9 Acrylic Resins

Acrylic resins are polymers of acrylic or methacrylic methacrylate exhibit high weather resistance. This is
esters. They are sometimes modified with monomers due to its low hygroscopic functional group. It is used
such as acrylonitrile and styrene. The most common for coating materials.
acrylates are methyl acrylate, ethyl acrylate, n-butyl
acrylate, and 2-ethylhexyl acrylate. Methacrylates in- 9.2.1.2 Methacryloyl Isocyanate and
clude methyl methacrylate, ethyl methacrylate, butyl
Derivatives
methacrylate, and higher alcohol esters.
The resins are used either as molding powders or Alkenoylcarbamates can be readily polymerized by
casting syrups. Acrylic resins are often used as hybrid themselves or with any other vinyl compounds. The
resins in combination with urethanes, epoxides, and carbamates formed from alcohols with a small num-
silicones. ber of carbon atoms are available in a stable solid
Since coatings are not the primary goal of this form under the atmospheric conditions and can be
topic, coating applications will be dealt with only
dissolved easily in various solvents.
marginally, even when acrylic resins contribute high-
The acylurethane structure contributes to an en-
ly to this topic. Acrylic resins are also widely used
for dental applications. We treat this topic because of hancement of cohesion. Therefore, copolymers con-
its importance in a special chapter. Here we focus on taining alkenoylcarbamate units show various advan-
non-dental applications of acrylic resins. tageous properties such as high elasticity and good
An overview on acrylic and methacrylic ester adhesion.
polymers is given in the literature [1,2]. The introduction of an epoxy or aziridino group
introduces further reactive moieties. The modifica-
9.1 History tion to a blocked isocyanate structure provides the
alkenoylcarbamate compounds with the latent reac-
Acrylic acid was obtained through the air oxidation
tivity of an isocyanate group, which will be actu-
of acrolein by Redtenbacher in 1843. Methacrylic
alized from the blocked isocyanate structure under
acid was first prepared in 1865. Otto Röhm observed
the polymerization of acrylics. The production of heating.
acrylates started in 1927 by Röhm&Haas. In 1936 Methyl N-methacryloylcarbamate, phenyl N-
poly(methyl methacrylate) (PMMA) was prepared by methacryloylcarbamate, benzyl N-methacryloylcar-
a casting process. bamate, and a series of other methacryloyl carba-
mates can be synthesized from methacryloyl iso-
9.2 Monomers cyanate by adding the appropriate alcohols to metha-
cryloyl isocyanate [8]. The synthesis is shown in
A large variety of monomers is known, because of Figure 9.2. The reaction is conducted at low tem-
the possibility of esterifying the acrylic acid and
peratures. Also an exchange of the alcohol group
methacrylic acid with various alcohols. The most
in the carbamate is possible. For example, ethyl N-
common monomers are shown in Table 9.1. Some
acrylate-based monomers are shown in Figure 9.1. methacryloylcarbamate can be reacted with
2-ethylhexyl alcohol in the presence of a radical poly-
merization inhibitor such as hydroquinone (HQ) at
9.2.1 Specialities 120 °C. The ethoxy moiety is then replaced by the
9.2.1.1 Cyclohexyl Methacrylates 2-ethylhexyloxy moiety to result in 2-ethylhexyl N-
Polymers containing cyclohexyl methacrylate and re- methacryloylcarbamate. This product is a viscous liq-
lated compounds such as 4-methylcyclohexylmethyl uid [9].

Reactive Polymers: Fundamentals and Applications. http://dx.doi.org/10.1016/B978-0-12-814509-8.00009-9

Copyright © 2018 Elsevier Inc. All rights reserved. 325
326 Reactive Polymers: Fundamentals and Applications

Table 9.1 Monomers for Acrylic Resins

Monomer Remarks Reference

Acrylic monomers
Acrylic acid
Methyl acrylate
Ethyl acrylate
n-Butyl acrylate
2-Ethylhexyl acrylate
Trimethylol propane triacrylate a [3]
Aziridine derivatives a [4]
Methacrylic monomers
Methyl methacrylate b
Ethyl methacrylate
2-Hydroxyethyl methacrylate
n-Butyl methacrylate c
Ethylene glycol dimethacrylate a
Poly(ethylene glycol)dimethacrylate
3-Methacryloxypropyl-trimethoxysilane (MPTS) [5]
Cyclohexyl methacrylate d [6]
4-Methylcyclohexylmethyl methacrylate [7]
Methacryloyl isocyanate [7]
2-Methacryloyloxyethyl isocyanate [7]
Methyl N -methacryloylcarbamate [8]
Phenyl N -methacryloylcarbamate [8]
2-Ethylhexyl N -methacryloylcarbamate [9]
2-Isocyanatoethyl methacrylate [10]
2-(Acryloyloxy)ethyl piperidine-1-carboxylate e [11]
2-(Acryloyloxy)ethyl morpholone-4-carboxylate e [11]
2-(Perfluoro-(1,1-bis-isopropyl)-2-propenyl)oxyethyl methacrylate [12]
a Crosslinker.
b Standard.
c Flexible.
d Improved weatherability.
e Low viscosity.

Figure 9.2 Synthesis of methyl N -methacryloylcarba-

mate and phenyl N -methacryloylcarbamate [8].
Figure 9.1 Acrylate-based monomers.
9: Acrylic Resins
Figure 9.3 Synthesis of acrylic acid and methyl
methacrylate.
9.2.2 Synthesis
9.2.2.1 Monomers
Acrylic acid is synthesized by the oxidation of
propene via acrolein. Methyl methacrylate is syn-
thesized from acetone via the acetone cyanhydrin
(ACH). The reactions are shown in Figure 9.3. The
conventional process for the synthesis of methyl
methacrylate runs via the acetone cyanhydrin. Other
technical processes include:
• The ACH-based process (Röhm&Haas, Mitsubishi
Gas Chemical),
• The i-butylene oxidation process (Lucky, Japan
Methacrylic),
• The tert-butanol oxidation process (Kyodo, Mit-
subishi Rayon),
• The propyne carbonylation (Shell, ICI), and
• The hydrocarbonylation of ethene [13].
9.2.2.2 Esterification
The reaction of methacrylic acid with an alcohol re-
sults in the respective ester. Also, an olefin can be
added to the acid in the presence of anhydrous cata-
lysts. Ethylene oxide reacts to form the hydroxy alkyl
327
Figure 9.4 Esterification reactions of methacrylic
acid.
esters. Diazomethane reacts to the methyl esters. The
reactions are shown in Figure 9.4.
9.2.3 Manufacture
Various structural elements, such as rods, sheets,
tubes, and molding powders, are produced by bulk
polymerization. The most common method for the
production of sheets is the batch cell method. The
polymerization process releases a lot of heat and has
to be carried out slowly, in order to avoid an adverse
effect on the optical properties. If the polymerization
in bulk quantities proceeds too fast, even the boiling
point can be crossed and thus bubbles are formed. In-
homogeneous temperature distribution during poly-
merization may cause streaks in the material.
9.3 Special Additives
9.3.1 Ultraviolet Absorbers
Examples of ultraviolet absorbers are shown in Ta-
ble 9.2.
328 Reactive Polymers: Fundamentals and Applications

Table 9.2 Ultraviolet Absorbers for Acrylic Resins [14]

Compound
Benzotriazole ultraviolet absorbers
2-(5-Methyl-2-hydroxyphenyl)benzotriazole
2-[2-Hydroxy-3,5-bis(α, α-dimethylbenzyl)phenyl]-2H-benzotriazole
2-(3,5-Di-tert -butyl-2-hydroxyphenyl)benzotriazole
2-(3-tert -Butyl-5-methyl-2-hydroxyphenyl)-5-chlorobenzothiazole
2-(3,5-Di-tert -Butyl-2-hydroxyphenyl)-5-chlorobenzothiazole
2-(3,5-Di-tert -amyl-2-hydroxyphenyl)benzotriazole
2-(2 -Hydroxy-5 -tert -octylphenyl)benzotriazole
2-Hydroxybenzophenone ultraviolet absorbers
2-Hydroxy-4-methoxybenzophenone
2-Hydroxy-4-octoxybenzophenone
2,4-Dihydroxybenzophenone
2-Hydroxy-4-methoxy-4 -chlorobenzophenone
2,2 -Dihydroxy-4-methoxybenzophenone
2,2 -Dihydroxy-4,4 -dimethoxybenzophenone
Salicylic acid phenyl ester ultraviolet absorbers
p-tert -Butylphenyl salicylate
p-Octylphenyl salicylate

Table 9.3 Flame Retardants

Compound Remarks Reference
Phosphoric acid esters [15]
Chlorinated polyphosphates [15]
Halogenated polyphosphonate [15]
Ammonium polyphosphonate, [16]
carbon nanotubes
Alkyl acid phosphate Synergist [15]
Zirconium phosphate Inorganic [17]
Tetrabromobisphenol A [18]
Tri(acryloyloxyethyl) phosphate Reactive [17]
2,2-Bis(4-hydroxy-3,5-dibromo- [18]
phenyl)propane
Tricresyl phosphate [18]
Tris(2-chloroethyl)phosphate [18]
Antimony trioxide Inorganic [18]
Zirconium hydroxide Inorganic [18]
Barium metaborate Inorganic [18]
Tin oxide Inorganic [18]
Montmorillonite, butyl acrylate Inorganic [19]

