Showcasing research from Professor Kwon's laboratory,

Department of Materials Science and Engineering, As featured in:

Seoul National University, Seoul, South Korea.
Volume 22
Number 23
7 December 2020

Green
Pages 8049-8534

Synthesis of solvent-free acrylic pressure-sensitive adhesives

via visible-light-driven photocatalytic radical polymerization Chemistry
Cutting-edge research for a greener sustainable future
rsc.li/greenchem

without additives

Solvent-free acrylic PSAs were prepared through visible-

light driven photocatalytic free radical polymerization.
Combined experiments and quantum chemical calculations
suggest that N-vinyl-based monomer facilitates the electron
transfer between the monomer and the photocatalyst, ISSN 1463-9262

which is responsible for the enhanced rate and conversion PAPER

Jens Langanke, Walter Leitner et al.
A green route to polyurethanes: oxidative carbonylation of
industrially relevant aromatic diamines by CO2 -based
methyl formate

of polymerization. Viscoelasticity, mechanical strength and

adhesion performance of acrylic PSAs were nicely adjusted
See Johannes Gierschner,
in a broad range by controlling the monomer composition, Wonjoo Lee, Min Sang Kwon et al.,
suggesting that our new method would replace the existing Green Chem., 2020, 22, 8289.
photoinitiated free radical polymerization.

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Synthesis of solvent-free acrylic pressure-sensitive

Cite this: Green Chem., 2020, 22,
adhesives via visible-light-driven photocatalytic
8289 radical polymerization without additives†
Jong-Ho Back,a Yonghwan Kwon,b,c Juan Carlos Roldao,d Youngchang Yu,a
Hyun-Joong Kim,e Johannes Gierschner, *d Wonjoo Lee*a and
Published on 23 October 2020. Downloaded on 1/14/2021 2:42:53 AM.

Min Sang Kwon *b

Research on solvent-free acrylic pressure-sensitive adhesives (PSAs) has tremendously grown over the last
few decades due to the stringent regulations to control volatile organic compound emissions. They are
mostly prepared in the presence of photoinitiators using high-energy UV light that causes several issues
such as those associated with radiation safety. Herein, for the first time, solvent-free acrylic PSAs were
prepared through visible-light-driven photocatalytic free radical polymerization. Importantly, we found
that the use of N-vinyl-based monomers noticeably enhances the rate and conversion of polymerizations,
thereby eliminating the need for additives (e.g. α-haloester and sacrificial electron donor) that are usually
required for photoredox-mediated free radical polymerization, but concurrently needs an additional
purification process to remove residues. Combined experiments and quantum chemical calculations
suggest that N-vinyl-based monomers facilitate electron transfer between monomers and photocatalysts,
Received 17th August 2020, which is responsible for the enhanced rate and converison of polymerization. Viscoelasticity, mechanical
Accepted 23rd October 2020
strength and adhesion performance of acrylic PSAs were well adjusted in a broad range by controlling the
DOI: 10.1039/d0gc02807j monomer composition, suggesting that our new method would replace the existing photoinitiated free
rsc.li/greenchem radical polymerization.

