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Photocurable Oil-Based Thermosets Containing Modifiers from Renewable Sources for Coating Applications
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  • Vojtěch Jašek*
    Vojtěch Jašek
    Institute of Materials Chemistry, Faculty of Chemistry, Brno University of Technology, 61200 Brno, Czech Republic
    *Email: [email protected]
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    Orcidhttps://orcid.org/0000-0002-8020-4948
  • Jan Fučík
    Jan Fučík
    Institute of Environmental Chemistry, Faculty of Chemistry, Brno University of Technology, 612 00 Brno, Czech Republic
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    Orcidhttps://orcid.org/0000-0002-3408-4383
  • Otakar Bartoš
    Otakar Bartoš
    Institute of Materials Chemistry, Faculty of Chemistry, Brno University of Technology, 61200 Brno, Czech Republic
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  • Silvestr Figalla
    Silvestr Figalla
    Institute of Materials Chemistry, Faculty of Chemistry, Brno University of Technology, 61200 Brno, Czech Republic
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  • Radek Přikryl
    Radek Přikryl
    Institute of Materials Chemistry, Faculty of Chemistry, Brno University of Technology, 61200 Brno, Czech Republic
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ACS Polymers Au

Cite this: ACS Polym. Au 2024, 4, 6, 527–539
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https://doi.org/10.1021/acspolymersau.4c00068
Published October 28, 2024

Copyright © 2024 The Authors. Published by American Chemical Society. This publication is licensed under

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Abstract

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Coating materials involving nature-inspired compounds or renewable sources have recently attracted vast attention. This article presents the synthesis of modified rapeseed oil (MRO) as a precursor possessing high biobased carbon content suitable for cured thermosets formation. Two reactive diluents based on renewable sources, methacrylated methyl 3-hydroxybutyrate (M3HBMMA) and ethyl 3-hydroxybutyrate (E3HBMMA), were successfully synthesized. Lastly, isosorbide monomethacrylate (MISD) was suggested and produced as a polarity modifier miscible with modified curable oil systems capable of increasing the thermoset surface energy. All synthesized compounds were structurally analyzed via NMR, ESI-MS, and FTIR. The characterized reactive substances were coated on paper, stainless steel, and beech wood to investigate their suitability for forming thin layers. The paper dip coating verified the reactive diluting properties of M3HBMMA, resulting in the average formed coating deviation decrease (87.5% for undiluted MRO and 28.0% for 50 wt % M3HBMMA containing MRO). Also, the additional cured thermoset weight decreased from 350 to 69 wt % for the same systems. The standardized bend test applied on the coated stainless steel specimens revealed the thermoset’s flexibility and adhesion increase from a 12 ± 2° bending angle of 100% pure MRO to a 121 ± 2° bending angle measured for 40 wt % E3HBMMA containing the MRO-based thermoset. The coated beech wood samples underwent the standardized cross-hatch test investigating the substrate’s coating quality. The 100% MRO reached a level 1 rating (second worst), while the system with 40 wt % of MISD obtained a level 5 rating (the best).

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1. Introduction

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Curable vegetable oil-based precursors are attractive, available, and highly studied materials based on renewable sources, seeking their utility in various application fields. (1−3) The vast amount of attention toward this thermoset-forming group of compounds attracts their high carbon content obtainable from natural sources, which can improve eventual CO2 emissions calculation due to its addition to conventionally petroleum-based systems. (4,5) Triacylglycerols containing unsaturated fatty acids [monounsaturated fatty acids (MUFA) and polyunsaturated fatty acids (PUFA)] can be effectively transformed into materials capable of being modified to reactive systems suitable for material purposes. (6) Product carbon footprint (PCF) calculation is conventionally performed according to ISO 14067. The usage of modified vegetable oils favors the PCF-calculated values since the carbon utilized in the oil’s structure is interpreted negatively in the summarization due to the plant’s CO2 utilization. Therefore, the PCF levels referred to by the supplier and the producer of oil-based curable systems can improve the eventual CO2 emission levels. (47) Unsaturated double bonds undergo epoxidization, forming epoxy functional group formation within the oil carbon backbone. (7−9) The most described, studied, and published are epoxidization mixtures containing hydrogen peroxide (H2O2) reacting with specific monocarboxylic acid (formic (10,11) and acetic (12,13)) to form percarboxylic acid, which reacts with double bonds producing the epoxy groups. This reaction was previously described in numerous articles. (10−13) In our previous paper, we included the process of residual peroxide removal via potassium iodide (KI) and sodium thiosulfate (Na2S2O3) to limit the presence of free peroxide in the epoxidized oil. (14) These species can complicate further oil transformations to reactive precursor compounds capable of radical polymerization. (15) Such systems are typically synthesized from acrylic, (16) methacrylic, (17) or itaconic acid. (18) Also, the respective anhydrides of named acyl donors are used to modify epoxidized oils. (19,20) Modified reactive vegetable oils are perspective materials for SLA 3D printing, (2,3,17) pultrusion, (21,22) or multicomponent coatings. (1) Light-emitting diodes (LEDs) play a critical role in their availability and functionality. This irradiation source was introduced in 2002 and gained massive popularity due to numerous aspects: low energy consumption, low cost for production, minor heat generation during the emitting, or the countless possible wavelengths reaching hardware constructions assured by particular doped components. LEDs are usually used in 3D printers or other instrumentation for thermoset fabrication and ensure adequate and available progress in photocurable materials research. (46)
The organic and polymeric layers applied on metal substrates are a big group of precursor primers formulated for the coating industry. (23) Flexible, transparent, and inert surface treatment mainly serves as an anticorrosive protection for these substrates. (24−26) Several devices and products are exhibited in highly wet surroundings, often containing various salts, acidic, or basic components, which leads to the metal reactivity with the enriched water solution, resulting in the devices’ surface changes and damages. (23) Apart from the reactive acrylic and methacrylic curable vegetable oils, many other material types are incorporated into such systems. Alkyds (polyester resins modified by additional acids or fatty acids) are often used for these purposes, usually in combination with specific rheological modifiers such as styrene, vinyl toluene, methyl methacrylate, butyl acrylate, or acrylic/methacrylic acid. (23,27) These resins are commercially used, carrying particular market names such as CHS-ALKYD. (28) Due to the higher flexibility demands, the oil-urethane systems are also suitable for metal-coating applications. (29,30) Certain polyurethanes containing long-chain polyols and poly(methylene diphenyl diisocyanate) (PMDI) can be enriched with biobased content when various oils are incorporated. Particularly, mono- and diacylglycerides containing free hydroxyl groups, similar to pure castor oil, are added into the reactive polyurethane systems (as a part of the polyol component, which is eventually mixed with MDI). (29,30) In particular, the combined acrylic-urethane coatings combining high Tg acrylic polyol (interpreted with the Tg value of 75 °C) served as multifunctional layers exhibiting antigraffiti, anticontamination, and antiadhesion properties. (29) According to the literature, the acrylic and methacrylic radically polymerized coatings (containing certain reactive or functional additives such as amino acid compounds (24) or Henna leaves extract (25)) were described as exceptional anticorrosion treatments.
Generally, the coatings applied to the polar substrates require specific component selection to ensure the prepared products’ ideal adhesion, compatibility, and functionality. (31,32) The curable and organic coatings used for the paper coating must exhibit certain viscosity levels for the optimal performable coating technologies (such as dip coating). (33) The standard curable coating composition consists of multiple components: the main high-viscous matrix, usually representing 70 wt % of the system; the reactive diluents for the viscosity modification (∼25 wt %); photoinitiator represents up to 5 wt % in the system; eventually, the low-concentrated additives are present in such systems (surfactants, light stabilizer, and colorants). (34) Apart from the rheological modification, the coatings applied on wood substrates usually require other specific properties, such as sufficient mechanical properties, barrier properties, and compatibility with the polar-based surface. (35,36) The acrylated and methacrylated curable oils contain free hydroxyl groups within the carbon backbone structure (due to the nucleophilic substitution of carboxylic acid on the epoxy groups). (16,37) However, the overall surface tension and surface energy of cured thermosets are insufficient for optical compatibility with wood substrates. Specific components ensure the oil-based layers’ polarity increase, namely various silicones, (35) or solid phase polymers, and multicomponent systems such as nanocrystalline cellulose, liquefied wood dust, or liquefied pine sawdust. (36)
Polyurethanes are the mainly used thermoset systems for coating various substrates such as metals or woods. (53−55) The application of PU coatings relies on the chemical principle of mixing polyols and isocyanates. Then, they are applied on the particular surface. Then, the catalysts (mainly amines) are added, and a thermoset is formed. The toxicity and nonsustainable character of used isocyanates are the main adverse effects of PU coatings. (53−55) The thermoplastic coatings are also often used in numerous applications. Poly(lactic-co-glycolic) acid (PLGA) or poly(vinyl acetate) (PVAc) are often used for coating applications (56) and exhibit a sustainable potential compared to commercially used styrene–butadiene polymers. (57) However, the thermoplastic systems required additional reactive diluents for coating processing. Therefore, the VOC has a major adverse effect on these systems from a sustainability and economic viewpoint. (56,57,61) The idea formulated and suggested in this work is to incorporate a reactive diluent into the coating. The reactivity of curable precursors ensures the incorporation of the diluent into the formed coat, which minimizes VOC in the product. The application of biobased structures also enhances the sustainable character of such formed products. (59,60)
This paper is focused on the coating system formulation based on the methacrylated rapeseed oil (MRO) as a main component, and liquid curable additives, methacrylated methyl 3-hydroxybutyrate (M3HBMMA), methacrylated ethyl 3-hydroxybutyrate (E3HBMMA), and isosorbide monomethacrylate (MISD), modifying the layer’s rheology and polarity. The syntheses of all named components are described in our previously published articles. (14,38,39) The methacrylated oils, alkyl carboxylates, or modified isosorbide can be used for various different applications beyond the coatings, such as stereolithography 3D printing, (42) waterborne adhesives, (50) or thermoset-based pultrusion. (58) The other material utilities benefit mainly from the mentioned compounds’ biobased content and availability. This work directly focuses on applying suggested, synthesized, and characterized curable systems suitable for coating purposes. Various substrates were selected for the coating experiments: paper, stainless steel, and beech wood. All chosen materials were coated and characterized, and the applied layers were tested from a coating-forming capability standpoint. The dip coating and transparent layer-assisted coating were the experimentally investigated approaches. This paper’s innovative aspect lies in using our previously novel-synthesized less viscous methacrylated alkyl 3-hydroxycarboxylates, which have not yet been used for coating applications. Also, isosorbide monomethacrylate’s upgraded production was described previously, and the coating application is the novel proposed utility for this reactive compound.

2. Experimental Section

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2.1. Materials

Epoxidized rapeseed oil was produced in our previously published paper (14) from virgin rapeseed oil obtained from FICHEMA Inc. (Czech Republic). Despite the complete synthesis of alkyl carboxylates described in our recent paper, (38) we used methyl and ethyl 3-hydroxybutyrates purchased at Sigma-Aldrich. Isosorbide used for isosorbide monomethacrylate synthesis was obtained from Novaphene, India. Other reactants, methacrylic anhydride (MAAH, 94%), methacrylic acid (MAA, 98%), catalysts potassium carbonate (K2CO3, 99%), triethylamine (TEA, 99%), photoinitiator phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide (BAPO, 97%), solvent ethyl acetate (EtAc, 99%), and neutralization base sodium hydroxide (NaOH, 99%), were purchased at Sigma-Aldrich. The cellulose paper, stainless steel, and beech wood were all obtained from BAUHAUS, Czech Republic (local construction producer).

2.2. Structural Verification Methods

Nuclear magnetic resonance (NMR) was used to obtain the 1H and 13C spectra for structural confirmation. Bruker Avance III 500 MHz (Bruker, Billerica, MA, USA) with a measuring frequency of 500 MHz for 1H NMR and 126 MHz for 13C NMR was used for the measurements at the temperature of 30 °C using d-chloroform (CDCl3) as a solvent. Tetramethylsilane (TMS) served as an internal standard. The chemical shifts (δ) are expressed in part per million (ppm) units referenced by a solvent. Coupling constant J has (Hz) unit with coupling expressed as s─singlet, d─doublet, t─triplet, q─quartet, p─quintet, m─multiplet.
The molecular structure was also confirmed by mass spectrometry (MS) (Bruker EVOQ LC-TQ) using electrospray ionization (ESI). Product scan spectra were obtained by fragmentation of the following [M + H]+ precursor ions for all synthesized molecules (MRO, M3HBMMA, E3HBMMA, and MISD). Collision energy spread (5–20 eV) improved the collected MS/MS data quality. The obtained mass spectra were compared to their in silico prediction by CFM-ID 4.0, (40) which also proposed the product ion structure for the most intensive masses.
Fourier-transform infrared spectroscopy (FTIR) served as an additional structure-verification method. The infrared spectrometer [Bruker Tensor 27 (Billerica, MA, USA)] was used, and the attenuated total reflectance (ATR) method was applied, where a diamond served as a dispersion component. The diode laser served as the irradiation source. A Michelson interferometer eventually quantified the measured signal. All illustrated spectra were composed of 32 total scans with a resolution of 2 cm–1.
Differential scanning calorimetry (DSC) confirmed the curability of the products. Also, this technique served for the comparison of compounds’ reactivity─the lower the peak temperature (Tp) is, the more reactive the system is. The compounds (MRO, M3HBMMA, E3HBMMA, and MISD) were mixed with Luperox DI [tert-butyl peroxide, 1% (w/w) quantity added to the system]. The solutions were transferred to aluminum pans (5–7 mg) and sealed with the hermetic lid. The used instrument [DSC 2500 model from TA Instruments (New Castle, DE, USA)] served for the analysis. The sample exhibited continual heat increase (30–215 °C) with a 10 °C min–1 heating ramp.
Thermogravimetric analysis (TGA) determined every synthesized reactive precursor’s inflection points (Tmax). The samples used for TGA were the cured compounds analyzed by DSC previously. TGA performed on a TGA Q500 instrument [TA Instruments (New Castle, DE, USA)] illustrated the degradation process by the particular weight loss dependencies. The samples (5 mg) were measured under the following conditions: equilibration at 40 °C; heating to 600 °C at a heating rate of 10 °C/min under N2; heating to 650 °C at a heating rate of 10 °C/min under an air atmosphere.
The acidity value served as a method for determining the purity. Based on the reaction mechanics, methacrylic acid is the only secondary product in all syntheses. Therefore, determination of the acidity value prior to and after purification provides information regarding purity. The acidity value was measured according to ISO 660:2020.
The contact angle measurement investigated the hydrophobicity of the coated paper. We used a goniometer (the deviation ±1°) for the analysis, and See Software 7.0 was used for the surface energy quantification. The liquids used for the Lewis acid theory measurements were water, glycerol (polar), and di-iodo methane (nonpolar). Every coated paper sample (including 0–50 wt % M3HBMMA) underwent 10 measurements for every liquid. The final contact angle values were composed of the average values of all measurements. The surface energy levels were obtained from the software mentioned software.

2.3. Synthesis of Methacrylated Rapeseed Oil

The synthesis (Scheme 1) was described in detail in our previous article. (14) The particular mass amount of epoxidized rapeseed oil (ERO) (calculated respectively to the OOC value, for the OOC reaching 6.1%, the total weight of ERO was 389 g) was mixed with MAA in the molar ratio (epoxy groups:MAA) = (1:1.5), which resulted in 195 g of MAA. This mixture was homogenized and set to 110 °C. Once the solution reached the reaction temperature, 2.6 wt % of catalyst (TEA, 15.6 g) was added to the mixture. The reaction lasted 24 h for the epoxy groups’ conversion maximized conversion. The eventual postreaction solution was mixed with EtAc (50 wt %) for the viscosity decrease, and the residual acidity was neutralized with NaOH in water solution (equimolar to the measured acidity). After neutralization, the mixture was washed with distilled water to remove the methacrylic salts. Eventually, the product was separated from EtAc via vacuum distillation. The obtained FTIR and 1H NMR spectral product confirmations are listed below (spectra are available in the Supporting Information):

Scheme 1

Scheme 1. Methacrylation of Epoxidized Rapeseed Oil (ERO) Resulting in Methacrylated Rapeseed Oil (MRO) Production
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1H NMR of methacrylated rapeseed oil (500 MHz, CDCl3): δ 6.16–6.09 (m, 2H), 5.58 (q, J = 2.1 Hz, 2H), 4.29 (dd, J = 11.9, 4.3 Hz, 2H), 4.18–4.08 (m, 3H), 2.30 (tt, J = 7.5, 2.3 Hz, 6H), 2.08–1.88 (m, 9H), 1.80–1.11 (m, 60H), 0.88 (tt, J = 7.1, 1.6 Hz, 7H).
FTIR spectrum absorption wavenumber intervals: O–H stretch of 3550–3200 cm–1, C–H stretch of (alkene) 3100–3000 cm–1, C–H stretch of 3000–2840 cm–1, C═O (ester) stretch of 1750–1735 cm–1, C═C stretch of 1662–1626 cm–1, C–O (ester) stretch of 1210–1163 cm–1, C═C bend of 840–790 cm–1.