9.3.2 Flame Retardants

Flame resistance can be imparted by incorporat-
ing certain organic phosphoric acid esters to acrylic
resins. Some flame retardants are shown in Table 9.3
and in Figure 9.5.
However, these organic phosphoric acid esters
usually have a plasticizing effect. They are likely not
only to substantially lower the heat distortion temper- Figure 9.5 Chlorinated polyphosponate (Phosgard
C-22 R™, Monsanto).
ature of the acrylic resin products, but also to lower
9: Acrylic Resins
their mechanical strength. Further, the water absorp-
tivity of the resin products tends to increase by the in-
corporation of such flame retardants, and when used
outdoors, the resin products are likely to undergo de-
formation or crazing upon absorption of water.
For a copolymer of methyl methacrylate, α-
methylstyrene, styrene, maleic anhydride, and metha-
crylic acid, a synergism has been observed. When
two types of flame retardants, i.e., a halogen-con-
taining condensed phosphoric acid ester or a halo-
genated polyphosphonate and an alkyl acid phos-
phonate, are combined, superior flame resistance and
physical properties will be imparted by the synergis-
tic effect of the components.
Here, it is possible to reduce the amount of the
main flame retardant to a level of about 20% even
when the flame resistance should meet the standard
of V-0 of the UL Standards [20].
Therefore, it is possible to avoid the deterioration
of the physical properties, particularly the deteriora-
tion of the heat resistance, which is a serious prob-
lem when a great amount of the flame retardant is
added [15].
UV curable flame retardant resins can be obtained
by blending phosphate acrylate with an epoxy acry-
late resin [21]. The flammability has been character-
ized by limiting oxygen index, UL 94 flammability
rating and a cone calorimeter. Further, thermogravi-
metric analysis (TGA) and several IR based methods
were used. The flame retardant efficiency increases
as expected with the amount of flame retardant. The
TGA indicated that the blends with flame retardant
have lower initial decomposition temperatures and
higher char residues than the neat samples. In con-
trast, the release rate increases remarkably. IR mea-
surements indicate a lower thermo-oxidative stabil-
ity [21].
9.4 Curing
The polymerization of acrylic resins occurs essen-
tially by a radical mechanism.
A method has been developed to monitor the
photopolymerization of resins, based on the rigid-
body pendulum rheometer. Data obtained from a dif-
ferential photocalorimeter and from the rigid-body
pendulum rheometer were compared. The differen-
tial photocalorimeter data obtained with polyester
acrylates from a tetrafunctional polyester acrylate
and propoxylated neopentyl glycol diacrylate showed
329
Table 9.4 Polymerization Initiators for Casting
Initiator Remarks
Azobis-type catalysts [15]
2,2 -Azobis(isobutyronitrile) preferred
2,2 -Azobis(2,4-dimethylvaleronitrile) preferred
Diacylperoxide-type catalysts [15]
Lauroyl peroxide
Dibenzoyl peroxide
Bis(3,5,5-trimethylhexanoyl)peroxide preferred
Perester-type catalysts [23]
tert -Amylperoxy-2-ethylhexanoate
tert -Butylperoxy-2-ethylhexanoate
Percarbonate-type catalysts [15]
Bis(4-tert -Butylcyclohexyl)peroxydicarbonate preferred
UV curing catalysts [3]
2,2-Dimethoxy-2-phenylacetophenone
Benzophenone and
Methyldiethanolamine
Acylphosphine oxide [24]
only minimal variations. However, when a rigid-body
pendulum rheometer was used, differences in cur-
ing rate, crosslinking, and hardening processes were
readily observable [22].
9.4.1 Initiator Systems
Traditional radical polymerization initiators may be
used for the casting polymerization. Common cata-
lysts are shown in Table 9.4. Polymerization initiators
particularly suitable for the continuous sheet-forming
process are those having a decomposition tempera-
ture, at a half-life of 10 hours, in the range of 40 °C
to 80 °C.
9.4.2 Promoters
Special initiator systems for cold curing were de-
veloped. An effective initiator promoter system con-
sists of a zinc 2-ethylhexanoate solution, a cobalt 2-
ethylhexanoate, and as peroxide source tert-butylper-
oxybenzoate [25].
9.4.3 Two-Photon
Polymerization
The microfabrication by two-photon polymerization
has been investigated using resins based on thiol-ene
chemistry [26]. Resins containing different amounts
of a tetrafunctional acrylic monomer and a tetrafunc-
330
tional thiol molecule have been used to create com-
plex microstructures.
When microfabrication is carried out using higher
writing velocities, it produces stronger polymeric
microstructures. Also, the amount of shrinkage typi-
cally observed in the production of three-dimensional
microstructures is reduced. It has been confirmed
that the thiol-acrylate mixture in the resins pro-
motes the monomer conversion, thus inducing a
higher degree of the formation of a crosslinked net-
work [26].
9.5 Properties
Acrylic resins are appreciated for their exceptional
clarity and optical properties. Acrylics show a slow
burning behavior and can be formulated as self-
extinguishing.
Acrylic resins are excellent in transparency, trans-
lucency, surface gloss, and weather resistance and
further have a high surface hardness and a superior
design adaptability.
Therefore, they find a wide variety of applications
in interior materials for vehicles, exterior materials
for household electrical appliances and building ma-
terials (exterior) for example, regardless of whether
they are outdoor or indoor applications.
However, acrylic resins generally exhibit poor
flexibility and low impact resistance and, therefore,
pose a problem in that they are prone to fracture when
given an extraneous load or impact.
9.5.1 Electrical Properties
Acrylic resins are easily electrically charged by fric-
tion because of their high surface resistivity. Thus
they are deteriorated in appearance by adhesion of
rubbish or dust, or they bring about an undesir-
able situation by electrostatic electrification in parts
of electronic equipment. Antistatic properties to the
acrylic resin can be imparted by [27]:
• Kneading a surfactant with the acrylic resin, or ap-
plying a surfactant on the surface of the acrylic
resin,
• Kneading a vinyl copolymer having a poly(oxy-
ethylene) chain and a sulfonate, carboxylate or
quaternary ammonium salt structure, with an acry-
late resin,
Reactive Polymers: Fundamentals and Applications
• Kneading a polyether-ester amide with a methyl
methacrylate-butadiene-styrene copolymer,
• Adding a functional polyamide elastomer,
• Adding a polyamide-imide elastomer having a low
content of hard segments.
9.5.2 Hydrolytic and
Photochemical Stability
Methacrylate based polymers have a better hydrolytic
stability than the corresponding acrylate polymers.
They are much more stable than vinyl acetate poly-
mers.
Acrylic and methacrylic resins are not very sen-
sitive to ultraviolet radiation. However, ultraviolet
absorbers improve stability. Adding ultraviolet ab-
sorbers, e.g., to acrylic windows, also protects the
interior from UV radiation.
9.5.3 Recycling
PMMA depolymerizes nearly qualitatively (ca. 96%)
on pyrolysis into the monomer. This property is at-
tractive for thermal recycling of unmixed PMMA
wastes. The situation in the case of acrylates is dif-
ferent.
9.5.4 Pyrolysis
Chromatography
The determination of the chemical composition dis-
tribution of acrylic resins is not straightforward [28].
Pyrolysis-gas chromatography analysis of acrylic
resins can yield problems in the recovery of the hy-
droxyl and acid functional fragments that are form-
ing.
To overcome these problems, pyrolysis-liquid
chromatography can be used. The validation and
quantification of hydroxyl acrylate-, hydroxyl metha-
crylate-, hydroxyl propylacrylate-, and hydroxyl pro-
pylmethacrylate resins by pyrolysis-liquid chroma-
tography has been described.
Also, off-line size-exclusion chromatography cou-
pled to pyrolysis-liquid chromatography can be per-
formed to determine the chemical composition dis-
tribution over the molecular weight distribution of a
core-shell waterborne acrylic resin [28].
9: Acrylic Resins
9.6 Applications and Uses
