emulsifier,
and DOSS, an anionic emulsifier to not only resolve the problems of instabil-
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ities of the earlier PSAs but also to make a good hybrid emulsifier, affecting
the structure of PSAs film and increasing shear and peel strength of EPSA
without a significant trade-off in terms of tack. When an anionic emulsifier
is hybridized with a nonionic emulsifier, the two kinds of emulsifier can
be alternatively absorbed on the surface of emulsion latexes. The alternative
effect decreases the static tension on the surface of emulsion latexes, and ulti-
mately improves the stability of the reaction system. The hybrid emulsifier
KENON30=DOSS=SVS with the ratio 2:1:1 being used in the emulsion poly-
merization prepared the most stable emulsion latex with good shelf life.
The effect of the type of hybrid emulsifiers on adhesive properties of EPSA
is shown in Table 6. Therein, tack, peel, and shear strength of PSAs, synthe-
sized by different hybrid emulsifiers and reported in Table 6, can be seen.
According to the results shown in Table 6, PSA23 in which hybrid emulsi-
fiers of KENON30=DOSS=SVS with the ratio 2:1:1 presented a huge increase in
shear strength up to 240 kPa and in peel strength up to 0.35 N=mm while being
still too tacky. These results are clearly connected to the decrease in static ten-
sion on the surface of emulsion latexes, produced by alternative effects of non-
ionic emulsifier, KENON30, and anionic emulsifier, DOSS, and an increase in
interconnections between the microgels produced by an active anionic emulsi-
fier, SVS, which can attend the polymerization reaction and be a part of the poly-
meric chains. Although the effect of active anionic emulsifier resulted in a
substantial increase in the shear strength of PSA20, the visible particles in the
emulsion latex showed that the hybrid emulsifier of KENON30 and SVS can lead
to a stable polymerization. As a result, the optimized emulsifier content,
KENON30=DOSS=SVS, was selected as the most suitable composition of emul-
sifiers stabilizing the emulsion polymer, and consequently, enhancing the
adhesion properties of PSAs for the further studies of this project.

3.2. Effect of Emulsifier Content and Initiator Concentration

Different contents of the hybrid emulsifier, 0.5 part, 1.25 part, 2.5 part, and 5
part, were selected to fulfill the emulsion polymerization with the same ratio
 186 J. Khanjani et al.

as was used to produce PSA23. We had already synthesized PSA23 using 5 parts
of the optimized hybrid emulsifier and 0.1 part of initiator, but our attempts to
accomplish the polymerization and produce stable emulsion latexes using 2.5
parts of hybrid emulsifier and the same part of initiator was failed. According
to the emulsion polymerization theory, we know that the particle size of emul-
sion latexes is continuously growing with the polymerization process. There-
fore, more emulsifier molecules are required to keep the polymerization
stable. When the content of emulsifiers is little, the particle size of the emulsion
latexes is large and no blue gloss is observed and the amount of formed latexes
is small. As the polymerization further processes, no more emulsifier molecules
can be supplied to be absorbed on the surface of the latexes. As a result, the sur-
face covering ratio of the emulsifier molecules decreases which results in the
unstable polymerization or even de-emulsification. But if the emulsifiers are
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overused, the number of emulsion latexes increases considerably and the par-
ticle size of the latexes becomes very small, which means the surface area
enlarges significantly. Then, the intermolecular interaction is so strong that the
viscosity of the reaction system increases rapidly, which makes the stirring diffi-
cult. On the other hand, the initiator concentration strongly involves with gain-
ing PSA with stable emulsion latex, appropriate structure of PSA film, and high
adhesion performance as an increase or decrease in it will strongly affect the
molecular weight and consequently the structure of PSA. Different levels of
initiator in terms of the total weight of the monomers are present in the polymer-
ization system for manufacturing EPSA in industry. Accordingly, different levels
of initiator were used to accomplish the emulsion polymerization in different
contents of the optimized hybrid emulsifier in order to adjust the level of emul-
sifier and initiator for carrying out emulsion polymerization and obtaining the
appropriate ratio of initiator=hybrid emulsifier which could result in a formu-
lation for direct synthesis of PSA with high peel and shear strength while being
too tacky. Tables 7–9 show the effect of the initiator concentration on the
properties of emulsion latexes and adhesion performance of the PSAs synthe-
sized by 0.63 part, 1.25 part, and 2.5 part of the optimized hybrid emulsifier,
KENON30=DOSS=SVS, respectively.
According to the results which are shown in the tables, it can be clearly
seen that increasing the amount of initiator in each level of emulsifier results
in the instability of the emulsion latexes, changing the emulsion appearance
from milky white to visible particles and decrease in shear strength of PSA
synthesized. Increasing the emulsifier content leads to an increase in the
number of particles and decrease in the size of particles which in turn affects
the maximum level of initiator allowed for accomplishing the emulsion poly-
merization and obtaining stable emulsion latex with good adhesion perfor-
mance. The higher the level of hybrid emulsifier used the lower the
concentration of initiator was allowed to be used for emulsion polymeriza-
tion. According to Fig. 2, there was a downward trend in the maximum level
of initiator with an increasing level of hybrid emulsifier, being 0.6 part
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TABLE 7 The Effect of Initiator Concentration on the Final Properties of Emulsion Latexes and Adhesion Properties of PSAs with 0.63 part (wt%) of
Hybrid Emulsifier

