Polymer Bulletin

Poly(2-ethyl hexyl acrylate-co-methyl allyl polyethylene glycols ether–co-acrylic acid)

pressure-sensitive adhesives: Synthesis, Characterization, Investigations of Adhesive
and Thermal Properties
--Manuscript Draft--

Manuscript Number: POBU-D-22-00413

Full Title: Poly(2-ethyl hexyl acrylate-co-methyl allyl polyethylene glycols ether–co-acrylic acid)
pressure-sensitive adhesives: Synthesis, Characterization, Investigations of Adhesive
and Thermal Properties

Article Type: Original Article

Section/Category: Polymer Characterization

Funding Information:

Abstract: In the present study, solvent-based acrylic copolymers were successfully synthesized
by “solution polymerization” using methyl allyl polyethylene glycols ether, acrylic acid,
and 2-ethyl hexyl acrylate for the fabrication of high performance pressure sensitive
adhesive tapes. Different techniques (NMR, FTIR, TGA/DTG, Contact Angles, PSAs
Test) were used to characterize the physical and thermal properties of the copolymers.
The obtained copolymers were investigated as a possible adhesive for permanent or
removable applications such as security labels for power equipment, foil tape for HVAC
ductwork, automotive interior trim assembly, and sound/vibration dampening films.
When the contact angles of the synthesized copolymers were examined, it was
observed that while the amount of acrylic acid in the copolymer content was constant,
the contact angle increased with the increase in the percentage of HPEG. In addition,
while the amount of HPEG was constant in the copolymers, it was observed that the
contact angle decreased with the increase in the percentage of acrylic acid. As a result,
it was determined that the obtained copolymers showed hydrophilic character and
wetted the contact surface. When the thermal properties of the copolymers were
examined, while the acrylic acid ratio was constant, the thermal stability increased with
increasing HPEG amount. While the HPEG ratio is constant in the copolymer content,
the decrease in thermal stability with increasing acrylic acid is thought to be due to
decarboxylation. Also, The 7 percent reduction in DTG curves is evidence of
decarboxylation of copolymers. According to the results of the pressure sensitive
adhesive test, it was observed that the surface wetting degree of the copolymers
changed in direct proportion to the amount of acrylic acid increased and inversely
proportional to the amount of HPEG, and the potential of the adhesives obtained in
addition to be high performance pressure sensitive adhesive tapes.

Corresponding Author: HAKAN AKAT, Prof

Ege Universitesi Fen Fakultesi
Izmir, TURKEY

Corresponding Author Secondary

Information:

Corresponding Author's Institution: Ege Universitesi Fen Fakultesi

Corresponding Author's Secondary

Institution:

First Author: Berna Körpınar

First Author Secondary Information:

Order of Authors: Berna Körpınar

Ece Atman Çay

HAKAN AKAT, Prof

Order of Authors Secondary Information:

Author Comments: Dear Editor-in-Chief

Powered by Editorial Manager® and ProduXion Manager® from Aries Systems Corporation
 I am submitting a manuscript for consideration for publication in Polymer BULLETIN.
The manuscript is entitled “Poly(2-ethyl hexyl acrylate-co-methyl allyl polyethylene
glycols ether–co-acrylic acid) pressure-sensitive adhesives: Synthesis,
Characterization, Investigations of Adhesive and Thermal Properties”.It has not been
published elsewhere and it has not been submitted simultaneously for publication
elsewhere. Thank you very much for your consideration.
Yours Sincerely,
Prof. Dr. Hakan AKAT
Ege Univ. Faculty of Science
Department of Chemistry, Division of Physical Chemistry
Bornova 35100, Izmir Turkey
Tel:+90 541 9428203
fax:+90 232 3888264
e-mail: hakan.akat@ege.edu.tr

Suggested Reviewers: Mehmet Atilla Tasdelen

Yalova ÜniversitesiMühendislik Fakültesi: Yalova UniversitesiMuhendislik Fakultesi
tasdelen@yalova.edu.tr
expert