Acrylic resins have been widely used as materials for
various parts of electronics products, household ap-
pliances, office automation appliances, etc. because
of their excellent transparency and stiffness [27].
They are used in the sanitary sector, as surrogate for
ordinary glass.
9.6.1 Acrylic Premixes
An acrylic resin composition can be used as raw ma-
terial for an acrylic premix for producing an acrylic
artificial marble. Acrylic artificial marbles are ob-
tained by blending an acrylic resin with inorganic
fillers such as aluminium hydroxide. They have an
excellent appearance, soft feeling, and weatherabil-
ity and are widely used for kitchen counters, lavatory
dressing tables, waterproof pans, etc.
Artificial marbles are generally produced by fill-
ing a slurry mold. This mold is obtained by dispers-
ing inorganic fillers in an acrylic syrup. The filled
slurry must be cured at relatively low temperature.
The acrylic syrup has a comparatively low boiling
temperature. Consequently a long time is required for
molding which causes low productivity. To overcome
these drawbacks, the acrylic syrup can be blended
with a crosslinked resin powder having a specific de-
gree of swelling.
On the other hand, an acrylic premix for an arti-
ficial marble, with excellent low shrinking properties
has been prepared by blending the acrylic syrup with
a thermoplastic acrylic resin powder, which is poorly
soluble in the syrup. The acrylic syrup consists es-
sentially of methyl methacrylate or a (meth)acrylic
monomer mixture and PMMA or an acrylic copoly-
mer.
To impart strength, solvent resistance, and di-
mension stability to a molded article, instead of
pure methyl methacrylate monomer, a polyfunctional
(meth)acrylic monomer may be added. It is prefer-
able to replace the methyl methacrylate monomer by
neopentyl glycol dimethacrylate up to 50%, since the
molded article then has a remarkably excellent sur-
face gloss [29].
The acrylic syrup may be obtained by dissolving
the component acrylic polymer in the monomer, or
a syrup can be obtained by partial polymerization of
the component in the monomer.
To the premix curing agents, such as dibenzoyl
peroxide, lauroyl peroxide, tert-butyl hydroperox-
331
ide, cyclohexanone peroxide, methylethylketone per-
oxide, tert-butylperoxyoctoate, tert-butylperoxyben-
zoate, dicumyl peroxide, 1,1-bis(tert-butylperoxy)-
3,3,5-trimethylcyclohexane, 2,2 -azobis(isobutyroni-
trile), are added. The filler then is added and heat
and pressure curing takes place for 10 minutes un-
der conditions of a mold temperature of 130 °C and a
pressure of 100 kg/cm2 to obtain an acrylic artificial
marble with a thickness of 10 mm.
9.6.2 Epoxy Acrylates
An epoxy acrylate resin precursor was synthesized
and used with different multifunctional acrylate mono-
mers, i.e., trimethylol propane triacrylate, tripropy-
lene glycol diacrylate, 1,6-hexanediol diacrylate [30].
The viscosity of the prepared formulations de-
creases with increasing amounts of 1,6-hexanediol
diacrylate and tripropylene glycol diacrylate. Nearly
all of the components in the formulation show a sig-
nificant effect on the mar resistance of the cured
films.
Blends of epoxy acrylate resins with ethoxylated
phenol acrylate, tripropylene glycol diacrylate, and
trimethylol propane triacrylate have been cured by
UV light using the photoinitiator Darocure® 1173
[31]. From these compounds in the form of films the
kinetics of thermal degradation reactions were stud-
ied with TGA in inert atmosphere. It was found that
the films are degrading in two steps. The samples
with the monofunctional and trifunctional monomers
show better properties than the samples with the di-
functional monomer [32].
In epoxy acrylate films that are filled with nano-
particles from alumina modified with tripropylene
glycol diacrylate the self-healing property of the
films is improved. The hardness of the samples with
nanoparticles was found to be less than that of the
samples without any nanoparticles. Also, the gloss of
films with the nanoparticles remains high [33].
Low-shrinkage high-strength dental restorative
materials were prepared from epoxy acrylates that
were modified with urethane acrylates [34]. Silica
nanoparticles modified with 3-trimethoxysilylpropyl-
methacrylate were used as a reinforcing filler.
Curing can be done with visible light. The poly-
mer composites exhibit a greatly reduced degree of
shrinkage and better mechanical and physical proper-
ties in comparison to conventional bisphenol A gly-
332
Table 9.5 Momomers for Poly(urethane) Acrylate Resins [36]
Type Components
Polyester polyol Ethylene glycol, adipic acid, 1,6-hexanediol
Isocyanate Isophorone diisocyanate
Acrylate 2-Hydroxyethyl methacrylate
Diluents Ethoxylated phenol monoacrylate, 1,6-hexanediol diacrylate, dipropylene glycol diacrylate,
trimethylol propane triacrylate, propoxylated trimethylol propane triacrylate, pentaerythrol
triacrylate
cidyl dimethacrylate based dental restorative materi-
als [34].
9.6.3 Urethane Acrylates
The effect of UV curable urethane acrylate resin
treatments on the surface properties of softwood was
investigated. An oligomer derived from 2-hydrox-
yethyl methacrylate and toluene diisocyanate could
be easily applied to the woods. The surface hardness
and moisture excluding efficiency of treated woods
were markedly enhanced. An increased dimensional
stability could be achieved [35].
Environmental friendly UV curable poly(urethane)
acrylate resins for coating of metal surfaces have
been developed [36]. The components are listed in
Table 9.5.
Different formulations were developed using var-
ious reactive diluents as given in Table 9.5. These
samples were cured under UV radiation. The poly-
(urethane acrylate)s have a good performance as pro-
tective coatings.
The reactive diluents effect a significant enhance-
ment of the properties. Owing to different functional-
ity of reactive diluents highly crosslinked structures
can be formed which lead to excellent mechanical
and chemical properties. Best results were obtained
with pentaerythrol triacrylate as reactive diluent [36].
In the photo-aging reactions of an aliphatic poly-
(urethane) acrylate resin two stages were found. In
the first stage a crosslinking of the unreacted acry-
late moieties is formed. Also oxidation reactions
occur. In the second stage, the oxidation rate de-
creases and products of photodegradation are formed
at a constant rate. A heterogeneous distribution of
the residual acrylate units occurs across the coating
films [37].
Reactive Polymers: Fundamentals and Applications
9.6.4 High-Performance
Biocomposite
An environmentally friendly acrylic resin has been
examined with respect to a high-performance bio-
composite. Parameters such as the onset of cur-
ing reaction, the degree of cure at certain temper-
atures, and the swelling equilibrium data were an-
alyzed. The crosslinking density after curing the
resin at 180 °C for 10 min indicates the comple-
tion of curing to a major extent under those condi-
tions [38].
9.6.5 Solid Polymer
Electrolytes
In conventional batteries with electrolytic solutions,
the possible leakage of the electrolyte solution or elu-
tion of the electrode substance outside the battery
presents a problem in long-term reliability. Batter-
ies and electric double layer capacitors using a solid
polymer electrolyte are free of these problems. Also,
these can be easily reduced in thickness.
For installing a solid polymer electrolyte into a
battery or electric double layer capacitor, a method
of using an electrolyte and a trifunctional methacrylic
compound as the main components for the solid poly-
mer electrolyte has been developed. The monomer
for the solid polymer electrolyte is prepared from 2-
isocyanatoethyl methacrylate and a branched oligo
glycol. Such a glycol can be prepared by the etheri-
fication of glycerol, ethylene glycol, and propylene
glycol. The isocyanate group adds with the pen-
dent hydroxyl groups resulting in a trifunctional
methacrylate ester [10]. The synthesis is shown in
Figure 9.6. Also, a mixture of poly(ethylene gly-
col)dimethacrylate and methoxypoly(ethylene gly-
9: Acrylic Resins 333

