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Keywords: Interfacial polymerization has been used to encapsulate essential oils (EOs). Nevertheless, interfacial polymer
Fragile capsule ization to form polymeric interface of EOs with the environment has been poorly studied. The objective of this
Polyurethane study was to develop a kind of polyurethane (PU) based shell microencapsulated EOs to induce controlled de
Lavender fragrance
livery. In this study, ethylene glycol based PU microcapsules were prepared to release medicinal lavender oil
Controlled release
from some textiles with controlled delivery mechanism and mechanical stimuli. Various diisocyanates and
ethylene glycol (EG) are used to synthesize the PU based shell microcapsules for optimization and reveal
structure property relationship of shell structure in controlled release issue. The sensing mechanical stimuli of the
polymer capsules is achieved by using a short molecule, EG. The original lavender fragrance was encapsulated in
PU shells by the interfacial interaction of toluene diisocyanate, isophorone diisocyanate, or methylene bisphenol
diisocyanate with EG at the interface of oil and water phases. The fragrance capsules were characterized by
Fourier Transform Infrared (FT-IR) spectroscopy, particle size distribution (PSD) analysis, polarized optical
microscopy (POM) and scanning electron microscopy (SEM) investigations. The release behavior of the fragrance
capsules was determined by periodic weight checks over 30 days. According to the release analysis, the efficient
* Corresponding author.
E-mail address: cemil.alkan@gop.edu.tr (C. Alkan).
https://doi.org/10.1016/j.colsurfa.2022.129888
Received 1 June 2022; Received in revised form 3 August 2022; Accepted 5 August 2022
Available online 6 August 2022
0927-7757/© 2022 Elsevier B.V. All rights reserved.
A. Özsevinç and C. Alkan Colloids and Surfaces A: Physicochemical and Engineering Aspects 652 (2022) 129888
EOs encapsulation ratio of the particles were 34.90%, 39.84% and 48.70% for particles produced using toluene
diisocyanate, isophorone diisocyanate, and methylene bisphenol diisocyanate respectively. The average particle
size was determined in a range of 10–30 µm for the particles produced used any diisocyanate, which meant they
were at commonly used sizes for textile applications. The -NH, -C––O, -C-O-C, and -C-N peaks in the structure of
the PU were determined by FT-IR to demonstrate successful synthesis. SEM images revealed that microparticles
with medicinal lavender oil were fragile to increase the release rate when needed.
1. Introduction acetate in lavender oil have narcotic and sedative effects [28]. Gednay
et al. drizzled 5 drops of lavender oil on a cotton muslin cloth and placed
Scientific developments increased manufacturing innovative prod it next to the patients. They found that sleep quality improved in a short
ucts with Essential oils (EOs) in the textile materials. Microencapsula time due to breathing [29]. In addition, Peng et al. determined the
tion is one of the most versatile techniques, small microcapsules can be relaxing effect of acetylcholine released by lavender oil on the transition
produced and applied to textiles efficiently, improving their dynamics, to sleep [30]. Several authors have provided overviews of the potential
comfort or adding functionality. Microcapsules are small particles that applications of encapsulated EOs within food and medicine [31–37].
have numerous industrial applications. Controlled release of drugs, Polycondensation reactions taking place at the boundary of two
textiles, cosmetics, adhesives, inhibitors, are some well known phases to form the shells of microcapsules or matrix microspheres were
examples. used in this work to prepare controlled delivery particles. Based on the
Microencapsulation technology targets to impart further miscella shell-forming materials, this technology is capable of preparing poly
neous functionality using different techniques in production means and amine, polyurea, polyurethane, polythiourea, polyester, polyepoxide,
applications. They focused largely on improving the thermal comfort polyacrylamide and polysiloxane microcapsules. Over the past two de
properties of textiles by encapsulating phase-changing materials [1–7]. cades, microcapsules prepared by interfacial polycondensation have
The popularity of textile products containing odor capsules is increasing been widely used in carbonless paper, cosmetics, pharmacy, agriculture,
day by day. The production of these capsules is still not well known due energy storage/transfer, thermal insulation/regulation and information
to their commercial importance. Fragrances cannot be directly applied and magnetic recording [38].