Introduction PSAs are a special class of adhesive materials that can be

classified by their chemical composition into the following cat-
Since the first industrial application of adhesive tape in 1874 egories: rubber-based, acrylic, and silicon.1,3 Acrylic PSAs are
by Johnson & Johnson, pressure-sensitive adhesives (PSAs) one of the most widely used PSAs owing to their superior pro-
have been extensively utilized in various fields such as perties (e.g. resistance to oxidation, transparency, non-yellow-
masking tapes, removable labels, decorative films, protective ing, and high adhesion performance).1,3,7–9 The world market
films, and medical tapes, which are mainly used to adhere to a for acrylic PSAs was valued at US$ 8.84 billion in 2017 and
variety of substrates under light pressure.1–3 In particular, expected to reach US$ 11.72 billion by 2022.10 In particular,
PSAs are crucial to the assembly of electronics, such as smart solvent-free acrylic PSA market has grown tremendously over
phones, which are essential in our daily life.4–6 the last few decades because (1) many governments have been
enforcing more stringent regulations to control volatile organic
compound emissions and (2) there can be huge possibilities to
reduce the costs by eliminating the drying process and the
a
Center for Advanced Specialty Chemicals, Korea Research Institute of Chemical recapturing of the evaporated solvents.1,3,11,12
Technology, Ulsan 44412, Republic of Korea. E-mail: [email protected] Solvent-free acrylic PSAs are mostly prepared in the pres-
b
Department of Materials Science and Engineering, Seoul National University,
ence of photoinitiators using high-energy UV light that often
Seoul 00826, Republic of Korea. E-mail: [email protected]
c
Department of Materials Science and Engineering, Ulsan National Institute of raises several issues associated with the generation of ozone,
Science and Technology (UNIST), Ulsan 689-798, Republic of Korea radiation safety,13,14 energy efficiency, and curing depth.15,16
d
Madrid Institute for Advanced Studies, IMDEA Nanoscience, Calle Faraday 9, Visible-light-driven curing is thus highly required, especially
Campus Cantoblanco, 28049 Madrid, Spain. E-mail: [email protected] for certain PSAs. For example, UV-shielding PSAs incorporate
e
Research Institute of Agriculture and Life Sciences, College of Agriculture and Life
UV absorbers, and thereby, conventional UV-light curing leads
Sciences, Seoul National University, Seoul 08826, Republic of Korea
† Electronic supplementary information (ESI) available. See DOI: 10.1039/ to a low curing rate and monomer conversion and thus results
d0gc02807j in poor cohesion.17,18 Visible-light curing is also necessary for

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Scheme 1 (a) Conventional photoinitiators used for photocurable solvent-free acrylic PSAs and the underlying mechanism. (b) Proposed mecha-
nism of photoredox-mediated free radical polymerization as suggested by Choi and co-workers (left) and the chemical structures of photoredox
catalysts used in this study (right). (c) Schematic representation of the two-step process for the preparation of solvent-free acrylic PSAs via visible-
light driven photoredox-mediated free radical polymerization. Network structure was formed by the crosslinking reaction of poly(ethylene glycol)
diacrylate (PEGDA, Mn: 700 g mol−1) and the remaining monomers.

medical PSA tapes directly attached to human skin, due to Instead, solvent-free acrylic PSAs were successfully prepared
fairly harmless visible light. In spite of these advantages, only through photoredox-mediated free radical polymerization with a
few studies on this topic have so far been reported and most of low catalyst loading of an organic photocatalyst (as low as 50 ppm;
those rely on visible-light photoinitiators (Scheme 1a).19,20 50 × 10−6 mol% with respect to the total amount of monomers)
The use of photocatalysts (PCs) has emerged as a powerful under visible light (455 nm) LED irradiation conditions.
strategy in the field of photomediated polymerization.21–25 Unlike Importantly, we found that the use of N-vinyl-based monomers
traditional photoinitiators, PCs are regenerated in the photo- (N-vinylpyrrolidone and N-vinylcaprolactam) largely enhances the
catalytic cycle, and thus, only a small amount of PC is needed for rate and conversion of bulk polymerization and film curing,
the polymerization. Soft irradiation conditions such as thereby eliminating the need for additives such as α-haloester and
daylight26,27 and LED bulbs are usually required because most a sacrificial electron donor that are commonly used for photo-
PCs exhibit substantial absorption of visible light. Since photo- redox-mediated free radical polymerization, but requires an
controlled radical polymerizations based on visible-light photo- additional purification process to remove residues. We also con-
catalysis were first presented,28 a number of photocatalytic firmed that the viscoelasticity, mechanical properties, and PSA per-
polymerizations including photoredox-mediated free radical formance of solvent-free PSAs were freely adjusted over a wide
polymerization,28–33 photoredox-mediated atom transfer radical range, and thus, the resulting acrylic PSAs could be utilized for
polymerization (ATRP),34–39 and photoinduced electron/energy release coatings, general-purpose PSAs, and high-shear PSAs.
transfer reversible addition–fragmentation chain transfer
(PET-RAFT) polymerization25,40–44 have been actively developed
over the last few years. Therefore, we envisaged that visible-light Results and discussion
driven photocatalytic polymerizations could be utilized as a core
strategy to prepare solvent-free acrylic PSAs (Scheme 1b). Strategy
Herein, we report a new method for the solvent-free acrylic In our previous work, we discovered highly efficient organic
PSAs, which does not rely on common UV photoinitiators. PCs based on a systematic computer-aided-design strategy,

