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Article

Plasticized Polylactide Film Coating Formation from Redispersible Particles

by
Oleksiy Myronyuk
1,*,
Denys Baklan
1,
Anna Bilousova
1,
Illia Smalii
1,
Victoria Vorobyova
2,
Vita Halysh
3 and
Inna Trus
3
1
Department of Chemical Technology of Composite Materials, Chemical Technology Faculty, Igor Sikorsky Kyiv Polytechnic Institute, Beresteiskyi Ave. 37, 03056 Kyiv, Ukraine
2
Physical Chemistry Department, Chemical Technology Faculty, Igor Sikorsky Kyiv Polytechnic Institute, Beresteiskyi Ave. 37, 03056 Kyiv, Ukraine
3
Department of Ecology and Technology of Plant Polymers, Chemical Engineering Faculty, Igor Sikorsky Kyiv Polytechnic Institute, Beresteiskyi Ave. 37, 03056 Kyiv, Ukraine
*
Author to whom correspondence should be addressed.
AppliedChem 2025, 5(3), 14; https://doi.org/10.3390/appliedchem5030014
Submission received: 6 May 2025 / Revised: 4 June 2025 / Accepted: 17 June 2025 / Published: 9 July 2025
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Abstract

The aim of this work was to improve the technology for obtaining coating based on plasticized polylactide from its aqueous suspensions. For this purpose, a film formation process with additional heating was developed, and the influence of plasticizers on the film-formation temperature was investigated. It is shown that using only mechanical emulsification, it is possible to obtain a material with an average particle size of 2.4 microns, which is suitable for further research and modification for film materials. The introduction of epoxidized fatty acids (oleic and linolic) was found to reduce the film-formation temperature by 20–30 °C compared to the unplasticized polymer, which puts them on par with the classical plasticizer, polyethylene glycol, reducing the film-formation temperature by 36% at the same concentration.

