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Non-Conventional Features of Plant Oil-Based Acrylic Monomers in Emulsion Polymerization

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Non-Conventional Features of Plant Oil-Based Acrylic Monomers in Emulsion Polymerization molecules Review Non-Conventional Features of Plant Oil-Based Acrylic Monomers in Emulsion Polymerization Ananiy Kohut 1, Stanislav Voronov 1, Zoriana Demchuk 2 , Vasylyna Kirianchuk 1, Kyle Kingsley 2, Oleg Shevchuk 1, Sylvain Caillol 3 and Andriy Voronov 2,* 1 Department of Organic Chemistry, Institute of Chemistry and Chemical Technologies, Lviv Polytechnic National University, 79000 Lviv, Ukraine; [email protected] (A.K.); [email protected] (S.V.); [email protected] (V.K.); [email protected] (O.S.) 2 Department of Coatings and Polymeric Materials, North Dakota State University, Fargo, ND 58108-6050, USA; [email protected] (Z.D.); [email protected] (K.K.) 3 ICGM, Univ Montpellier, CNRS, ENSCM, 34095 Montpellier, France; [email protected] * Correspondence: [email protected] Academic Editor: Dimitrios Bikiaris Received: 8 June 2020; Accepted: 29 June 2020; Published: 30 June 2020 Abstract: In recent years, polymer chemistry has experienced an intensive development of a new field regarding the synthesis of aliphatic and aromatic biobased monomers obtained from renewable plant sources. A one-step process for the synthesis of new vinyl monomers by the reaction of direct transesterification of plant oil triglycerides with N-(hydroxyethyl)acrylamide has been recently invented to yield plant oil-based monomers (POBMs). The features of the POBM chemical structure, containing both a polar (hydrophilic) fragment capable of electrostatic interactions, and hydrophobic acyl fatty acid moieties (C15-C17) capable of van der Waals interactions, ensures the participation of the POBMs fragments of polymers in intermolecular interactions before and during polymerization. The use of the POBMs with different unsaturations in copolymerization reactions with conventional vinyl monomers allows for obtaining copolymers with enhanced hydrophobicity, provides a mechanism of internal plasticization and control of crosslinking degree. Synthesized latexes and latex polymers are promising candidates for the formation of hydrophobic polymer coatings with controlled physical and mechanical properties through the targeted control of the content of different POBM units with different degrees of unsaturation in the latex polymers. Keywords: biobased polymers; plant oil-based monomers; mixed micelles; methyl-β-cyclodextrin inclusion complex; emulsion polymerization 1. Introduction The problem of depletion of fossil raw materials has become of global importance and is complicated not only by economic but also environmental and political factors [1]. However, synthetic polymers are still one of the most widely used materials in everyday use. Environmental analysis shows that huge amounts of plastic waste are found in the environment, and their contribution to the ever-increasing amount of solid waste is a significant environmental threat [2]. Plant oils are low-cost raw materials for the manufacture of monomers and polymers [3–5], which have several advantages over conventional polymeric materials, namely biodegradability, non-toxicity, biocompatibility, and hydrophobicity. Therefore, an important task for synthetic chemists is to consider renewable raw materials as an alternative to raw counterparts of fossil origin. Due to the wide range of plant oils, the variety of their chemical compositions, and, in many cases, abandon of resources, they became an interesting object to be used in polymers synthesis as a renewable raw material. Molecules 2020, 25, 2990; doi:10.3390/molecules25132990 www.mdpi.com/journal/molecules Molecules 2020, 25, x FOR PEER REVIEW 2 of 19 Molecules 2020, 25, 2990 2 of 19 abandon of resources, they became an interesting object to be used in polymers synthesis as a renewable raw material. The total production of plant oils in in the world in in 2019 amounted amounted to to more more than than 200 200 million million tons, tons, of which about 15% are used as raw materials for the synthesis of new chemical compounds and materials [6]. [6]. The The presence presence of of plan plantt oils oils or their derivatives (fatty ac acids)ids) in various compositions of polymeric materials improves their optical (gloss), ph physicalysical (flexibility, (flexibility, adhesion) [7,8], [7,8], and chemical (resistance toto water water and and chemicals) chemicals) properties properties [9]. The [9]. synthesis The synthesis of biobased of biobased monomers monomers from renewable from renewableresources isresources a promising is a platform promising for theplatform synthesis for andthe implementationsynthesis and implementation of new environmentally of new environmentallyfriendly industrial friendly polymer