Yeliz yıldırım
Ege University: Ege Universitesi
yeliz.yildirim@ege.edu.tr
expert

Ayhan Oral
Canakkale Onsekiz Mart Universitesi - Anafartalar Kampusu
ayhanoral@comu.edu.tr
expert

Kamil şirin
Manisa Celal Bayar Üniversitesi: Manisa Celal Bayar Universitesi
sirin.kamil@gmail.com
expert

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1
2 Poly(2-ethyl hexyl acrylate-co-methyl allyl polyethylene glycols ether–co-acrylic acid)
3 pressure-sensitive adhesives: Synthesis, Characterization, Investigations of Adhesive
4
5
and Thermal Properties
6
7 Berna Körpınara,b, Ece Atman Çaya, Hakan Akata*
8 a
Department of Chemistry, Faculty of Science, Ege University, 35100, Bornova, Izmir, Turkey
9
10 b
Department of Chemistry, Arts and Science Faculty, Celal Bayar University, 45140, Manisa, Turkey
11
12
13 *Corresponding Author: hakan.akat@ege.edu.tr, Tel:+902323888264
14
15 *Orcid Id: https://orcid.org/0000-0003-4002-5352
16
17 ABSTRACT
18
19
20
21 In the present study, solvent-based acrylic copolymers were successfully synthesized by
22
23 “solution polymerization” using methyl allyl polyethylene glycols ether, acrylic acid, and 2-
24
25
26 ethyl hexyl acrylate for the fabrication of high-performance pressure-sensitive adhesive tapes.
27
28 Different techniques (NMR, FTIR, TGA/DTG, Contact Angles, PSAs Test) were used to
29
30
characterize the physical and thermal properties of the copolymers. The obtained copolymers
31
32
33 were investigated as a possible adhesive for permanent or removable applications such as
34
35 security labels for power equipment, foil tape for HVAC ductwork, automotive interior trim
36
37
38 assembly, and sound/vibration dampening films. When the contact angles of the synthesized
39
40 copolymers were examined, it was observed that while the amount of acrylic acid in the
41
42
43 copolymer content was constant, the contact angle increased with the increase in the percentage
44
45 of HPEG. In addition, while the amount of HPEG was constant in the copolymers, it was
46
47
48
observed that the contact angle decreased with the increase in the percentage of acrylic acid. As
49
50 a result, it was determined that the obtained copolymers showed hydrophilic character and
51
52 wetted the contact surface. When the thermal properties of the copolymers were examined,
53
54
55 while the acrylic acid ratio was constant, the thermal stability increased with increasing HPEG
56
57 amount. While the HPEG ratio is constant in the copolymer content, the decrease in thermal
58
59
60 stability with increasing acrylic acid is thought to be due to decarboxylation. Also, The 7
61
62
63
64
65
 percent reduction in DTG curves is evidence of decarboxylation of copolymers. According to
1
2 the results of the pressure-sensitive adhesive test, it was observed that the surface wetting
3
4
5 degree of the copolymers changed in direct proportion to the amount of acrylic acid increased
6
7 and inversely proportional to the amount of HPEG, and the potential of the adhesives obtained
8
9
10 in addition to being high-performance pressure sensitive adhesive tapes.
11
12
13 Keywords Solvent-based acrylic adhesive, Polyethylene Glycol Monomethylallyl Ether
14
15 (HPEG), acrylic acid, 2-ethylhexylacrylate(2-EHA), solution polymerization, PSAs
16
17
18
19
20
21 1. Introduction
22
23 Pressure-sensitive adhesives (PSAs) are a class of materials that can quickly adhere to
24
25 any surface under minimal pressure load. This category of adhesive is an aggressive
26
27
adhesive in dry form and adheres permanently to any surface. Pressure-sensitive adhesives
28 (PSA) form a strong bond with short contact times and under light pressure. PSAs adhere
29
30 immediately to a substrate (the material on which the PSA is applied) without the need for
31
32 activating agents (heat, water, solvent, etc.). Among the various adhesive classes, PSAs are
33
34 the most common adhesive found in consumer products. Self-adhesive tapes and labels of
35
36 all kinds are ubiquitous in everyday life. Acrylic, silicone, polyurethane, or rubber-based
37
38
synthetic polymers are the preferred adhesive materials for use in commercial PSA systems