1. Introduction

There is a global transition from petroleum-based plastics to bio-based and biocompostable plastics. Many countries have adopted relevant standards for the net zero carbon transition, and plastics have been shown to be low carbon throughout their life cycle [1].
Polylactide is currently one of the most represented bio-based plastics on the commercial market (probably second only to the group of polyhydroxyalkanoates [2]), and its production is being increased by several companies, such as Nature Works LLC, which will reach a capacity of 150 kt in 2021. The expected annual world production of PLA in 2027 is 6.6 million tons [3]. However, this represents close to 1% of annual plastic production, indicating the growth potential to replace petroleum-based plastics.
Polylactide is currently used in packaging, biomedical devices, agricultural films, and additive manufacturing technologies, particularly 3D printing. However, its potential in the coatings industry, which is considered one of the most important polymer applications, is not yet realized, primarily as a film-forming agent. And there are several notable factors that limit this application. As is well known, the modern paint and coating industry works with several classes of systems: solvent-based systems (anticorrosion coatings and some wood coatings, plastic coatings, etc.), high-solid systems (without liquid carriers or with a significantly reduced quantity), and water-based systems (the polymer particles are dispersed and stabilized in water). The latter solution is the most ecological, helping to reduce the content of harmful volatile organic compounds. An obstacle to the use of polylactide in the composition of mortar paints is the relatively small number of solvents compatible with this polymer, which causes the problems of adequate selection and impossibility of using traditional industrial systems of aromatic, medium-polar solvents with reduced toxicity. However, an obstacle to obtaining PLA dispersions is that PLA, unlike currently commercialized acrylic, polyurethane, or alkyd dispersions [4,5], cannot be synthesized in a similar way from a monomer using radical reactions.
The method of solvent evaporation allows dispersions of polymer particles with a high solid content to be obtained and consists of the successive preparation of a polylactide solution and its dispersion (mechanical and ultrasonic) in an aqueous medium. It results in stabilization of the dispersion particles by surfactants and thickeners, and in the last step, the removal of the solvent from the dispersion particles via continuous evaporation takes place [6,7]. Although this method uses a solvent, it can be captured and regenerated in analogy to the smoothing processes of printed 3D parts [8,9]. The dispersions obtained in this way can form films at elevated temperatures compared to room temperature, as the glass transition temperature (Tg) of modern polylactide grades is between 55 and 65 °C [10] and the minimum film formation temperature (MFFT) is between the Tg and the melting point of the polymer (Tm). For all applications of polylactide, from coatings that cure at elevated temperatures to those that do not require heating for film formation, reducing the MFFT is therefore an important challenge. Plasticizers are known to reduce the Tg and Tm by reducing intermolecular interactions between polymer chains, so their introduction can be considered a promising tool for reducing the MFFT.
There are several known ways to plasticize polylactide: (1) by combining it with other more elastic polymers, e.g., natural rubber [11], polycaprolactone [12], or poly-butylene succinate adipate [11], both through melt compounding and chemical grafting; (2) by introducing monomeric or oligomeric plasticizers, e.g., polyethylene glycol (PEG) [13], citrates [14] and adipates [15], or oligomeric lactic acid, which has been shown to decrease the Tg of PLA by 35 °C at a 25 wt. % content [16]. The low-molecular-weight plasticizers are more technological because the additive concentration can be controlled according to the desired glass transition temperature reduction so that other important properties such as the hardness, heat resistance, tackiness, etc., are not affected.
The best known and most studied plasticizer for PLA is polyethylene glycol [17], but it is also water soluble, which can cause its transfer from dispersed PLA particles to the aqueous phase. The same is true for plasticizers such as glycerin, ethylene glycol, etc. Such a transition would not be a problem if the plasticizers were concentrated on the surface of the PLA particles after evaporation of the water, but because they are low-molecular-weight liquids, they can be absorbed by the substrate or coalesce into droplets separate from the polymer, forming macroheterogeneous regions. Another problem is the gradual migration of this plasticizer, especially in humid conditions [18]. Thus, effective plasticizers for polylactide particles are derived from aqueous dispersions that are not water soluble.
To date, a number of works have been devoted to solving the problem of synthesizing plasticizers specifically for polylactide, in which the efficiency is evaluated for extrusion composites [19] or films obtained from a solution [20]. In our work, we consider the process of the film formation of particles obtained from aqueous dispersions, which is characterized by its peculiarities close to the technologies of water dispersion and powder coatings, where plasticizers can significantly affect the temperature of film formation.
The aim of this work was to improve the technology for obtaining coatings based on plasticized polylactide from its aqueous suspensions. For this purpose, aqueous dispersions of polylactide were obtained, the application process was developed, film formation was studied, and the influence of plasticizers on the film-formation temperature was investigated. The efficiency of plasticizers for PLA based on water-insoluble epoxidized fatty acids (oleic and linoleic) was demonstrated.

2. Materials and Methods

2.1. Materials

The polylactide used in this study was Ingeo Biopolymer 4060D (NatureWorks, Minnetonka, MN, USA) with a density of 1.24 g/cm3, a glass transition temperature of 55–60 °C, an average molecular weight (Mw) of 190 kD, and a D-lactide content of 12%. This grade was chosen for its relatively low glass transition point, which arises from the amorphous structure and exceeds its suitability for film applications.
PEG-400, dibutyl phthalate (DBP), ethylene glycol (EG), and glycerin were used as plasticizers. PEG-400 is one of the most widely used and effective plasticizers for PLA polymers [21,22,23], and it was chosen as a reference. Although DBP is a fossil-based phthalate plasticizer, it is known to be compatible with a wide range of polymers, so it was chosen as a historical reference. Ethylene glycol and glycerol have been used in some research [24]. All named substances were purchased from the local supplier HLR Ukraine (Chemlaborreactiv LLC, Brovary, Ukraine).
Oleic acid and linoleic acid were used for the synthesis of epoxy-oleic acid and epoxy-linoleic acid, respectively. The solvent used was dichloromethane (methylene chloride) (Thermo Fisher Scientific, Waltham, MA, USA). Meta-chloroperoxybenzoic acid (m-CPBA) (Sigma-Aldrich, St. Louis, MO, USA), sodium bicarbonate (Sigma-Aldrich, St. Louis, MO, USA), and anhydrous sodium sulfate (Sigma-Aldrich, St. Louis, MO, USA) were used for the synthesis of epoxy-oleic and epoxy-linoleic acids, respectively. High-performance liquid chromatography-grade hexane and ethyl acetate (Sigma-Aldrich, St. Louis, MO, USA) were used for chromatography.