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which addresses several issues in organocatalyzed photoredox- tively good conversion (αt = 14.4%) and high molecular weight
mediated ATRP39 and PET-RAFT.43 Of these, 2,4,5,6-tetrakis (Mn = 664 kg mol−1) only in 30 s; furthermore, it also showed
(diphenylamino)-1,3-benzenedicarbonitrile (4DP-IPN) was an appropriate viscosity to proceed with the film curing
found to be one of the most efficient PCs because of (1) high process.
visible-light absorption, (2) efficient generation of long-lived We then performed the same polymerization with 4DP-IPN
triplet excitons, (3) proper redox potentials, and (4) high of 50 ppm (instead of the photoinitiator) under an Ar atmo-
photochemical and electrochemical stability, resulting in a sphere and 455 nm LED irradiation conditions (Table 1,
successful control over the polymerization of methyl methacry- entry 2). Poly(EHA-co-AA-co-IBOA) was obtained with a rather
late (MMA) at very low catalyst loadings (0.5 ppm, 0.5 × 10−6 good conversion (αt = 9.9%) and molecular weight (Mn =
mol%).39 We therefore selected 4DP-IPN as a PC for this study 948 kg mol−1) and thus proper viscosity, but in a much longer
and also investigated 2,4,5,6-tetra-9H-carbazol-9-yl-1,3-benze- time of 280 s. We attributed this slow reaction rate to an
nedicarbonitrile (4Cz-IPN) and eosin Y as a comparison for the inefficient initiation process that probably originates from the
chosen PC (Scheme 1b and Fig. S1†). absence of α-haloester and sacrificial electron donors such as
N,N-diisopropylethylamine (DIPEA), which is commonly
Bulk polymerization
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required to undergo photoredox-mediated free radical

We first investigated the photo-initiated bulk polymerization polymerization.28,45,46 In fact, the addition of diethyl 2-bromo-
of acrylic monomers, which is the first step in the preparation 2-methylmalonate (DBM) considerably enhanced the rate of
of solvent-free acrylic PSAs; in fact, solvent-free acrylic PSAs are polymerization (Table 1, entry 3); however, this may require
commonly prepared through the UV-induced radical photo- additional purification processes to remove residues and/or
polymerization of acrylic monomers, followed by UV-induced contaminants from the additives.
film curing in a sequential manner (Scheme 1c). As a control According to several recent studies, the rate of polymeriz-
experiment, the polymerization of 2-ethylhexyl acrylate (EHA) ation and the final conversion are substantially increased in
with acrylic acid (AA) and isobornyl acrylate (IBOA) was per- photomediated radical polymerizations by the addition of
formed in the presence of a photoinitiator of 450 ppm under N-vinylpyrrolidone (NVP) as a comonomer.30,47,48 Several
an Ar atmosphere and UV irradiation conditions (Table 1, hypotheses have been proposed to explain such a rate
entry control). The monomer type and composition used in enhancement; however, the conclusion remains somewhat
this polymerization is a type and composition generally uti- controversial.30,47,48 We therefore incorporated NVP as a como-
lized in the conventional solvent-free acrylic PSAs.1 This nomer to increase the rate of bulk polymerization. Here, the
control experiment gave poly(EHA-co-AA-co-IBOA) with a rela- total amount of high Tg monomers (i.e. IBOA and NVP) was

Table 1 Results of the bulk polymerization. Negative control (entries control and 1), different amounts of N-vinylpyrrolidone (NVP, entries 2 and
5–8), additive (diethyl 2-bromo-2-methylmalonate = DBM, entry 3), different PC amounts (entries 6, 11, and 12) and different types of N-vinyl mono-
mers (entry 13) were employed. Total conversion of bulk polymerization (αt) was characterized by 1H-NMR (see Fig. S10†). Number average mole-
cular weight (Mn) was characterized by size exclusion chromatography (SEC). Đ represents dispersity

Entry Additive [IBOA] : [NVP] : [PC]a Time (s) αt (%) Mn (kg mol−1) Đ

Control b
— 30 : 0 : 0.045 30 14.4 665 1.77

1 — 30 : 0 : 0 >4200 0 — —

2 — 30 : 0 : 0.005 280 9.9 948 1.52

3 DBM 30 : 0 : 0.005 12 12.5 278 2.28

4 — 20 : 10 : 0 >4200 0 — —
5 — 25 : 5 : 0.005 220 11.3 709 1.74
6 — 20 : 10 : 0.005 145 10.6 655 1.64
7 — 10 : 20 : 0.005 90 10.9 353 1.82
8 — 0 : 30 : 0.005 60 13.4 143 2.32