39 because of their excellent performance. Acrylics can be optimized for the formulation of a
40
41 PSA product by varying certain preparation parameters. Acrylics are typically random
42
43 copolymers of 2-ethylhexyl acrylate (2-EHA) with a short side chain and low glass
44
45 transition temperature (Tg) of n-butyl acrylate (BA), along with side-chain acrylic, that sets
46
47 Tg such as methyl acrylate and an acrylic acid (AA), which improves adhesion to polar
48
49
substrates and optimizes the elongation properties of the material. PSAs can be applied as
50 solvent-based, water-based (dispersions), or solvent-free systems[1]. Surface energy also
51
52 affects the strength of the pressure-sensitive bond. Surface energy is a measure of an
53
54 adhesive's ability to wet and adhere to a surface[2]. Better wetting also promotes surface
55
56 penetration where microscopic surface irregularities can be filled to produce adhesive locks
57
58 that increase the strength of the mechanical bond[3,4]. Adhesives with a lower FYE than
59
the free surface energy (FYE) of a substrate will readily wet the substrate surface and form
60
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65
 strong adhesive bonds[5]. If adequate contact is maintained between the substrate and the
1
2 adhesive, physical interactions or bonds between the atoms of the two surfaces will cause
3
4
the surface to become wet. Such physical interactions result from very limited
5 intermolecular forces. Wetting can be due to (a) acid-base interactions, (b) the formation of
6
7 weak hydrogen bonds, or (c) van der Waals forces (dipole-dipole and dispersion forces).
8
9 The degree of wetting depends on the difference between the substrate's SYEs and the
10
11 adhesive materials. Wetting occurs spontaneously under these conditions. In general, the
12
13 polymer exhibits a visco-elastic form and develops adhesion to the material and adhesion
14
15
to each other at the molecular level(cohesion). The adhesive does not require any chemical
16 or physical reaction to result in bonding. To characterize a pressure-sensitive adhesive, three
17
18 properties must be known, which are peel adhesion, tack, and adhesion, also known as
19
20 cohesion.
21
22
23
Adhesion is a phenomenon that keeps two surfaces in contact. It is measured as the force
24 required to separate the two surfaces and is thus considered a peeling adhesion. In this type
25
26 of adhesion, pressure comes into play. The concept of tack is the ability to stick instantly.
27
28 There is no pressure in this case. The third, cohesion, also known as shear strength, is
29
30 resistance to shear forces. The latter allows the adhesive to be held under tension. There
31
32 may be commercially available pressure-sensitive adhesives in acrylic, polyurethane,
33
34
polyester, or silicone construction. Acrylic self-adhesive polymers can be synthesized with
35 many acrylic ester monomers. Acrylic pressure-sensitive adhesives are divided into 3 types.
36
37 These; are solvent-based, water-based, and solvent-free acrylic adhesives. The solvent-
38
39 based pressure-sensitive adhesive market is developing rapidly and is finding a variety of
40
41 uses. These adhesives are frequently used in the production of single or double-sided tapes,
42
43 labels, self-adhesive bioelectrodes, decorative PVC markings, and marking tapes. Acrylic
44
polymers consist of a combination of soft (with low Tg), hard (with high Tg) functional
45
46 monomers. Soft monomers such as n-butyl, 2-ethylhexyl, n-octyl acrylate are effective in
47
48 tack adhesion, which has the feature of sticking without pressure and peel adhesion, which
49
50 has the feature of peeling off the surface after applying pressure. Hard monomers such as
51
52 methyl and ethyl acrylate affect the cohesion properties described as internal adhesion at
53
54 the molecular level. Functional monomers such as acrylic acid and acrylic amide contain a
55 reactive moiety for crosslinking reactions. Acrylic polymers are most widely used as PSA
56
57 in commercial products such as tapes, labels, and protective films due to their low cost, non-