Emulsion Initiator
Sample no appearance Tack (cm) Peel (N=mm) Shear (kPa) Gel content Shelf Polymerization concentration Conversion %

PSA24 Milk white 10.7 0.49 423 49 Good Good 0.25 98

187
PSA25 Milk white 8.7 0.68 304 49 Good Good 0.5 96
PSA26 Fine blue 8.0 0.75 280 49 Poor Poor 0.6 90
PSA27 Visible particles 17.2 0.25 260 43 Poor Poor 0.75 84
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TABLE 8 The Effect of Initiator Concentration on the Final Properties of Emulsion Latexes and Adhesion Properties of PSAs with 1.25 Part (wt%) of
Hybrid Emulsifier

Emulsion Peel Gel Initiator

Sample no appearance Tack (cm) (N=mm) Shear (kPa) content Shelf Polymerization concentration Conversion %

PSA28 Milk white 8.8 0.38 665 49.0 Good Good 0.25 96

188
PSA29 Milk white 7.6 0.97 386 48.5 Good Good 0.5 90
PSA30 Visible particles 7.0 0.33 211 33.0 Poor Poor 0.75 60
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TABLE 9 The Effect of Initiator Concentration on the Final Properties of Emulsion Latexes and Adhesion Properties of PSAs with 2.5 part (wt%) of
Hybrid Emulsifier

Emulsion Shear Gel Initiator

Sample no appearance Tack (cm) Peel (N=mm) (kPa) content Shelf Polymerization concentration Conversion %

189
PSA31 Milk white 4.3 0.39 442 50 Good Good 0.25 98
PSA32 Fine blue 4.1 0.53 302 44 Poor Good 0.5 82
 190 J. Khanjani et al.

FIGURE 2 Maximum initiator concentration downward trend for stable emulsion polymeriza-
tion with the increase in the content of Hybrid emulsifier. (color figure available online).
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initiator in the lowest content of hybrid emulsifier, 0.625% of the total weight
of monomers, and 0.1 part of initiator in the highest level of hybrid emulsi-
fier, 5% of the total weight of the monomers. Consequently, the most suitable
adjustment of the initiator concentration and the content of hybrid emulsifier
was seen in PSA29, resulting in a significant increase in peel strength to
0.97 N=mm and in shear strength to 0.386 KPa while being still tacky. This
adjustment in the initiator concentration and emulsifier level, 1.25:0.5, was
used for further investigations in this study.

3.3. Effect of 2-EHA as a Soft Monomer on the Adhesion Properties

of PSAs
The effect of n-BA=2-EHA monomer composition on the adhesion perfor-
mance of PSA29 which was our best version of PSAs in terms of tack, peel,
and shear resistance, stability of emulsion latex, and its appearance, was
investigated. Different ratios of n-BA=2-EHA, 1:0, 2:1, 1:2, and 0:1, were selec-
ted as soft monomers in the same formulation as PSA29 according to initiator
concentration, content and type of hybrid emulsifier, and type and level of
hard monomers in order to carry out semi-batch emulsion polymerization,
resulting in production of PSA33, PSA34, and PSA35. The results are shown
in Table 10. Also, two commercial PSA samples, V205 and V218, which are

TABLE 10 The Effect of 2-EHA on the Final Properties of the PSA29

Sample BA%=2- Gel Tack Shear Peel Tg Tg Conversion

no EHA% content (cm) (kPa) (N=mm) (DSC) (equation 1) %

PSA29 100 49 7.6 386 0.97 37
c 33.3
c 98

PSA33 67=34 50 6.5 296 0.58 46
c 43
c 99
PSA34 34=67 50 5.5 900 0.55 63
c 60
c 99
PSA35 100 50 4.5 525 0.53 55
c 53
c 99
V 205 – – 8 700 0.42 – –
V 218 – – 6 504 0.53 – –
 Emulsion Semi-Batch Terpolymerization Using Hybird Emulsifiers 191

two of the most common industrial PSAs, manufactured by BASF Company

(Ludwigshafen, Germany), were tested and their adhesion properties were
reported and compared with PSA29, PSA33, PSA34, and PSA35 in this table.
Regarding the results reported in Table 10, a decrease in the peel strength
was observed although still having high peel strength when the 2-EHA con-
tent was increased to more than 50%. When the 2-EHA content increased to
more than 50% wt, the peel strength was retained at a constant level. This
behavior can be explained by the relation between viscoelastic dissipation
energy produced during adhesive debonding and the molecular network
parameters of the acrylic adhesives, Mc (crosslink molecular weight of the
microgels) and Me (the entanglement molecular weight of the free chains
in the adhesive network morphology). According to the studies of Moghbeli
et al. [3], with an increase in the 2-EHA content in the adhesive composition,
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Mc showed a peak at 50%, whereas Me increased uniformly. Nonetheless, the