2.2. Epoxidized Plasticizers Synthesis and Characterization

Oleic acid (5 g, 0.018 mol, 1 eq.) was mixed with 50 mL of dry dichloromethane (CH2Cl2) in a three-necked flask at room temperature, followed by m-CPBA (4.6 g, 0.022 mol, 1.2 eq., 70 wt. %) under constant stirring. The reaction was left to stir for 16 h at room temperature. After completion of the reaction, the mixture was washed with 50 mL of an unsaturated NaHCO3 solution and distilled water (3 × 30 mL), dried over anhydrous Na2SO4, and filtered, and the solvent was evaporated under a vacuum. Purification was carried out via column chromatography (hexane/ethyl acetate 9:1) to give 4.1 g (80–90%) of oleic acid epoxide, which was confirmed through NMR spectroscopy in Chlorophorm-d, and the strength of the static magnetic field 9.4 T was as follows(Figure 1a): δ 2.91 (s, 2 h), 2.37 (t, J = 7.5 Hz, 2 h), 1.7–1.58 (m, 3 h), 1.5 (s, 7 h), 1.43–1.15 (m, 23 h), 0.94–0.87 (m, 3 h). The same method was used to synthesize epoxy linoleic acid, and the result was confirmed via NMR spectroscopy (Figure 1b).
The analysis of proton magnetic resonance (1H NMR) spectra revealed significant changes in the chemical environment of hydrogen atoms, confirming the successful course of the epoxidation reaction. In the spectrum of the initial unsaturated carboxylic acid (compound C18H34O2), characteristic signals are recorded in the range of δ ~5.3 ppm, corresponding to the protons of the alkene group (–CH=CH–). After the reaction to form the compound (C18H34O3), these signals disappear completely, indicating the disappearance of the double bonds. Instead, new peaks in the range of δ ~2.7–3.2 ppm appear in the product spectrum, typical of protons associated with the epoxy fragment. A similar synthesis and characterization of linoleic acid was performed. Also, FTIR spectra were obtained for synthesized epoxidized organic acids (Figure A1, Appendix A). The IR spectrum shows peaks characteristic of organic acids. CH2 stretching occurred at 2923 cm−1 for epoxy oleic acid and at 2913 cm−1 for epoxy linoleic acid, and CH3 stretching occurred at 2857 cm−1 and 2848 cm−1 for epoxy oleic acid and epoxy linoleic acid, respectively. Ant-symmetric axial stretching occurred at 1706 and 1690 cm−1 for epoxy oleic acid and epoxy linoleic acid, respectively. The IR spectrum lacks peaks corresponding to fatty acid carbon–carbon double bonds (–C=C–), indicating successful epoxidation. Meanwhile, the IR spectra of epoxidized oleic and linoleic acids show peaks corresponding to oxirane bonds at 920 and 852 cm−1 for epoxy oleic acid and 896 and 818 cm−1 for epoxy linoleic acid [25,26].

2.3. Obtaining Polylactide Dispersions

Initially, 0.17 g of sodium dodecyl sulfate (SDS) was dissolved in 42.86 mL of distilled water at 25 °C using a top-drive stirrer at a speed of no more than 40 rpm. Maintaining a low stirring speed was critical to prevent heavy foaming, which made it difficult to distribute the components evenly. After the surfactant (SDS) was completely dissolved, 40 mL of a 15 wt. % solution of PLA 4060D in dichloromethane was gradually added to the mixture. Dichloromethane was chosen as the solvent because of its optimal evaporation rate. The stirring process lasted for 3 h with a gradual increase in the water bath temperature from 25 to 60 °C by 5 °C every 15 min, after which the system was held at 60 °C for the rest of the time. The dispersion was then stirred at low speed and vacuumed to remove residual dichloromethane. Dry particles from the dispersion were obtained via centrifugation followed by drying on an adhesive coating at room temperature. This process resulted in micrometer-sized PLA particles suitable for further research and modification for film materials.