9.7 Special Formulations

9.7.1 Coatings
9.7.1.1 Hybrid Coatings
Hybrid coating materials have been synthesized us-
ing an acrylate end capped polyester, 1,6-hexanediol
diacrylate, tetraethoxysilane, and 3-trimethoxysilyl-
propylmethacrylate [40]. The hybrid materials were
cast onto a poly(carbonate) (PC) substrate and cured
by UV light. In this way, a hybrid film with covalent
linkages between the inorganic and the organic net-
works is formed.
The pencil hardness of these materials is higher
than 1H, whereas that of an uncoated PC substrate
is 6B. The hardness enhancement after coating may
due to the incorporation of the acrylate resin.
The oxygen permeability coefficients of the film
coated with the hybrid material on a 3-aminopropyl-
triethoxysilane treated PC substrate is 1.67 × 10−3
GPU, whereas that of uncoated the PC substrate is
8.07 × 10−3 GPU.
The low oxygen permeation rates have been ex-
plained by the good adhesion between the hybrid
coating layer and the PC substrate and a dense struc-
ture induced by an increase of the network den-
Figure 9.6 Synthesis of a methacrylate monomer for sity [40].
a solid electrolyte [10]. Poly(zinc acrylate) resins can be prepared by the
reaction of poly(acrylic acid) and zinc oxide. An alu-
minum paint based on such a resin was found to sus-
col) mono methacrylate can serve as a monomer for tain the temperature up to 800 °C. These coatings also
solid polyelectrolyte polymers [39]. exhibit an excellent solvent resistance, scratch hard-
It is desirable for a three-dimensional network ness, and a drying time within 10 min [41].
structure to be formed. The polymerization is initi-
ated by conventional peroxides or azo compounds. 9.7.1.2 Cationic Acrylic Resins
The whole formulation for a battery consists of: Cationic acrylic resins have been described [42].
1. Methacrylic monomer, These resins are based on copolymers made from
esters of acrylic or methacrylic acids having sec-
2. Polymerization initiator, ondary or tertiary amino groups, monoesters of dihy-
dric alcohols and acrylic or methacrylic acids, esters
3. Polymerization retarder, of monohydric alcohols and acrylic or methacrylic
acids, and, optionally, further vinyl monomers such
4. Electrolyte salt, as styrene.
Acrylic-based coating compositions that have
5. Organic solvent, and good light and UV resistance even without addition
of UV absorbers, and also impart the notable good
6. Inorganic particles. corrosion resistance known from epoxy resins to sub-
strates made of base metals, have been developed.
The process for manufacturing a complete battery is It was found that the chain extension of acrylic
described in detail elsewhere [10]. resins by reacting amino-functional acrylic copoly-
334
mers with multifunctional epoxy compounds, or
epoxide-functional acrylic resins with multifunc-
tional amines, leads to high molar mass resins that
form films even without the addition of crosslink-
ing agents. These materials can be used to prepare
coatings that impart good corrosion resistance and
low propensity to degradation upon irradiation with
light [43]. The method of preparation has been de-
tailed [43].
9.7.1.3 Miniemulsion Polymerization
Waterborne acrylic resins with a solid content higher
than 40% were obtained by the miniemulsion poly-
merization of methyl methacrylate, butyl acrylate,
and acrylic acid [44]. A hydrocarbon coumarone-
indene resin was used as osmotic agent.
Hydrocarbon coumarone-indene resins are cheap
polymers widely used for coatings and pressure-
sensitive adhesives. The resin leads to a higher hy-
drophobicity for the acrylic latex film and acts as
osmotic agent in miniemulsion polymerization thus
preventing Ostwald ripening. Ostwald ripening oc-
curs in solid solutions or liquid sols and describes
the change of an inhomogeneous structure over time,
i.e., small crystals or sol particles dissolve, and rede-
posit onto larger crystals or sol particles [45]. Latexes
are obtained with particle sizes, size distributions,
and stability comparable to those obtained using n-
hexadecane as osmotic agent.
However, the monomer conversion and molecu-
lar weight were found to be lower. This indicates
the occurrence of a chain-transfer reaction. A faster
film hardness development was achieved with the hy-
drocarbon coumarone-indene resin in comparison to
n-hexadecane [44].
9.7.1.4 Silane and Siloxane Acrylate
Resins
Weather-resistant resin coatings can be prepared by
an addition polymerization reaction of n-butyl acry-
late, methyl methacrylate, n-butyl methacrylate, and
MPTS. The weather-resistant silicone/acrylic resin
coatings are then blended with TiO2 . The viscosity of
the resin decreases with increasing content of MPTS,
whereas the thermal stability at high temperature in-
creases [46,47,5]. Coatings with 30% MPTS have es-
pecially good weather-resistant properties.
Reactive Polymers: Fundamentals and Applications
UV curable formulations for UV-transparent opti-
cal fiber coatings have been developed. Poly(dimethyl
siloxane-acrylate) resins showed the best perfor-
mance with respect to the monomer reactivity and
the UV-transparency of the polymer coating. An
acylphosphine oxide proved to be the best suited be-
cause of its high reactivity, fast photolysis, and lack
of absorbing of the byproducts of photo curing at the
wavelength of operation [24].
9.7.1.5 Acrylic Grafted Polyether Resins
Coating compositions have been prepared from an
acrylic grafted polyether resin [48]. Here the smallest
difunctional hydroxyl phenyl segment used to form
the acrylic grafted polyether resin has a molecular
weight greater than about 500 Da. The smallest di-
functional hydroxyl phenyl segment used to form
the acrylic grafted polyether resin does not com-
prise two or more non-impaired hydroxyl groups at-
tached to two or more different five-membered or
six-membered carbon atom rings in a segment with
a molecular weight less than about 500 Da.
The acrylic grafted polyether resin can be pre-
pared by reacting a dihydroxyl compound or a di-
amine compound with a phenol stearic acid com-
pound to produce a diphenol, then by reacting the
diphenol with a diglycidyl ether compound to form a
polyether resin, and mixing the polyether resin with
an ethylenically unsaturated monomer component in
the presence of an initiator to form the acrylic grafted
polyether resin [48].
9.7.1.6 Electronic Devices
In semiconductor devices including a ferroelectric
film or a dielectric film with a high dielectric con-
stant, a surface coating has been proposed. This coat-
ing is made of an acrylic resin which prevents the
degradation of the polarization properties of the fer-
roelectric or a film with a high dielectric constant,
respectively, on the semiconductor device [49].
9.7.1.7 Corrosion Protection
Poly(aniline) (PANI) can be synthesized by a chemi-
cal oxidative polymerization reaction using methane-
sulfonic acid as dopant and ammonium peroxodisul-
fate as oxidizer [50]. PANI was dispersed in a
polyester acrylate resin and used as coating on gal-
vanized steel when cured by UV light.
9: Acrylic Resins
Electrochemical studies show a long-term active
anodic ennoblement due to the presence of PANI.
The mechanism of action in corrosion protection by
PANI can be traced back a redox action that effects a
healing process.
9.7.1.8 Carbon Fibers
Different oxidation surface treatments for carbon
fibers were checked with respect to the interfacial
adhesion with an acrylate resin [51]. The resin was
cured by an electron beam. The 90° flexural strength
of unidirectional composites was measured in order
to assess the interfacial adhesion. Low values were
obtained, which could be explained by the creation
of a weak interphase.
However, after a post curing procedure a dramatic
improvement of the flexural strength occurred. It is
suspected that the formation of the interphase could
be the origin of the low transverse mechanical prop-
erties of the electron beam cured composites.
9.7.1.9 Conservation of Marble
Marble and stone used as building materials are sus-
ceptible to environmental damage. Acrylic resins can
be used as carriers of suitable pigments for the pro-
tection of the surface of a monument. Copolymers
of ethyl methacrylate and methyl acrylate have been
extensively applied as a protective agent for stone
building materials since the 1950s.
The photodegradation of acrylic resins contain-
ing titanium dioxide pigments has been studied under
UV irradiation. Two kinds of TiO2 , anatase and a
mixture of anatase and rutile, were used in different
concentrations. The changes caused by the irradia-
tion treatment were monitored by Fourier transform
infrared spectroscopy, gel permeation chromatogra-
phy, and solubility measurements. The presence of
anatase pigment significantly improved the photosta-
bility [52]. Films of acrylic resins of varying compo-
sitions were applied both on a dolomitic white marble
support and on potassium bromide disks and exposed
to UV light. The main degradation pathway under ul-
traviolet irradiation is the chain scission. The rates of
photodegradation may be related to the type of ester
group and to the presence of the α-methyl group in
the main chain [53].
Blends of acrylic resins and fluoroelastomer are
also suitable materials in stone protection. Films of
335
a copolymer of ethyl methacrylate and methyl acry-
late blended with a copolymer of vinylidene fluoride
and hexafluoropropene were investigated by means
of FT-IR spectroscopy and FT-IR microspectroscopy
before and after UV and thermal treatments. A high
content of fluoroelastomer increases the stability of
these blends. A solution of a blend described above
in tetrahydrofuran was successfully applied to a mar-
ble surface of the Saint Maria Cathedral in Lucca,
Toscana [54].
Degradation by Lipase. Layers of an aged acrylic
resin, a fifteenth-century tempera painting on panel
and a nineteenth-century oil painting on canvas have