Mc=Me decreased only as the 2-EHA level increased adhesive which showed
that fracture energy during adhesive debonding was lowered as Mc=Me
decreased. In other words, by an increase in the 2-EHA level to 50 wt% and
an increase in Me, the bulk-fracture energy of acrylic PSAs was decreased.
At higher Mc=Me values, the microfibrils needed higher energy to deform
and fracture during the peeling process. By an increase in the 2-EHA level
above 50 wt%, no significant change in peel was observed although the
Mc=Me value of the PSAs decreased [3]. This behavior could be attributed
to other parameters that affect the peel strength according to the adhesion
rheological model presented by Gent and Schults [21].
Interestingly, a synergistic effect in increasing the shear resistance was
observed at 67 wt% 2-EHA of the total soft monomer level. This behavior
could be attributed to a good interconnection between the microgels and
the free chains of the contacting particles in the PSA film. Shear resistance
is known to depend on both the gel content and the entanglement density,
which influence the network morphology. It seemed that the interconnec-
tions were dependent on the Mc=Me value, which should vary according
to the 2-EHA level in the EPSA. The EPSA with the ratio 67%=34% wt of
2-EHA=BA showed the highest shear resistance, 900 kPa, in contrast with
all other PSAs synthesized in this study and the commercial EPSA reported
in Table10. Above the 67 wt% level of 2-EHA in the monomer feed, the shear
resistance started to decrease. This behavior was in accordance with what
was reported by Torbing and Klein who showed that acrylic PSAs with
Mc > Me and Mw > 2Me achieved a high shear resistance without a signifi-
cant trade-off in peel and tack [19].
Figure 3 illustrates the trend of tack and Tg of the emulsion acrylic PSAs
versus the 2-EHA proportion in the monomer composition of our synthesized
terpolymers. Increasing the 2-EHA level in the terpolymerization reaction
increased tack energy. The tack performance was mainly affected by the
polymer chain mobility of the adhesive surface rather than the adhesive bulk
 192 J. Khanjani et al.
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FIGURE 3 a) Effect of 2-EHA=BA content on PSA Tack; b) Effect of 2-EHA=BA content on PSA
Tg(
C). (color figure available online).

property. The tack enhancement for the acrylic emulsion PSAs was a result of
the increased mobility of the surface segments arising from the decreased
Tg of the PSAs with more 2-EHA units. Nevertheless, the variation of tack
was not remarkable because the acrylic adhesives consisted of both soft
monomers n-BA and 2-EHA units with sufficiently low Tg values to wet
the substrates sufficiently.

4. CONCLUSIONS

This study confirms the possibility of adjusting the adhesion properties of

PSA by direct synthesis rather than by formulation. The synthesis was based
on free radical semi-batch emulsion polymerization of soft mononers, n-BA
and 2-EHA, and hard monomers, St, VAc, BMA, and MMA, along with 1 part
of a multifunctional monomer, AA, in order to control the composition of the
 Emulsion Semi-Batch Terpolymerization Using Hybird Emulsifiers 193

latex particles, the structure of the PSA films, and tack properties. Measuring
tack properties of copolymers and terpolymers synthesized in this study con-
firmed that the monomer composition, 47 parts 2-EHA, 22 parts n-BA, 25
parts VAc, 5 parts BMA, and 1 part AA, shows the best adhesion performance
in terms of tack, peel, and shear strength among all the PSAs synthesized in
this study and in contrast with other commercial PSAs tested herein. Different
anionic and nonionic emulsifiers’ investigation for synthesis of acrylic emul-
sion terpolymers showed that KENON30=DOSS=SVS hybrid emulsifier is the
best composition for stabilizing the emulsion latexes and enhancing the tack
properties of PSA films. The optimized ratio of KENON30=DOSS=SVS hybrid
emulsifier was 2:1:1. Optimized concentration of free radical initiator and the
effects on the adhesion performance of PSAs were studied in different levels
of hybrid emulsifier. There was an adjustment of the initiator=hybrid emulsi-
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fier level with the ratio 1.25=0.5 wt% of the total weight of the optimized
monomer composition. This content and level of hybrid emulsifier, along
with the optimized initiator concentration, can meet the industrial strict
requirements of adhesion performance, stability, and shelf life of emulsion
pressure sensitive adhesives. The effect of 2-EHA on the optimized tack
properties of PSA was studied using different levels of hybrid of two soft
monomers, 2-EHA=BA in the synthesis of acrylic terpolymer. A substantial
increase in the shear strength was observed at 67 wt% 2-EHA in the monomer
composition of soft monomers, 2-EHA=BA, or 47 parts of 2-EHA in the total
monomer composition, without a significant trade-off in peel strength and
tack. PSA34 with the adhesion parameters, tack of 5.5 cm, peel of 0.53 N=mm,
mm, and shear of 900 kPa, showed a higher adhesion performance in com-
parison with commercially frequently used PSAs, V218 and V205, produced
by BASF, as a result of studying the variables affecting emulsion polymeriza-
tion, morphology, and structure of the network of microgels of the film of
PSAs. This behavior could be attributed to this optimum chain network
morphology, which led to a good interconnection between the microgels
in the emulsion adhesive film.