to textiles due to their volatile properties. For this reason, they are In recent years, lavender oil has been put on a pedestal for its unique
applied to textile materials by enclosing the fragrances in a shell and ability to protect against neurological damage. Traditionally, lavender
protecting them from external influences [8,9]. Most commercially has been used to treat neurological issues like migraines, stress, anxiety
available fragrance microcapsules are based on amine-formaldehyde, and depression, so it’s exciting to see that the research is finally catching
but their use is limited due to their environmental impact [10]. Micro up to history [39]. There are several studies showing the effects of
capsules containing volatiles can be made with gelatin and arabic gum lavender oil on stress and anxiety levels. A study from 2019 found that
by a complex conversion method in a variety of sizes. In this method, the inhaling Lavandula is one of the most powerful anxiolytic oils, as it re
microcapsules can adhere to each other, and the particle size can form duces peri-operative anxiety and can be considered a potential sedative
coarser particles at different intervals, because the microcapsules are for patients undergoing surgical procedures and anesthesia [40]. In
generally low molecular weight polymers and the mechanical strength 2013, evidence-based studies for the effect of lavender oil were reviewed
of the microcapsule to external influences is low and breaks quickly. One and published, where supplementing some people with 80-milligram
of the most effective methods for producing polyurethane odor capsules capsules of lavender essential oil helped alleviate anxiety, sleep distur
is the interfacial polymerization technique [11]. The molecular weight bance and depression. Additionally, in the study there were no adverse
of the diol used in the production directly affects the mechanical prop side effects, drug interactions or withdrawal symptoms from using lav
erties of the microcapsules and the release time. The higher the molec ender oil [41]. English lavender (Levandulae aetheroleum) oil is well
ular weight, the higher the mechanical strength and release time [12]. In known as the most effective among lavender species on therapeutic
the literature, different essential oils (such as orange, lemon, jasmine, applications and called as medicinal lavender in somewhere [42,43].
and lavender) with different particle sizes were prepared and applied to In this study, medicinal lavender oil was selected to produce poly
textile materials and the release, washing, and friction properties were urethane odor capsules by reacting a diol with 3 different isocyanates. It
studied [13–17]. From the summary of the literature, it can be is to show the possible PU shell materials for controlled delivery of
concluded that the polymerization method, mixing rate, type of medicinal lavender oil comparatively. It is not only optimization of the
fragrance, wall material components, capsule size, and mechanical shell structure but also making clear the chemical structure property
properties of the fabricated capsules significantly affect the odor release relationships in the shell. These capsules were found as candidates of
properties of the microcapsules. It is also shown that the washing controlled release materials for which release rate may be increased by
resistance changes depending on the application methods and the mechanical stimuli. Showing their application of them to textiles was
crosslinkers used on the textiles, directly affecting the duration of due to demonstrate their easily exploitation in textile form.
application and the number of microcapsules adhering to the fabric
[18–24]. 2. Material and methods
EOs are complex mixtures of volatile compounds extracted from
different parts of plants by different methods. There is a large diversity 2.1. Materials
of these natural substances with varying properties that lead to their
common use in several areas [25]. One of the most studied fragrances is The materials used for the synthesis of the PU fragrance capsules are
lavender oil as EOs have been widely studied for being a signal molecule toluene-2,4-diisocyanate (TDI) from Across Organics company, iso
[26]. EOs are generally lipophilic compounds with low molecular phorone diisocyanate (IPDI) and 4,4′ -diphenylmethane diisocyanate
weight (<300 g mol− 1) and low boiling point that acts at low quantities (DPMDI) from Sigma-Aldrich company as isocyanates, ethylene glycol
(from 1 ng to 1 μg). The main essential oil compounds of lavender oil are (EG) from Merck company as diol, dibutyltin dilaurate (DBDTL) from
linalool, linalyl acetate, and cineole. Linalyl acetate is the most impor Merck company as a catalyst and polyvinyl alcohol (Moviol 3–96) from
tant of them, which determines the quality of lavender [27]. Essential Merck company as a suspension agent.
oils can be taken by inhalation, massage or orally. When we examine the
studies on the benefits of lavender oil, we find that linalool and linalyl
2
A. Özsevinç and C. Alkan Colloids and Surfaces A: Physicochemical and Engineering Aspects 652 (2022) 129888
Table 1
Recipes of controlled delivery systems.