2.4. Synthesis of Methacrylated Alkyl Carboxylates (M3HBMMA and E3HBMMA)

The syntheses producing methacrylated alkyl carboxylates (Scheme 2) were described, studied, and summarized in our published paper. (38) The particular alkyl 3-hydroxybutyrate [methyl 3-hydroxybutyrate (M3HB), 300 g, or ethyl 3-hydroxybutyrate (E3HB) 300 g] was mixed with MAAH in an equimolar ratio (1:1) (392 g of MAAH for M3HB, and 350 g of MAAH for E3HB). The catalyst K2CO3 was added in a 1 wt % concentration (7 g into M3HB and 6.5 g into E3HB). The mixture was set to 80 °C, and the reaction was performed for 24 h. The reaction mechanics of methacrylation by methacrylic anhydride was investigated and published in our previous article. (48) The catalyst was potassium acetate; however, the basicity is the main catalytic factor. Therefore, potassium acetate and potassium carbonate can achieve sufficient basic conditions. The eventual mix was neutralized similarly to the MRO described in the previous section (Section 2.3). The neutralized product was structurally analyzed by using FTIR, ESI-MS, 1H NMR, and 13C NMR:

Scheme 2

Scheme 2. Methacrylation of Alkyl Carboxylates Producing Methacrylated Methyl and Ethyl 3-Hydroxybutyrate (M3HBMMA and E3HBMMA)
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2.4.1. Methacrylated Methyl 3-Hydroxybutyrate (M3HBMMA)

1H NMR (CDCl3, 500 MHz): δ (ppm) 6.07–6.06 (dq; J = 1.96; 1.02; 0.98; 0.98 Hz; 1H), 5.56–5.53 (p; J = 1.60; 1.60; 1.58; 1.58 Hz; 1H), 5.35–5.29 (dp; J = 7.32; 6.26; 6.26; 6.25; 6.25 Hz; 1H), 3.68 (s; 3H), 2.72–2.67 (dd; J = 15.34; 7.29 Hz; 1H), 2.57–2.53 (dd; J = 15.35; 5.79 Hz; 1H), 1.92 (dd; J = 1.63; 1.01 Hz; 3H), 1.35–1.34 (d; J = 6.36 Hz; 3H).
13C NMR (CDCl3, 126 MHz): δ (ppm) 170.70; 166.59; 136.47; 125.41; 67.68; 51.73; 40.74; 19.89; 18.23.
ESI-MS analyzed the precursor [M + H]+ 187.1 m/z. Fragments: 155.1, 101.1, and 69.2 m/z according to CFM ID 4.0.
FTIR spectrum absorption wavenumber intervals: C–H stretch. 3000–2840 cm–1, C═O (ester) stretch. 1750–1735 cm–1, C═C stretch. 1662–1626 cm–1, C–O (ester) stretch. 1210–1163 cm–1, C═C bend. 840–790 cm–1.

2.4.2. Methacrylated Ethyl 3-Hydroxybutyrate (E3HBMMA)

1H NMR (CDCl3, 500 MHz): δ (ppm) 6.07–6.06 (dd; J = 1.75; 0.97 Hz; 1H), 5.54–5.53 (q; J = 1.63; 1.63; 1.63 Hz; 1H), 5.35–5.29 (dp; J = 7.50; 6.24; 6.24; 6.24; 6.24 Hz; 1H), 4.16–4.10 (qd; J = 7.11; 7.06; 7.06; 0.96 Hz; 2H), 2.69–2.65 (dd; J = 15.28; 7.42 Hz; 1H), 2.55–2.51 (dd; J = 15.29; 5.75 Hz; 1H), 1.94–1.91 (m; 3H), 1.34–1.33 (d; J = 6.28 Hz; 3H), 1.25–1.22 (t; J = 7.13; 7.13 Hz; 3H).
13C NMR (CDCl3, 126 MHz): δ (ppm) 170.21; 166.54; 136.46; 125.33; 67.71; 60.57; 41.01; 19.85; 18.19; 14.14.
ESI-MS analyzed precursor [M + H]+ 201.0 m/z. Fragments: 156.0, 115.1, and 73.2 m/z according to the CFM ID 4.0.
FTIR spectrum absorption wavenumber intervals: C–H stretch. 3000–2840 cm–1, C═O (ester) stretch. 1750–1735 cm–1, C═C stretch. 1662–1626 cm–1, C–O (ester) stretch. 1210–1163 cm–1, C═C bend. 840–790 cm–1.

2.5. Synthesis of Isosorbide Monomethacrylate

Isosorbide monomethacrylate synthesis (Scheme 3) was described, investigated, and experimentally verified in our previous article. (39) The reaction catalysis mechanics is similar to M3HBMMA and E3HBMMA reactions. (48) Isosorbide (1 mol, 146.2 g) was melted at 60 °C and mixed with catalyst K2CO3 (0.01 mol, 0.98 g). Once the reactant melted, MAAH (1 mol, 154.2 g) was transferred into a dripping funnel and continually mixed drop by drop into the melted isosorbide (this process lasted 4 h). After the MAAH quantitative addition, the temperature was decreased to 40 °C, and the reaction lasted an additional 8 h. After the reaction, the formed MAA was distilled from the product mixture. Liquid–liquid extraction (LLE) purification involves the addition of distilled water (300 g). The water phase containing MISD was extracted by EtAc (300 g) to transfer MISD into the EtAc solution. Lastly, MISD was separated from EtAc by vacuum distillation. This process was repeated three times to maximize the product yield. Pure MISD was characterized via FTIR, ESI-MS, and 1H NMR:

Scheme 3

Scheme 3. Partial Methacrylation of Isosorbide Resulting in Isosorbide Monomethacrylate (MISD) Production Involving the Purification by Liquid–liquid Extraction (LLE)
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1H NMR (CDCl3, 500 MHz): δ (ppm) 6.17–6.11 (dt, J = 15.6, 1.3 Hz, 2H); 5.64–5.59 (dt, J = 3.1, 1.5 Hz, 2H); 5.24–5.18 (m, 1H); 4.92–4.88 (t, J = 5.1 Hz, 1H); 4.68–4.61 (t, J = 4.8 Hz, 1H); 4.57–4.49 (dd, J = 4.4, 1.2 Hz, 1H); 4.44–4.38 (dd, J = 4.6, 1.1 Hz, 1H); 4.37–3.33 (d, J = 3.2 Hz, 1H); 4.21–3.69 (m, 10H); 3.66–3.51 (dd, J = 9.5, 6.0 Hz, 1H); 2.68–2.51 (d, J = 7.0 Hz, 1H); 1.98–1.94 (m, 6H).
ESI-MS analyzed the precursor [M + H]+ 215.1 m/z. Fragments: 129.1 and 62.9 m/z according to CFM ID 4.0.
FTIR spectrum absorption wavenumber intervals: O–H stretch. 3550–3200 cm–1, C–H stretch. 3000–2840 cm–1, C═O (ester) stretch. 1750–1735 cm–1, C═C stretch. 1662–1626 cm–1, C–O (ester and alcohol) stretch. 1210–1163 cm–1, C═C bend. 840–790 cm–1.

2.6. Dip Coating With the Oil-Based Mixture

The dip coating was applied to hydrophilic paper to verify the rheological modification of MRO using a low-viscosity reactive diluent, M3HBMMA, resulting in the hydrophobic coated paper formation. The coating process consisted of the following steps. The particular coating solutions were prepared (0, 10, 20, 30, 40, and 50 wt % of M3HBMMA in MRO), and 1 wt % of photoinitiator BAPO was added. The complete solution was placed into the Petri dish, and a preweighted piece of paper was dipped into the solution for 10 s. The coated paper was removed from the curable mixture, and the excess precursor solution was separated for 1 min. Subsequently, the coated paper was exhibited to the blue irradiation of LED (8 mW/cm2 of irradiation power, 405 nm wavelength) for 20 min. The formed layer thickness was measured; the added polymer weight was analyzed, and the hydrophobic character after the coating was confirmed. The scheme of performed dip coating is displayed in Figure 1.

Figure 1

Figure 1. Performed dip coating using oil-based curable solution forming a hydrophobic paper.

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2.7. Transparent Layer-Assisted Coating by the Oil-Based Mixture

The metal and wood were coated by an oil-based precursor solution via a transparent layer-assisted approach, as schematically displayed in Figure 2. This procedure was chosen due to the laboratory scale of experiments. The rotating cylinders are an up-scaled alternative to this process. In this article, we aimed for the proposed presentation of the rheological, mechanical, and chemical properties of the used materials. The metal was coated by the oil solution containing E3HBMMA (0, 10, 20, 30, and 40 wt %) due to E3HBMMA’s flexibility character, assuring better adhesion and mechanical properties of the eventual product. The beech wood was treated by the curable system involving MISD (0, 10, 20, 30, and 40 wt %) to study the wood-thermoset adhesion enhancement and increased resistance against mechanical damage. The prepared MRO-based curable mixture was poured on the substrate’s surface, covered by the transparent (PP) layer, set to a defined layer thickness, and cured by an LED irradiation source (8 mW/cm2 of irradiation power, 405 nm wavelength) for 10 min. The polymer cover on the metal substrate was analyzed using applied norm ASTM D522. The polymer coating on the beech wood was investigated via the cross-hatch method, ISO 2409.

Figure 2

Figure 2. Performed transparent layer-assisted coating of stainless steel and beech wood by an oil-based curable coating system.

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3. Results and Discussion

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3.1. Oil-Based Coating Component Characterization

The synthesized products were characterized via numerous structure-verification methods, and the results and spectra obtained are given in the Supporting Information. The 1H NMR spectra of all obtained compounds [methacrylated rapeseed oil (a), methacrylated methyl 3-hydroxybutyrate (b), isosorbide monomethacrylate (c), and ethyl 3-hydroxybutyrate (d)] are shown in Figure 3 to present successful syntheses. The chosen reaction conditions for methacrylation of M3HBMMA, E3HBMMA, and MISD are based on the results from our previous publications. (38,39,48) It was found that MISD’s conversion reached above 90% conversion after 10 h (39,48); the conversions of M3HBMMA and E3HBMMA were monitored in time (59.5% M3HBMMA and 45.6% E3HBMMA). (38) Based on these results, the synthesis was set to 24 h to achieve the maximal conversion. The chosen reaction temperatures were selected from between 60 and 80 °C, and most of the reactions achieved high yields in a published review focused on the DMAP-catalyzed methacrylation. (49) The catalyst’s load was set to 1 mol % in our work. However, the catalyst concentration was much higher in previously published articles (10 mol %), while the reaction time lasted 16–24 h. (50) Based on these published results, we chose 80 °C and 24 h reaction time for M3HBMMA and E3HBMMA and 12 h for MISD.

Figure 3

Figure 3. Obtained 1H NMR spectra of all synthesized curable compounds used for the coating applications. (a) Methacrylated rapeseed oil (MRO), (b) methacrylated methyl 3-hydroxybutyrate (M3HBMMA), (c) isosorbide monomethacrylate (MISD), and (d) ethyl 3-hydroxybutyrate (E3HBMMA). Reproduced from ref (38). Available under the CC-BY-4.0 license. 2022 by Vojtch Jaek et al.

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The 1H NMR spectra of M3HBMMA (Figure 3b) and E3HBMMA (Figure 3d) contain minimum undefined signals (E3HBMMA contains only negligible peaks at 3.7 and 1.6 ppm), which are probably minor impurities from the methacrylation (either residual MAA of MAAH). The spectrum of MRO (Figure 3a) contains wider regions of connected multiplet peaks. This results from an undefined triacylglyceride complex structure containing several fatty acids. As a result, these particular signals form wide shift intervals, which are integrated (displayed in the Supporting Information). The essential signals lie in shifts 5.6 and 6.1 ppm, confirming the presence of unsaturated double bonds of methacrylate functional groups. The 1H NMR spectrum of MISD (Figure 3c) reveals the racemic mixture of exo and endo monomethacrylates. This is a consequence of nonselective chemical synthesis using anhydride as an acyl donor. However, all the signals in the spectrum confirm the structure of the monomethacrylated isosorbide. All presented spectral numerical values were previously published in our articles on synthesis kinetics, catalysis, and product isolation. (14,38,39)
All products were also characterized via thermal analyses (TGA and DSC) to report their additional properties. The results are shown in Figure 4 [TGA results in (a) and (b); DSC illustrated in (c)]. The differences are evident from both analyses. TGA uncovered the exceptional thermal stability of MRO due to its complex carbon structure (Tmax reaching 417.5 °C) compared to MISD reaching a lower thermal stability (Tmax 343.2 °C). The lowest thermal stability exhibits both M3HBMMA and E3HBMMA (Tmax around 285 °C) due to ester bonding in their structure. The performed DSC uncovered the specific difference between MRO and other compounds since the measured exothermic peak reached a much lower maximum value compared to M3HBMMA, E3HBMMA, and MISD but formed a much wider signal. This outcome signalizes lower and longer-lasting reactivity of MRO. The other three systems exhibited narrow, high peaks, signalizing exceptional and quantitative curability. The comparison of MISD with methacrylated alkyl carboxylates uncovers a higher MISD reactivity due to the lower Tp value (117.1 °C) than M3HBMAA and E3HBMMA (Tp reaching 161.0 and 156.7 °C, respectively). The combined results from TGA and DSC show a positive impact on final cured thermoset properties since MRO enhances the thermal stability and MISD, M3HBMMA, and E3HBMMA increase the reactivity of the precursor system. All measured values and results are summarized in Table 1. The summarization involves the gravimetric yields determined by the weight measurement compared with the theoretical calculation. Also, the products’ purity is present in Table 1, which is determined by the residual acidity value compared to the initial value prior to methacrylic acid isolation. Lastly, the biobased weight content is included in the summarized results. The values were determined according to their structure and meticulously analyzed via NMR, ESI-MS, and FTIR. The importance of biobased content determination is detailed and described in the published literature. (51)

Figure 4

Figure 4. Thermal analysis of synthesized products. (a) TGA integral results, (b) TGA derivative results, and (c) DSC curability study.

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Table 1. Summarized Results of Thermal Analyses and Syntheses
systemDSC peak temperature Tp (°C)TGA inflection point Tmax (°C)bio-based mass content (%)product yield (gravimetrically) (%)purity (acid value) (%)
MRO179.1417.576.6294.598.9
M3HBMMA161.0284.855.8598.399.8
E3HBMMA156.7285.574.9398.099.9
MISD117.1343.268.3061.899.5

3.2. Dip Coating of a Hydrophilic Paper

The paper is the fibrous cellulose substrate exhibiting a highly hydrophilic character due to the many unbonded free hydroxyl groups within the cellulose carbon backbone structure. This characteristic property leads to the paper’s modification using several polymeric or organic-based systems, assuring the paper’s wetting prevention. (41) Apart from the structural characterization of the coated organic layer, the rheological, adhesive, and mechanical properties must be studied to perform the coating process successfully. The enhancement of MRO material properties by the methacrylated alkyl carboxylates was investigated in our published papers. (14,42) The decreased apparent viscosity is evident from the results illustrated in Table 2. We used measured rheological characterization from our previous work. The particular weight contents of M3HBMMA are directly connected with the viscosity value in Table 2. (14) SLA 3D printing was the leading application field in the published works. This article mainly focuses on the rheological and coating-applicable enhancements of alkyl carboxylates in MRO-based systems. The dependency of MRO apparent viscosity on the methacrylated alkyl carboxylate (M3HBMMA) is summarized in Table 2.
Table 2. Obtained Rheological Dependency of the Methacrylated Alkyl Carboxylate in Methacrylated Rapeseed Oil (MRO)a
MRO rheological modification
wM3HBMMA (wt %)η (mPa s)
01790.2
51254.6
10836.0
15594.7
20420.0
25301.3
30234.7
35189.7
40158.6
45142.6
a

Reproduced from ref (14). Available under the CC-BY-4.0 license. 2023 by Vojtch Jaek et al.

Based on our previous findings, we prepared the defined varying concentrations of M3HBMMA as a rheological modifier and reactive diluent in our synthesized MRO-based curable system. Methacrylated alkyl carboxylates exhibit specific low apparent viscosity (∼3 mPa s); (14) therefore, they were selected as potential candidates for reactive diluting purposes. Also, we decided to use M3HBMMA for the paper coating (E3HBMMA was chosen for the metal coating) due to the molecules’ innovativeness in the coating utility field. Previously, methacrylated alkyl carboxylates were applied mainly for SLA 3D printing. (42) The dip coating was performed with the prepared photoinitiator-containing curable system with the varying weight content of M3HBMMA, and the layer thickness was measured in different paper regions. Subsequently, the weight content increased by the thermoset surface treatment was analyzed via gravimetry. Eventually, the hydrophobic character assured by the polymer coating was confirmed for all prepared specimens. The dip coating performed using different curable systems is displayed in Figure 5. The paper coating measurement results are shown in Figure 7.

Figure 5

Figure 5. Performed paper-dip coating using an oil-based curable system involving the reactive diluent, methacrylated methyl 3-hydroxybutyrate (M3HBMMA), in varying weight concentrations. (a) 0% M3HBMMA, (b) 10% M3HBMMA, (c) 20% M3HBMMA, (d) 30% M3HBMMA, (e) 40% M3HBMMA, and (f) 50% M3HBMMA.

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Figure 6

Figure 6. Performed contact angle measurements for 50 wt % of the M3HBMMA system. (a) Measurement with water, (b) measurement with glycerol, and (c) measurement with di-iodo methane.