2.4. Characterization Methods

Chemical analysis was performed via 1H NMR spectroscopy (400 MHz, CDCl3; Bruker Avance III HD 400 MHz, equipped with a 5 mm broadband probe) and FTIR spectroscopy in transmission mode (IRSpirit, Shimadzu, Kyoto, Japan).
The surface topography of the obtained films was studied using a MIRA3 LMU scanning electron microscope (Tescan, Brno, Czech Republic) at a 10 kV acceleration voltage and 12 pA current. To reduce the surface charge, the samples were coated with a 10 nm thick tungsten layer using a precision coating and etching system (682 PECS, Gatan, Inc., Pleasanton, CA, USA). Optical microscopy images were obtained on a Konus Academy-2 upright optical microscope using a calibrated UCMOS 1300 digital camera (Sigeta Optics, Kiev, Ukraine) and ToupView software (ver. 4.11.23945.2023.1121, ToupTek, Hangzhou, Zhejiang, China). A tensile strength test was conducted accordingly to the procedure described in ISO 527-3:2018 [27] (TSE504, Shenzhen Wance Testing Machine Co., Ltd., Shenzhen, China). The melt flow index was determined for samples with 5 wt. % of plasticizers in accordance with the procedure described in ISO 1133:2022 [28] (MFI452B, Shenzhen Wance Testing Machine Co., Ltd., Shenzhen, China).
Hansen solubility parameters for PLA and epoxidized plasticizers were determined using the following solvents: water, dichloromethane, isopropyl alcohol, hexane, ethyl acetate, n-butanol, cyclohexane, dimethylformamide, o-xylene, and dimethyl sulfoxide or their mixtures. To determine the solubility parameters of PLA, dichloromethane and tetrahydrofuran were used as solvents. Ethyl acetate and isopropyl alcohol were used as solvents to determine the solubility parameters of epoxy-oleic acid and epoxy-linoleic acid. All these solvents except water were purchased from Sigma-Aldrich (Merck).
The coordinates of the solubility points and centers in D, P, H coordinates (Hansen sphere calculation) were calculated with Excel (Microsoft, Redmond, MA, USA) using the HSP Excel spreadsheet prepared by Dr. Diaz de los Rios [29,30].

3. Results and Discussion

3.1. Re-Dispersable PLA Particle Characterization

The obtained stabilized dispersion of the polylactide solution in dichloromethane has an average particle size of about 3 μm and an average mass of about 8 μm (Figure 2). The particles are stable in the purification and washing process; no coalescence is observed during the processing.
The particles obtained from the synthesis are spherical with a rather high degree of polydispersity (Figure 3a). The size of the primary particles varies from 0.3 to 20 μm, they are significantly aggregated but without visible interstices, indicating the possibility of redispersion in the liquid.
At least some of the large particles obtained by this method are hollow (Figure 3b, upper right) with a wall thickness of 0.2–0.4 μm. This may be due to the peculiarities of the process of removing the solvent, dichloromethane, from the emulsion droplets during particle formation. The polymer from the solution concentrates and precipitates at the interface, forming a shell, while the solvent occupies the core of the particle, which remains hollow after removal. The method of synthesizing hollow particles by evaporating the solvent from the emulsion is mentioned in some reviews [21,22,23,24,25,26,27,28,29,30,31,32,33] and experimental works [34,35]. The surface of large particles is less uniform than that of small particles and contains thin spots and craters, in which holes are sometimes formed (Figure 3c).
As can be seen from the particle size distribution curves (Figure 4), despite the presence of visually coarse particles of 20 μm, the number-average particle size (d50%) is 2.4 μm and the main particle fraction is 1–7 μm. This distribution is close to that of dispersion particles, which contradicts the fact that a significant amount of particle volume (solvent) was evaporated during the preparation. Such size stability may be explained by the formation of a particle’s shell with a hollow (or porous) inner volume.
The particles obtained from the synthesis are spherical with a rather high degree of polydispersity (Figure 4a). The size of the primary particles varies from 0.3 to 20 μm, and they are significantly aggregated but without visible interstices, indicating the possibility of redispersion in the liquid.
The resulting emulsions were centrifuged, and the precipitate from the particles was washed several times with deionized water. The particles were then dried on a filter and additionally at 60 °C and sieved through a 44 μm sieve. The powder obtained is rather hygroscopic and was therefore stored in a desiccator.