industrial materials polymer [10]. However, materials biomass[10]. However, molecules biomass rarely molecules possess suitable rarely possessreactive suitable functions reactive for radical functions polymerization. for radical polymerization. Indeed, the Indeed, double the bonds double of bonds vegetable of vegetable oils are oilspoorly are reactivepoorly reactive in radical in polymerization. radical polymerization. Therefore, Therefore, synthesizing synthesizing radically radically polymerizable polymerizable biobased biobasedmonomers monomers is a real challengeis a real challenge [11]. It should[11]. It sh beould noted be thatnoted methods that methods for the for synthesis the synthesis of vinyl of vinylmonomers monomers based based on soybean, on soybean, olive, olive, and linseed and linseed oils through oils through plant plant oil direct oil direct transesterification transesterification with withN-(hydroxyethyl)acrylamide N-(hydroxyethyl)acrylamide [10,12 ,[10,12,13]13] has been has recentlybeen recently developed developed along along with methodswith methods of their of theircopolymerization copolymerization [14]. [14]. The The ability ability of of these these plant plant oil-based oil-based monomers monomers (POBMs) (POBMs) toto undergoundergo free radical (co)polymerization(co)polymerization reactions reactions has beenhas confirmedbeen confirmed and demonstrated and demonstrated [12,14,15]. [12,14,15]. The conversion, The conversion,polymerization polymerization rate, and molecular rate, and weight molecular of the polymersweight ofhave the polymers been shown have to dependbeen shown on unsaturation to depend onof theunsaturation plant oil chosen of the forplant POBMs oil chosen synthesis for POBMs [12,14]. synthesis [12,14]. 2. Features Features of of Synthesis Synthesis of of Vinyl Vinyl Monomers from Plant Oils Tang etet al. al. [16 ][16] reported report oned the on synthesis the synthesis of N-hydroxyalkylamides of N-hydroxyalkylamides and methacrylate and methacrylate hydrophobic hydrophobicmonomers through monomers the through interaction the ofinteraction plant oil of triglycerides plant oil triglycerides with amino with alcohols amino (Figure alcohols1). (FigureThey developed 1). They developed a new interesting a new interesting approach approach that involves that theinvolves use of the a two-step use of a two-step process. process. In the first In thestage, first the interactionstage, the ofinteraction triglycerides of with triglyceride amino alcoholss with with amino the formationalcohols ofwithN-hydroxyalkylamides the formation of Nby-hydroxyalkylamides the amidation reaction: by the amidation reaction: Figure 1. TransformationTransformation of of triglycerides in in N-hydroxyalkylamides and and methacrylate methacrylate monomers. monomers. Reprinted with permission from [[16].16]. Copy Copyrightright (2015) American Chemical Society. Aminoalcohols, namely namely ethanolamine ethanolamine (R (R = =H,H, n n= 1),= 1),3-amino-1-propanol 3-amino-1-propanol (R = (R H,= nH, = 2), n =and2), N-methylethanolamineand N-methylethanolamine (R = (R CH= 3CH, n 3=, n1),= were1), were used used as aschemicals chemicals which which enables enables the the synthesis synthesis of of a wide range of new monomers. In the second stage,stage, the corresponding monomers were synthesized by the interactioninteraction betweenbetween N-hydroxyethylamidesN-hydroxyethylamides R’–C(O)–N(R)–(CHR’–C(O)–N(R)–(CH22))nn–CH2OHOH and methacrylic anhydride. In such aa way,way, methacrylate methacrylate monomer monomer CH CH2=2=C(CHC(CH33)–C(O)–O–CH)–C(O)–O–CH22–(CH–(CH22)n–N(R)–C(O)––N(R)–C(O)– (CH2))77–CH=CH–(CH–CH=CH–(CH2)27)–CH7–CH3 based3 based on on high high oleic oleic soybean soybean oil oil was was synthesized. synthesized. A study of free radical polymerization of these monomers revealed that the double bonds in the fatty acidacid chainschains remain remain una unaffectedffected during during the the reaction. reaction. The The synthesized synthesized methacrylate methacrylate monomers monomers based basedon high on oleic high soybean oleic soybean oil, depending oil, depending on the nature on the of na theture branches of the inbranches the side in chain, the side have chain, a wide have range a wideof glass range transition of glass temperatures transition temperatures [16]. In further [16]. studies, In further Tang studies, and co-authors Tang and used co-authors more than used twenty more thanamino twenty alcohols amino to establish alcohols the to mechanism establish the of amidation mechanism of plantof amidation oils, in particular of plant high-oleicoils, in particular soybean high-oleicoil [8]. Depending soybean onoil the [8]. nature Depending of the acylon the fatty nature acid of and the amide acyl structures,fatty acid and the polymersamide structures, have a wide the Molecules 2020, 25,
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