9c — 0 : 30 : 0.005 720 0 — —
10d — 0 : 30 : 0.005 60 3.9 394 2.11

11 — 20 : 10 : 0.0005 520 9.5 510 1.65

12 — 20 : 10 : 0.05 1160 12.9 688 1.84

13e — 20 : 10 : 0.005 170 9.1 560 1.81

a
[EHA] : [AA] = 65 : 5 (e.g. for entry 6 in Table 1, [EHA] : [AA] : [IBOA] : [NVP] : [PC] was set as 65 : 5 : 20 : 10 : 0.005). 4DP-IPN was used as a photo-
catalyst (PC). b Photoinitiator was used instead of a photocatalyst. Polymerization was performed. c Without argon bubbling. d In the presence of
0.3 wt% of MEHQ. e N-Vinylcaprolactam (NVC) was used instead of NVP.

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fixed at 30 mol% to minimize the change in Tg of the resulting and, concurrently, (2) it has a radical character at the Cv2
PSAs. carbon atom, resulting in sufficient reactivity to an acrylic
Table 1 shows the results of the bulk polymerization in the monomer. This can be seen from the molecular orbital (MO)
presence of NVP; the optimal catalyst loading was found to be analysis, which confirms a significant weight of the tc-NVP•+
50 ppm (Table 1, entries 6, 11, and 12). As expected, the rate of resonance structure to NVP•+. Neutral NVP shows a bonding
polymerization was considerably enhanced as the amount of character between N and CO (see Fig. 1e), indicating that the
NVP increased (Table 1, entries 2 and 5–8). Interestingly, an zwitterionic resonance structure (N+, O−; see z-NVP in Fig. 1d)
increase in the amount of NVP resulted in a significant has a relatively high weight vs. the neutral one. This is con-
decrease in the number average molecular weight (Mn), indi- firmed by the rather short N–CO bond length (1.38 Å). On the
cating that NVP might act as an initiator as well as a monomer other hand, the CN bond with vinylene C is relatively long with
of photomediated polymerization. However, considering both N–CV1 = 1.39 Å, while CV1–CV2 = 1.34 Å is short. In NVP•+, the
the NVP content and the resulting Mn, only a small amount of electron density at the N–CO bond is reduced (Fig. 1f ), so
NVP might be involved in the initiation process. that N–CO is long (1.49 Å), while N–CV1 is short (1.33 Å), and
CV1–CV2 is elongated (1.39 Å), indeed suggesting a partial
Polymerization mechanism
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radical character at CV2.