been removed by the action of lipases. Lipases
are hydrolytic enzymes that act on glycerol ester
bonds. These enzymes are a less aggressive alter-
native to highly polar organic solvents or alkaline
mixtures [55].
9.7.1.10 Thermotropic Coatings
Relationships between the scattering domain parame-
ters and the light-shielding properties of thermotropic
systems with fixed domains have been established
[56,57]. Thermotropic layers were formulated with
an acrylic resin.
By spectroscopic techniques the solar optical
properties, the switching temperature, the switching
process, and the residual transmittance in the opaque
state were assessed.
The hemispheric solar transmittance values are
80–87% in the clear and 75 to 85% in the scattering
state. The diffuse solar transmittance values increase
significantly from 14 to 40% below the switching
temperature to 36 to 70% at elevated temperatures.
The thermotropic resins exhibit a steep and rapid
switching process with switching temperatures be-
tween 45 °C and 70 °C.
Additives with a short chain length and roughly
spherical particles with dimensions between 0.5
and 3 µm show a significant increase in diffuse
solar transmittance above the switching threshold.
Additive types with long-chain molecules develop
anisotropic scattering domains resembling distorted
disks with a diameter up to 50 µm and a thickness
of 100–400 nm. Disk-like scattering features yield
enhanced light-shielding properties [57].
336
9.7.2 Tackifier Resins
Acrylic resins are suitable as tackifier resins in
pressure-sensitive adhesive applications. They can be
prepared by free-radical polymerization. The acrylic
tackifier is then blended with a natural rubber base
in various ratios. Investigation of the mechanical
properties showed that blends with a good pressure-
sensitive adhesive performance have a higher loss of
tangent-δ at higher frequencies [58].
9.7.3 Concrete
Concrete carbonation is an important factor that af-
fects reinforced concrete durability [59]. One of the
major consequences of this phenomenon is the initia-
tion of reinforcement corrosion. Reinforcement loses
their protections initially protected by the basic envi-
ronment nature of concrete. The migration of carbon
dioxide takes place in the concrete through the gas
phase when the concrete is not completely saturated
and through the liquid phase in the form of carbonate
ions.
The effect of acrylic resin and epoxy resin coat-
ings on the durability of the concrete subjected to
accelerated carbonation was investigated. The main
issue was to minimize the carbonation depth in con-
crete elements in order to increase the service life of
reinforced concrete structures. The results of these
experiments showed a beneficial contribution of the
epoxy resin coating in decreasing the carbonation
depth in comparison to the acrylic coating [59].
9.7.4 Ionomers
Compositions from ionomers and imidized acrylic
resins have been described [60]. The imidized acrylic
resin can be obtained by treating an acrylic polymer
with ammonia or a monoalkyl amine. The primary
amine preferably employed in the imidization step is
methylamine, but higher aliphatic amines can also be
employed. The imidized acrylic resin has a degree of
imidization of 20–100%.
Articles prepared from these compositions ex-
hibit improved heat resistance properties, such as in-
creased Vicat temperature, increased stiffness/modu-
lus at room temperature, and elevated temperatures
below the melting point of the ionomer, and an in-
creased upper use temperature at a given stiffness
over those of the ionomers alone. The Vicat tempera-
ture is determined according to ASTM D1525 [61].
Reactive Polymers: Fundamentals and Applications
9.7.5 Porous Superabsorbent
Resins
A system composed of a surfactant and a foam sta-
bilizer has been used in preparing porous superab-
sorbent resins of poly(sodium acrylic acid), which
is obtained by free-radical solution polymerization
of partially neutralized acrylic acid with mechanical
agitation of eggbeater [62]. Different types of surfac-
tant, including anionic surfactant sodium n-dodecyl
benzene sulfate, cationic surfactant cetyltrimethyl
ammonium bromide, and nonionic surfactant alkyl-
phenols poly(oxyethylene), are used as blowing agent
to produce pores by mechanical agitation, and tri-
ethanolamine is used as foam stabilizer.
A synergistic effect of sodium n-dodecyl benzene
sulfate with triethanolamine has been found and the
packing density is decreased, which could be proved
by the clearly porous morphology. Also, the water
absorbing capacity of superabsorbent resins is en-
hanced. As a result, such a method can get poly(so-
dium acrylic acid) superabsorbent resins without the
use of any organic solvents. This method provides
an environmentally beneficial way to prepare super-
absorbent resins for hygiene and biomedical prod-
ucts [62].
9.7.6 Drug Release Membranes
The feasibility of a transdermal delivery system
(TDS) for 17-β-estradiol was investigated by in vitro
release studies. Unilaminate adhesive devices capa-
ble of releasing 17-β-estradiol in a controlled fashion
over a period up to 216 hours have been developed
using acrylic resins. The release of drug from the ad-
hesive devices seems to obey a zero-order kinetics.
Acetyltributyl citrate, triethyl citrate, propylene
glycol and myristic acid are plasticizers that can mod-
ify the release patterns of the drug. The study demon-
strated that the acrylic resins are suitable polymers
for the preparation of 17-β-estradiol TDS adhesive
devices [63].
9.7.7 Support Materials for
Catalysts
Palladium-tin catalysts can be deposited on acrylic
resins bearing carboxylic functional groups. The
resins act as support materials for the catalysts. The
catalysts are suitable for the selective hydrogenation
9: Acrylic Resins
of 100 ppm aqueous nitrate solutions. The materials
exhibit different Sn contents and show different re-
duction temperatures.
A high COOH content in the support is important
in the control of the selectivity of the catalysts limit-
ing ammonia formation [64].
Copper ion catalysts can be immobilized on
acrylic resins (rather than acrylonitrile resins) with
aminoguanidyl groups. They are prepared by mod-
ification of the nitrile groups in an acrylonitrile,
vinyl acetate, and divinylbenzene terpolymer using
aminoguanidine carbonate.
The catalysts act on the oxidation of HQ to p-ben-
zoquinone with hydrogen peroxide as oxidant. The
catalytic activity and selectivity in the Cu(II)-resin
system increases in comparison to the reaction with-
out a catalyst and the reaction with native Cu(II)
ions [65].
9.7.8 Electron Microscopy
Acrylic resins can be used for low-temperature em-
bedding of samples in electron microscopy [66].
9.7.9 Stereolithography
Three-dimensional objects can be built without the
use of molds by stereolithography. The objects are
obtained layer by layer by polymerizing a low-
viscosity liquid resin under a laser beam. The kinetic
behavior of the resin is essential for a complete cur-
ing which occurs in the small zone exposed to laser
irradiation.
The isothermal kinetic behavior of a commercial
acrylic resin for stereolithography has been analyzed
by differential photocalorimetric analysis. A kinetic
model accounting for the effect of auto-acceleration,
the vitrification, and light intensity has been set
up [67].
9.7.10 Electronic Applications
An acrylate resin has been investigated as a passi-
vation layer for thin-film transistor arrays. In com-
parison to a conventional nitride film, the acrylate
resin-based passivation layer exhibits a flat surface
and a low dielectric constant. The high transmit-
tance and good planarization characteristics of the
acrylate resin film enhance the brightness and aper-
337
ture ratio of thin-film transistors liquid crystal dis-
plays [68].
9.7.11 Magnetic Applications
Paramagnetic crosslinked ethoxylate acrylate resin
supports can be prepared by the entrapment of mag-
netite particles in the course of suspension polymer-
ization of allylamine, trimethylol propane ethoxylate
triacrylate, and trimethylol propane trimethacrylate.
The magnetic beads can be used as support in solid-
phase peptide synthesis. Throughout the synthesis
steps of the peptide the beads are stable and their
magnetic properties are conserved [69].
Nickel plating graphite nanosheets can be pre-
pared by electroless plating method using graphite
nanosheets [70]. These are used in polymer magnetic
composites based on acrylate pressure-sensitive ad-
hesives. The composites are fabricated by a solution
blend method.
The composites were characterized by scanning
electron microscopy and other microscopic meth-
ods. The measurements show that the nanosheets
are homogeneously dispersed in the acrylate resin
and a relatively uniform and compact Ni coating is
formed [70].
9.7.12 Nanocomposites
Nanocomposites can be used to improve the prop-
erties of the cured formulations significantly. In Ta-
ble 9.6 the usage of such compositions is summa-
rized.
Highly transparent photo curable bisphenol A
epoxy polyacrylate/silica nanocomposites have been
prepared by a sol–gel process. The composites are ap-
plicable to the direct encapsulation of organic light-
emitting devices [74].
Nanocomposite coatings for wood flooring have
been prepared from acrylate resins. The nanoparticles
are added to the neat acrylate formulation that con-
tains in addition a defoaming agent and a photoinitia-
tor. Zirconia nanoparticles tend to decrease the curing
reaction. However, alumina nanoparticles do not af-
fect the curing [75].
To improve the surface hardness of acrylate coat-
ings, both silica nanoparticles and alumina micro-
particles have been added to acrylate formulations
[76]. Regular mixing of the nanoparticles into acry-
late formulations, however, leads to highly viscous
338 Reactive Polymers: Fundamentals and Applications