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Figure 7

Figure 7. Paper dip coating analysis results involving the layer thickness measurement for the systems with varying layer thickness measured in the different coated-paper regions and the thermoset weight content gravimetric analysis.

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The varying system viscosities and results of the coating technology process are evident in Figure 5. The pure MRO system (Figure 5a) contains cured drips on the bottom of the treated paper compared with the systems with higher reactive diluent content (Figure 5d–f). The rapid polymeric weight content is also observable from the demonstrated pictures since the coated paper with 0 wt % of M3HBMMA bent the paper due to most of the thermoset content. The insufficient viscosity decrease is detectable for the systems below 30 wt % of M3HBMMA (Figure 5a–c). This outcome confirms the reactive diluent requirements in other paper-coating articles in the published literature: the reactive diluent content was generally set to approximately 25 wt % (34) or 30 wt % for particularly oil-coated paper. (41) The measured coated layer thicknesses (Figure 7) also further investigated the formed coat homogeneity in the different measured paper regions. The 0 wt % M3HBMMA-coated system exhibited a layer thickness interval ranging from 640 to 1200 μm (87.5% spread across the coated area). On the other hand, the slightest thickness deviations exhibited the most diluted paper, reaching a 28.0% spread. The breaking concentration for the potential applications (30 wt % M3HBMMA content) reached 43.6% inconsistency across the coated substrate. These values can be decreased by selecting alternative coating techniques. The thermoset weight content on the coated paper varied from 350 wt % increase (0 wt % of M3HBMMA) to 69 wt % (50 wt % of M3HBMMA).
We measured the contact angle to quantify the surface energy value for all of the prepared coated papers. The results are summarized in Table 3. The demonstrated contact angle measurements using water, glycerol, and di-iodo methane are displayed in Figure 6. The results confirm that the hydrophobic character slightly increases with M3HBMMA content. This minor trend is caused by the free hydroxyl functional group minimization in the system with the rising M3HBMMA content. The hydroxyl groups are present in the MRO structure (see Scheme 1). However, the hydrophobic character is basically unchanged with the reactive diluent content. The repulsive character toward water is simplified in Figure 5. According to available sources, the uncoated paper exhibits exceptional hydrophilic character. (52)
Table 3. Summarized Results of Contact Angle Measurements
systemcontact angle (Water)contact angle (Di-Iodo Methan)contact angle (Glycerol)free surface energy γS (mJ/m2)
0% M3HBMMA85° ± 3°35° ± 3°71° ± 3°42.6
10% M3HBMMA86° ± 2°35° ± 2°73° ± 1°42.0
20% M3HBMMA88° ± 3°34° ± 2°72° ± 1°42.9
30% M3HBMMA90° ± 3°34° ± 3°73° ± 2°42.9
40% M3HBMMA90° ± 1°34° ± 1°72° ± 3°42.9
50% M3HBMMA91° ± 3°33° ± 3°75° ± 3°42.9

3.3. Transparent Layer-Assisted Metal Coating

The metal coating was formed from an MRO-based curable system containing E3HBMMA as a reactive diluent. According to the used norm for coating analysis and the industrial requirements for polymer coatings on metal surfaces, the adhesion and flexibility of the applied coat are the key parameters. (43) Based on our previous findings, E3HBMMA is a suitable candidate for the MRO system reactive diluting since this curable monomer exhibits low Tg value (below 25 °C), convenient storage modulus (860 MPa at 28 °C), and relatively high flexibility. (42) On the other hand, MRO reaches high cross-linking density (56.4 kmol/m3) and exceptional thermal stability (heat-resistant index reaching 170.3 °C). (14) These factors, in combination, signify the E3HBMMA’s suitability for the conveniently applied flexible and thermally stable polymer coating on the stainless steel surface. The coating process was performed using curable systems with different E3HBMMA weight contents (from 0 up to 40 wt %), and following the used norm, the bending procedure was done. The applied polymer coat thickness consistency was measured, and the bending angle at the layer deformation was determined. The results of the experimental investigations are shown in Figure 8.

Figure 8

Figure 8. Formed polymer coating on stainless steel substrates, coating thicknesses, and bending angle measurement results. The experimental bending angle apparatus for MRO-based thermoset coatings. (a) 0 wt % E3HBMMA, (b) 10 wt % E3HBMMA, (c) 20 wt % E3HBMMA, (d) 30 wt % E3HBMMA, and (e) 40 wt % E3HBMMA.

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The average thickness of formed layers formed at all substrates containing five triplicates in total reached 388 ± 8 μm, which results in an approximate 2% relative deviation across all prepared and coated systems. This value is sufficient according to the used norm. The determined bending angles are summarized for all prepared specimens in Figure 8a–e. The system’s flexibility and durability increase continually and gradually based on the determined bending angles. The MRO system containing 0 wt % E3HBMMA reached a bending angle of 12 ± 2°, while the most flexible system containing 40 wt % of E3HBMMA reached 121 ± 2°, signifying the significant flexibility and adhesion increase. The published metal bending tests were usually performed at a 15° bending angle. (43) The trend did not progress between E3HBMMA concentrations of 10 and 20 wt % probably due to the standard measurement potential failed tests. However, the increasing flexibility and adhesion trend with the increasing E3HBMMA content was confirmed from the perspective of all prepared systems.

3.4. Transparent Layer-Assisted Wood Coating

The wood coating is commonly applied for surface treatment, assuring the hydrophobicity of the polar system, the gloss and color modification of particular products, and the protective character of the substrate. The oil-based wood coatings are often unmodified (pure oils such as castor and linseed oils are used) due to their spontaneous cross-linking in the air oxidizing conditions and increased temperatures. (23) The curable wood coating systems have advantages such as faster manufacture, property regulations, and more quantitative molecular site formation. The polarity of the layer-forming system influences the adhesion, durability, and protective properties since wood is a highly polar system. Various strategies leading to the coat’s surface energy increase are often incorporated, such as silica particle presence (44) or other polar substance addition (chitosan). (45) Isosorbide monomethacrylate (MISD) served as an oil-soluble polarity modifier in the article. The cross-hatch (norm ISO 2409) method was selected as an investigation method, and the coating thickness measurements were used to evaluate the coating characteristics. The varying MISD content was set for the wood coating experiments (from 0 wt. up to 40 wt % of MISD in an MRO-based curable system). The demonstrated cross-hatch tests (including the pictures of used tapes), the coating thickness measurements, and the outlined thermoset layer ratings are summarized in Figure 9. The complete cross-hatch pictures are given in the Supporting Information.

Figure 9

Figure 9. Wood coating results involving an MRO-based curable system with the polarity modifier isosorbide monomethacrylate (MISD). The illustrative cross-hatch tests for (a) 0 wt % of MISD and (b) 40 wt % of MISD. The coating thickness measurements for all prepared systems and the ISD 2409 adhesion and coating quality rating based on the cross-hatch results.

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We included the illustrative pictures of the edge coating examples (0 and 40 wt % of MISD in MRO-based coating) presented in Figure 9a,b to emphasize the enormous coating quality increase with the most MISD in the layer. The cross-hatch test uncovered the poor damage resistance of 0 wt % of the MISD-containing MRO system, resulting in cracks along the knife cut (see Figure 9a). The adhesion tape test also demonstrated the poor adhesion of unmodified MRO coating due to a solid hydrophobic character. The 0 wt % MISD system reached the level 1 rating, verifying the used curable system’s inferior adhesive and protective properties. On the other hand, the 40 wt % of MISD containing MRO-based mixture coated on the beech wood reached significantly better results. The formed layer knife damage resulted in unobservable cracks along the formed cross, signing the formed coat’s enhanced antidamage characteristics and convenient mechanical properties. Moreover, the tape test proved the exceptional adhesive character of 40 wt % MISD-containing polymer coating since no removed parts were found on the used tape. This outcome assured a level 5 rating for this system, which is the highest obtainable level. The other systems (added in the Supporting Information) demonstrated the apparent improvement of adhesion and the increased damage-protective character of MRO-based coatings with the rising MISD content. Also, the coating thickness reached an average value of 206 ± 12 μm less than a 6% deviation among the prepared samples. This value fulfills the norm’s definition.

3.5. Surface Morphology Investigation

We performed optical microscopy to investigate noncoated and coated substrates’ morphology and surface character. The obtained images are shown in Figure 10. The paper substrate morphology comparison uncovers the fibrous character of noncoated paper which is exceptionally hydrophilic and the smooth and continual surface after the coating. The coated metal images illustrate the coated shine surface’s mechanical and optical protection. The coated wood exhibits tunable protection against mechanical damage. Also, irradiation protection can proceed when appropriate colorants and additives are added to the thermoset structure due to the continual distribution of the coat.

Figure 10

Figure 10. Optical microscopy of all coated substrates. (a) Noncoated paper, (b) coated paper, (c) noncoated stainless steel, (d) coated stainless steel, (e) noncoated beech wood, and (f) coated beech wood.

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4. Conclusions

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This article presents the syntheses and coating applications of curable methacrylated rapeseed oil (MRO), low-viscosity reactive methacrylated alkyl carboxylates (M3HBMMA and E3HBMMA), and water-soluble highly polar isosorbide monomethacrylate (MISD). The productions of named reactive compounds were structurally confirmed via meticulous cross-analysis involving 1H NMR, 13C NMR, ESI-MS, and FTIR analytical methods. In total, four curable systems were formed to use MRO as a main coating binder for polymer coatings, M3HBMMA and E3HBMMA served as a low-viscous rheology modifier, and MISD’s role was the MRO-based thermoset’s polarity and surface energy increase. The rheological, mechanical, adhesive, and intermolecular properties were investigated via a polymer coating for various substrates, hydrophilic paper, stainless steel, and beech wood. The diluting properties of M3HBMMA were verified based on the paper dip coating results. The layer 87.5% thickness spread for a 100% MRO system decreased to 28.0% measured for a system containing 50 wt % M3HBMMA. Moreover, the additional polymer weight content attached to the paper specimen decreased from 350 to 69 wt %, a significant result for the potential industrial applicability. The paper hydrophobicity was verified via the water contact angle. The flexibility-enhancing factor of E3HBMMA in the MRO-based coating was investigated via metal coating experiments. The bending angle measured for the 100% MRO system reached 12 ± 2°, while the layer containing 40 wt % of E3HBMMA endured the bending to 121 ± 2°. This result confirmed the exceptionally enhanced thermoset coating’s flexibility and adhesion toward the stainless steel substrate. Lastly, the wood coating involved the synthesized polarity modifier, MISD. The surface energy changes affecting the coat’s quality were confirmed since the coating rating based on the norm ISO 2409 reached level 5 (the highest) for the system involving 40 wt % of MISD, while the 100% MRO system obtained a level 1 rating (second worst). Based on the results, the synthesized curable monomers succeeded as a potential reactive coating material precursor.

Supporting Information

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The Supporting Information is available free of charge at https://pubs.acs.org/doi/10.1021/acspolymersau.4c00068.

  • Synthesized products’ measured NMR, ESI-MS, and FTIR spectra and complete wood coating documentation (PDF)

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Most electronic Supporting Information files are available without a subscription to ACS Web Editions. Such files may be downloaded by article for research use (if there is a public use license linked to the relevant article, that license may permit other uses). Permission may be obtained from ACS for other uses through requests via the RightsLink permission system: http://pubs.acs.org/page/copyright/permissions.html.

Author Information

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  • Corresponding Author
  • Authors
    • Jan Fučík - Institute of Environmental Chemistry, Faculty of Chemistry, Brno University of Technology, 612 00 Brno, Czech Republic;  Orcidhttps://orcid.org/0000-0002-3408-4383
    • Otakar Bartoš - Institute of Materials Chemistry, Faculty of Chemistry, Brno University of Technology, 61200 Brno, Czech Republic
    • Silvestr Figalla - Institute of Materials Chemistry, Faculty of Chemistry, Brno University of Technology, 61200 Brno, Czech Republic
    • Radek Přikryl - Institute of Materials Chemistry, Faculty of Chemistry, Brno University of Technology, 61200 Brno, Czech Republic
  • Author Contributions

    CRediT: Vojtech Jasek conceptualization, data curation, investigation, methodology, visualization, writing - original draft; Jan Fučík formal analysis, investigation; Otakar Bartoš formal analysis, investigation; Silvestr Figalla supervision, validation; Radek Přikryl supervision, validation.

  • Notes
    The authors declare no competing financial interest.

Acknowledgments

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V.J. and J.F. acknowledge the financial support from the Ministry of Education, Youth and Sport of the Czech Republic (project No. FCH-S-24-8592) and (project No. FCH-S-24-8591).