58
59 toxicity, transparency, and good weather resistance[6]. Many traditional PSAs are designed
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61
62
63
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 with multiple components for use in room temperature applications. However, the demand
1
2 for single-component acrylic PSAs with high adhesion properties, which can be applied at
3
4
high temperatures, has been increasing rapidly in recent years. Abusafieh et al synthesized
5 a cross-linked poly(methyl methacrylate-acrylic acid) copolymer, which may be suitable
6
7 for potential bone implant applications. They obtained this copolymer with a structure
8
9 containing both hydrophobic and hydrophilic components, which can swell by absorbing
10
11 the water in the environment in a controlled manner when left in the saltwater environment.
12
13 They emphasized that the degree of swelling depends on the volumetric ratio of hydrophilic
14
15
acrylic acid and hydrophobic methyl methacrylate and that the obtained copolymer can be
16 used in bone implants by absorbing body fluid and providing better adhesion to the
17
18 implant[7]. Kotiyan et al synthesized a pressure-sensitive adhesive for drug delivery into
19
20 the skin by using 2-ethylhexyl acrylate and acrylic acid monomers by radical solution
21
22 polymerization method. It has been proven that the obtained adhesive is suitable for use to
23
24 transport drugs into the skin due to its compatibility with the skin[8]. Liu et al. obtained a
25
series of acrylate-based coating materials with high ink absorption and fast-drying
26
27 properties (MBAH) by emulsion copolymerization method using methacrylate (MMA),
28
29 butyl acrylate (BA), allyl polyethylene glycol (APEG) and hydroxyethyl methacrylate
30
31 (HEMA). They discussed and analyzed the effect of hydrophilic APEG in MBAH. They
32
33 are then covered with MBAH polyester fabric. The ink absorption performances of MBAH
34
35 on polyester fabrics were extensively characterized by the ink drying time value and the ink
36 absorption rate and showed that the resulting adhesive exhibited high ink absorption when
37
38 APEG was 7% by weight of the total monomers. In conclusion, this study showed the
39
40 possibility of obtaining a new acrylate copolymer with high ink absorption properties and
41
42 the potential application of a series of acrylate-based coating materials obtained as practical
43
44 finishing agents for inkjet printing[9]. Diakoumakos et al. aimed to find the conditions
45
46 under which oligomeric acrylic polyol resins with a low polydispersity (D= Mw/Mn) and
47 relatively low viscosity can be synthesized using the free radical polymerization method to
48
49 be used as a resin in solid content coatings. It has been emphasized that the obtained resins
50
51 have lower polydispersity and a certain molecular weight, showing better coating film
52
53 properties[10]. Lu et al synthesized poly(butyl acrylate-vinyl acetate-acrylic acid) based
54
55 acrylic pressure-sensitive adhesives (PSAs) by solution polymerization for the production
56
57
of high-performance pressure-sensitive adhesive tapes. The synthesized PSAs have
58 emphasized that they have high shear strength[11]. Kowaski et al investigated the adhesion
59
60 properties of cross-linked pressure-sensitive acrylic adhesive (PSA) using aluminum
61
62
63
64
65
 acetylacetonate on various substrates such as stainless steel, glass, polyethylene,
1
2 polypropylene, polytetrafluoroethylene, polycarbonate, and poly(methyl methacrylate).
3
4
They emphasized that the obtained acrylic adhesive showed high stickiness[12]
5
6 In this study, solvent-based acrylic copolymers were synthesized and the potential
7
8 of the synthesized copolymers as pressure-sensitive adhesives was investigated. The effects
9
10 of HPEG, EHA, and AA in different ratios used in copolymer synthesis on molecular weight
11
12
(Mw), polydispersity (Mw/Mn), contact angles, thermal stability, and dependence of
13 adhesive properties on copolymer composition were investigated. The effectiveness of the
14