Microcapsules Phase Lavender Fragrance (mL) Water (mL) Isocyanate (mL) PVA (gr) EG (mL) DBDTL (mL)
OP 20 7.50 TDI
Mic.1 AP1 120 2
AP2 50 2.91 0.50
OP 20 7.50 IPDI
Mic.2 AP1 120 2
AP2 50 1.98 0.50
OP 20 7.50 DPMDI
Mic.3 AP1 120 2
AP2 50 1.71 0.50
Mic.: Microcapsule, O.P: Oil phase, A.P1: Aqueous phase 1, A.P2: Aqueous phase 2.
2.2. Methods the first water phase was prepared using 120 mL of water and 2 g of
Moviol (protective colloid). Then the oil-water phase was mixed in the
Polyurethane fragrance capsules were synthesized by interfacial homogenizer with stirring at 4000 rpm for 5 min. The emulsion was
polymerization technique as shown in Fig. 1 (with stirring at 200 rpm for transferred to the reactor. The second water phase containing 50 mL
2 h at 70 ◦ C, in a jacketed glass reactor). Then, the fragrance capsules water, 0.5 mL DBDTL and another mass of ethylene glycol (with the
were washed with 30% ethanol and dried at room temperature. The same molar mass as the isocyanate) was prepared and mixed with the
materials used for polymerization are listed in Table 1. The oil phase was emulsion in the reactor.
prepared by mixing 20 mL of lavender oil and 7.5 mL of isocyanate, and The microencapsulation rates were calculated with the following
3
A. Özsevinç and C. Alkan Colloids and Surfaces A: Physicochemical and Engineering Aspects 652 (2022) 129888
Fig. 3. Particle size distribution graphs of Mic.1, Mic.2 and Mic.3 fragrance capsules with medicinal lavender oil.
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A. Özsevinç and C. Alkan Colloids and Surfaces A: Physicochemical and Engineering Aspects 652 (2022) 129888
Table 3
Particle size parameters for fragrance microcapsules.
Microcapsules d (0.1) (μm) d (0.5) (μm) d (0.9) (μm) Specific Surface Area (m2/g) d (3,2) (μm) d (4,3) (μm)
chemicals as the empty capsules were prepared with the same prepa 3.3. POM and SEM investigations
ration procedure of Mic.1 but without medicinal lavender oil. The spe
cific FT-IR spectral peaks of PU polymers (-NH, -C = O, -CN, - CH, -CH2 The morphology of the microcapsules studied by POM (bright field
and -C-O-C) were determined for the fragrance capsules and shown with 1200x magnification) and SEM showed clearly that the lavender oil
together with the peaks of the empty PU capsules FT-IR spectrum in was successfully produced in a spherical microencapsulated form with
Fig. 2. Then there were some other peaks in Mics 1, 2, and 3 due to PU shells. The POM images before controlled release were shown in
medicinal lavender. The one at around 1700 cm− 1 is the distinctive Fig. 4 as the fragility was monitored by the images from SEM in Fig. 5.
example. The other examples were found at 950 cm− 1, 1300 cm− 1, and SEM images showed the microcapsules 3D morphology better than
1350 cm− 1. The peak not well distributed and at around 2267 cm− 1 was POM because that they were not distributed into water by means of a
due to the remnant isocyanate which was known as inevitable in PU surfactant. During controlled release, the microcapsules were applied to
production. However, Fig. 2 shows that no residual diisocyanates were an abrupt force every 10 days. It can be seen that the microparticles
left in the capsules at the end of washing with ethanol. produced could be broken easily. SEM images of Mic. 1, Mic. 2, and Mic.
As a result, it is clearly seen that PU fragrance capsules with me 3 before (1, 2, and 3) and after (1a, 2a, and 3a) of release showed that
dicinal lavender oil were successfully prepared. The major peak as the particles were similar in size, shape and fragility. In addition, mi
signments generally present in PU structures were shown also in Table 2. crocapsules with size of 20–50 µm were consistent with the distribution
of the particle size and suitable use in textiles. Fig. 6. clearly showed the
3.2. PSD analysis size determination and shape of the microparticles. Particle sizes were
found consistent with PSD results.