ACKNOWLEDGMENT

The authors wish to acknowledge financial support by the Samed Chemical

Industrial Company. The generosity of Mr. Kooshki and Mr. Hosseini of the
Samed Company and Ferdowsi University of Mashad is also greatly appreciated.

REFERENCES

[1] Yang-Ping, B., Zhao, L., and Shao, L., J. Appl. Polym. Sci. 115, 1125–1130 (2010).
[2] Aymonier, A. and Leclercq, D., J. Appl. Polym. Sci. 89, 2749–2756 (2003).
 194 J. Khanjani et al.

[3] Moghbeli, M. R., Zamir, S. M., and Molaee, B., J. Appl. Polym. Sci. 108, 606–613
(2008).
[4] Benedek, I. and Heymans, L. J., Pressure-Sensitive Adhesives Technology,
(Marcel Dekker Inc., New York, 1997).
[5] Garrat, J., Lovell, P. A., Shea, A. J., and Viney, R. D., Macromol. Symp. 151, 487
(2000).
[6] Lakrout, H., Creton, C., Ahn, D., and Shull, K. R., Macromol. 34, 7448 (2001).
[7] Anderson, C., Pressure Sensitive Adhesive Articles and Method of Making Same,
U.S. Patent 3, 769, 254 (1973).
[8] Jovanovic, R. and Dube, M. A., Ind. Eng. Chem. Res. 44, 6668–6675 (2005).
[9] Tobing, S. D. and Kelin, A., J. Appl. Polym. Sci. 79, 2230 (2001).
[10] Aubery, D. W. and Ginosatis, S., Adhes. 12, 189 (1981).
[11] Mao, T. J. and Reegen, S. L., in Proceedings of the Symposium on Adhesion and
Cohesion, P. Weiss (Ed.) (Elsevier, Amsterdam, 1962), p. 209.
Downloaded by [North West University] at 23:00 20 December 2014

[12] Tobing, S. D., Kelin, A., Sperling, L. H., and Petresko, B., J. Appl. Polym. Sci. 81,
2109 (2001).
[13] Satas, D., Handbook of Pressure Sensitive Adhesive Technology 2nd ed., (Van
Nostrand Reinhold, New York, 1989), p. 400.
[14] Bernard, M. M. and Calif, L. V., Emulsion pressure-sensitive adhesive polymers
exhibiting excellent guillotine performance, U.S. Patent 5, 264, 532 (1993).
[15] Krepski, L. R., Filiatrault, T. D., McCracken, S. D., Kavanagh, M. A., and
Gaddam, B. N., Acrylic pressure-sensitive adhesive with aziridine crosslinking
agents, U.S. Patent 0246390 A1 (2009).
[16] Pirrima, I., Emulsion Polymerization, (Academic Press, New York, 1982), p. 319.
[17] Lovell, P. A. and El-Aasser, M. S., Emulsion Ploymerization and Emulsion
Polymers, (Wiley, New York, 1997).
[18] Jovanovic, R. and Dube, M. A., J. Macromol. Sci. Polym. Rev. 44, 1 (2004).
[19] Torbing, S. D. and Klein, A., J. Appl. Polym. Sci. 79, 2558 (2001).
[20] Spada, L. T. and Koch, C. A., Acrylic pressure-sensitive adhesives for low-energy
surfaces and corrugated board, U.S. Patent 5,817,426 (1998).
[21] Brooks, T. W., Kell, R. M., Boss, L. G., and Nordhaus, D. E., TAPPI Proceedings.
TAPPI Polymers, Laminations and Coatings Conference, Boston, September
1984, p. 469.
[22] Chalykh, A. E., Chalykh, A. A., Gerasimov, V. K. Polym. Sci. Ser. A. 44, 1054
(2002).
[23] Lili, Q. and Dube, M. A., J. Appl. Polym. Sci. 124, 349–364 (2012).