15 ratio of monomers containing hydrophilic ends in the copolymer composition on the
16
17 adhesive property was discussed according to the results obtained. It is thought that this
18
19 study will be a data source about other acrylic-based pressure-sensitive adhesives in the
20
21 literature.
22
23 2. Experimental
24
25 2.1 Materials
26
27
28 2-Ethylhexyl Acrylate (2-EHA, 99%, Merck, USA), Acrylic Acid (AA, 99%, Merck, USA),
29 Polyethylene Glycol Monomethylallyl Ether (HPEG, Norchem LLC), 2,2'-
30
31 Azobisizobutyronitrile (AIBN, 99%, Aldrich), Ethyl Acetate (99%, Merck, USA), Methyl
32
33 Alcohol (99%, Merck, USA).
34
35
36 2.2 Instrumentation
37
38 Fourier transform infrared spectroscopy (FTIR) spectra of synthesized copolymers were
39
40 acquired using a PerkinElmer FTIR spectrometer. Molecular weights and polydispersities
41
42 of the linear polymers were determined by gel permeation chromatography (GPC) using a
43
44 Viscotek GPC max autosampler system consisting of a pump, three ViscoGEL GPC
45
columns (G2000HHR, G3000HHR, and G4000HHR), a Viscotek UV detector, and a
46
47 Viscotek differential refractive index (RI) detector with THF as eluent at a flow rate of 1.0
48
49 mL/min at 30 °C. TG measurements of polymer samples were obtained on PerkinElmer
50
51 Diamond TA/TGA between 25 and 600 °C at a constant heating rate of 10 °C/min in a 100
52
53 mL/min nitrogen atmosphere. The contact angles of the pure water-copolymer interface
54
55 were measured with the help of the Attension Theta Flex Theta Optical Tensiometer device.
56 The loop tack test of synthesized copolymers was acquired using loop tack devotrans DVT
57
58 BPD NN 200N device, which is a single column model used in capacities up to 3 kN. The
59
60
61
62
63
64
65
 Peel test of obtained copolymers was acquired using PA-1000-180 180° Peel Adhesive
1
2 Testing Machine.
3
4
5
6
7 2.3 Synthesis of Solvent-Based Acrylic Copolymers
8
9 The copolymers were synthesized by solution polymerization in ethyl acetate solvent
10
11 containing 1% AIBN initiator and different ratios of 2-EHA, AA, and HPEG monomers.
12
13 All copolymers obtained in the pure form were dried in a vacuum oven and characterized.
14
15 The copolymer compositions and the molecular weights and polydispersity indexes of the
16
17 obtained copolymers are given in Table 1.
18
19
20
21
22 2.4 Measurement Contact Angles of the pure water-copolymers interface
23
24 The contact angle is the angle that meets the liquid-vapor boundary of a drop and the solid
25
26 surface. It measures the wettability of a solid surface by a liquid with the Young's equation.
27
28 The theoretical explanation of the contact is due to consideration of the thermodynamic
29
30 equilibrium between the three phases: liquid phase, solid phase, and gas or vapor phase.
31
32
Solid-vapor interface energy, solid-liquid interface energy, and liquid-vapor interface
33 energy then equilibrium contact angle is determined by Young's equation[13,14]. The
34
35 contact angles of the pure water-copolymers interface were measured with the help of the
36
37 Attension Theta Flex Theta Optical Tensiometer device.
38
39
40 2.5 PSAs Test
41
42 Exact and suitable test methods for PSAs are needed to appoint that a given adhesive will
43
44 perform satisfactorily for its intended use. Characteristics of PSAs are categorized by peel
45
46 adhesion, cohesive strength, and tack. Tack is the dominant property of PSAs. To determine
47
48 the tack property, various testing methods are suggested, for example, rolling ball tack test,
49 probe tack test, and loop tack test. The loop tack test is one well-known method. The ends
50
51 of an adhesive strip are folded to form a teardrop shape. The bottom of the loop is brought
52
53 in contact with a rigid substrate at a constant rate until the contact length in the longitudinal
54
55 direction reaches a certain amount (usually 25.4mm). After a short contact time (usually 1
56
57 sec), the top of the loop is brought upward at the same rate as in the bonding phase until
58
59
detachment occurs. The pulling force is recorded as a tack curve[15]. The “Loop Tack” test