3.2. Film Formation

To obtain a uniform layer of particles on the glass substrate, the particles were redispersed in water, and the suspension was applied to the glass surface. After slow evaporation of the excess moisture at 80 °C, a uniform layer of densely packed particles (Figure 5) with a thickness of 120 μm was obtained. In this layer, the presence of pores and cracks (Figure 5a) caused by the contraction of the wet suspension during water removal is noticeable. Figure 5b shows that at the surface of the layer, there are mainly small particles, which can be explained by the action of Stokes’ law during the sedimentation of polymer particles in water.
This effect is an artifact of the deposition technique and will be absent if, for example, a layer is obtained by air spraying.
To study the process of particle fusion and the formation of a continuous layer at elevated temperatures, the glass sample obtained from the suspension was placed on a metal surface heated to 160 °C on one side, while the other side was in contact with air. This made it possible to create a temperature gradient in the sample (Figure 6a) and to record different stages of the transition from particles to a continuous film.
In general, the effect can be divided into stages such as the fusion of particles into larger aggregates (Figure 6b → Figure 6c), which occurs due to the transition of the polymer into a viscous-fluid state and the surface tension of the melt. The collapse of interparticle voids and surface flattening are due to melt spreading (Figure 6c → Figure 6d). Finally, the formation of a solid film is due to the removal of residual trapped air (Figure 6d → Figure 6e). The time needed for the removal of air bubbles at 160 °C, as it is indicated on Figure 6e, is 6 min. It can be reduced by an increase in the sintering temperature via a viscosity decrease, but thermal degradation of the polymer is to be taken into account. Both particle fusion and the removal of air from the melt are determined by the melt viscosity, which is a function of the temperature. The removal of air bubbles is a time-dependent process and therefore requires that the material be held at elevated temperatures for some time. As can be seen in Figure 6a, these process steps are accompanied by a transition of the material from opaque white to transparent white, which is caused by a change in the number of light-scattering planes.
At the level of individual particles (Figure 7), an increase in the number of holes in the craters (Figure 7a) is observed even after slight heating to 100 °C, which is caused by the coincidence of the increase in the molecular mobility of macromolecular segments and their highly oriented state in these meshes of the particle. Further holding at an elevated temperature results in fusion of the particle shells (Figure 7b), but the melt viscosity is still high at this stage. As the viscosity decreases, rounding of the pore walls between the particles is observed (Figure 7c), and then, there is almost complete closure of the pores, except for large contract defects (Figure 7d), which are further tightened and flattened along with surface irregularities (Figure 7e).
The fusion process of these particles is similar to that used in powder bed fusion technologies (see e.g., [36,37]), with the main factors being melt viscosity and its surface tension [38]. In addition to lowering the particle fusion temperature, the use of low-molecular-weight plasticizers will also reduce the melt viscosity and thus the film-formation time.