References

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    Jalil, M. J.; Hadi, A.; Azmi, I. S. Catalytic Epoxidation Of Palm Oleic Acid Using In Situ Generated Performic Acid–Optimization And Kinetic Studies. Mater. Chem. Phys. 2021, 270, 124754– 124761,  DOI: 10.1016/j.matchemphys.2021.124754
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    Hernández-Cruz, M. C.; Meza-Gordillo, R.; Domínguez, Z.; Rosales-Quintero, A.; Abud-Archila, M.; Ayora-Talavera, T.; Villalobos-Maldonado, J. J. Optimization And Characterization Of In Situ Epoxidation Of Chicken Fat With Peracetic Acid. Fuel 2021, 285, 119127  DOI: 10.1016/j.fuel.2020.119127
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    Addli, M. A.; Azmi, I. S.; Fadzil, A. F. M.; Jalil, M. J. In Situ Epoxidation Of Castor Oil Via Peracetic Acid Mechanism With Applied Synergistic Of Sulfate-Impregnated Zeolite Sm–5 As Catalyst. Polym. Bull. 2024, 81 (9), 8105– 8117,  DOI: 10.1007/s00289-023-05085-w
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    Jašek, V.; Fučík, J.; Melcova, V.; Figalla, S.; Mravcova, L.; Krobot, Š.; Přikryl, R. Synthesis Of Bio-Based Thermoset Mixture Composed Of Methacrylated Rapeseed Oil And Methacrylated Methyl Lactate: One-Pot Synthesis Using Formed Methacrylic Acid As A Continual Reactant. Polymers 2023, 15 (8), 1811– 1832,  DOI: 10.3390/polym15081811
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    Synthesis of Bio-Based Thermoset Mixture Composed of Methacrylated Rapeseed Oil and Methacrylated Methyl Lactate: One-Pot Synthesis Using Formed Methacrylic Acid as a Continual Reactant
    Jasek, Vojtech; Fucik, Jan; Melcova, Veronika; Figalla, Silvestr; Mravcova, Ludmila; Krobot, Stepan; Prikryl, Radek
    Polymers (Basel, Switzerland) (2023), 15 (8), 1811CODEN: POLYCK; ISSN:2073-4360. (MDPI AG)
    Methacrylated vegetable oils are promising bio-based polymerizable precursors for potential material application in several fields, such as coating technologies or 3D printing. The reactants' availability for their prodn. is an enormous advantage, but the modified oils also exhibit high apparent viscosity values and poor mech. properties. This work focuses on a way to produce oil-based polymerizable material precursors in a mixt. with a viscosity modifier in a one-batch process. The required methacrylic acid for the modification of epoxidized vegetable oils can be obtained as a secondary product of the methacrylation of Me lactate forming a polymerizable monomer along with the acid. This reaction results in a yield of over 98% of methacrylic acid. Epoxidized vegetable oil can be added into the same batch using acid for oil modification which results in the one-pot mixt. of both methacrylated oil and Me lactate. The structural verifications of products were provided via FT-IR, 1H NMR, and volumetric methods. This two-step reaction process produces a thermoset mixt. with a lower apparent viscosity of 142.6 mPa·s in comparison with methacrylated oil exhibiting a value of 1790.2 mPa·s. Other phys.-chem. properties of the resin mixt. such as storage modulus (E' = 1260 MPa), glass transition temp. (Tg = 50.0°C), or polymn. activation energy (17.3 kJ/mol) are enhanced in comparison with the methacrylated vegetable oil. The synthesized one-pot mixt. does not require addnl. methacrylic acid due to the use of the one formed in the first step of the reaction, while the eventual thermoset mixt. exhibits enhanced material properties compared to the methacrylated vegetable oil itself. Precursors synthesized in this work may find their purpose in the field of coating technologies, since these applications require detailed viscosity modifications.
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    Reyhani, A.; McKenzie, T. G.; Fu, Q.; Qiao, G. G. Fenton-Chemistry-Mediated Radical Polymerization. Macromol. Rapid Commun. 2019, 40 (18), 1900220– 1900236,  DOI: 10.1002/marc.201900220
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    Ho, Y. H.; Parthiban, A.; Thian, M. C.; Ban, Z. H.; Siwayanan, P.; Lai, J.-Y. Acrylated Biopolymers Derived Via Epoxidation And Subsequent Acrylation Of Vegetable Oils. Int. J. Polym. Sci. 2022, 2022, 1– 12,  DOI: 10.1155/2022/6210128
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    Guit, J.; Tavares, M. B. L.; Hul, J.; Ye, C.; Loos, K.; Jager, J.; Folkersma, R.; Voet, V. S. D. Photopolymer Resins With Biobased Methacrylates Based On Soybean Oil For Stereolithography. ACS Applied Polymer Materials 2020, 2 (2), 949– 957,  DOI: 10.1021/acsapm.9b01143
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    Photopolymer Resins with Biobased Methacrylates Based on Soybean Oil for Stereolithography
    Guit, Jarno; Tavares, Marjory B. L.; Hul, Jerzy; Ye, Chongnan; Loos, Katja; Jager, Jan; Folkersma, Rudy; Voet, Vincent S. D.
    ACS Applied Polymer Materials (2020), 2 (2), 949-957CODEN: AAPMCD; ISSN:2637-6105. (American Chemical Society)
    The accessibility of renewable materials that are both sustainable and competitive is essential to accommodate the rapid growth in consumption of 3D printing materials. We have developed biobased photopolymer resins based on modified soybean oil for application in com. stereolithog. printers. First, soybean oil methacrylates with various functionalities were successfully synthesized from epoxidized soybean oil as an alternative to com. available soybean oil acrylate. A library of photoresins was created by mixing up to 80% of the biobased (meth)acrylate oligomers with biobased diluents and a photoinitiator. The resin compn. was optimized to achieve a max. biobased content and a low viscosity. The manufd. parts demonstrated complete layer fusion and accurate print quality. Stiffness and toughness can be tuned by altering the chem. compn. or the no. of functional groups per oligomer. These biobased materials can be employed to reduce the environmental impact of additive manufg. while being competitive with current fossil-based resins from com. manufacturers.
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  18. 18
    Li, P.; Ma, S.; Dai, J.; Liu, X.; Jiang, Y.; Wang, S.; Wei, J.; Chen, J.; Zhu, J. Itaconic Acid As A Green Alternative To Acrylic Acid For Producing A Soybean Oil-Based Thermoset: Synthesis And Properties. ACS Sustainable Chem. Eng. 2017, 5 (1), 1228– 1236,  DOI: 10.1021/acssuschemeng.6b02654
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    Itaconic Acid as a Green Alternative to Acrylic Acid for Producing a Soybean Oil-Based Thermoset: Synthesis and Properties
    Li, Peng; Ma, Songqi; Dai, Jinyue; Liu, Xiaoqing; Jiang, Yanhua; Wang, Sheng; Wei, Jingjing; Chen, Jing; Zhu, Jin
    ACS Sustainable Chemistry & Engineering (2017), 5 (1), 1228-1236CODEN: ASCECG; ISSN:2168-0485. (American Chemical Society)
    In this paper, itaconic acid was monomethylated with methanol to produce monomethyl itaconate, and then monomethyl itaconated epoxidized soybean oil (IESO) was obtained by melt ring-opening esterification of monomethyl itaconate with ESO. For comparison, acrylated epoxidized soybean oil (AESO) was also synthesized from ESO and acrylic acid with the same synthetic method. The chem. structures of monomethyl itaconate, IESO, and AESO were characterized in detail by differential scanning calorimetry (DSC), FTIR, and 1H NMR. The isothermal thermogravimetric anal. at 30, 60, and 90 °C indicated that monomethyl itaconate exhibited extremely low volatility even at 90 °C, while acrylic acid volatilized very fast even at 30 °C, which suggested that monomethyl itaconate could be used as a green alternative to acrylic acid. Under UV radiation, IESO showed good copolymn. ability with reactive monomers such as glycidyl methacrylate modified itaconic acid (IG), trimethylolpropane triacrylate (TMPTMA), and styrene. The cured neat IESO exhibited similar properties to the neat AESO, and the IESO/reactive monomers systems showed higher glass transition temp. (Tg), modulus, and comparable or better tensile strength and coating properties than the AESO/reactive monomers systems.
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    Decostanzi, M.; Lomège, J.; Ecochard, Y.; Mora, A.-S.; Negrell, C.; Caillol, S. Fatty Acid-Based Cross-Linkable Polymethacrylate Coatings. Prog. Org. Coat. 2018, 124, 147– 157,  DOI: 10.1016/j.porgcoat.2018.08.001
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    Fatty acid-based crosslinkable polymethacrylate coatings
    Decostanzi, Melanie; Lomege, Juliette; Ecochard, Yvan; Mora, Anne-Sophie; Negrell, Claire; Caillol, Sylvain
    Progress in Organic Coatings (2018), 124 (), 147-157CODEN: POGCAT; ISSN:0300-9440. (Elsevier B.V.)
    In this paper, novel epoxy prepolymers from oleic acid-based monomers were crosslinked to prep. thermosets for coating application. For this purpose, methacrylate moiety was firstly added to oleic acid via Steglich esterification prior to conventional radical polymn. The resulting oleic acid-based polymer was obtained with a no. mol. wt. 40,000 g/mol (DP = 110). Then the internal unsaturations of this polymer were epoxidized at different epoxy contents to provide crosslinkable functionalities. Based on a study of the internal epoxy reactivity of a model compd. with different nucleophiles, the synthesized oleic-based polymers with epoxy functions hanging off the main chain were successfully crosslinked with succinic anhydride. Dynamic mech. and thermal analyses, as well as swelling index properties have been studied for all the resulting thermosets. Addnl., the properties of coatings on steel substrates were studied to det. coating hardness, and adhesion. The results of this work provide evidence of the potential of these materials as bio-based coatings and adhesives.
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  20. 20
    Silva, J. A. C.; Dever, S.; Siccardi, A.; Snelling, D.; Al Qabani, I.; Thompson, S.; Goldberg, K.; Baudoin, G.; Martins Lacerda, T.; Quirino, R. L. Itaconic Anhydride As A Bio-Based Compatibilizer For A Tung Oil-Based Thermosetting Resin Reinforced With Sand And Algae Biomass. Coatings 2023, 13 (7), 1188– 1203,  DOI: 10.3390/coatings13071188
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    Thomas, J.; Patil, R. Enabling Green Manufacture Of Polymer Products Via Vegetable Oil Epoxides. Ind. Eng. Chem. Res. 2023, 62 (4), 1725– 1735,  DOI: 10.1021/acs.iecr.2c03867
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    Enabling Green Manufacture of Polymer Products via Vegetable Oil Epoxides
    Thomas, Jomin; Patil, Renuka
    Industrial & Engineering Chemistry Research (2023), 62 (4), 1725-1735CODEN: IECRED; ISSN:0888-5885. (American Chemical Society)
    A review. The industrial application of epoxidized vegetable oil is being diversified and commercialized at a rapid pace. It is attributed to its environment friendly nature compared to the synthetic Bisphenol A epoxides which are deemed toxic. However, there are concerns that the incorporation of such epoxidized vegetable oil has an undesirable impact on the main performance properties of tires due to its inherent flexible polymer chain. At the same time, new product innovations and synthesis capabilities can help us develop polymer products in a more sustainable fashion. This review first outlines the inherent challenges, the progress made thus far, and future opportunities for epoxidized vegetable oil derivs. Next, the main application areas of these epoxides, such as plasticizers, coatings, and composites, are discussed in-depth. Possible design guidelines for surpassing the challenges to equiv. performance are also examd. A meticulous overview of the existing literature is conducted to summarize the recent approaches to epoxidized vegetable oil deriv. products with a crit. anal. of some of them. This contribution attempts to highlight epoxidized vegetable oil derivs. on the basis of existing challenges, recent research advancements, and their prospective future.
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    Liu, K.; Madbouly, S. A.; Kessler, M. R. Biorenewable Thermosetting Copolymer Based On Soybean Oil And Eugenol. Eur. Polym. J. 2015, 69, 16– 28,  DOI: 10.1016/j.eurpolymj.2015.05.021
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    Biorenewable thermosetting copolymer based on soybean oil and eugenol
    Liu, Kunwei; Madbouly, Samy A.; Kessler, Michael R.
    European Polymer Journal (2015), 69 (), 16-28CODEN: EUPJAG; ISSN:0014-3057. (Elsevier Ltd.)
    A novel biorenewable thermoset based on acrylated epoxidized soybean oil (AESO) and methacrylated eugenol (ME) was prepd. via free radical polymn. The chem. compns. of the monomers were investigated using proton NMR (1H NMR) technique. The properties of this resin system were investigated using small amplitude oscillatory shear flow rheol., dynamic mech. anal. (DMA), thermogravimetric anal. (TGA), and compression testing. Soxhlet extn. was also performed on the cured thermoset to det. the percentage of monomers that are incorporated into the crosslink network. In addn., the gelation time of this resin at different curing temp. was also monitored using a rheometer. The Soxhlet extn. data indicated that more than 95% of the monomers were incorporated into the crosslink network. Gelation time study showed that this resin system can become a solid within 10 min. This resin system possesses high strength and modulus, and it is thermally stable up to 300 °C. This high biorenewable content resin system possesses good mech. properties, high thermal stability, and fast curing speed, making it a suitable matrix resin for the pultrusion process and other composite manufg. processes.
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    Athawale, V. D.; Nimbalkar, R. V. Waterborne Coatings Based On Renewable Oil Resources: An Overview. J. Am. Oil Chem. Soc. 2011, 88 (2), 159– 185,  DOI: 10.1007/s11746-010-1668-9
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    Waterborne Coatings Based on Renewable Oil Resources: an Overview
    Athawale, Vilas D.; Nimbalkar, Ramakant V.
    Journal of the American Oil Chemists' Society (2011), 88 (2), 159-185CODEN: JAOCA7; ISSN:0003-021X. (Springer)
    A review. Polyurethane dispersions are gaining in importance due to their environmentally friendly coating system, versatile coating properties and ease of application. An enormous amt. of research is focused on waterborne coatings such as waterborne alkyds, water-reducible alkyds, alkyd-acrylic hybrids, oil modified polyurethane dispersions and their composite latexes. This review gives a comprehensive compilation of recent studies on the synthesis and applications of waterborne coatings. The article specifically covers all of the research work carried out in the field of waterborne alkyd-acrylics, polyurethane dispersions and their hybrid latexes systematically.
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    Mousaa, I. M.; Radi, H. Photosynthesis Of Anticorrosive Protective Coatings For Steel Substrate Based On Acrylated Oil Containing Unsaturated Amino Acid Compounds. Prog. Org. Coat. 2017, 107, 18– 28,  DOI: 10.1016/j.porgcoat.2017.03.006
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    Photosynthesis of anticorrosive protective coatings for steel substrate based on acrylated oil containing unsaturated amino acid compounds
    Mousaa, I. M.; Radi, H.
    Progress in Organic Coatings (2017), 107 (), 18-28CODEN: POGCAT; ISSN:0300-9440. (Elsevier B.V.)
    Novel environment friendly anticorrosive coating formulations for mild steel substrate based on acrylated oil were prepd. by using unsatd. amino acid compds. In the first, epoxidized soybean oil acrylate (ESOA) was hardened and modified by the different functionality of monomers to be used in anticorrosive coating formulations. In this article, new corrosion inhibitors were synthesized through two steps. In step one, renewable resource based palm oil was epoxidized under a well-established condition to form epoxidized triglyceride ester of palm oil (EPO). FTIR and oxirane content anal. were used to confirm the formation of the epoxidn. reaction. In step two, the EPO was reacted chem. with 4-aminobenzoic acid (AB) and 2-aminoacrylic acid (AA) under controlled conditions of an inert atm. and high temp. to produce EPO/AB and EPO/AA adducts. The prepd. adducts were characterized by FTIR-spectroscopy and oxirane content anal. The adducts are evaluated as corrosion inhibitors via adding different concns. of them to the ESOA coating formulations. Then all coating films were subjected to UV irradn. Degrees of rusting, blistering, failure at scribe, and wt. loss values were measured for all UV cured films, in addn. to the chem. and mech. measurements. The obtained exptl. results revealed that the cured coating films contg. EPO/AB inhibitor displayed higher resistance to corrosion on the mild steel substrate than EPO/AA without any effect on the mech. and chem. properties of cured films. Also, the optimum concn. of the prepd. inhibitors was to be 0.5%.
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    Zulkifli, F.; Ali, N.; Yusof, M. S. M.; Isa, M. I. N.; Yabuki, A.; Wan Nik, W. B. Henna Leaves Extract As A Corrosion Inhibitor In Acrylic Resin Coating. Prog. Org. Coat. 2017, 105, 310– 319,  DOI: 10.1016/j.porgcoat.2017.01.017
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    Henna leaves extract as a corrosion inhibitor in acrylic resin coating
    Zulkifli, F.; Ali, Nora'aini; Yusof, M. Sukeri M.; Isa, M. I. N.; Yabuki, A.; Wan Nik, W. B.
    Progress in Organic Coatings (2017), 105 (), 310-319CODEN: POGCAT; ISSN:0300-9440. (Elsevier B.V.)
    This study utilizes optical measurements, thermo-impedance anal., potentiodynamic polarization studies and morphol. observations of henna leaves ext. (HLE) incorporated in an acrylic resin coating. The acrylic resin coating with 0.2 wt/vol% HLE (AC2) had the best performance protecting metal from corrosion. XRD and DSC anal. demonstrate that an increase in the crystallite size limits the close packed structure, which increases the free vol. and reduces the Tg of the coating. Open circuit potential (OCP) measurements demonstrate that the AC2 coating has a uniform potential due to the lower rate of coating barrier destruction. Electrochem. impedance spectroscopy (EIS) indicates that AC2 has the highest coating resistance, Rc (4.79 × 108 Ω), and lowest coating capacitance, Cc (3.32 × 10-9 F/cm2). An elevation in temp. caused coating deterioration for all of the coatings. AC2 has the lowest dielec. const., εr, indicating less water uptake and lower ionic cond. An addnl. study of potentiodynamic polarization demonstrates that AC2 has shifted to the noble potential and gives the lowest corrosion c.d., icorr, reading. The corrosion rate is the lowest for AC2 (3.93 × 10-7 mm/yr), while the polarization resistance is the highest at 7.44 × 107 Ω. An SEM morphol. study indicates that AC2 has lesser delamination and greater coverage of HLE in the coating.
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    Uzoma, P. C.; Liu, F.; Xu, L.; Zhang, Z.; Han, E.-H.; Ke, W.; Arukalam, I. O. Superhydrophobicity, Conductivity And Anticorrosion Of Robust Siloxane-Acrylic Coatings Modified With Graphene Nanosheets. Prog. Org. Coat. 2019, 127, 239– 251,  DOI: 10.1016/j.porgcoat.2018.11.018
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    Superhydrophobicity, conductivity and anticorrosion of robust siloxane-acrylic coatings modified with graphene nanosheets
    Uzoma, Paul C.; Liu, Fuchun; Xu, Long; Zhang, Zhichao; Han, En-Hou; Ke, Wei; Arukalam, I. O.
    Progress in Organic Coatings (2019), 127 (), 239-251CODEN: POGCAT; ISSN:0300-9440. (Elsevier B.V.)
    The effects of low-cost graphene nanosheets in org. coatings were investigated. The hydrophobic org. siloxane-acrylic resin was synthesized by soln. polymn. of acrylic monomers while the graphene nanosheets were modified using fluorosilane, and applied on LY12 aluminum substrate via spraying and a two-step coating system. The superhydrophobic, conductive, anticorrosion, self-cleaning, oleophilic and phys. behaviors were comprehensively characterized. The results obtained revealed that addn. of modified graphene increases the surface cond. (≥ 2 μS/cm) and the water contact angle (≥ 152°) with low sliding angle (≤ 7°). The polarization measurement showed a pos. shift in the corrosion potential signifying an inhibition of the cathodic reaction. Also, the two-step coated sample gave a good corrosion protection barrier as further confirmed by the electrochem. impedance parameters. The coating revealed good resistance to dirt adhesion, and its superhydrophobic-oleophilic property offered a promising application in oil-water sepn. The phys. integrity of the coatings was not extensively affected including after 120 days of outdoor exposure to snowing, de-freezing and surface wetting.