Table 9.6 Acrylate Resins with Nanocomposites

Compostion Usage Reference

SiO2 , epoxy, acrylate Coatings [71]
Ag, acrylate Nano imprint lithography [72]
CaCO3 , acrylate Toughening for PVC [73]
SiO2 , bisphenol A, epoxy, acrylate Light emitting diodes [74]
SiO2 , epoxy, acrylate Coatings [71]
ZrO2 , acrylate Wood flooring [75]
Al2 O3 , SiO2 , acrylate Coatings [76]
TiO2 , ZrO2 , thiol-acrylate Surface treatment [77]
Ag, acrylate Conductive filler [78]
SiO2 , urethane, acrylate Coatings [79]
SiO2 , acrylate Coatings [80,81]
ZnO, acrylate pH buffering [82]

solutions that are inappropriate for coating formula-
tions.
This incompatibility can be avoided by a surface
modification of nanoparticles using trialkoxysilanes,
such as 3-methacryloxypropyl-trimethoxysilane and
vinyltrimethoxysilane. These compounds may be
crosslinked with the acrylate resin in the course of
curing. The cured composites exhibited a significant
improvement of the abrasion resistance [76].
Silver plating graphite nanosheets can be used to
obtain a conductive filler with a high electrical con-
ductivity. The conductive filler can be prepared by
electroless plating using graphite nanosheets from
expanded graphite. As a binder, an acrylate resin is
used [78].
By the process of surface functionalization with
both nanofluid inducing surface groups and with re-
active acrylate surface groups solvent-free nanofluids
can be fabricated. These can be incorporated in re-
active coatings, films, and bulk materials and com-
posites. The nanofluid particles exhibit a surface ac-
tivity at the air/polymer interface similar to interfa-
cial nanoparticles in Pickering emulsions. This sur-
face activity, along with the intrinsic softness of the
nanofluid particles, could be used to provide an in-
trinsic lubrication for polymeric surfaces that are ex-
posed to frictional shear [83].
Chemical etching with concentrated sulfuric acid
and potassium dichromate was used to prepare acrylic
resin microsphere surfaces for high adhesion proper-
ties [84].
The influence of etching time and temperature on
the surface morphology of electroless nickel plated
acrylic resin microsphere was investigated. The op-
timal etching process conditions were identified as
follows: Etching temperature of 70 °C and an etching
time of 60–90 min.
9.7.13 Waste Water Treatment
A resin containing acrylic acid and 1,7-octadiene was
synthesized in beaded form by a two-step process
[85]: Suspension polymerization of ethylacrylate and
1,7-octadiene monomers, followed by hydrolysis us-
ing either 98% H2 SO4 or 10 M NaOH.
Acrylic acid and divinylbenzene containing resins
were also synthesized by the same process for the
purpose of comparing a rigid divinylbenzene with
a flexible 1,7-octadiene crosslinking agent in the
acrylic acid resins.
The swelling of the resins in distilled water shows
that replacing divinylbenzenes with 1,7-octadiene
makes the resin to achieve a greater swelling in a
significantly shorter time. 1,7-Octadiene also shows
an increase in crosslinking of 20% compared to 4%
in the case of divinylbenzene, without compromising
the loading rates of toxic heavy metal ions such as
Pb2+ , Cu2+ , and Cr3+ from water samples. Thus, the
acrylic acid 1,7-octadine resin was found to be useful
for the removal of the toxic heavy metal ions from
waste water samples [85].
9.7.14 Laminated Films
Laminated films of acrylic resins are constituted of
a soft layer formed of an acrylic resin with rubber
particles incorporated and a hard layer also formed
of an acrylic resin.
By incorporating rubber particles into an acrylic
resin, the flexibility is improved while all other pos-
9: Acrylic Resins
itive properties, such as transparency and surface
gloss, are maintained. To have a hard outer surface
two films, one of them filled with rubber particles and
one being unfilled, are combined.
The laminated film is excellent in surface hard-
ness, flexibility, and ability to prevent whitening from
occurring during molding or forming and hence is
suitable for use as a surface material for moldings,
such as interior materials for vehicles, exterior mate-
rials for household electrical appliances, and building
materials (exterior), which are obtained by a molding
or forming process requiring bending or stretching
[14].
9.7.15 Ink-Jet Printing Media
An ink-jet printing system is one wherein ink droplets
are jetted onto a surface of a printing medium and
attached thereon.
Therefore, the surface of the printing medium
needs to rapidly absorb the jetted ink droplets. The
printing media for use in the ink-jet printing system
are not limited to paper but include various materi-
als such as transparent resin films for overhead films
and metals. Some of these printing media have no hy-
drophilic surfaces. Therefore, in order to clearly print
information, an ink-receiving layer needs to be pro-
vided on the surface of a substrate constituting the
printing medium. The ink-jet printing media are re-
quired to have the following characteristics:
• Permeation of ink inside the ink-receiving layer
must be rapidly made, color running should not
take place, and clear color having high chromatic-
ity can be reproduced.
• In the multi-color printing using a combination
of ink components, each ink component must be
rapidly absorbed even if ink dots are superposed
on the same surface of the printing medium, and in
the high-speed printing, the printed surface must
be free from staining, and the ink absorption rate
and the ink absorption quantity both must be sat-
isfactory.
• The printing medium must have water resistance,
and even if the printed image is contacted by wa-
ter, running or bleeding of ink of the image must
not take place.
• Even if the ink-jet printing media are stored in the
superposed state, they must be free from blocking.
339
• Even if the printed matter is stored for a long pe-
riod of time, color fading should not take place.
Proposals for forming an ink-receiving layer con-
taining hydrophilic resins include [86]:
• Starch and other water-soluble cellulose deriva-
tives,
• Poly(vinyl alcohol), modified poly(vinyl alcohol),
• Poly(vinyl pyrrolidone),
• Poly(vinyl acetal), and
• Hydrophilic acrylic copolymer having a cross-
linked structure on the substrate surface.
A hydrophilic acrylic copolymer having a cross-
linked structure consists of acrylamide, methacry-
lamide and other amides, acrylic acid and acrylic
esters, such as glycidyl acrylate and the correspond-
ing methacrylate derivatives, respectively. Examples
of crosslinking agents include divinylbenzene, ethy-
lene glycol acrylate, and triethylene glycol diacrylate.
A suitable polymerization initiator is 2,2 -azobis(2 -
amidinopropane)hydrochloride or dibenzoyl perox-
ide in toluene. The polymerization is carried out
in aqueous isopropyl alcohol and poly(oxyethylene)
nonylphenyl ether [86]. The copolymer was isolated
and a dispersion was prepared that was applied on
wood-free paper and poly(ethylene terephthalate).
References
[1] J.W. Nemec, W. Bauer, Acrylic and methacrylic
ester polymers, in: J.I. Kroschwitz (Ed.), Ency-
clopedia of Polymer Science and Engineering,
vol. 1, 2nd edition, John Wiley & Sons, Inc.,
New York, 1985, pp. 211–234.
[2] H.W. Coover Jr., J.M. McIntire, Acrylic and
methacrylic ester polymers, in: J.I. Kroschwitz
(Ed.), Encyclopedia of Polymer Science and En-
gineering, vol. 1, 2nd edition, John Wiley &
Sons, Inc., New York, 1985, pp. 234–305.
[3] S. Yin, A. Merlin, A. Pizzi, X. Deglise, B.
George, M. Sylla, Structure-property relation-
ship and influences of phenolic compounds on
the mechanical and thermomechanical proper-
ties of UV-cured acrylic resin networks, J. Appl.
Polym. Sci. 92 (6) (2004) 3499–3507.
[4] F. Xie, Z.H. Liu, D.Q. Wei, Curing kinetics and
properties of acrylic resin cured with aziridine
340
crosslinker, Chin. J. Polym. Sci. 20 (1) (2002)
65–70.
[5] H.S. Park, D.J. Chung, H.S. Hahm, S.K. Kim,
W.B. Im, S.J. Kim, Preparation and physical
properties of weather resistant silicone/acrylic
resin coatings, J. Chem. Eng. Jpn. 37 (2) (2004)
158–165.
[6] H. Nomura, Y. Kimata, H. Kanai, Y. Yokota,
M. Yoshida, Weatherability of Hals copolymer-