Research on microparticles begins with particle size and its distri It is noteworthy to declare that the particles produced using in
bution analysis to determine its usefulness for the intended application teractions of commonly available diisocyanates and EG gave similar
in textiles. In general, particles with a size of 20–2000 µm are preferred results in particle size and its distribution, meaning that any can be used
for textile applications. Nano-sized particles are hazardous to health, for controlled release particle production. The size range of the particles
while the large particles affect the durability and some of the physical were found suitable for textile applications for all diisocyanates.
properties. Medicinal lavender particles are the main component of the
material system, i.e. the material becomes unusable after its release. 3.4. Release behavior
Medicinal lavender supports human psychology and fabric use in the
application is just to ease the application. Fabric is the support material. The produced medicinal lavender oil capsules were placed in a petri
PSD curves of the fragrance microcapsules for the 3 samples are dish and weighed every day for 30 days period. The weight percentage
shown in Fig. 3. The average particle sizes of the microcapsules were losses of the fragrance were monitored over 30 days, it was clear that
measured as 10–30 µm and the plots show that the particle sizes are they lost 40–45 wt% as an average in every try. While the fragrance
homogeneously distributed. release was very quick in the first 10 days, it was moderate in the second
Table 3 shows the particle weight percentages (d (0.1): the size of 10 days and slowed down in the last 10 days. Microcapsules were
particles in the first 10%, d (0.5): the size of particles in the first 50%, exposed to force every 10 days, and on the day after force application,
and the size of particles in the d (0.9): 90% of the original surface area, release was accelerated due to breaking the capsules. The percent
the surface area weighted average (d [2,3]), and the volume weighted change in weight of the fragrance capsules over 30 days is shown in
average of particle diameters (d [3,4]). The particle size distribution Fig. 7. Furthermore Fig. 7 showed that DPMDI-EG interactions resulted
results show that the fragrance microcapsules were successfully unim in particles encapsulating and releasing EOs more efficiently than the
odally distributed in a narrow scale convenient for textile applications. other 2 diisocyanate-EG interactions.
In addition, the release of lavender oil from microcapsules was
evaluated using FT-IR graphs before and after controlled release. The
FT-IR graphs before and after controlled release are shown in Fig. 8
5
A. Özsevinç and C. Alkan Colloids and Surfaces A: Physicochemical and Engineering Aspects 652 (2022) 129888
Fig. 5. SEM images of lavender oil fragrance microcapsules before controlled release (1, 2, and 3) and after controlled release (1a, 2a, and 3a).
along with the FT-IR graph of empty PU microcapsules. The -C– – O peak conditions released the EO contend by the expected time period.
in the medicinal lavender oil capsules (1740 cm-1) reduced after
controlled release and the graphs of the fragrance capsules FT-IR spectra 4. Conclusions
were similar to those of the empty PU capsules FT-IR spectra. The
carbonyl peak (-C–– O) was from the lavender oil and disappeared after Medicinal lavender oil capsules were successfully prepared through
the controlled release. This showed that the lavender oil was released interfacial polymerization. Time dependent lavender oil release from
from the microcapsules by the time. the shell was detected by periodical weight measurements. The micro
In spite that FT-IR spectroscopy was very effective in release capsules were intended to be fragile to increase the release behavior
provement, it was not quantitative. In this work, all the particles pro when the release rate reached to a plateau. The diameter of the micro
duced using different recipes but with the same technique and capsules was about 10–30 µm, these particle sizes are suitable for the use
6
A. Özsevinç and C. Alkan Colloids and Surfaces A: Physicochemical and Engineering Aspects 652 (2022) 129888
7
A. Özsevinç and C. Alkan Colloids and Surfaces A: Physicochemical and Engineering Aspects 652 (2022) 129888
Fig. 8. The FT-IR diagrams of the empty PU capsules, the medicinal lavender oil capsules before release (Mic-1a, 2a and 3a) and the medicinal lavender oil capsules
after release (Mic-1, 2 and 3).
8
A. Özsevinç and C. Alkan Colloids and Surfaces A: Physicochemical and Engineering Aspects 652 (2022) 129888
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