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    Ifijen, I. H.; Maliki, M.; Odiachi, I. J.; Aghedo, O. N.; Ohiocheoya, E. B. Review On Solvents Based Alkyd Resins And Water Borne Alkyd Resins: Impacts Of Modification On Their Coating Properties. Chemistry Africa 2022, 5 (2), 211– 225,  DOI: 10.1007/s42250-022-00318-3
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    Radoman, T. S.; Dzunuzovic, J. V.; Trifkovic, K. T.; Palija, T.; Marinkovic, A. D.; Bugarski, B.; Dzunuzovic, E. S. Effect Of Surface Modified Tio2 Nanoparticles On Thermal, Barrier And Mechanical Properties Of Long Oil Alkyd Resin-Based Coatings. Express Polymer Letters 2015, 9 (10), 916– 931,  DOI: 10.3144/expresspolymlett.2015.83
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    Kim, Y. S.; Cho, H. J.; Lee, H.; Kim, W. Y.; Jung, Y. C.; Lee, S. Y. Development Of A Multi-Functional Acrylic Urethane Coating With High Hardness And Low Surface Energy. Prog. Org. Coat. 2020, 147, 105748  DOI: 10.1016/j.porgcoat.2020.105748
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    Paraskar, P. M.; Prabhudesai, M. S.; Hatkar, V. M.; Kulkarni, R. D. Vegetable Oil Based Polyurethane Coatings–A Sustainable Approach: A Review. Prog. Org. Coat. 2021, 156, 106267  DOI: 10.1016/j.porgcoat.2021.106267
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    Vegetable oil based polyurethane coatings - A sustainable approach: A review
    Paraskar, Pavan M.; Prabhudesai, Mayur S.; Hatkar, Vinod M.; Kulkarni, Ravindra D.
    Progress in Organic Coatings (2021), 156 (), 106267CODEN: POGCAT; ISSN:0300-9440. (Elsevier B.V.)
    A review. The scientific community has been pooling all its resources, for the past decade, toward the development of "sustainable development" to usher into an eternally green and sustainable tomorrow. As part of this endeavor, the conventional petroleum-based polyurethane (PU) coatings have been replaced by their green counterparts, i.e., bio-based polyurethane coatings. These green alternatives provide a suitable replacement for the coating industry due to their easy availability, biodegradability, low cost, and lesser environmental impact. The prodn. of such green PU coatings is further facilitated by the utilization of bio-based materials, including vegetable oils and their derivs. such as Me ester, fatty acid, and other bio-renewable sources. This review discusses the different chem. modifications used to convert these bio-based precursors into desired polyols and isocyanates. Furthermore, the formulation of different PU coatings and their subsequent potential applications are also elaborated on in this review. The coatings sector has already been introduced to the notion of eco-friendly technologies such as UV-curable, less or zero solvent, waterborne, hyperbranched, and high solids coatings, complemented by the incorporation of renewable feedstock in monomer synthesis. The review examines the future hurdles that hinder the utilization of these materials in a wide range of applications and presents technologies that facilitate potential solns. and mention key players in the coating sectors that are at the forefront of bringing these revolutionary changes.
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    Wei, H.; Xia, J.; Zhou, W.; Zhou, L.; Hussain, G.; Li, Q.; Ostrikov, K.(K.). Adhesion And Cohesion Of Epoxy-Based Industrial Composite Coatings. Compos. B: Eng. 2020, 193, 108035  DOI: 10.1016/j.compositesb.2020.108035
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    Croll, S. G. Surface Roughness Profile And Its Effect On Coating Adhesion And Corrosion Protection: A Review. Prog. Org. Coat. 2020, 148, 105847  DOI: 10.1016/j.porgcoat.2020.105847
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    Surface roughness profile and its effect on coating adhesion and corrosion protection: A review
    Croll, S. G.
    Progress in Organic Coatings (2020), 148 (), 105847CODEN: POGCAT; ISSN:0300-9440. (Elsevier B.V.)
    A review. Specifications for coating many forms of infrastructure and equipment include abrasive cleaning, then measurement of surface profile and adhesion on the assumption that they are linked to long term prevention of corrosion undercutting the coating. Studies find no quant. connection between adhesion and corrosion protection, but many believe in a link. Although corrosion is a mol. phenomenon that starts at the interface, adhesion values are measured by a device attached to the coating at some distance from the interface, so it is difficult to directly connect corrosion with adhesion. Understanding how adhesion and the spread of corrosion under the coating are influenced by surface roughness entails surface metrol., fracture mechanics, surface energy and viscoelasticity. The impact of surface roughness can't be detd. by a simple, or single, statistical parameter for variation in substrate height variation. Conventional ''pull-off'' adhesion testing does not characterize coating-metal interactions that might prevent water and electrolyte causing corrosion, they must be detd. otherwise. The addnl. surface area created by the abrasion increases the no. of adhesive interactions and the local slope of the surface engages Mode II loading that increases the force that the interface can support. In order to prevent the diffusion of water and electrolyte across the interface, a coating should form well at the interface, be tough and as hydrophobic as realistically possible.
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    Tang, X.; Yan, X. Dip-Coating For Fibrous Materials: Mechanism, Methods And Applications. J. Sol-Gel Sci. Technol. 2017, 81 (2), 378– 404,  DOI: 10.1007/s10971-016-4197-7
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    Dip-coating for fibrous materials: mechanism, methods and applications
    Tang, Xiaoning; Yan, Xiong
    Journal of Sol-Gel Science and Technology (2017), 81 (2), 378-404CODEN: JSGTEC; ISSN:0928-0707. (Springer)
    A review. This paper presents a review on dip-coating for fibrous materials, mainly concd. on the mechanism, recently developed dip-coating methods and novel functional applications. The emphasis has been made here, to present theor. basis of dip-coating-induced film deposition, esp., the reported works to predict the thickness based on various processing parameters. Different modified dip-coating techniques to fabricate deposited films for fibrous substrate have also been gathered. The scope of reviewed dip-coating methods are not only conventional soln. and sol-gel-based dip-coating, but also recently developed vacuum-assisted, spin-assisted, photo-assisted and multi-layered dip-coating methods. An overview of reported and potential applications for coated fibrous materials has also been given, which mainly including self-cleaning, oil-water sepn., conductive textiles, fibrous-based energy storage devices, and photonic crystals, etc. This review is intended to give readers a good horizon for the present status concerning variety of studies and applications related to dip-coating. An effort has been made here to report the important contributions in the area of dip-coating for fibrous substrate, and crit. points regarding future research directions are outlined in the summary.
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    Fast photopolymerization of acrylate coatings: Achievements and problems
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    Progress in Organic Coatings (2018), 121 (), 151-159CODEN: POGCAT; ISSN:0300-9440. (Elsevier B.V.)
    A review. Coatings chemists often prep. (meth)acrylate coatings which meet their needs.However, anal. of kinetics of photopolymn. (UV-cure) is usually based on a classical scheme of the chain free radical polymns. That set of reactions with resp. rate consts. is valid only up till few percent of conversion of double bonds. Multiple studies of photopolymn. are focused not on reactions at large d.p. but on selection of new photoinitiators. In the present paper we focused on fundamentals of photopolymn. rather than on multitude of applications, different formulations, sources of light, etc., and we try to avoid repetition of widely discussed in the literature issues. A special attention is devoted to cage effect during photodissocn. of initiators. An increase of cage effect value with a d.p. increase affects overall efficiency of photoinitiator at large conversions. IUPAC terms and notions are suggested.
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    Enhancement of the properties of acrylic wood coatings with the use of biopolymers
    Hochmanska-Kaniewska, Patrycja; Janiszewska, Dominika; Oleszek, Tomasz
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    The objective of this study was to enhance the properties of water-borne acrylic coatings by modifying them with biopolymers. Water-borne coatings are more and more commonly used in the wood and furniture industry. To improve the performance of these coatings, there is a need to apply reinforcing agents. Among these, besides the well-studied inorg. nanoparticles, biopolymers are gaining increasing attention. In this study, a base acrylic coating material was filled with biopolymers having a wide variety of properties and functionalities, including nanocryst. cellulose and two types of liquefied wood, in amts. of 1.0%, 3.0% and 5.0% by dry wt. of coating. Two wood species, pine and beech, were selected for coating. Properties of the coatings were detd. in order to assess the quality of the new coating formulations. Bearing in mind that the main cause of coating failure during interior exposure is mech. defects, impact and abrasion resistance tests were performed. The abrasion resistance of the coatings was found to be increased by nanocryst. cellulose and liquefied wood, most significantly at 1% loading. The results also indicated improvement in the impact resistance of coatings filled with nanocryst. cellulose.
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    Liu, M.; Liu, Y.; Wang, P.; Ying, W.; Liu, Q.; Ding, G.; Chen, S. Synthesis And Properties Of A Photocurable Coating Based On Waste Cooking Oil. Coatings 2023, 13 (9), 1553– 1572,  DOI: 10.3390/coatings13091553
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    Nucleic Acids Research (2022), 50 (W1), W165-W174CODEN: NARHAD; ISSN:1362-4962. (Oxford University Press)
    The CFM-ID 4.0 web server (https://cfmid.wishartlab. com) is an online tool for predicting, annotating and interpreting tandem mass (MS/MS) spectra of small mols. It is specifically designed to assist researchers pursuing studies in metabolomics, exposomics and anal. chem. More specifically, CFM-ID 4.0 supports the: (1) prediction of electrospray ionization quadrupole time-of-flight tandem mass spectra (ESI-QTOF-MS/MS) for small mols. over multiple collision energies (10 eV, 20 eV, and 40 eV); (2) annotation of ESI-QTOF-MS/MS spectra given the structure of the compd.; and (3) identification of a small mol. that generated a given ESI-QTOF-MS/MS spectrum at one or more collision energies. The CFM-ID 4.0 web server makes use of a substantially improved MS fragmentation algorithm, a much larger database of exptl. and in silico predicted MS/MS spectra and improved scoring methods to offer more accurate MS/MS spectral prediction and MS/MS-based compd. identification. Compared to earlier versions of CFM-ID, this new version has an MS/MS spectral prediction performance that is ~ 22% better and a compd. identification accuracy that is ~ 35% better on a std. (CASMI 2016) testing dataset. CFM-ID 4.0 also features a neutral loss function that allows users to identify similar or substituent compds. where no match can be found using CFM-ID's regular MS/MS-to-compd. identification utility. Finally, the CFM-ID 4.0 web server now offers a much more refined user interface that is easier to use, supports mol. formula identification (from MS/MS data), provides more interactively viewable data (including proposed fragment ion structures) and displays MS mirror plots for comparing predicted with obsd. MS/MS spectra. These improvements should make CFM-ID 4.0 much more useful to the community and should make small mol. identification much easier, faster, and more accurate.
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    Wu, Q.; Hu, Y.; Tang, J.; Zhang, J.; Wang, C.; Shang, Q.; Feng, G.; Liu, C.; Zhou, Y.; Lei, W. High-Performance Soybean-Oil-Based Epoxy Acrylate Resins: “Green” Synthesis And Application In Uv-Curable Coatings. ACS Sustainable Chem. Eng. 2018, 6 (7), 8340– 8349,  DOI: 10.1021/acssuschemeng.8b00388
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    High-Performance Soybean-Oil-Based Epoxy Acrylate Resins: "Green" Synthesis and Application in UV-Curable Coatings
    Wu, Qiong; Hu, Yun; Tang, Jijun; Zhang, Jing; Wang, Cuina; Shang, Qianqian; Feng, Guodong; Liu, Chengguo; Zhou, Yonghong; Lei, Wen
    ACS Sustainable Chemistry & Engineering (2018), 6 (7), 8340-8349CODEN: ASCECG; ISSN:2168-0485. (American Chemical Society)
    Novel soybean-oil-based (SBO-based) epoxy acrylate (EA) resins were developed via ring-opening reaction of epoxidized soybean oil (ESO) with hydroxyethyl methacrylated maleate (HEMAMA) precursor, a synthesized unsatd. carboxylic acid having two active C=C groups and a side Me group. Exptl. conditions for the synthesis of the precursor and the SBO-based EA (ESO-HEMAMA) product were studied, and their chem. structures were confirmed by FT-IR, 1H NMR, 13C NMR, and gel permeation chromatog. Subsequently, the volatility of HEMAMA was studied and compared with acrylic acid (AA). Furthermore, gel contents and ultimate properties of the UV-cured ESO-HEMAMA resins were investigated and compared with a com. acrylated ESO (AESO) resin. At last, UV-curing behaviors of the SBO-based EA resins were detd. by real-time IR. It was found that the HEMAMA precursor showed much lower volatility than AA, and the optimal pure ESO-HEMAMA resin possessed a C=C functionality up to 6.02 per ESO and biobased content of 65.4%. Meanwhile, the obtained ESO-HEMAMA biomaterials exhibited much superior properties as compared to the AESO resin. For instance, the obtained pure ESO-HEMAMA material possessed a storage modulus at 25 °C of 1.00 GPa, glass transition temp. (Tg) of 70.1 °C, and tensile strength and modulus of 13.4 and 592.1 MPa, which were 9.4, 3.6, 6.9, and 15.7 times the values of the pure AESO material, resp. The resulting biomaterial with 30% of hydroxyethyl methacrylate diluent even reached a tensile strength of 28.4 MPa and Tg of 89.0 °C. Therefore, the developed SBO-based EA resins are very promising for applications in UV-curable coatings.
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    Jašek, V.; Melčová, V.; Figalla, S.; Fučík, J.; Menčík, P.; Přikryl, R. Study Of The Thermomechanical Properties Of Photocured Resins Based On Curable Monomers From Pla And Phb For Sla 3D Printing. ACS Applied Polymer Materials 2023, 5 (12), 9909– 9917,  DOI: 10.1021/acsapm.3c01730
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    Jašek, V.; Fučík, J.; Krhut, J.; Mravcova, L.; Figalla, S.; Přikryl, R. A Study Of Isosorbide Synthesis From Sorbitol For Material Applications Using Isosorbide Dimethacrylate For Enhancement Of Bio-Based Resins. Polymers 2023, 15 (17), 3640– 3658,  DOI: 10.3390/polym15173640
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    Synthesis and polymerization of bio-based acrylates: a review
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    Polymer Chemistry (2020), 11 (47), 7452-7470CODEN: PCOHC2; ISSN:1759-9962. (Royal Society of Chemistry)
    A review. Acrylates and polyacrylates have been produced massively due to their interesting applications like Plexiglas. However, the contemporary issues of fossil depletion assocd. with climate change have raised serious concerns. As a result, utilization of renewable resources such as lignocellulosic materials and the development of greener processes have been investigated intensively. Herein, we review the prepn. of competitive (meth)acrylates and the corresponding polymers made from bio-renewable resources with a specific focus on lignocellulose. While covering a few families of biosynthons to produce acrylates through different synthetic pathways, we also analyze the promising properties of the resulting materials.
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    Badía, A.; Agirre, A.; Barandiaran, M. J.; Leiza, J. R. Removable Biobased Waterborne Pressure-Sensitive Adhesives Containing Mixtures Of Isosorbide Methacrylate Monomers. Biomacromolecules 2020, 21 (11), 4522– 4531,  DOI: 10.1021/acs.biomac.0c00474
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    Removable Biobased Waterborne Pressure-Sensitive Adhesives Containing Mixtures of Isosorbide Methacrylate Monomers
    Badia, Adrian; Agirre, Amaia; Barandiaran, Maria J.; Leiza, Jose Ramon
    Biomacromolecules (2020), 21 (11), 4522-4531CODEN: BOMAF6; ISSN:1525-7797. (American Chemical Society)
    Growing environmental concerns are enforcing sustainable recycling processes for glass substrates, esp. bottles, where a fast cleaning and minimization of the use of solvents is desired. In this process, labels and adhesives are mostly removed by the addn. of harsh reagents, alk. solns., or high temp., increasing economic costs and harming the environment. Herein, high performance and biobased waterborne pressure-sensitive adhesives with fast removability in water have been developed using small percentages of isosorbide (derived from glucose)-based methacrylate monomers. Formulations contg. 2-octyl acrylate and isobornyl methacrylate and small amts. (1 wt %) of these monomers not only yield stronger adhesive fibrils, but also promote a removability in water 6x faster than that of nonisosorbide-based counterparts. This waterborne isosorbide contg. PSAs represents an alternative to current PSA formulations toward more sustainable glass recycling and reusing processes.
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    Thakur, S.; Misra, M.; Mohanty, A. K. Sustainable Hydrophobic And Moisture-Resistant Coating Derived From Downstream Corn Oil. ACS Sustainable Chem. Eng. 2019, 7 (9), 8766– 8774,  DOI: 10.1021/acssuschemeng.9b00689
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    Sustainable Hydrophobic and Moisture-Resistant Coating Derived from Downstream Corn Oil
    Thakur, Suman; Misra, Manjusri; Mohanty, Amar K.
    ACS Sustainable Chemistry & Engineering (2019), 7 (9), 8766-8774CODEN: ASCECG; ISSN:2168-0485. (American Chemical Society)
    Sustainable coating as a replacement for petroleum-derived materials is highly required for packaging and other applications to reduce the generation of land and ocean pollution. In this study, a novel approach has been introduced to incorporate hydrolyzable silane (-Si-OCH2CH3) groups in the downstream corn oil backbone (one of the coproducts of bioethanol industry) which has been consequently used for the fabrication of hydrophobic and moisture-resistant coating for paper substrate. SEM (SEM) images confirmed the uniform coating of the silane-modified epoxidized downstream corn oil (SECO) over the paper. The condensation reaction has taken place with the hydroxyl group of paper and SECO, and as a result, the no. of surface hydroxyl group was reduced to make a hydrophobic surface on coated paper with static water contact angle (WCA) of 129.4 ± 1.12°. SECO-coated paper showed almost 67% decrease in specific water vapor transmission rate compared to that of the uncoated filter paper. These results indicate that the SECO coating delivers excellent moisture barrier and hydrophobicity to the paper substrate. Thus, SECO might be a competitive substitute to petroleum-based polymers for fluorine-free hydrophobic and moisture-resistant coating. This research finding can find application esp. in huge paper packaging industries as well as cellulose-based products such as fiber and foam.
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  • Abstract