3.3. Plasticizer Effectiveness Assessment

The affinity of the plasticizer for the polymer was evaluated using the Hansen solubility parameter approach. For PLA 4060D, epoxidized acids, it was determined experimentally using a cloud point technique, which allows for determining the solubility spheres (Figure 8), and for other plasticizers, it was extracted from literature (Table 1).
Since the Hansen model assumes that Ra > Ro is a condition for polymer–plasticizer compatibility, all these plasticizers are compatible with polylactide. At the same time, the epoxidized acids of all these samples are closest (except for dibutyl phthalate) to the center of the PLA solubility sphere.
The transparency temperature was determined for different polymer–plasticizer pairs. For this, the plasticizer and PLA particles were mixed in a stirrer in a dry manner for 20 min. It was not possible to use an auxiliary solvent to disperse the plasticizer because liquids less polar than water (isopropyl alcohol, xylene, ethyl acetate) cause coagulation of the particles.
The prepared powder was sieved through a 44 μm sieve to ensure a uniform plasticizer distribution. The resulting powder was then placed between two microscopic glasses on the surface of the heating table. The melting of PLA particles, as it is shown in Figure 7 above, is a process that is accompanied by the decrease in the light-scattering surface quantity, and therefore, it is visually seen when the system reaches the stage that is shown in Figure 7d. It was noticed that the time of conditioning at each temperature is important because the particle sintering is a viscosity-dependent process and may require time at low temperatures. To account for this fact, the temperature was gradually increased by 2 °C and left for 5 min before the next step.
As shown in Figure 9, all the plasticizers considered have some melting point suppression ability. The most effective is PEG 400: at an extremely high load of 30 wt. %, the transparency point reaches 83 °C, and at loads of 10 and 15 wt. %, the melt film formation occurs at around 100 °C. It is known that the introduction of plasticizers reduces the mechanical properties of polymers (and PLA in particular [41]), so the minimum effective concentration should be chosen.
The synthesized epoxidized linoleic acid comes closest to the PEG-400 efficiency. It achieves comparable efficiencies with 5 wt. % more loading. Epoxidized oleic acid is less effective in melting point suppression and requires 7–8 wt. % more to be comparable to PEG-400. Monomeric ethylene glycol and glycerin are significantly less effective than epoxidized plasticizers, which may be explained by a higher RED, indicating a lower affinity compared to other plasticizers. However, this assumption does not hold for dibutyl phthalate, which has a RED value of 0.44.
The plasticizer affinity affects the value of the tensile strength (Figure 10) of films, obtained from water dispersions and sintering at temperatures 10 °C for 20 min higher than the transparency temperature from Figure 9.
The melt flow index depends on the type of plasticizer added (Figure 11). For 5 wt. % of plasticizer addition, an increase in the MFI of approximately 1.5 times is observed for the most compatible plasticizers (epoxy oleic acid, epoxy linoleic acid, and dibutyl phthalate), while the use of PEG-400 exceeds 20 g/10 min.
Generally, the less compatible a plasticizer is, the less it affects the strength of sintered films. This may be explained by the suggestion that poor affinity does not let the plasticizer incorporate into the particles and, in contrary, a thermodynamically good plasticizer sufficiently increases the polymer chain mobility and deformation ability. The obtained results repeat the pattern of existing research [42,43] in tensile strength decreases with plasticizer introduction. Alongside this, films obtained from sintered powders possess less strength due to the presence of coalescence process defects.
Thus, during the study, a dispersed material was obtained, which can be the basis of the production of coatings using the powder method or from aqueous dispersions. It is shown that the plasticizers (epoxidized fatty acids) synthesized in this work can reduce the film-formation temperature by 20–30 °C compared to the unplasticized polymer, which puts them on a par with PEG. These plasticizers are insoluble in water, so they can potentially be incorporated into the particles at the synthesis stage in the polymer solution.
The ways to improve the results of the work are, of course, the use of more efficient dispersion methods, which will reduce the particle size and thus, in the long run, reduce the film-formation temperature. As shown in [44], at a particle size of 200–500 nm, film formation is observed at temperatures above 60 °C. Considering the possibilities of plasticizers, this temperature can be reduced at least to a temperature slightly above room temperature.
Nevertheless, even this film-formation temperature is too high for conventional paint technology. For example, the basic values for this parameter for acrylic latexes and their copolymers are in the range from 2 to 30 °C [45,46,47], and for polyurethane, they are from 5 to 30 °C [48,49]. An additional resource for reducing the minimum film-formation temperature is also the use of coalescents, which will eventually be removed from the coating.
Alternatively, the technology can be adapted from the scenario of thermally cured coatings or powder coatings, which consists of sequentially applying the dispersion to the product using any suitable method, drying the aqueous phase, and then dosed heating, e.g., via infrared radiation. The amount of heat applied to the film can be adjusted to provide the required heating and cooling rates, as shown in [50,51], and can be used to regulate crystallization and, consequently, the mechanical properties of the polymer matrix. Plasticizers in the composition of coating particles will reduce the film-formation temperature so that they can be used for 3D-printed articles based on PLA.
Undoubtedly, to obtain a full-fledged technology of coatings based on polylactide, it is necessary to study the possibility of obtaining filled composites, the more precise regulation of the melt viscosity to increase flowability, and the control of shrinkage during crystallization, which is not so critical in the production of free films, but a big problem in obtaining coatings on substrates.
Prospective directions of research development are long-term leaching tests for all studied plasticizers, which will allow for a comparison of their long-term compatibility with polylactide in the presence of water and at elevated temperatures. This study would be especially important for low-molecular-weight plasticizers, including the epoxidized fatty acids synthesized in this work. Also important from the point of view of practical implementation would be the study of film formation in the presence of other bio-based components of compositions, such as fillers and pigments [52,53] and coalescents [54], which can influence the fusion processes of biopolymer particles.