60 is used to measure the tack force/strength of a pressure-sensitive adhesive (PSA) according
61
62
63
64
65
 to ASTM D6195. The "Loop Tack" test was used to measure the bond strength/strength of
1
2 pressure-sensitive adhesives (PSA) obtained according to ASTM D6195. For this, loops
3
4
were made with tapes with the label on the outside of the loop. The ring universal tester is
5 placed on the upper handle of the machine. The loop was brought into contact with the 1
6
7 cubic inch fixed at the ‘12 inch/min speed’ of the universal testing machine. When the tape
8
9 made contact with the entire face of 1 on the square surface, its direction was reversed and
10
11 the ring was pulled at the same rate. The maximum force/stress required to remove the loop
12
13 from 1 square surface was recorded.
14
15 The peel test is the most commonly used method for measuring adhesion in flexible
16
17 packaging. The peel test comes in a variety of forms, varying in angle and apparatus. Based
18
19 on the practical consideration of the adhesive bond, peel tests are usually determined at peel
20
21 angles θ of 90° or 180° or in a T-peel configuration. The peel strength is measured as the
22
23
amount of force acting on the width of the bonding surface when peeled at a constant
24 velocity. The ‘Peel test is used for the peel adhesion of single-coated adhesive tape when
25
26 peeled at a 180 degree angle forpressure sensitive adhesive (PSA) according to ASTM
27
28 D3330. For this, test materials were prepared in a rigid layer such as a few strips of tape and
29
30 a metal plate to be tested. The tape was applied to the substrate with even pressure using a
31
32 hand-held roller. The tape was then pulled from the plate at a 180 degree angle at a given
33
34
ratio and peel adhesion was measured[16].
35
36
37
38
39 3. Results and discussion
40
41
42 3.1 Characterization
43
44
45 The ‘solution polymerization technique’ is used in the synthetic approach for the direct
46
47 synthesis of polymers. The copolymers were successfully synthesized using solution
48 polymerization as seen in Fig. 1. When the spectrum obtained as a result of the 1H-NMR
49
50 analysis was evaluated (Fig. 2a-2b), the evidence that the synthesis of the copolymers
51
52 desired to be synthesized was carried out successfully was obtained. Fig. 3 shows FTIR
53
54 spectra of the copolymers. The FTIR absorption bands for C–H stretching of the copolymers
55
56 take place at 2850 and 2940 cm-1. While the characteristic strong absorption band of
57
58
carbonyl and the ether group appears at 1720 cm-1 1170 cm-1 (C-O-C); C–H bending appears
59 at 1380 cm-1. Looking at Fig. 2, the peak of C=C sp2 hybridization on the straight chain,
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61
62
63
64
65
 which is present in both acrylic acid, HPEG, and 2-EHA is seen at about 1600 cm-1 and is
1
2 not visible after copolymers synthesis. In addition, when the molecular weights of the
3
4
copolymers obtained were compared, the highest molecular weight was found in
5 Experiment 5 containing 2-EHA:AA:HPEG in the ratios of 75:5:20, and the lowest
6
7 molecular was found in Experiment 15 containing 2-EHA:AA: Found in containing 2-
8
9 EHA:AA:HPEG in the ratios of 70:10:20. The polydispersities of the copolymers were
10
11 determined as 2.12 and 3.99, respectively.
12
13
14
15
16 Table 1. Copolymer compositions, molecular weight, and polydispersity
17
18 Copolymer compositions Molecular Weight Polydispersity
19
20
21 EHA:AA:HPEG Mw Mn Mw/Mn
22
23 Exp. 1 90:10:0 83045 22028 3.77
24
Exp. 2 90:5:5 93350 29081 3.21
25
26 Exp. 3 80:10:10 44648 12830 3.48
27
Exp. 4 70:10:20 47730 13835 3.45
28
29 Exp. 5 75:10:15 238910 71961 3.32
30
Exp. 6 80:5:15 119500 29950 3.99
31
32 Exp. 7 85:5:10 93350 29081 3.21
33
34 Exp. 8 85:10:5 85417 24405 3.50
35 Exp. 9 75:5:20 81093 21625 3.75
36
37 Exp. 10 95:5:0 92408 23634 3.91
38 Exp. 11 95:0:5 148561 70076 2.12
39
40 Exp. 12 90:5:5 114008 37751 3.02
41 Exp. 13 85:10:5 63865 20535 3.11
42
43 Exp. 14 80:15:5 54739 16895 3.24
44 Exp. 15 80:20:0 44380 12864 3.45
45
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 1
2
3
4
5
6
7
8
9
10
11
12
13