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    Scheme 1

    Scheme 1. Methacrylation of Epoxidized Rapeseed Oil (ERO) Resulting in Methacrylated Rapeseed Oil (MRO) Production
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    Scheme 2

    Scheme 2. Methacrylation of Alkyl Carboxylates Producing Methacrylated Methyl and Ethyl 3-Hydroxybutyrate (M3HBMMA and E3HBMMA)
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    Scheme 3

    Scheme 3. Partial Methacrylation of Isosorbide Resulting in Isosorbide Monomethacrylate (MISD) Production Involving the Purification by Liquid–liquid Extraction (LLE)
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    Figure 1

    Figure 1. Performed dip coating using oil-based curable solution forming a hydrophobic paper.

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    Figure 2

    Figure 2. Performed transparent layer-assisted coating of stainless steel and beech wood by an oil-based curable coating system.

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    Figure 3

    Figure 3. Obtained 1H NMR spectra of all synthesized curable compounds used for the coating applications. (a) Methacrylated rapeseed oil (MRO), (b) methacrylated methyl 3-hydroxybutyrate (M3HBMMA), (c) isosorbide monomethacrylate (MISD), and (d) ethyl 3-hydroxybutyrate (E3HBMMA). Reproduced from ref (38). Available under the CC-BY-4.0 license. 2022 by Vojtch Jaek et al.

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    Figure 4

    Figure 4. Thermal analysis of synthesized products. (a) TGA integral results, (b) TGA derivative results, and (c) DSC curability study.

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    Figure 5

    Figure 5. Performed paper-dip coating using an oil-based curable system involving the reactive diluent, methacrylated methyl 3-hydroxybutyrate (M3HBMMA), in varying weight concentrations. (a) 0% M3HBMMA, (b) 10% M3HBMMA, (c) 20% M3HBMMA, (d) 30% M3HBMMA, (e) 40% M3HBMMA, and (f) 50% M3HBMMA.

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    Figure 6

    Figure 6. Performed contact angle measurements for 50 wt % of the M3HBMMA system. (a) Measurement with water, (b) measurement with glycerol, and (c) measurement with di-iodo methane.

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    Figure 7

    Figure 7. Paper dip coating analysis results involving the layer thickness measurement for the systems with varying layer thickness measured in the different coated-paper regions and the thermoset weight content gravimetric analysis.

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    Figure 8

    Figure 8. Formed polymer coating on stainless steel substrates, coating thicknesses, and bending angle measurement results. The experimental bending angle apparatus for MRO-based thermoset coatings. (a) 0 wt % E3HBMMA, (b) 10 wt % E3HBMMA, (c) 20 wt % E3HBMMA, (d) 30 wt % E3HBMMA, and (e) 40 wt % E3HBMMA.

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    Figure 9

    Figure 9. Wood coating results involving an MRO-based curable system with the polarity modifier isosorbide monomethacrylate (MISD). The illustrative cross-hatch tests for (a) 0 wt % of MISD and (b) 40 wt % of MISD. The coating thickness measurements for all prepared systems and the ISD 2409 adhesion and coating quality rating based on the cross-hatch results.

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    Figure 10

    Figure 10. Optical microscopy of all coated substrates. (a) Noncoated paper, (b) coated paper, (c) noncoated stainless steel, (d) coated stainless steel, (e) noncoated beech wood, and (f) coated beech wood.