ized acrylic resin precoated steel sheet, Tetsu
To Hagane-J, Iron Steel Inst. Jpn. 89 (1) (2003)
128–134.
[7] K. Nakamura, Y. Yokota, K. Takahashi,
M. Yoshida, Cyclohexylalkyl (meth) acrylate
ester-based resin composition. US Patent
6 686 413, assigned to Nippon Shokubai Co.,
Ltd., Osaka, JP, Feb. 3, 2004.
[8] S. Urano, R. Mizuguchi, N. Tsuboniwa,
K. Aoki, Y. Suzuki, T. Itoh, Carbamate phys-
ical property-improving reagent. US Patent
4 935 413, assigned to Nippon Paint Co., Ltd.,
Osaka, JP, Jun. 19, 1990.
[9] E. Yamanaka, N. Tsuboniwa, T. Morimoto,
M. Furukawa, S. Urano, Production of un-
saturated carbamic acid derivative. US Patent
5 606 096, assigned to Nippon Paint Co., Ltd.,
Osaka, JP, Feb. 25, 1997.
[10] M. Takeuchi, S. Naijo, Thermopolymerizable
composition for battery use. US Patent 6
562 513, assigned to Showa Denki Kabushiki
Kaisha, Tokyo, JP, May 13, 2003.
[11] M. Xiao, Z. Li, J. Nie, Synthesis and photopoly-
merization of 2-(acryloyloxy)ethyl piperidine-1-
carboxylate and 2-(acryloyloxy)ethyl morpholo-
ne-4-carboxylate, J. Appl. Polym. Sci. 119 (4)
(2011) 1978–1985.
[12] L. Chen, H. Shi, H. Wu, J. Xiang, Preparation
and characterization of a novel fluorinated acry-
late resin, J. Fluorine Chem. 131 (6) (2010) 731–
737.
[13] B.W.L. Jang, M.R. Gogate, J.J. Spivey, J.R.
Zoeller, R.D. Colberg, G.N. Choi, Synthesis of
Methyl Methacrylate from Coal-derived Syn-
gas, US Department of Energy Reports, Fischer
Tropsch Archive 94065/20, Research Triangle
Institute, Research Triangle Park, NC, 1999.
Reactive Polymers: Fundamentals and Applications
[14] K. Koyama, Y. Tadokoro, Acrylic resin lam-
inated film and laminated molding using the
same. US Patent 6 692 821, assigned to Sum-
itomo Chemical Company, Limited, Osaka, JP,
Feb. 17, 2004.
[15] S. Tayama, N. Kusakawa, Flame resistant
acrylic resin composition and process for its pro-
duction. US Patent 4 533 689, assigned to Mit-
subishi Rayon Company, Limited, Tokyo, JP,
Aug. 6, 1985.
[16] H. Changs, Z.-H. Kuo, K.-C. Tsai, T.-L.
Chen, Analysis on properties of water-based
fire-retardant nano-coatings, Adv. Mater. Res.
(Durnten-Zurich, Switzerland) 311–313 (3)
(2011) 1985–1992.
[17] W. Xing, G. Jie, L. Song, X. Wang, X. Lv, Y.
Hu, Flame retardancy and thermal properties of
epoxy acrylate resin/alpha-zirconium phosphate
nanocomposites used for UV-curing flame retar-
dant films, Mater. Chem. Phys. 125 (1–2) (2011)
196–201.
[18] F. Sawaragi, H. Sonezaki, Abrasion-resistant
coating composition for acrylic resin molded ar-
ticle. US Patent 6 177 138, assigned to Nippon
ARC Co., Ltd., Chiba, JP, Jan. 23, 2001.
[19] R. Kozlowski, M.A. Hassan, B. Obidzinski,
A.B. Shehata, M. Amer, Newly modified MMT
and its application with intumescent additives
as new flame retardant system for polyurethane
polymer, Polym.-Plast. Technol. Eng. 47 (9)
(2008) 902–909.
[20] Underwriter Laboratories, UL 94: Tests for
Flammability of Plastic Materials for Parts in
Devices and Appliance, 1st edition, Under-
writers Laboratories, Inc., 333 Pfingsten Road,
Northbrook, IL, 2000.
[21] X. Chen, L. Song, Y. Hu, Flammability and
thermal degradation of epoxy acrylate modi-
fied with phosphorus-containing compounds, J.
Appl. Polym. Sci. 115 (6) (2010) 3332–3338.
[22] H.-T. Chiu, M.-F. Cheng, Superior real time
method to evaluate photo-curing resin by means
of rigid-body pendulum rheometer, J. Appl.
Polym. Sci. 101 (5) (2006) 3402–3407.
[23] C.D. Diakoumakos, Q. Xu, F.N. Jones, J. Bagh-
dachi, L.M. Wu, Synthesis of acrylic resins
9: Acrylic Resins
for high-solids coatings by solution and separa-
tion polymerization, J. Coat. Technol. 72 (908)
(2000) 61–70.
[24] F. Masson, C. Decker, S. Andre, X. Andrieu,
UV-curable formulations for UV-transparent
optical fiber coatings I. Acrylic resins, Prog.
Org. Coat. 49 (1) (2004) 1–12.
[25] S.-I. Nonaka, R.B. Frings, C. Jaroszewski, G.F.
Grahe, Initiator composition for polymerizing
unsaturated monomers. US Patent 6 087 458, as-
signed to Dainippon Ink and Chemicals, Inc.,
Tokyo, JP, Jul. 11, 2000.
[26] L. Jiang, W. Xiong, Y. Zhou, Y. Liu, X. Huang,
D. Li, T. Baldacchini, L. Jiang, Y. Lu, Perfor-
mance comparison of acrylic and thiol-acrylic
resins in two-photon polymerization, Opt. Ex-
press 24 (12) (2016) 13687–13701.
[27] K. Kawakami, Y. Ishibashi, T. Suzuki, Acrylic
resin composition. US Patent 5 574 101, as-
signed to Asahi Kasei Kogyo Kabushiki Kaisha,
Osaka, JP, Nov. 12, 1996.
[28] A. van der Horst, Y. van Hooijdonk, A. Kroes,
Pyrolysis–liquid chromatography for the analy-
sis of acrylic resins, LC GC 29 (9) (2016) 488–
496.
[29] Y. Ikegami, S. Koyanagi, Y. Kishimoto, Y. Naka-
hara, Acrylic resin composition, acrylic premix,
process for producing acrylic artificial marble
and thickening agent. US Patent 6 323 259, as-
signed to Mitsubishi Rayon Co., Ltd., Tokyo, JP,
Nov. 27, 2001.
[30] P. Kardar, M. Ebrahimi, S. Bastani, M. Jalili,
Using mixture experimental design to study the
effect of multifunctional acrylate monomers on
UV cured epoxy acrylate resins, Prog. Org.
Coat. 64 (1) (2009) 74–80.
[31] A. Sharma, D. Agarwal, J. Singh, Study of
curing kinetics and thermal degradation of UV
curable epoxy acrylate resin, E-J. Chem. 5 (4)
(2008) 904–913.
[32] A. Sharma, D. Agarwal, J. Singh, Studies on
the influence of monomers on the performance
properties of epoxy acrylate resin, E-J. Chem.
5 (3) (2008) 521–528.
[33] P. Kardar, M. Ebrahimi, S. Bastani, Study the
effect of nano-alumina particles on physical-
341
mechanical properties of UV cured epoxy acry-
late via nano-indentation, Prog. Org. Coat.
62 (3) (2008) 321–325.
[34] C.-Y. Chen, C.-K. Huang, S.-P. Lin, J.-L. Han,
K.-H. Hsieh, C.-P. Lin, Low-shrinkage visible-
light-curable urethane-modified epoxy acry-
late/SiO composites as dental restorative materi-
als, Compos. Sci. Technol. 68 (13) (2008) 2811–
2817.
[35] K.-T. Lu, J.-W. Wu, Effects of UV curable ure-
thane acrylate resins treatments on the physi-
cal properties of medium- and small-diameter
softwoods, J. Appl. Polym. Sci. 121 (3) (2011)
1647–1653.
[36] A. Srivastava, D. Agarwal, S. Mistry, J. Singh,
UV curable polyurethane acrylate coatings for
metal surfaces, Pigment Resin Technol. 37 (4)
(2008) 217–223.
[37] F. Benard, B. Mailhot, J. Mallegol, J.L.
Gardette, Photoageing of an electron beam cured
polyurethane acrylate resin, Polym. Degrad.
Stab. 93 (6) (2008) 1122–1130.
[38] T. Behzad, M. Sain, Cure study of an acrylic
resin to develop natural fiber composites, J.
Appl. Polym. Sci. 92 (2) (2004) 757–762.
[39] T. Sato, K. Hata, T. Maruo, Polymer battery and
method of manufacture. US Patent 6 696 204, as-
signed to Nisshinbo Industries, Inc., Tokyo, JP,
Feb. 24, 2004.
[40] S. Lee, K.K. Oh, S. Park, J.-S. Kim, H. Kim,
Scratch resistance and oxygen barrier properties
of acrylate-based hybrid coatings on polycar-
bonate substrate, Korean J. Chem. Eng. 26 (6)
(2009) 1550–1555.
[41] G. Dhole, L.T. Gangotri, Heat resistance alu-
minum paint based on zinc acrylate resin,
Paintindia 58 (9) (2008) 71–78.
[42] I. Kriessmann, W. Paar, F. Holzer, W. Koch,
Water-dilutable coating binder combinations
which can be deposited cathodically, and their
use. US Patent 5 272 188, assigned to Vianova
Kunstharz, A.G., Werndorf, AT, Dec. 21, 1993.
[43] J. Billiani, R. Feola, W. Paar, Cationic acrylic
resins. US Patent 8 962 768, assigned to Allnex
Austria GmbH (AT), Feb. 24, 2015.
342
[44] S.B. Barrios, J.F. Petry, C.K. Weiss, C.L. Pet-
zhold, K. Landfester, Polymeric coatings based
on acrylic resin latexes from miniemulsion poly-
merization using hydrocarbon resins as osmotic
agents, J. Appl. Polym. Sci. 131 (15) (2014).
[45] Wikipedia, Ostwald ripening — wikipedia, the
free encyclopedia, 2017. Online; accessed, 30-
March-2017.
[46] H.S. Park, I.M. Yang, J.P. Wu, M.S. Kim, H.S.
Hahm, S.K. Kim, H.W. Rhee, Synthesis of
silicone-acrylic resins and their applications to
superweatherable coatings, J. Appl. Polym. Sci.
81 (7) (2001) 1614–1623.
[47] H.S. Park, S.R. Kim, H.J. Park, Y.C. Kwak, H.S.
Hahm, S.K. Kim, Preparation and characteriza-
tion of weather resistant silicone/acrylic resin
coatings, J. Coat. Technol. 75 (936) (2003) 55–
64.
[48] G.P. Craun, D. Bode, T.E. Banach, G.J. Ro-