According to (time-dependent) density functional theory, (TD) Initiation can be reasonably predicted from the combined
DFT, calculations as shown in Fig. 1a and Fig. S2,† the experiments and DFT calculations, whereas the catalyst regen-
initiation process most likely proceeds through the electron eration process is still largely unclear although several path-
transfer from NVP to 4DP-IPN in the excited state. Considering ways are shown in Fig. 1d. However, it should be noted that
the lowest singlet/triplet state (S1/T1) energies of 4DP-IPN, catalyst regeneration certainly exists because it was clearly
NVP, and methyl acrylate (MA), the initiation does not appear observed that the catalysts were almost preserved before and
to occur through the energy transfer pathway (Fig. S2†). In after the bulk polymerization (Fig. S3†). We are currently per-
fact, the highest occupied molecular orbital (HOMO) energy of forming further mechanistic investigations for the catalyst
NVP is 1.56 eV, higher than that of MA, which results in a rela- regeneration.
tively faster electron transfer from the HOMO of NVP to the
lowest singly occupied molecular orbital (SOMO) of 4DP-IPN in Curing of prepolymer mixture
S1 and/or T1 as compared to that between MA and the S1/T1 of We then investigated the visible-light curing process of the pre-
4DP-IPN (Fig. 1c). Moreover, the calculated MO diagrams of polymer mixture obtained above. Here, a small amount of the
4DP-IPN and NVP show that the photoinduced electron trans- cross-linker (i.e. poly(ethylene glycol) diacrylate, PEGDA,
fer (PeT) from NVP to 4DP-IPN should be endothermic. Hence, Mn: 700 g mol−1, 1 wt%) was further included in the prepoly-
only a very small amount of NVP is expected to participate in mer mixture for the curing process (Scheme 1c). Unlike the
the initiation process, which is in accordance with the experi- conventional UV-curing process, additional photoinitiators
mental results. Our hypothesis is also supported by the fact and/or photocatalysts were not required because the photo-
that the singlet and triplet excited state reduction potentials catalysts may not be consumed in the bulk polymerization; in
ðEred
*
Þ of 4DP-IPN are 0.93 V and 0.76 V, respectively,39 which fact, they mostly remain in the prepolymer mixture (Fig. S3†).
are similar to the voltage of ca. 1.1 V at which the electro- The resulting mixture was coated onto a backing film ( poly-
chemical polymerization of NVP starts to occur.49 A similar ethylene terephthalate film, 50 μm), and then a release film
rate enhancement was also observed for the structurally was subsequently covered on the surface; the final thickness of
similar monomer of N-vinylcaprolactam (NVC), implying that the film was set to ca. 120 μm. A string type LED (448 nm,
N-vinyl monomers might be used as an initiator as well as a 0.3 mW cm−2, three strings) was employed for film curing.
monomer for photomediated polymerizations (Table 1, The monomer conversion at the film (αf ) as a function of
entry 13). curing time is shown in Fig. 2a; the conversion is determined
The polymerization mechanism was further investigated in by using Fourier-transform infrared spectroscopy (FTIR)
detail. In Table 1, entries 9 and 10 show the results of polymer- measurements in ATR mode by which the time evolution of
izations carried out in the presence of oxygen and a radical the CvC bending peak at 830–795 cm−1 and the CvO stretch-
stabilizer (i.e. 4-methoxyphenol (MEHQ)), respectively. ing peak at 1760–1660 cm−1 are recorded as a function of the
Inhibition or significant retardation was observed in each wavenumber (Fig. 2b). Without additional photocatalysts and/
polymerization reaction, implying that the polymerization or photoinitiators, film curing successfully occurred as
obviously proceeds via a radical mechanism. In order to reveal expected and a significant increase in the cure rate was also
the radical intermediate involved in the initiation step, DFT observed in the presence of NVP, which is the same phenom-
calculations were performed for the relative energies of NVP enon observed in bulk polymerization (Fig. 2a). Despite this
radical cation (NVP•+) and its possible tautomers produced by rate enhancement, the cure rate is still far below the rate
endothermic PeT. Based on the DFT results, it is observed that observed in the conventional UV curing system (Fig. S4a†). We
tc-NVP•+ (one contributing resonance form of NVP•+) can be attributed this mainly to the low power density of the light
the most plausible candidate (Fig. 1d) since (1) it has signifi- source (Fig. S4†); a highly reliable high-power-density light
cantly lower energies compared to other tautomers (Fig. 1g) source is currently being setup.

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Fig. 1 (a) DFT calculated MO diagram of 4DP-IPN (left), NVP (middle), and MA (right). Calculated HOMO and LUMO topologies of 4DP-IPN, NVP,
and MA are also shown. (b) Chemical structures of NVP (left) and MA (right) are shown. (c) Schematic diagram for the endothermic electron transfer
from NVP (S0) to 4DP-IPN (T1). (d) Proposed mechanism of additive-free photoredox-mediated free radical polymerization. MO topologies of (e)
NVP (S0) and (f ) NVP•+ (D0) are shown with their chemical structure and bond length. (g) Relative energies of NVP and its possible tautomers calcu-
lated by DFT are shown.