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  • References

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      The use of biobased materials in additive manufg. is arising as a promising approach to modernize the polymer industry reducing its environmental impact. Herein, novel sustainable formulations are developed for digital light processing (DLP) using five vegetable oils-sunflower, canola, soybean, olive, and sesame oil-as feedstock. These vegetable oils are successfully modified incorporating photopolymerizable groups, i.e., acrylates, enabling printability. The oil-based formulations consisting of a functionalized oil and a photoinitiator are employed as inks for DLP without the need for further additives. The rheol. and curing behavior of all the inks and printed materials are carefully investigated. The values obtained for their crit. curing energy (Ec) range from 14.52 to 18.49 mJ cm-2, allowing for fast printing. Interestingly, it is found that Ec not only correlates with the av. no. of acrylate groups per mol. but also the viscosity plays a key role. Addnl., the thermal and mech. properties are studied and compared. In summary, sunflower and canola oil derivs. offer a better cost-performance ratio than the state-of-the-art soybean oil inks and can be employed for 3D printing of complex geometries with high speed and resoln. This work demonstrates the potential of using biobased and inexpensive materials as high performance inks for DLP 3D printing and opens new possibilities for the next generation of sustainable 3D printing.
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      This work reports for the first time the copolymn. studies of 11 newly synthesized epoxidized vegetable oils (EVOs) that reacted with a disulfide-based arom. dicarboxylic acid (DCA) to produce thermoset materials with recyclability properties. These new EVOs' reactivity and properties were compared with those of the two com. refs.: epoxidized linseed oil (ELO) and epoxidized soybean oil (ESO). The structure-reactivity correlation is proposed by differential scanning calorimetry (DSC) anal., corroborating the epoxy content of EVO monomers, the initiator effect, the copolymn. reaction enthalpy, and the temp. range. The thermomech. properties of the obtained thermosets were evaluated and discussed in correlation with the structure and reactivity of monomers by dynamic mech. anal. (DMA), tensile testing, and thermogravimetric anal. (TGA). It has been found that the higher the EVO functionality, the higher is the reactivity, crosslinking d., and final performances, with tan δ values ranging from 34 to 111°C. This study investigates the chem. recycling and the solvent resistance of these vitrimer-like materials that have a high bio-based carbon content, from 58 to 79%, with potential application in coating or composite materials in the automotive sector.
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      Linseed oil is characterized by an elevated concn. of highly unsatd. fatty acids such as linolenic and linoleic acids. This work has the objective to evaluate the effect of the high unsatn. of linseed oil on the reactivity and selectivity of the epoxidn. reaction. For this purpose, different kinetic expts. of linseed oil epoxidn. with performic acid, produced in situ, and phosphoric acid as catalyst, have been performed and interpreted with a biphasic kinetic model previously tested on soybean oil epoxidn. This model considers the contribution of the main reactions involved in each phase, including the side reactions such as performic acid decompn. and ring opening reactions. The expts. made have been simulated, with the mentioned kinetic model, after the evaluation by math. regression of the kinetic and thermodn. parameters of the model. Then, the obtained results have been compared with those described in the literature for soybean seed oil, considering, in particular, the effect of the different unsatd. fatty acids compn. on activity and selectivity.
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      Addli, M. A.; Azmi, I. S.; Fadzil, A. F. M.; Jalil, M. J. In Situ Epoxidation Of Castor Oil Via Peracetic Acid Mechanism With Applied Synergistic Of Sulfate-Impregnated Zeolite Sm–5 As Catalyst. Polym. Bull. 2024, 81 (9), 8105– 8117,  DOI: 10.1007/s00289-023-05085-w
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      Synthesis of Bio-Based Thermoset Mixture Composed of Methacrylated Rapeseed Oil and Methacrylated Methyl Lactate: One-Pot Synthesis Using Formed Methacrylic Acid as a Continual Reactant
      Jasek, Vojtech; Fucik, Jan; Melcova, Veronika; Figalla, Silvestr; Mravcova, Ludmila; Krobot, Stepan; Prikryl, Radek
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      Methacrylated vegetable oils are promising bio-based polymerizable precursors for potential material application in several fields, such as coating technologies or 3D printing. The reactants' availability for their prodn. is an enormous advantage, but the modified oils also exhibit high apparent viscosity values and poor mech. properties. This work focuses on a way to produce oil-based polymerizable material precursors in a mixt. with a viscosity modifier in a one-batch process. The required methacrylic acid for the modification of epoxidized vegetable oils can be obtained as a secondary product of the methacrylation of Me lactate forming a polymerizable monomer along with the acid. This reaction results in a yield of over 98% of methacrylic acid. Epoxidized vegetable oil can be added into the same batch using acid for oil modification which results in the one-pot mixt. of both methacrylated oil and Me lactate. The structural verifications of products were provided via FT-IR, 1H NMR, and volumetric methods. This two-step reaction process produces a thermoset mixt. with a lower apparent viscosity of 142.6 mPa·s in comparison with methacrylated oil exhibiting a value of 1790.2 mPa·s. Other phys.-chem. properties of the resin mixt. such as storage modulus (E' = 1260 MPa), glass transition temp. (Tg = 50.0°C), or polymn. activation energy (17.3 kJ/mol) are enhanced in comparison with the methacrylated vegetable oil. The synthesized one-pot mixt. does not require addnl. methacrylic acid due to the use of the one formed in the first step of the reaction, while the eventual thermoset mixt. exhibits enhanced material properties compared to the methacrylated vegetable oil itself. Precursors synthesized in this work may find their purpose in the field of coating technologies, since these applications require detailed viscosity modifications.
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      Ho, Y. H.; Parthiban, A.; Thian, M. C.; Ban, Z. H.; Siwayanan, P.; Lai, J.-Y. Acrylated Biopolymers Derived Via Epoxidation And Subsequent Acrylation Of Vegetable Oils. Int. J. Polym. Sci. 2022, 2022, 1– 12,  DOI: 10.1155/2022/6210128
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      Guit, J.; Tavares, M. B. L.; Hul, J.; Ye, C.; Loos, K.; Jager, J.; Folkersma, R.; Voet, V. S. D. Photopolymer Resins With Biobased Methacrylates Based On Soybean Oil For Stereolithography. ACS Applied Polymer Materials 2020, 2 (2), 949– 957,  DOI: 10.1021/acsapm.9b01143
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      Photopolymer Resins with Biobased Methacrylates Based on Soybean Oil for Stereolithography
      Guit, Jarno; Tavares, Marjory B. L.; Hul, Jerzy; Ye, Chongnan; Loos, Katja; Jager, Jan; Folkersma, Rudy; Voet, Vincent S. D.
      ACS Applied Polymer Materials (2020), 2 (2), 949-957CODEN: AAPMCD; ISSN:2637-6105. (American Chemical Society)
      The accessibility of renewable materials that are both sustainable and competitive is essential to accommodate the rapid growth in consumption of 3D printing materials. We have developed biobased photopolymer resins based on modified soybean oil for application in com. stereolithog. printers. First, soybean oil methacrylates with various functionalities were successfully synthesized from epoxidized soybean oil as an alternative to com. available soybean oil acrylate. A library of photoresins was created by mixing up to 80% of the biobased (meth)acrylate oligomers with biobased diluents and a photoinitiator. The resin compn. was optimized to achieve a max. biobased content and a low viscosity. The manufd. parts demonstrated complete layer fusion and accurate print quality. Stiffness and toughness can be tuned by altering the chem. compn. or the no. of functional groups per oligomer. These biobased materials can be employed to reduce the environmental impact of additive manufg. while being competitive with current fossil-based resins from com. manufacturers.
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      Li, P.; Ma, S.; Dai, J.; Liu, X.; Jiang, Y.; Wang, S.; Wei, J.; Chen, J.; Zhu, J. Itaconic Acid As A Green Alternative To Acrylic Acid For Producing A Soybean Oil-Based Thermoset: Synthesis And Properties. ACS Sustainable Chem. Eng. 2017, 5 (1), 1228– 1236,  DOI: 10.1021/acssuschemeng.6b02654
      18
      Itaconic Acid as a Green Alternative to Acrylic Acid for Producing a Soybean Oil-Based Thermoset: Synthesis and Properties
      Li, Peng; Ma, Songqi; Dai, Jinyue; Liu, Xiaoqing; Jiang, Yanhua; Wang, Sheng; Wei, Jingjing; Chen, Jing; Zhu, Jin
      ACS Sustainable Chemistry & Engineering (2017), 5 (1), 1228-1236CODEN: ASCECG; ISSN:2168-0485. (American Chemical Society)
      In this paper, itaconic acid was monomethylated with methanol to produce monomethyl itaconate, and then monomethyl itaconated epoxidized soybean oil (IESO) was obtained by melt ring-opening esterification of monomethyl itaconate with ESO. For comparison, acrylated epoxidized soybean oil (AESO) was also synthesized from ESO and acrylic acid with the same synthetic method. The chem. structures of monomethyl itaconate, IESO, and AESO were characterized in detail by differential scanning calorimetry (DSC), FTIR, and 1H NMR. The isothermal thermogravimetric anal. at 30, 60, and 90 °C indicated that monomethyl itaconate exhibited extremely low volatility even at 90 °C, while acrylic acid volatilized very fast even at 30 °C, which suggested that monomethyl itaconate could be used as a green alternative to acrylic acid. Under UV radiation, IESO showed good copolymn. ability with reactive monomers such as glycidyl methacrylate modified itaconic acid (IG), trimethylolpropane triacrylate (TMPTMA), and styrene. The cured neat IESO exhibited similar properties to the neat AESO, and the IESO/reactive monomers systems showed higher glass transition temp. (Tg), modulus, and comparable or better tensile strength and coating properties than the AESO/reactive monomers systems.
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      https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC28XhvFKns73E&md5=21985d3d9d8ff343a2d61df2a4ed3f46
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      Decostanzi, M.; Lomège, J.; Ecochard, Y.; Mora, A.-S.; Negrell, C.; Caillol, S. Fatty Acid-Based Cross-Linkable Polymethacrylate Coatings. Prog. Org. Coat. 2018, 124, 147– 157,  DOI: 10.1016/j.porgcoat.2018.08.001
      19
      Fatty acid-based crosslinkable polymethacrylate coatings
      Decostanzi, Melanie; Lomege, Juliette; Ecochard, Yvan; Mora, Anne-Sophie; Negrell, Claire; Caillol, Sylvain
      Progress in Organic Coatings (2018), 124 (), 147-157CODEN: POGCAT; ISSN:0300-9440. (Elsevier B.V.)
      In this paper, novel epoxy prepolymers from oleic acid-based monomers were crosslinked to prep. thermosets for coating application. For this purpose, methacrylate moiety was firstly added to oleic acid via Steglich esterification prior to conventional radical polymn. The resulting oleic acid-based polymer was obtained with a no. mol. wt. 40,000 g/mol (DP = 110). Then the internal unsaturations of this polymer were epoxidized at different epoxy contents to provide crosslinkable functionalities. Based on a study of the internal epoxy reactivity of a model compd. with different nucleophiles, the synthesized oleic-based polymers with epoxy functions hanging off the main chain were successfully crosslinked with succinic anhydride. Dynamic mech. and thermal analyses, as well as swelling index properties have been studied for all the resulting thermosets. Addnl., the properties of coatings on steel substrates were studied to det. coating hardness, and adhesion. The results of this work provide evidence of the potential of these materials as bio-based coatings and adhesives.
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    20. 20
      Silva, J. A. C.; Dever, S.; Siccardi, A.; Snelling, D.; Al Qabani, I.; Thompson, S.; Goldberg, K.; Baudoin, G.; Martins Lacerda, T.; Quirino, R. L. Itaconic Anhydride As A Bio-Based Compatibilizer For A Tung Oil-Based Thermosetting Resin Reinforced With Sand And Algae Biomass. Coatings 2023, 13 (7), 1188– 1203,  DOI: 10.3390/coatings13071188
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    21. 21
      Thomas, J.; Patil, R. Enabling Green Manufacture Of Polymer Products Via Vegetable Oil Epoxides. Ind. Eng. Chem. Res. 2023, 62 (4), 1725– 1735,  DOI: 10.1021/acs.iecr.2c03867
      21
      Enabling Green Manufacture of Polymer Products via Vegetable Oil Epoxides
      Thomas, Jomin; Patil, Renuka
      Industrial & Engineering Chemistry Research (2023), 62 (4), 1725-1735CODEN: IECRED; ISSN:0888-5885. (American Chemical Society)
      A review. The industrial application of epoxidized vegetable oil is being diversified and commercialized at a rapid pace. It is attributed to its environment friendly nature compared to the synthetic Bisphenol A epoxides which are deemed toxic. However, there are concerns that the incorporation of such epoxidized vegetable oil has an undesirable impact on the main performance properties of tires due to its inherent flexible polymer chain. At the same time, new product innovations and synthesis capabilities can help us develop polymer products in a more sustainable fashion. This review first outlines the inherent challenges, the progress made thus far, and future opportunities for epoxidized vegetable oil derivs. Next, the main application areas of these epoxides, such as plasticizers, coatings, and composites, are discussed in-depth. Possible design guidelines for surpassing the challenges to equiv. performance are also examd. A meticulous overview of the existing literature is conducted to summarize the recent approaches to epoxidized vegetable oil deriv. products with a crit. anal. of some of them. This contribution attempts to highlight epoxidized vegetable oil derivs. on the basis of existing challenges, recent research advancements, and their prospective future.
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    22. 22
      Liu, K.; Madbouly, S. A.; Kessler, M. R. Biorenewable Thermosetting Copolymer Based On Soybean Oil And Eugenol. Eur. Polym. J. 2015, 69, 16– 28,  DOI: 10.1016/j.eurpolymj.2015.05.021
      22
      Biorenewable thermosetting copolymer based on soybean oil and eugenol
      Liu, Kunwei; Madbouly, Samy A.; Kessler, Michael R.
      European Polymer Journal (2015), 69 (), 16-28CODEN: EUPJAG; ISSN:0014-3057. (Elsevier Ltd.)
      A novel biorenewable thermoset based on acrylated epoxidized soybean oil (AESO) and methacrylated eugenol (ME) was prepd. via free radical polymn. The chem. compns. of the monomers were investigated using proton NMR (1H NMR) technique. The properties of this resin system were investigated using small amplitude oscillatory shear flow rheol., dynamic mech. anal. (DMA), thermogravimetric anal. (TGA), and compression testing. Soxhlet extn. was also performed on the cured thermoset to det. the percentage of monomers that are incorporated into the crosslink network. In addn., the gelation time of this resin at different curing temp. was also monitored using a rheometer. The Soxhlet extn. data indicated that more than 95% of the monomers were incorporated into the crosslink network. Gelation time study showed that this resin system can become a solid within 10 min. This resin system possesses high strength and modulus, and it is thermally stable up to 300 °C. This high biorenewable content resin system possesses good mech. properties, high thermal stability, and fast curing speed, making it a suitable matrix resin for the pultrusion process and other composite manufg. processes.
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      Athawale, V. D.; Nimbalkar, R. V. Waterborne Coatings Based On Renewable Oil Resources: An Overview. J. Am. Oil Chem. Soc. 2011, 88 (2), 159– 185,  DOI: 10.1007/s11746-010-1668-9
      23
      Waterborne Coatings Based on Renewable Oil Resources: an Overview
      Athawale, Vilas D.; Nimbalkar, Ramakant V.
      Journal of the American Oil Chemists' Society (2011), 88 (2), 159-185CODEN: JAOCA7; ISSN:0003-021X. (Springer)
      A review. Polyurethane dispersions are gaining in importance due to their environmentally friendly coating system, versatile coating properties and ease of application. An enormous amt. of research is focused on waterborne coatings such as waterborne alkyds, water-reducible alkyds, alkyd-acrylic hybrids, oil modified polyurethane dispersions and their composite latexes. This review gives a comprehensive compilation of recent studies on the synthesis and applications of waterborne coatings. The article specifically covers all of the research work carried out in the field of waterborne alkyd-acrylics, polyurethane dispersions and their hybrid latexes systematically.
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    24. 24
      Mousaa, I. M.; Radi, H. Photosynthesis Of Anticorrosive Protective Coatings For Steel Substrate Based On Acrylated Oil Containing Unsaturated Amino Acid Compounds. Prog. Org. Coat. 2017, 107, 18– 28,  DOI: 10.1016/j.porgcoat.2017.03.006
      24
      Photosynthesis of anticorrosive protective coatings for steel substrate based on acrylated oil containing unsaturated amino acid compounds
      Mousaa, I. M.; Radi, H.
      Progress in Organic Coatings (2017), 107 (), 18-28CODEN: POGCAT; ISSN:0300-9440. (Elsevier B.V.)
      Novel environment friendly anticorrosive coating formulations for mild steel substrate based on acrylated oil were prepd. by using unsatd. amino acid compds. In the first, epoxidized soybean oil acrylate (ESOA) was hardened and modified by the different functionality of monomers to be used in anticorrosive coating formulations. In this article, new corrosion inhibitors were synthesized through two steps. In step one, renewable resource based palm oil was epoxidized under a well-established condition to form epoxidized triglyceride ester of palm oil (EPO). FTIR and oxirane content anal. were used to confirm the formation of the epoxidn. reaction. In step two, the EPO was reacted chem. with 4-aminobenzoic acid (AB) and 2-aminoacrylic acid (AA) under controlled conditions of an inert atm. and high temp. to produce EPO/AB and EPO/AA adducts. The prepd. adducts were characterized by FTIR-spectroscopy and oxirane content anal. The adducts are evaluated as corrosion inhibitors via adding different concns. of them to the ESOA coating formulations. Then all coating films were subjected to UV irradn. Degrees of rusting, blistering, failure at scribe, and wt. loss values were measured for all UV cured films, in addn. to the chem. and mech. measurements. The obtained exptl. results revealed that the cured coating films contg. EPO/AB inhibitor displayed higher resistance to corrosion on the mild steel substrate than EPO/AA without any effect on the mech. and chem. properties of cured films. Also, the optimum concn. of the prepd. inhibitors was to be 0.5%.
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    25. 25
      Zulkifli, F.; Ali, N.; Yusof, M. S. M.; Isa, M. I. N.; Yabuki, A.; Wan Nik, W. B. Henna Leaves Extract As A Corrosion Inhibitor In Acrylic Resin Coating. Prog. Org. Coat. 2017, 105, 310– 319,  DOI: 10.1016/j.porgcoat.2017.01.017
      25
      Henna leaves extract as a corrosion inhibitor in acrylic resin coating
      Zulkifli, F.; Ali, Nora'aini; Yusof, M. Sukeri M.; Isa, M. I. N.; Yabuki, A.; Wan Nik, W. B.
      Progress in Organic Coatings (2017), 105 (), 310-319CODEN: POGCAT; ISSN:0300-9440. (Elsevier B.V.)
      This study utilizes optical measurements, thermo-impedance anal., potentiodynamic polarization studies and morphol. observations of henna leaves ext. (HLE) incorporated in an acrylic resin coating. The acrylic resin coating with 0.2 wt/vol% HLE (AC2) had the best performance protecting metal from corrosion. XRD and DSC anal. demonstrate that an increase in the crystallite size limits the close packed structure, which increases the free vol. and reduces the Tg of the coating. Open circuit potential (OCP) measurements demonstrate that the AC2 coating has a uniform potential due to the lower rate of coating barrier destruction. Electrochem. impedance spectroscopy (EIS) indicates that AC2 has the highest coating resistance, Rc (4.79 × 108 Ω), and lowest coating capacitance, Cc (3.32 × 10-9 F/cm2). An elevation in temp. caused coating deterioration for all of the coatings. AC2 has the lowest dielec. const., εr, indicating less water uptake and lower ionic cond. An addnl. study of potentiodynamic polarization demonstrates that AC2 has shifted to the noble potential and gives the lowest corrosion c.d., icorr, reading. The corrosion rate is the lowest for AC2 (3.93 × 10-7 mm/yr), while the polarization resistance is the highest at 7.44 × 107 Ω. An SEM morphol. study indicates that AC2 has lesser delamination and greater coverage of HLE in the coating.
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    26. 26
      Uzoma, P. C.; Liu, F.; Xu, L.; Zhang, Z.; Han, E.-H.; Ke, W.; Arukalam, I. O. Superhydrophobicity, Conductivity And Anticorrosion Of Robust Siloxane-Acrylic Coatings Modified With Graphene Nanosheets. Prog. Org. Coat. 2019, 127, 239– 251,  DOI: 10.1016/j.porgcoat.2018.11.018
      26
      Superhydrophobicity, conductivity and anticorrosion of robust siloxane-acrylic coatings modified with graphene nanosheets
      Uzoma, Paul C.; Liu, Fuchun; Xu, Long; Zhang, Zhichao; Han, En-Hou; Ke, Wei; Arukalam, I. O.
      Progress in Organic Coatings (2019), 127 (), 239-251CODEN: POGCAT; ISSN:0300-9440. (Elsevier B.V.)
      The effects of low-cost graphene nanosheets in org. coatings were investigated. The hydrophobic org. siloxane-acrylic resin was synthesized by soln. polymn. of acrylic monomers while the graphene nanosheets were modified using fluorosilane, and applied on LY12 aluminum substrate via spraying and a two-step coating system. The superhydrophobic, conductive, anticorrosion, self-cleaning, oleophilic and phys. behaviors were comprehensively characterized. The results obtained revealed that addn. of modified graphene increases the surface cond. (≥ 2 μS/cm) and the water contact angle (≥ 152°) with low sliding angle (≤ 7°). The polarization measurement showed a pos. shift in the corrosion potential signifying an inhibition of the cathodic reaction. Also, the two-step coated sample gave a good corrosion protection barrier as further confirmed by the electrochem. impedance parameters. The coating revealed good resistance to dirt adhesion, and its superhydrophobic-oleophilic property offered a promising application in oil-water sepn. The phys. integrity of the coatings was not extensively affected including after 120 days of outdoor exposure to snowing, de-freezing and surface wetting.
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    27. 27
      Ifijen, I. H.; Maliki, M.; Odiachi, I. J.; Aghedo, O. N.; Ohiocheoya, E. B. Review On Solvents Based Alkyd Resins And Water Borne Alkyd Resins: Impacts Of Modification On Their Coating Properties. Chemistry Africa 2022, 5 (2), 211– 225,  DOI: 10.1007/s42250-022-00318-3
      There is no corresponding record for this reference.
    28. 28
      Radoman, T. S.; Dzunuzovic, J. V.; Trifkovic, K. T.; Palija, T.; Marinkovic, A. D.; Bugarski, B.; Dzunuzovic, E. S. Effect Of Surface Modified Tio2 Nanoparticles On Thermal, Barrier And Mechanical Properties Of Long Oil Alkyd Resin-Based Coatings. Express Polymer Letters 2015, 9 (10), 916– 931,  DOI: 10.3144/expresspolymlett.2015.83
      There is no corresponding record for this reference.
    29. 29
      Kim, Y. S.; Cho, H. J.; Lee, H.; Kim, W. Y.; Jung, Y. C.; Lee, S. Y. Development Of A Multi-Functional Acrylic Urethane Coating With High Hardness And Low Surface Energy. Prog. Org. Coat. 2020, 147, 105748  DOI: 10.1016/j.porgcoat.2020.105748
      There is no corresponding record for this reference.
    30. 30
      Paraskar, P. M.; Prabhudesai, M. S.; Hatkar, V. M.; Kulkarni, R. D. Vegetable Oil Based Polyurethane Coatings–A Sustainable Approach: A Review. Prog. Org. Coat. 2021, 156, 106267  DOI: 10.1016/j.porgcoat.2021.106267
      30
      Vegetable oil based polyurethane coatings - A sustainable approach: A review
      Paraskar, Pavan M.; Prabhudesai, Mayur S.; Hatkar, Vinod M.; Kulkarni, Ravindra D.
      Progress in Organic Coatings (2021), 156 (), 106267CODEN: POGCAT; ISSN:0300-9440. (Elsevier B.V.)