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15
16
Fig. 1 Synthesis of solvent-based Acrylic copolymers
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26
27
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32
33
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44
45 Fig. 2 NMR spectrum of copolymers with HPEG(2a), without HPEG (2b)
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 1
2
3
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5
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7
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9
10
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12
13
14
15
16
17
18
19
20 Fig.3 FT-IR spectra of copolymers
21
22
23 The thermal stability of obtained copolymers was investigated using thermogravimetric
24
25 analysis. When TGA and DTG thermograms(Fig. 4a,4b,) are examined while the acrylic
26
acid ratio was constant, the thermal stability increased with increasing HPEG amount.
27
28 While the HPEG ratio is constant in the copolymer content, the decrease in thermal stability
29
30 with increasing acrylic acid is thought to be due to decarboxylation. Also, the 7 percent
31
32 reduction in DTG curves(Fig.5a,5b) is evidence of decarboxylation of copolymers.
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
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57
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59 Fig. 4a TGA thermogram of copolymers with an increased ratio of HPEG
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65
 1
2
3
4
5
6
7
8
9
10
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15
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26 Fig. 4b TGA thermogram of copolymers with an increased ratio of AA
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28
29
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32
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50
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56 Fig. 5a DTG curve of copolymers with an increased ratio of HPEG
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 1
2
3
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5
6
7
8
9
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24
25
26
27 Fig. 5a DTG curve of copolymers with an increased ratio of AA
28
29
30 When the contact angles of the synthesized copolymers(Table 2) were examined, it was
31
32 observed that while the amount of acrylic acid in the copolymer content(Fig.6) was
33
34
constant, the contact angle increased with the increase in the percentage of HPEG. In
35 addition, while the amount of HPEG was constant(Fig.7) in the copolymers, it was observed
36
37 that the contact angle decreased with the increase in the percentage of acrylic acid. As a
38
39 result, it was determined that the obtained copolymers showed hydrophilic character and
40
41 wetted the contact surface.
42
43 Table 2. Contact Angles of the pure water-copolymers interface
44
45
46
Experiment AA HPEG 2-EHA Average Contact Angle
47
48 1 10 0 90 17,5
49 13 10 5 85 52,4
50
3 10 10 80 63,1
51
52 5 10 15 75 72,7
53 10 20 70 107,6
4
54
55 11 0 5 95 24,2
56 12 5 5 90 40,4
57 10 5 85 52,4
58 8
59 14 15 5 80 63,1
60 15 20 5 75 86,9
61
62
63
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 10 5 0 95 8,9
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33 Fig. 6 Average Contact Angles images of exp.1,2,3,4,5 with an increased ratio of HPEG
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 3.2 PSAs Test
1
2 Loop tack and Peel adhesion test results of synthesized polymers are given in Table 3a-
3
4
3b. When the table is examined, the best loop tack and peel result was obtained in Trial
5 12 containing AA:HPEG:2-EHA at 10:5:85 ratios. It was observed that the surface
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7 wetting degree of the copolymers changed inversely with the increasing amount of
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9 HPEG.
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11 Table 3a. Loop Tack-Peel Test result when HPEG amount is constant in the copolymer
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13 composition