bideau, L.S. Howard, Acrylic grafted polyether
resins based on phenol steric acid and coating
compositions formed therefrom. US Patent Ap-
plication 20160032040, Feb. 4, 2016.
[49] K. Umeda, K. Matsunaga, Semiconductor de-
vice including acrylic resin layer. US Patent
6 730 948, assigned to Matsushita Electric In-
dustrial Co., Ltd., Osaka, JP, May 4, 2004.
[50] S. Jafarzadeh, A. Adhikari, P.-E. Sundall, J. Pan,
Study of PANI-meSA conducting polymer dis-
persed in UV-curing polyester acrylate on galva-
nized steel as corrosion protection coating, Prog.
Org. Coat. 70 (2–3) (2011) 108–115.
[51] F. Vautard, P. Fioux, L. Vidal, J. Schultz, M.
Nardin, B. Defoort, Influence of the carbon fiber
surface properties on interfacial adhesion in car-
bon fiber-acrylate composites cured by electron
beam, Composites, Part A, Appl. Sci. Manuf.
42A (7) (2011) 859–867.
[52] P. Spathis, E. Karagiannidou, A.E. Magoula,
Influence of titanium dioxide pigments on the
photodegradation of paraloid acrylic resin, Stud.
Conserv. 48 (1) (2003) 57–64.
[53] M.J. Melo, S. Bracci, M. Camaiti, O. Chiantore,
F. Piacenti, Photodegradation of acrylic resins
used in the conservation of stone, Polym. De-
grad. Stab. 66 (1) (1999) 23–30.
Reactive Polymers: Fundamentals and Applications
[54] E. Benedetti, A. D’Alessio, M.F. Zini, E. Bra-
manti, N. Tirelli, P. Vergamini, G. Moggi, Char-
acterization of acrylic resins and fluoroelastomer
blends as potential materials in stone protection,
Polym. Int. 49 (8) (2000) 888–892.
[55] R. Bellucci, P. Cremonesi, G. Pignagnoli, A pre-
liminary note on the use of enzymes in conserva-
tion: the removal of aged acrylic resin coatings
with lipase, Stud. Conserv. 44 (4) (1999) 278–
281.
[56] K. Resch, G.M. Wallner, R.W. Lang, Spectro-
scopic investigations of phase-separated ther-
motropic layers based on UV cured acrylate
resins, Macromol. Symp. 265 (2008) 49–60.
[57] K. Resch, G.M. Wallner, Morphology of phase-
separated thermotropic layers based on UV
cured acrylate resins, Polym. Adv. Technol.
20 (12) (2009) 1163–1167.
[58] Y.C. Leong, L.M.S. Lee, S.N. Gan, The vis-
coelastic properties of natural rubber pressure-
sensitive adhesive using acrylic resin as a tack-
ifier, J. Appl. Polym. Sci. 88 (8) (2003) 2118–
2123.
[59] A. Merah, M.M. Khenfer, Y. Korichi, The ef-
fect of industrial coating type acrylic and epoxy
resins on the durability of concrete subjected to
accelerated carbonation, J. Adhes. Sci. Technol.
29 (22) (2015) 2446–2460.
[60] X.S. Fan, Ionomers modified with imidized
acrylic resins. US Patent 8 691 917, assigned to
E. I. du Pont de Nemours and Company, Wilm-
ington, DE, Apr. 8, 2014.
[61] ASTM, Standard Test Method for Vicat Soft-
ening Temperature of Plastics, ASTM Stan-
dard D1525-09, ASTM International, West Con-
shohocken, PA, 2009.
[62] J. Bao, S. Chen, B. Wu, M. Ma, Y. Shi, X. Wang,
A novel foaming approach to prepare porous su-
perabsorbent poly(sodium acrylic acid) resins, J.
Appl. Polym. Sci. 132 (3) (2015).
[63] M. Rafiee-Tehrani, N. Safaii-Nikui, H. Peteriet,
T. Beckert, Acrylic resins as rate-controlling
membranes in novel formulation of a nine-
day 17 β-estradiol transdermal delivery system:
In vitro and release modifier effect evaluation,
Drug Dev. Ind. Pharm. 27 (5) (2001) 431–437.
9: Acrylic Resins
[64] A. Roveda, A. Benedetti, F. Pinna, G. Strukul,
Palladium-tin catalysts on acrylic resins for the
selective hydrogenation of nitrate, Inorg. Chim.
Acta 349 (2003) 203–208.
[65] I. Owsik, B. Kolarz, The oxidation of hy-
droquinone to p-benzoquinone catalysed by
cu(II) ions immobilized on acrylic resins with
aminoguanidyl groups Part 1, J. Mol. Catal. A,
Chem. 178 (1–2) (2002) 63–71.
[66] P. Gounon, Low-temperature embedding in
acrylic resins, in: M.A.N. Hajibagheri (Ed.),
Electron Microscopy Methods and Protocols, in:
Methods Mol. Biol., vol. 117, Humana Press,
Inc., Totowa, 1999, pp. 111–124.
[67] A. Maffezzoli, R. Terzi, Effect of irradiation in-
tensity on the isothermal photopolymerization
kinetics of acrylic resins for stereolithography,
Thermochim. Acta 321 (1–2) (1998) 111–121.
[68] W.-F. Zhou, J.-S. Xue, X. Ming, X. Liu, J. Guo,
Z.-Y. Xie, C.-T. Zhao, X. Chen, T.-Y. Min, Low
dielectric acrylate resin as passivation layer on
TFT-LCD, Yejing Yu Xianshi 26 (1) (2011) 19–
22.
[69] P.G. Sasikumar, M. Kempe, Magnetic CLEAR
supports for solid-phase synthesis of peptides
and small organic molecules, Int. J. Pept. Res.
Ther. 13 (1–2) (2007) 129–141.
[70] Y. Zhang, S. Qi, F. Zhang, Y. Yang, G. Duan,
Preparation and magnetic properties of polymer
magnetic composites based on acrylate resin
filled with nickel plating graphite nanosheets,
Appl. Surf. Sci. 258 (2) (2011) 732–737.
[71] N.G.N. Salleh, M.F. Yhaya, A. Hassan, A. Abu
Bakar, M. Mokhtar, Development of scratch-
and abrasion-resistant coating materials based
on nanoparticles, cured by radiation, Int. J.
Polym. Mater. 58 (8) (2009) 422–451.
[72] P. Wang, J. Guo, H. Wang, Y. Zhang, J. Wei,
Functionalized multi-walled carbon nanotubes
filled ultraviolet curable resin nanocomposites
and their applications for nanoimprint lithogra-
phy, J. Phys. Chem. C 113 (19) (2009) 8118–
8123.
[73] Y. Quan, M. Yang, T. Liang, Q. Yan, D. Liu,
R. Jin, Effects of the reinforcement and tough-
ening of acrylate resin/caCO3 nanoparticles on
343
rigid poly(vinyl chloride), J. Appl. Polym. Sci.
103 (6) (2007) 3940–3949.
[74] Y.-C. Chou, Y.-Y. Wang, T.E. Hsieh, Transparent
photo-curable co-polyacrylate/silica nanocom-
posites prepared by sol-gel process, J. Appl.
Polym. Sci. 105 (4) (2007) 2073–2082.
[75] V. Landry, B. Riedl, P. Blanchet, Alumina and
zirconia acrylate nanocomposites coatings for
wood flooring: photocalorimetric characteriza-
tion, Prog. Org. Coat. 61 (1) (2008) 76–82.
[76] F. Bauer, R. Flyunt, K. Czihal, H. Ernst, S. Nau-
mov, M.R. Buchmeiser, UV curing of nanopar-
ticle reinforced acrylates, Nucl. Instrum. Meth-
ods Phys. Res., Sect. B, Beam Interact. Mater.
Atoms 265 (1) (2007) 87–91.
[77] N. Nakayama, T. Hayashi, Preparation and char-
acterization of TiO2 –ZrO2 and thiol-acrylate
resin nanocomposites with high refractive in-
dex via UV-induced crosslinking polymeriza-
tion, Composites, Part A, Appl. Sci. Manuf.
38A (9) (2007) 1996–2004.
[78] Y. Zhang, S. Qi, X. Wu, G. Duan, Electrically
conductive adhesive based on acrylate resin
filled with silver plating graphite nanosheet,
Synth. Met. 161 (5–6) (2011) 516–522.
[79] S.W. Kim, Characterization of UV curable hy-
brid hard coating materials prepared by sol-gel
method, Korean J. Chem. Eng. 28 (1) (2011)
298–303.
[80] H.-I. Hsiang, Y.-L. Chang, C.-Y. Chen, F.-S.
Yen, Silane functional effects on the rheology
and abrasion resistance of transparent SiO/UV-
curable resin nano-composites, Mater. Chem.
Phys. 120 (2–3) (2010) 476–479.
[81] H.-I. Hsiang, Y.-L. Chang, C.-Y. Chen, F.-S.
Yen, Silane effects on the surface morphology
and abrasion resistance of transparent SiO2 /UV-
curable resin nano-composites, Appl. Surf. Sci.
257 (8) (2011) 3451–3454.
[82] H.-E. Yin, K.-H. Kuo, W.-Y. Chiu, Synthe-
sis of UV-curable resin/ZnO composite films
as pH buffering material, e-Polymers (2010),
http://dx.doi.org/10.1515/epoly.2010.10.1.640.
[83] J. Texter, Z. Qiu, R. Crombez, J. Byrom,
W. Shen, Nanofluid acrylate composite resins-
initial preparation and characterization, Polym.
Chem. 2 (8) (2011) 1778–1788.
344
[84] P. Huang, J. Hu, K.J. Wang, Y.T. Wang, The
influence of etching time on the surface mor-
phology of electroless nickel plated acrylic
resins microsphere, in: Dianchi Advanced Ma-
terials Forum 2014, in: Advanced Materials
Research, vol. 1058, Trans Tech Publications,
2014, pp. 89–92.
[85] S. Wasim Ali, M.A. Malik, S. Jan, K. Naeem,
Comparison of rigid divinylbenzene with flex-
ible 1, 7-octadiene crosslinks in acrylic acid
Reactive Polymers: Fundamentals and Applications
resins – effects on kinetics of swelling and load-
ing of heavy metal ions from water, J. Appl.
Polym. Sci. 131 (21) (2014).
[86] M. Sato, M. Yamagishi, Hydrophilic acrylic
copolymers, hydrophilic acrylic resin parti-
cles and ink-jet recording media. US Patent
6 063 488, assigned to Soken Chemical & Engi-
neering Co., Ltd., JP, May 16, 2000.