4. Conclusions

The paper considers the method of obtaining polylactide films based on aqueous dispersions of redispersed powders, the process of film formation with additional heating, and the influence of plasticizers on this process.
It is shown that using only mechanical emulsification, it is possible to obtain a material with an average particle size of 2.4 µm. At least a fraction of the particles obtained using this method are hollow.
It was found that the introduction of synthesized plasticizers—epoxidized oleic and linoleic fatty acids—affected the temperature of film formation: the first at a 20 wt. % concentration reduces this temperature by 25 °C and the second by 30 °C, which is comparable to the effectiveness of the classical plasticizer, polyethylene glycol, reducing it by 36 °C at the same concentration. At the same time, these plasticizers are insoluble in water and completely bio-based.
The results of the study can be used to develop the technology of water-dispersion coatings based on polylactide, both those intended for curing at ambient temperature and those that require heating.

Author Contributions

Conceptualization, O.M. and V.V.; methodology, O.M.; validation, O.M. and D.B.; formal analysis, O.M. and D.B.; investigation, O.M., D.B. and A.B.; resources, O.M. and V.V.; data curation, O.M., D.B., A.B., I.S., V.H. and I.T.; writing—original draft preparation, O.M., D.B. and A.B.; writing—review and editing, O.M. and D.B.; visualization, D.B.; supervision, O.M.; project administration, O.M. and V.V.; funding acquisition, O.M. and V.V. All authors have read and agreed to the published version of the manuscript.

Funding

This research was funded by Ministry of Education and Science of Ukraine, agreement number PH/53-2024 (26.09.2024) (European Union aid instrument for fulfilling Ukraine’s obligations in the Framework Program of the European Union for Scientific Research and Innovation “Horizon 2020”).

Institutional Review Board Statement

Not applicable.

Informed Consent Statement

Not applicable.

Data Availability Statement

The original contributions presented in the study are included in the article; further inquiries can be directed to the corresponding author.

Conflicts of Interest

The authors declare no conflicts of interest.

Abbreviations

The following abbreviations are used in this manuscript:
PLAPolylactide
PEGMinimum film forming temperature
DBPDibutyl phthalate
EGEthylene glycol
m-CPBAMeta-chloroperoxybenzoic acid
SDSSodium dodecyl sulfate
REDRelative energy difference
MFIMelt flow index

Appendix A

Appliedchem 05 00014 g0a1
Figure A1. FTIR spectra of epoxy oleic acid and epoxy linoleic acid.
Figure A1. FTIR spectra of epoxy oleic acid and epoxy linoleic acid.
Appliedchem 05 00014 g0a1