      A review. The scientific community has been pooling all its resources, for the past decade, toward the development of "sustainable development" to usher into an eternally green and sustainable tomorrow. As part of this endeavor, the conventional petroleum-based polyurethane (PU) coatings have been replaced by their green counterparts, i.e., bio-based polyurethane coatings. These green alternatives provide a suitable replacement for the coating industry due to their easy availability, biodegradability, low cost, and lesser environmental impact. The prodn. of such green PU coatings is further facilitated by the utilization of bio-based materials, including vegetable oils and their derivs. such as Me ester, fatty acid, and other bio-renewable sources. This review discusses the different chem. modifications used to convert these bio-based precursors into desired polyols and isocyanates. Furthermore, the formulation of different PU coatings and their subsequent potential applications are also elaborated on in this review. The coatings sector has already been introduced to the notion of eco-friendly technologies such as UV-curable, less or zero solvent, waterborne, hyperbranched, and high solids coatings, complemented by the incorporation of renewable feedstock in monomer synthesis. The review examines the future hurdles that hinder the utilization of these materials in a wide range of applications and presents technologies that facilitate potential solns. and mention key players in the coating sectors that are at the forefront of bringing these revolutionary changes.
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    31. 31
      Wei, H.; Xia, J.; Zhou, W.; Zhou, L.; Hussain, G.; Li, Q.; Ostrikov, K.(K.). Adhesion And Cohesion Of Epoxy-Based Industrial Composite Coatings. Compos. B: Eng. 2020, 193, 108035  DOI: 10.1016/j.compositesb.2020.108035
      There is no corresponding record for this reference.
    32. 32
      Croll, S. G. Surface Roughness Profile And Its Effect On Coating Adhesion And Corrosion Protection: A Review. Prog. Org. Coat. 2020, 148, 105847  DOI: 10.1016/j.porgcoat.2020.105847
      32
      Surface roughness profile and its effect on coating adhesion and corrosion protection: A review
      Croll, S. G.
      Progress in Organic Coatings (2020), 148 (), 105847CODEN: POGCAT; ISSN:0300-9440. (Elsevier B.V.)
      A review. Specifications for coating many forms of infrastructure and equipment include abrasive cleaning, then measurement of surface profile and adhesion on the assumption that they are linked to long term prevention of corrosion undercutting the coating. Studies find no quant. connection between adhesion and corrosion protection, but many believe in a link. Although corrosion is a mol. phenomenon that starts at the interface, adhesion values are measured by a device attached to the coating at some distance from the interface, so it is difficult to directly connect corrosion with adhesion. Understanding how adhesion and the spread of corrosion under the coating are influenced by surface roughness entails surface metrol., fracture mechanics, surface energy and viscoelasticity. The impact of surface roughness can't be detd. by a simple, or single, statistical parameter for variation in substrate height variation. Conventional ''pull-off'' adhesion testing does not characterize coating-metal interactions that might prevent water and electrolyte causing corrosion, they must be detd. otherwise. The addnl. surface area created by the abrasion increases the no. of adhesive interactions and the local slope of the surface engages Mode II loading that increases the force that the interface can support. In order to prevent the diffusion of water and electrolyte across the interface, a coating should form well at the interface, be tough and as hydrophobic as realistically possible.
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    33. 33
      Tang, X.; Yan, X. Dip-Coating For Fibrous Materials: Mechanism, Methods And Applications. J. Sol-Gel Sci. Technol. 2017, 81 (2), 378– 404,  DOI: 10.1007/s10971-016-4197-7
      33
      Dip-coating for fibrous materials: mechanism, methods and applications
      Tang, Xiaoning; Yan, Xiong
      Journal of Sol-Gel Science and Technology (2017), 81 (2), 378-404CODEN: JSGTEC; ISSN:0928-0707. (Springer)
      A review. This paper presents a review on dip-coating for fibrous materials, mainly concd. on the mechanism, recently developed dip-coating methods and novel functional applications. The emphasis has been made here, to present theor. basis of dip-coating-induced film deposition, esp., the reported works to predict the thickness based on various processing parameters. Different modified dip-coating techniques to fabricate deposited films for fibrous substrate have also been gathered. The scope of reviewed dip-coating methods are not only conventional soln. and sol-gel-based dip-coating, but also recently developed vacuum-assisted, spin-assisted, photo-assisted and multi-layered dip-coating methods. An overview of reported and potential applications for coated fibrous materials has also been given, which mainly including self-cleaning, oil-water sepn., conductive textiles, fibrous-based energy storage devices, and photonic crystals, etc. This review is intended to give readers a good horizon for the present status concerning variety of studies and applications related to dip-coating. An effort has been made here to report the important contributions in the area of dip-coating for fibrous substrate, and crit. points regarding future research directions are outlined in the summary.
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    34. 34
      Khudyakov, I. V. Fast Photopolymerization Of Acrylate Coatings: Achievements And Problems. Prog. Org. Coat. 2018, 121, 151– 159,  DOI: 10.1016/j.porgcoat.2018.04.030
      34
      Fast photopolymerization of acrylate coatings: Achievements and problems
      Khudyakov, Igor V.
      Progress in Organic Coatings (2018), 121 (), 151-159CODEN: POGCAT; ISSN:0300-9440. (Elsevier B.V.)
      A review. Coatings chemists often prep. (meth)acrylate coatings which meet their needs.However, anal. of kinetics of photopolymn. (UV-cure) is usually based on a classical scheme of the chain free radical polymns. That set of reactions with resp. rate consts. is valid only up till few percent of conversion of double bonds. Multiple studies of photopolymn. are focused not on reactions at large d.p. but on selection of new photoinitiators. In the present paper we focused on fundamentals of photopolymn. rather than on multitude of applications, different formulations, sources of light, etc., and we try to avoid repetition of widely discussed in the literature issues. A special attention is devoted to cage effect during photodissocn. of initiators. An increase of cage effect value with a d.p. increase affects overall efficiency of photoinitiator at large conversions. IUPAC terms and notions are suggested.
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    35. 35
      Bai, J.; Yu, Q. Preparation And Characterization Of A Silicone Raft-Modified Aqueous Acrylic Resin Coating For Wood Antifouling. Colloids Surf., A 2023, 677, 132385  DOI: 10.1016/j.colsurfa.2023.132385
      There is no corresponding record for this reference.
    36. 36
      Hochmańska-Kaniewska, P.; Janiszewska, D.; Oleszek, T. Enhancement Of The Properties Of Acrylic Wood Coatings With The Use Of Biopolymers. Prog. Org. Coat. 2022, 162, 106522  DOI: 10.1016/j.porgcoat.2021.106522
      36
      Enhancement of the properties of acrylic wood coatings with the use of biopolymers
      Hochmanska-Kaniewska, Patrycja; Janiszewska, Dominika; Oleszek, Tomasz
      Progress in Organic Coatings (2022), 162 (), 106522CODEN: POGCAT; ISSN:0300-9440. (Elsevier B.V.)
      The objective of this study was to enhance the properties of water-borne acrylic coatings by modifying them with biopolymers. Water-borne coatings are more and more commonly used in the wood and furniture industry. To improve the performance of these coatings, there is a need to apply reinforcing agents. Among these, besides the well-studied inorg. nanoparticles, biopolymers are gaining increasing attention. In this study, a base acrylic coating material was filled with biopolymers having a wide variety of properties and functionalities, including nanocryst. cellulose and two types of liquefied wood, in amts. of 1.0%, 3.0% and 5.0% by dry wt. of coating. Two wood species, pine and beech, were selected for coating. Properties of the coatings were detd. in order to assess the quality of the new coating formulations. Bearing in mind that the main cause of coating failure during interior exposure is mech. defects, impact and abrasion resistance tests were performed. The abrasion resistance of the coatings was found to be increased by nanocryst. cellulose and liquefied wood, most significantly at 1% loading. The results also indicated improvement in the impact resistance of coatings filled with nanocryst. cellulose.
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    37. 37
      Liu, M.; Liu, Y.; Wang, P.; Ying, W.; Liu, Q.; Ding, G.; Chen, S. Synthesis And Properties Of A Photocurable Coating Based On Waste Cooking Oil. Coatings 2023, 13 (9), 1553– 1572,  DOI: 10.3390/coatings13091553
      There is no corresponding record for this reference.
    38. 38
      Jašek, V.; Fučík, J.; Ivanová, L.; Veselý, D.; Figalla, S.; Mravcova, L.; Sedlacek, P.; Krajčovič, J.; Přikryl, R. High-Pressure Depolymerization Of Poly(Lactic Acid) (Pla) And Poly(3-Hydroxybutyrate) (Phb) Using Bio-Based Solvents: A Way To Produce Alkyl Esters Which Can Be Modified To Polymerizable Monomers. Polymers 2022, 14 (23), 5236– 5254,  DOI: 10.3390/polym14235236
      There is no corresponding record for this reference.
    39. 39
      Jašek, V.; Fučík, J.; Melčová, V.; Přikryl, R.; Figalla, S. Improvements In The Production Of Isosorbide Monomethacrylate Using A Biobased Catalyst And Liquid–Liquid Extraction Isolation For Modifications Of Oil-Based Resins. ACS Omega 2024, 9 (23), 24728– 24738,  DOI: 10.1021/acsomega.4c01275
      There is no corresponding record for this reference.
    40. 40
      Wang, F.; Allen, D.; Tian, S.; Oler, E.; Gautam, V.; Greiner, R.; Metz, T. O.; Wishart, D. S. Cfm-Id 4.0–A Web Server For Accurate Ms-Based Metabolite Identification. Nucleic Acids Res. 2022, 50 (W1), W165– W174,  DOI: 10.1093/nar/gkac383
      40
      CFM-ID 4.0 - a web server for accurate MS-based metabolite identification
      Wang, Fei; Allen, Dana; Tian, Siyang; Oler, Eponine; Gautam, Vasuk; Greiner, Russell; Metz, Thomas O.; Wishart, David S.
      Nucleic Acids Research (2022), 50 (W1), W165-W174CODEN: NARHAD; ISSN:1362-4962. (Oxford University Press)
      The CFM-ID 4.0 web server (https://cfmid.wishartlab. com) is an online tool for predicting, annotating and interpreting tandem mass (MS/MS) spectra of small mols. It is specifically designed to assist researchers pursuing studies in metabolomics, exposomics and anal. chem. More specifically, CFM-ID 4.0 supports the: (1) prediction of electrospray ionization quadrupole time-of-flight tandem mass spectra (ESI-QTOF-MS/MS) for small mols. over multiple collision energies (10 eV, 20 eV, and 40 eV); (2) annotation of ESI-QTOF-MS/MS spectra given the structure of the compd.; and (3) identification of a small mol. that generated a given ESI-QTOF-MS/MS spectrum at one or more collision energies. The CFM-ID 4.0 web server makes use of a substantially improved MS fragmentation algorithm, a much larger database of exptl. and in silico predicted MS/MS spectra and improved scoring methods to offer more accurate MS/MS spectral prediction and MS/MS-based compd. identification. Compared to earlier versions of CFM-ID, this new version has an MS/MS spectral prediction performance that is ~ 22% better and a compd. identification accuracy that is ~ 35% better on a std. (CASMI 2016) testing dataset. CFM-ID 4.0 also features a neutral loss function that allows users to identify similar or substituent compds. where no match can be found using CFM-ID's regular MS/MS-to-compd. identification utility. Finally, the CFM-ID 4.0 web server now offers a much more refined user interface that is easier to use, supports mol. formula identification (from MS/MS data), provides more interactively viewable data (including proposed fragment ion structures) and displays MS mirror plots for comparing predicted with obsd. MS/MS spectra. These improvements should make CFM-ID 4.0 much more useful to the community and should make small mol. identification much easier, faster, and more accurate.
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    41. 41
      Wu, Q.; Hu, Y.; Tang, J.; Zhang, J.; Wang, C.; Shang, Q.; Feng, G.; Liu, C.; Zhou, Y.; Lei, W. High-Performance Soybean-Oil-Based Epoxy Acrylate Resins: “Green” Synthesis And Application In Uv-Curable Coatings. ACS Sustainable Chem. Eng. 2018, 6 (7), 8340– 8349,  DOI: 10.1021/acssuschemeng.8b00388
      41
      High-Performance Soybean-Oil-Based Epoxy Acrylate Resins: "Green" Synthesis and Application in UV-Curable Coatings
      Wu, Qiong; Hu, Yun; Tang, Jijun; Zhang, Jing; Wang, Cuina; Shang, Qianqian; Feng, Guodong; Liu, Chengguo; Zhou, Yonghong; Lei, Wen
      ACS Sustainable Chemistry & Engineering (2018), 6 (7), 8340-8349CODEN: ASCECG; ISSN:2168-0485. (American Chemical Society)
      Novel soybean-oil-based (SBO-based) epoxy acrylate (EA) resins were developed via ring-opening reaction of epoxidized soybean oil (ESO) with hydroxyethyl methacrylated maleate (HEMAMA) precursor, a synthesized unsatd. carboxylic acid having two active C=C groups and a side Me group. Exptl. conditions for the synthesis of the precursor and the SBO-based EA (ESO-HEMAMA) product were studied, and their chem. structures were confirmed by FT-IR, 1H NMR, 13C NMR, and gel permeation chromatog. Subsequently, the volatility of HEMAMA was studied and compared with acrylic acid (AA). Furthermore, gel contents and ultimate properties of the UV-cured ESO-HEMAMA resins were investigated and compared with a com. acrylated ESO (AESO) resin. At last, UV-curing behaviors of the SBO-based EA resins were detd. by real-time IR. It was found that the HEMAMA precursor showed much lower volatility than AA, and the optimal pure ESO-HEMAMA resin possessed a C=C functionality up to 6.02 per ESO and biobased content of 65.4%. Meanwhile, the obtained ESO-HEMAMA biomaterials exhibited much superior properties as compared to the AESO resin. For instance, the obtained pure ESO-HEMAMA material possessed a storage modulus at 25 °C of 1.00 GPa, glass transition temp. (Tg) of 70.1 °C, and tensile strength and modulus of 13.4 and 592.1 MPa, which were 9.4, 3.6, 6.9, and 15.7 times the values of the pure AESO material, resp. The resulting biomaterial with 30% of hydroxyethyl methacrylate diluent even reached a tensile strength of 28.4 MPa and Tg of 89.0 °C. Therefore, the developed SBO-based EA resins are very promising for applications in UV-curable coatings.
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    42. 42
      Jašek, V.; Melčová, V.; Figalla, S.; Fučík, J.; Menčík, P.; Přikryl, R. Study Of The Thermomechanical Properties Of Photocured Resins Based On Curable Monomers From Pla And Phb For Sla 3D Printing. ACS Applied Polymer Materials 2023, 5 (12), 9909– 9917,  DOI: 10.1021/acsapm.3c01730
      There is no corresponding record for this reference.
    43. 43
      Yadav, M.; Saha, J. K.; Ghosh, S. K. Surface, Chemical, And Mechanical Properties Of Polyurethane-Coated Galvanized Steel Sheets. J. Mater. Eng. Perform. 2024, 1– 16,  DOI: 10.1007/s11665-024-09171-6
      There is no corresponding record for this reference.
    44. 44
      Zhu, Y.; Zhu, W.; Li, Z.; Feng, Y.; Qi, W.; Li, S.; Wang, X.; Chen, M. Enhancement Of Wood Coating Properties By Adding Silica Sol To Uv-Curable Waterborne Acrylics. Forests 2023, 14 (2), 335– 348,  DOI: 10.3390/f14020335
      There is no corresponding record for this reference.
    45. 45
      Teacă, C.-A.; Roşu, D.; Mustaţă, F.; Rusu, T.; Roşu, L.; Roşca, I.; Varganici, C.-D. Natural Bio-Based Products For Wood Coating And Protection Against Degradation: A Review. BioResources 2019, 14 (2), 4873– 4901,  DOI: 10.15376/biores.14.2.Teaca
      There is no corresponding record for this reference.
    46. 46
      Patil, R. S.; Thomas, J.; Patil, M.; John, J. To Shed Light On The Uv Curable Coating Technology: Current State Of The Art And Perspectives. Journal of Composites Science 2023, 7 (12), 513– 528,  DOI: 10.3390/jcs7120513
      There is no corresponding record for this reference.
    47. 47
      Thomas, J.; Patil, R. S.; Patil, M.; John, J. Navigating The Labyrinth Of Polymer Sustainability In The Context Of Carbon Footprint. Coatings 2024, 14 (6), 774– 786,  DOI: 10.3390/coatings14060774
      There is no corresponding record for this reference.
    48. 48
      Jašek, V.; Fučík, J.; Krhut, J.; Mravcova, L.; Figalla, S.; Přikryl, R. A Study Of Isosorbide Synthesis From Sorbitol For Material Applications Using Isosorbide Dimethacrylate For Enhancement Of Bio-Based Resins. Polymers 2023, 15 (17), 3640– 3658,  DOI: 10.3390/polym15173640
      There is no corresponding record for this reference.
    49. 49
      Veith, C.; Diot-Néant, F.; Miller, S. A.; Allais, F. Synthesis And Polymerization Of Bio-Based Acrylates: A Review. Polym. Chem. 2020, 11 (47), 7452– 7470,  DOI: 10.1039/D0PY01222J
      49
      Synthesis and polymerization of bio-based acrylates: a review
      Veith, Clemence; Diot-Neant, Florian; Miller, Stephen A.; Allais, Florent
      Polymer Chemistry (2020), 11 (47), 7452-7470CODEN: PCOHC2; ISSN:1759-9962. (Royal Society of Chemistry)
      A review. Acrylates and polyacrylates have been produced massively due to their interesting applications like Plexiglas. However, the contemporary issues of fossil depletion assocd. with climate change have raised serious concerns. As a result, utilization of renewable resources such as lignocellulosic materials and the development of greener processes have been investigated intensively. Herein, we review the prepn. of competitive (meth)acrylates and the corresponding polymers made from bio-renewable resources with a specific focus on lignocellulose. While covering a few families of biosynthons to produce acrylates through different synthetic pathways, we also analyze the promising properties of the resulting materials.
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      https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BB3cXit1yhtb7L&md5=bd6861cbd5650e5ede8fc48e84beb750
    50. 50
      Badía, A.; Agirre, A.; Barandiaran, M. J.; Leiza, J. R. Removable Biobased Waterborne Pressure-Sensitive Adhesives Containing Mixtures Of Isosorbide Methacrylate Monomers. Biomacromolecules 2020, 21 (11), 4522– 4531,  DOI: 10.1021/acs.biomac.0c00474
      50
      Removable Biobased Waterborne Pressure-Sensitive Adhesives Containing Mixtures of Isosorbide Methacrylate Monomers
      Badia, Adrian; Agirre, Amaia; Barandiaran, Maria J.; Leiza, Jose Ramon
      Biomacromolecules (2020), 21 (11), 4522-4531CODEN: BOMAF6; ISSN:1525-7797. (American Chemical Society)
      Growing environmental concerns are enforcing sustainable recycling processes for glass substrates, esp. bottles, where a fast cleaning and minimization of the use of solvents is desired. In this process, labels and adhesives are mostly removed by the addn. of harsh reagents, alk. solns., or high temp., increasing economic costs and harming the environment. Herein, high performance and biobased waterborne pressure-sensitive adhesives with fast removability in water have been developed using small percentages of isosorbide (derived from glucose)-based methacrylate monomers. Formulations contg. 2-octyl acrylate and isobornyl methacrylate and small amts. (1 wt %) of these monomers not only yield stronger adhesive fibrils, but also promote a removability in water 6x faster than that of nonisosorbide-based counterparts. This waterborne isosorbide contg. PSAs represents an alternative to current PSA formulations toward more sustainable glass recycling and reusing processes.
      >> More from SciFinder ®
      https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BB3cXpvVGrurk%253D&md5=bfe04e6ba46bc96fc7d238021e99856e
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      Thomas, J.; Patil, R. S.; Patil, M.; John, J. Addressing The Sustainability Conundrums And Challenges Within The Polymer Value Chain. Sustainability 2023, 15 (22), 15758– 15777,  DOI: 10.3390/su152215758
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      Thakur, S.; Misra, M.; Mohanty, A. K. Sustainable Hydrophobic And Moisture-Resistant Coating Derived From Downstream Corn Oil. ACS Sustainable Chem. Eng. 2019, 7 (9), 8766– 8774,  DOI: 10.1021/acssuschemeng.9b00689
      52
      Sustainable Hydrophobic and Moisture-Resistant Coating Derived from Downstream Corn Oil
      Thakur, Suman; Misra, Manjusri; Mohanty, Amar K.
      ACS Sustainable Chemistry & Engineering (2019), 7 (9), 8766-8774CODEN: ASCECG; ISSN:2168-0485. (American Chemical Society)
      Sustainable coating as a replacement for petroleum-derived materials is highly required for packaging and other applications to reduce the generation of land and ocean pollution. In this study, a novel approach has been introduced to incorporate hydrolyzable silane (-Si-OCH2CH3) groups in the downstream corn oil backbone (one of the coproducts of bioethanol industry) which has been consequently used for the fabrication of hydrophobic and moisture-resistant coating for paper substrate. SEM (SEM) images confirmed the uniform coating of the silane-modified epoxidized downstream corn oil (SECO) over the paper. The condensation reaction has taken place with the hydroxyl group of paper and SECO, and as a result, the no. of surface hydroxyl group was reduced to make a hydrophobic surface on coated paper with static water contact angle (WCA) of 129.4 ± 1.12°. SECO-coated paper showed almost 67% decrease in specific water vapor transmission rate compared to that of the uncoated filter paper. These results indicate that the SECO coating delivers excellent moisture barrier and hydrophobicity to the paper substrate. Thus, SECO might be a competitive substitute to petroleum-based polymers for fluorine-free hydrophobic and moisture-resistant coating. This research finding can find application esp. in huge paper packaging industries as well as cellulose-based products such as fiber and foam.
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      https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC1MXmtlWitL0%253D&md5=de68754e92b47141ac1eda5b0fe7d1c4
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      Xu, H.; Tu, J.; Xiang, G.; Zhang, Y.; Guo, X. A Thermosetting Polyurethane With Excellent Self-Healing Properties And Stability For Metal Surface Coating. Macromol. Chem. Phys. 2020, 221 (20), 2000273– 2000281,  DOI: 10.1002/macp.202000273
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      Wang, T.; Segura, J. J.; Graversen, E.; Weinell, C. E.; Dam-Johansen, K.; Kiil, S. Simultaneous Tracking Of Hardness, Reactant Conversion, Solids Concentration, And Glass Transition Temperature In Thermoset Polyurethane Coatings. Journal of Coatings Technology and Research 2021, 18 (2), 349– 359,  DOI: 10.1007/s11998-020-00407-3
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      Wang, J.; Wu, H.; Liu, R.; Long, L.; Xu, J.; Chen, M.; Qiu, H. Preparation Of A Fast Water-Based Uv Cured Polyurethane-Acrylate Wood Coating And The Effect Of Coating Amount On The Surface Properties Of Oak (Quercus Alba L.). Polymers 2019, 11 (9), 1414– 1427,  DOI: 10.3390/polym11091414
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      Sadeghi, I.; Lu, X.; Sarmadi, M.; Langer, R.; Jaklenec, A. Micromolding Of Thermoplastic Polymers For Direct Fabrication Of Discrete. Multilayered Microparticles. Small Methods 2022, 6 (9), 2200232– 2200243,  DOI: 10.1002/smtd.202200232
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      Shibryaeva, L. S.; Lyusova, L. R.; Karpova, S. G.; Naumova, Y. A. Structure And Properties Of Films And Coatings Made Of A Styrene-Butadiene Thermoplastic Elastomer. Russian Journal of Physical Chemistry B 2022, 16 (2), 334– 345,  DOI: 10.1134/S199079312202021X
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      Zhang, C.; Yan, M.; Cochran, E. W.; Kessler, M. R. Biorenewable Polymers Based On Acrylated Epoxidized Soybean Oil And Methacrylated Vanillin. Materials Today Communications 2015, 5, 18– 22,  DOI: 10.1016/j.mtcomm.2015.09.003
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      Sharmin, E.; Zafar, F.; Akram, D.; Alam, M.; Ahmad, S. Recent Advances In Vegetable Oils Based Environment Friendly Coatings: A Review. Industrial Crops and Products 2015, 76, 215– 229,  DOI: 10.1016/j.indcrop.2015.06.022
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      Alam, M.; Akram, D.; Sharmin, E.; Zafar, F.; Ahmad, S. Vegetable Oil Based Eco-Friendly Coating Materials: A Review Article. Arabian Journal of Chemistry 2014, 7 (4), 469– 479,  DOI: 10.1016/j.arabjc.2013.12.023
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      Alam, M.; Ahmed, M.; Altaf, M.; Shaik, J. P. Fabrication Of Multiwalled Carbon Nanotube-Reinforced Rapeseed-Oil-Based Polyurethane Coatings For Anticorrosive Applications. Polym. Int. 2023, 72 (1), 126– 137,  DOI: 10.1002/pi.6468
      There is no corresponding record for this reference.

  • Supporting Information

    Supporting Information

    The Supporting Information is available free of charge at https://pubs.acs.org/doi/10.1021/acspolymersau.4c00068.

    • Synthesized products’ measured NMR, ESI-MS, and FTIR spectra and complete wood coating documentation (PDF)


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