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16 Copolymer Composition Deneme 6 Deneme 12 Deneme 10
17 AA 0 10 20
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19 HPEG 5 5 5
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21 2-EHA 95 85 75
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23 Loop Tack/Peel (N/25
0.5/0.8 17.4/21.4 1.2/0.8
24 mm)
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27 Table 3b. Loop Tack-Peel Test result when AA amount is constant in the copolymer
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29 composition
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32 Copolymer Composition Deneme 1 Deneme 3 Deneme 5
33 AA 5 5 5
34
35 HPEG 0 10 20
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37 2-EHA 95 85 75
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Loop Tack/Peel (N/25
39 1.83/10.7 0.75/3.3 0.5/3.5
40 mm)
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43 When the loop tack and peel tests of copolymers are compared with the studies in the
44
45
literature Marquez et al obtained a peel result in the range of 7-15 N/25mm and a tack
46 result in the range of 7-27 N/25mm[17]. Zhang et al obtained peel results in the range
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48 of 3.5-19 N/25mm with 2-EHA, MMA, BA, and HPA monomers[18]. Czech et al
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50 obtained peel values in the range of 1.6-21.5 N/25mm with 2-EHA, AA, EAcr, MA
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52 monomers[19]. Zhu et al 2020 obtained 14.78-19.39 N/25mm tack, 18.64-22.68 N/25
53
54 mm peel results with BA, HEA, and AA monomers and in the presence of HDDA
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crosslinker[20]. Tobing et al obtained 2.625-8.325 N/25 mm 90⁰ peel in the adhesive
57 synthesized by solution polymerization technique with BA and AA monomers, and
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 3.95-5.25 N/25mm 90⁰ peel in the adhesive synthesized by emulsion polymerization
1
2 with the same amount and same monomers[21].
3
4
5 4. Conclusion
6
7
8 Poly(2-ethyl hexyl acrylate-co-methyl allyl polyethylene glycols ether-co-acrylic
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10 acid) pressure-sensitive adhesives were synthesized by solution polymerization. Different
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12 techniques (NMR, FTIR, TGA/DTG, Contact Angles, PSAs Test) were used to characterize
13 the physical and thermal properties of the copolymers. The effects of HPEG, EHA, and AA
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15 in different ratios used in copolymer synthesis on molecular weight (Mw), polydispersity
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17 (Mw/Mn), contact angles, thermal stability, and dependence of adhesive properties on
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19 copolymer composition were investigated. It was observed that the contact angle decreased
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21 with the increasing amount of AA, and the contact angle increased with increasing HPEG
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23
ratio in the composition of the copolymers. According to the TGA/DTG curves of
24 copolymers, while the acrylic acid ratio was constant, the thermal stability increased with
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26 increasing HPEG amount. However, the thermal stability of the copolymers decreased as
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28 decarboxylation occurred with an increasing amount of AA. It was observed that increasing
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30 the amount of both AA and HPEG in the copolymer composition increased the molecular
31
32 weight. When the loop tack and peel table tables of the copolymer are examined, the best
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34
loop tack and peel result was obtained in experiment 12 containing AA:HPEG:2-EHA at
35 10:5:85 ratios.
36
37
38 References
39
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