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Appliedchem 05 00014 g001
Figure 1. 1H–NMR spectra: (a) epoxidized oleic acid; (b) epoxidized linoleic acid.
Figure 1. 1H–NMR spectra: (a) epoxidized oleic acid; (b) epoxidized linoleic acid.
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Figure 2. Polylactide dichloromethane water dispersion particle size distribution.
Figure 2. Polylactide dichloromethane water dispersion particle size distribution.
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Figure 3. Morphology of synthesized PLA particles: (a,b) at low magnification; (c) high magnification of particle with pores.
Figure 3. Morphology of synthesized PLA particles: (a,b) at low magnification; (c) high magnification of particle with pores.
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Figure 4. Granulometry of synthesized PLA particles: (a) differential; (b) cumulative curves.
Figure 4. Granulometry of synthesized PLA particles: (a) differential; (b) cumulative curves.
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Figure 5. Morphology of the layer of dried particles on the substrate: (a) flat surface; (b) cross-section.
Figure 5. Morphology of the layer of dried particles on the substrate: (a) flat surface; (b) cross-section.
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Figure 6. Optical microscopy of film-formation steps: (a) optical microscopy of temperature gradient; (b) larger aggregate of PLA particles; (c) transition to viscous-fluid state; (d) surface flattening and interparticle voids collapse; (e) formation of a solid film.
Figure 6. Optical microscopy of film-formation steps: (a) optical microscopy of temperature gradient; (b) larger aggregate of PLA particles; (c) transition to viscous-fluid state; (d) surface flattening and interparticle voids collapse; (e) formation of a solid film.
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Figure 7. Film formation from PLA suspension particles: (a) hole number increase; (b) particle shell fusion; (c) pore wall rounding; (d) pore closure; (e) surface smoothing.
Figure 7. Film formation from PLA suspension particles: (a) hole number increase; (b) particle shell fusion; (c) pore wall rounding; (d) pore closure; (e) surface smoothing.
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Figure 8. Hansen solubility spheres projection: (a–c)—PLA 4060D; (d–f)—epoxy oleic acid; (g–i)—epoxy linoleic acid.
Figure 8. Hansen solubility spheres projection: (a–c)—PLA 4060D; (d–f)—epoxy oleic acid; (g–i)—epoxy linoleic acid.
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Figure 9. Transparency points for PLA–plasticizer mixtures.
Figure 9. Transparency points for PLA–plasticizer mixtures.
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Figure 10. Tensile strength for PLA–plasticizer (9:1) mixtures.
Figure 10. Tensile strength for PLA–plasticizer (9:1) mixtures.
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Figure 11. Melt flow index for PLA–plasticizer (19:1) mixtures.
Figure 11. Melt flow index for PLA–plasticizer (19:1) mixtures.
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Table 1. Hansen solubility parameters and sphere radius.
Table 1. Hansen solubility parameters and sphere radius.
SampleδDδPδHR0RaREDReference
PLA 4060D16.59.96.48.5
Epoxy oleic acid16.611.19.8 3.60.42
Epoxy linoleic acid16.611.410.5 4.40.51
PEG-40014.67.59.4 5.40.64[39]
Dibutyl phthalate17.88.64.1 3.70.44[40]
Ethylene glycol17.011.026.0 19.72.31[40]
Glycerol17.412.129.3 23.12.71[40]
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Myronyuk, O.; Baklan, D.; Bilousova, A.; Smalii, I.; Vorobyova, V.; Halysh, V.; Trus, I. Plasticized Polylactide Film Coating Formation from Redispersible Particles. AppliedChem 2025, 5, 14. https://doi.org/10.3390/appliedchem5030014

AMA Style

Myronyuk O, Baklan D, Bilousova A, Smalii I, Vorobyova V, Halysh V, Trus I. Plasticized Polylactide Film Coating Formation from Redispersible Particles. AppliedChem. 2025; 5(3):14. https://doi.org/10.3390/appliedchem5030014

Chicago/Turabian Style

Myronyuk, Oleksiy, Denys Baklan, Anna Bilousova, Illia Smalii, Victoria Vorobyova, Vita Halysh, and Inna Trus. 2025. "Plasticized Polylactide Film Coating Formation from Redispersible Particles" AppliedChem 5, no. 3: 14. https://doi.org/10.3390/appliedchem5030014

APA Style

Myronyuk, O., Baklan, D., Bilousova, A., Smalii, I., Vorobyova, V., Halysh, V., & Trus, I. (2025). Plasticized Polylactide Film Coating Formation from Redispersible Particles. AppliedChem, 5(3), 14. https://doi.org/10.3390/appliedchem5030014

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