Viscoelastic properties of the cured films Viscoelasticity of the laminated PSA (thickness: 0.8 mm) was
characterized by dynamic mechanical analysis (DMA) with a
It is essential to characterize the viscoelastic properties of PSAs shear sandwich clamp (frequency: 0.01–100 Hz, temperature:
because the tack, peel, and shear strength of PSAs greatly rely 23 °C, strain: 1%, see the ESI† for details).
on their viscoelastic properties.1,50 According to Chang, visco- Six different PSAs were first designed by considering certain
elastic windows can be constructed by the measurement of factors (e.g. glass transition temperature (Tg) and polar monomer
dynamic storage modulus (G′) and dynamic loss modulus (G″) contents), which are known to affect the viscoelastic properties of
at the application frequencies and temperature, which identify PSAs (Table 2). We then prepared six different prepolymer mix-
the potential applications of PSAs (Fig. 3a).50 Therefore, we tures in a series of bulk polymerizations with fixed PEGDA and
investigated the viscoelastic properties of the PSAs prepared NVP contents (1 wt% and 10 mol%) and varying amounts of
using our strategy and constructed the viscoelastic windows. EHA, AA, and IBOA. It should be noted that NVP was fixed at

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of PSAs, e.g. silicone PSAs.50 Although the prepared PSAs could

not cover the region 3 and 4 due to its intrinsic material’s limit-
ation, storage modulus of acrylic PSAs could be controlled in a
quite wide range, which mostly covers the region 1, 2, and 5. It
thus suggests that the prepared PSAs can be utilized in most
applications such as release coatings, general-purpose PSAs, and
high-shear PSAs where conventional acrylic PSAs are used.8,50

Mechanical and PSA properties of the cured films

Finally, we investigated the mechanical and adhesive pro-
Fig. 2 (a) The film conversion (αf ) is plotted as a function of curing time
for different NVP contents (entries 2 and 5–8 in Table 1), and (b) FT-IR
perties, film conversion, and gel fraction of the prepared PSAs
spectra over irradiation time are shown (entry 6 in Table 1). (Table 3). Film curing for all compositions was successful as
indicated by the high film conversion (>86%), and the gel frac-
tion varied from 88.3% to 95.0%.
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Single lap shear tests were conducted to obtain the strain–

10 mol% to enhance the rate and final conversion of both bulk stress curves by using a universal testing machine (UTM) with
polymerization and film curing. Although NVP was incorporated a constant cross-head speed (1 mm s−1, see the ESI† for
as a boosting monomer, the polymerization rate was still slow in details). As shown in Fig. 3d and Table 3, both the lap shear
certain compositions (Table 2, entry 6), which implies the neces- strength and elongation at breaks generally increased as the
sity of further research on the mechanism of photoredox- amount of high Tg monomer (e.g., IBOA and NVP) increased,
mediated free radical polymerization. which implies that the toughness of PSAs can be easily
Storage modulus increased as the amount of high Tg adjusted by the monomer composition. The lap shear
monomer (e.g., IBOA and NVP) increased, as expected (Fig. 3b strengths of the prepared PSAs (0.189–0.254 MPa) correspond
and Fig. S5a†). As shown in Fig. 3c, the prepared PSAs did not well with those of the previously reported photoresponsive
cover the region 3 and 4, which are usually covered by other types acrylic adhesives (0.150–0.341 MPa).51,52

Fig. 3 (a) Viscoelastic window of PSAs and the proposed application area according to each region.50 (b) Frequency–storage modulus curve and (c)
the viscoelastic window of various PSAs (entries 1–6 in Table 2). (d) Strain–stress curve of lap shear test, (e) the extension–force curve from the 180°
peel test (substrate: stainless steel), and (f ) the extension–force curve from the loop tack test of various PSAs (substrate: stainless steel, entries 1–6
in Table 2). The irradiation time of blue LED for film curing was set as 60 min for all PSAs.

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Table 2 Results of the bulk polymerization for the preparation of solvent-free acrylic PSAs with different monomer compositions; Tg,cal was the
expected glass transition temperature calculated by the Flory–Fox equation. Tg,exp was the experimental glass transition temperature of the cured
film and was characterized by differential scanning calorimetry (see Fig. S7†)

Entry [EHA] : [AA] : [IBOA]a Tg,cal (°C) Tg,exp (°C) Time (s) αt (%) Mn (kg mol−1) Đ

1 50 : 10 : 30 −17.6 −22.3 170 11.60 156 3.23

2 50 : 5 : 35 −12.1 −30.3 130 11.65 336 1.95
3 60 : 5 : 25 −30.1 −34.4 115 9.11 512 1.78
4 70 : 5 : 15 −44.0 −42.2 130 10.12 740 1.72
5 80 : 5 : 5 −56.8 −49.7 115 8.68 573 1.69
6 90 : 0 : 0 −65.0 — (not observed) 1273 9.44 1075 1.61
a
[NVP] : [PC] = 10 : 0.005.

Table 3 Lap shear strength, elongation at break, peel strength, loop tack, gel fraction and film conversion of various PSAs (entries 1–6 in Table 2).
The characterization methods were detailed in the ESI.† The irradiation time of blue LED for film curing was set as 60 min for all PSAs
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Peel strength (N cm−1) Loop tack (N cm−1)

Entry Lap shear Elongation at break Stainless Stainless Film conversion Gel fraction
(Table 2) strength (MPa) (mm mm−1) steel Glass steel Glass (αf, %) (%)

1 0.242 (±0.007) 47.50 (±5.64) 9.90a (±1.12) 5.87 (±0.34) 1.15 (±0.30) 5.59 (±0.45) 90.6 90.8
2 0.254 (±0.013) 42.36 (±2.25) 4.51 (±0.31) 4.73 (±0.16) 4.59 (±0.69) 7.51 (±0.57) 86.3 88.8
3 0.246 (±0.007) 37.89 (±3.55) 4.17 (±0.37) 3.52 (±0.24) 5.15 (±0.57) 7.63 (±0.44) 90.3 92.4
4 0.224 (±0.003) 26.71 (±2.79) 4.59 (±0.16) 2.56 (±0.11) 3.35 (±0.18) 4.39 (±0.47) 90.8 88.3
5 0.228 (±0.009) 28.34 (±3.03) 2.05 (±0.15) 1.59 (±0.09) 3.38 (±0.36) 4.56 (±0.43) 94.4 95.0
6 0.189 (±0.014) 13.62 (±0.98) 0.40 (±0.08) 0.26 (±0.04) 1.98 (±0.28) 2.17 (±0.59) 93.3 93.2
a
Stick-slip was observed in a debonding experiment.

The PSA properties of the prepared PSA films were assessed radical polymerization. Both bulk polymerization and film
by a 180° peel and loop tack test with different types of sub- curing proceeded smoothly in the presence of a small amount
strates (stainless steel and glass), using a 50 μm thick poly- of an organic photocatalyst under visible-light irradiation con-
ethylene terephthalate as a backing film (Fig. 3e, f, and ditions. Combined experimental and quantum chemical
Table 3, see the ESI† for details). The loop tack was higher for studies revealed that N-vinyl monomers greatly enhanced the
a glass substrate as compared to stainless steel, since PSAs rate and monomer conversion of both bulk polymerization
show a better wettability for a glass with a higher surface and film curing, resulting in the successful preparation of
energy and lower roughness than stainless steel.53 In contrast, solvent-free acrylic PSAs without any additives under extremely
the peel strength was higher in stainless steel, which may orig- mild conditions. Through investigations of viscoelastic,
inate from superior mechanical interlocking between PSAs mechanical, and adhesive properties of the PSAs prepared by
and rough surface of stainless steel. For the PSAs listed in the developed method, we clearly confirmed that our method
Table 3, entry 1, despite its superior peel strength, loop tack can be broadly applied to prepare solvent-free acrylic PSAs for
value was inferior and stick-slip was observed in a debonding a variety of applications. Therefore, we believe that our work
experiment (Fig. 3e, dark grey line), which is normally might address a variety of challenging tasks related to solvent-
observed in glassy polymers. Conclusively, optimal peel free acrylic PSAs, particularly for UV-shielding PSAs and
strength (4.17–4.59 N cm−1, stainless steel) and loop tack medical PSA tapes.
(3.35–4.59 N cm−1, stainless steel) were found in most compo-
sitions (entries 2–4), which are comparable to commercially
available PSAs, for example, duct tape ( peel strength: 4 N Conflicts of interest
cm−1; tack: 5 N cm−1).54,55 These results further confirmed
that our strategy can be broadly applied to prepare solvent-free There are no conflicts to declare.
acrylic PSAs for a variety of applications.

Acknowledgements
Conclusions The work at SNU was supported by the Technology Innovation
Program (20010768, Development of Fast Curing Structural
In summary, for the first time, solvent-free acrylic PSAs were Adhesive with High Performance for Dissimilar Materials on
fabricated via an organocatalyzed photoredox-mediated free High Speed Process) funded by the Ministry of Trade, Industry

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Paper Green Chemistry

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