The Use of Renewable Feedstock in UV-curable Materials - A New Age For Polymers and Green Chemistry

Progress in Polymer Science 38 (2013) 932962
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Progress in Polymer Science

journal homepage: www.elsevier.com/locate/ppolysci
The use of renewable feedstock in UV-curable materials A new age for polymers and green chemistry
Laurent Fertier, Houria Koleilat, Mylne Stemmelen, Olivia Giani, Christine Joly-Duhamel, Vincent Lapinte, Jean-Jacques Robin
Institut Charles Gerhardt Montpellier UMR5253 CNRS-UM2-ENSCM-UM1 Equipe Ingnierie et Architectures Macromolculaires, Universit Montpellier II Bat 17 cc1702, Place Eugne Bataillon 34095 Montpellier Cedex 5, France
a r t i c l e
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a b s t r a c t
This review aims to cover the state of the art of renewable feedstock use in materials production using photopolymerization processes. This area of investigation is an emerging eld of research, and it combines biosourced molecules with a cheap and rapid radiative processing method that avoids any emission of volatile organic compounds. The main classes of naturally occurring molecules and macromolecules such as lipids, amino acids, carbohydrates, polyenes, etc. are detailed. The way they are used or integrated in photopolymerizable systems are described in relation to their applications: coatings, biomaterials, biodegradable drug delivery systems, microelectronics or optoelectronics. This critical review takes into account the reactivity of the various compounds as well as their cytotoxicity, biodegradability and nally their end uses. 2012 Elsevier Ltd. All rights reserved.
Article history: Received 18 July 2012 Received in revised form 10 December 2012 Accepted 19 December 2012 Available online 4 January 2013 Keywords: Photopolymerization Renewable resources Vegetable oil Carbohydrates Amino acids Natural rubbers
Contents 1. 2. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 933 Renewable macromolecules as raw precursors for UV-cured materials . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 934
Abbreviations: 5-CAGA, 5-ring membered cyclic acetalglycerin acrylate; 6-CAGA, 6-ring membered cyclic acetalglycerin acrylate; AEMA, Aminoethylmethacrylate; API, Acrylatedpolyisoprene; BMA, n-butyl methacrylate; CCCA, Cyclic carbonate carbamateacrylate; DAAm, N,N-dimethylacrylamide; DMAc, Dimethylacetamide; DMAP, N,N-dimethylamino pyridine; DMF, Dimethylformamide; DMPA, 2,2-dimethoxy-2-phenylacetophenone; DMSO, Dimethylsulfoxide; DS, Substitution degree; ECLO, Epoxidized cyclohexene-derivatized linseed oil; ECM, Extracellular matrix; EDC, 1-ethyl-3-(3dimethylaminopropyl)-carbodiimidehydrochloride; ENLO, Epoxynorbornene linseed oil; EO, Epoxidized oil; EPI, Epoxypolyisoprene; ESBO, Epoxidized soybean oil; ESO, Epoxidized sunower oil; F, Phenylalanine; GCA, Glycerin carbonateacrylate; GMA, Glycidyl methacrylate; HA, Hyaluronic acid; HBA, Hyperbranched acrylate; HEMA, 2-hydroxyethyl methacrylate; HMPP, 2-hydroxy-2-methylphenyl-1-propanone (Darocur 1173); hMSC, Human mesenchymal stem cells; HPN, Hybrid polymer network; I, Isoleucine; iBMA, Isobutyl methacrylate; IEMA, 2-isocyanatoethylmethacrylate; IPN, Interpenetrating polymer network; K, Lysine; L, Leucine; LbL, Layer by layer; LCST, Low critical solution temperature; LMOGs, Low molecular weight organogelators; LO, Linseed oil; M, Methionine; MA, Methacrylic anhydride; MAG, Monoacylglycerol (monoglyceride); MDI, Methylene bis(4phenylisocyanate); MMA, Methyl methacrylate; NELO, Norbornenylepoxidized linseed oil; NHS, N-hydroxysuccinimide; NIPAAm, N-isopropylacrylamide; NMA, N-methylolacrylamide; NMP, N-methyl-2-pyrrolidone; NR, Natural rubber; NVP, 1-vinyl-2-pyrrolidinone; PBS, Phosphate buffer solution; PDMS, Polydimethylsiloxane; PEG, Poly(ethylene glycol); PEGDA, Polyethylene glycol diacrylate; PI, Polyisoprene; PLLA, Poly(L-lactide); PNIPAAm, Poly(Nisopropylacrylamide); PUR, Polyurethane; RAFT, Reversible addition-fragmentation chain transfer polymerization; SA, Succinic anhydride; SBO, Soybean oil; SIPN, Semi-interpenetrating polymer network; SMCs, Smooth muscle cells; SolA, Solketalacrylate; T, Threonine; TAG, Triacylglycerol (triglyceride); TDI, Toluene diisocyanate; TEC, Thiol-ene coupling; TEOS, Tetraethylorthosilicate; TPGDA, Tripropylene glycol diacrylate; V, Valine; VA-086, 2,2 -Azobis[2methyl-N-(2-hydroxyethyl)propionamide]; VAPG, Valine-alanine-proline-glycine; W, Tryptophan. Corresponding author. Tel.: +33 4 67 14 41 57; fax: +33 4 67 14 40 28. E-mail address: Jean-Jacques.Robin@univ-montp2.fr (J.-J. Robin). 0079-6700/$ see front matter 2012 Elsevier Ltd. All rights reserved. http://dx.doi.org/10.1016/j.progpolymsci.2012.12.002
L. Fertier et al. / Progress in Polymer Science 38 (2013) 932962
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3.
4.
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Lipids . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2.1.1. Glycerol derivatives . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2.1.2. Unsaturated oils . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2.1.3. Epoxidized oils . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2.2. Polysaccharides . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2.2.1. Acrylate moiety . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2.2.2. Other photocrosslinkable moieties . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2.3. Natural rubbers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Renewable molecules as functional groups for UV-cured materials. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3.1. Sugars . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3.1.1. Macromolecules based on (meth)acrylated monomers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3.1.2. Macromolecules based on vinyl/allyl monomers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3.1.3. Specic use: photoinitiator water-soluble complexes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3.2. Amino acids . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3.2.1. Hydrogels based on (meth)acrylate precursors. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3.2.2. Photoresponsive hydrogels based on cinnamate precursors . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Photoreactive biosourced molecules . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4.1. Coumarin-derived compounds . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4.2. Cinnamate-derived compounds . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4.3. Natural acids . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4.4. Furans . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Conclusion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
2.1.
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1. Introduction The increasing number of research studies devoted to the development of biosource-based materials reveals the great potential of renewable raw molecules and their ability to substitute for petrochemical-based materials. The construction of bioreneries and the availability of molecules such as glycerin derived from biodiesel production are a great evolution of the chemical industry. Until now, only a few examples of biosourced polymers have been available, and the famous polyamide 11 is synthesized from castor oil, a vegetable oil also used in the preparation of polyurethanes. In recent years, there has been a real explosion in the number of studies on the development of materials derived from biomass. Typical monomers such as acrylic acid, epichlorohydrin and acrylonitrile can be now produced from biosourced feedstock. The industrial production of green polyethylene in Brazil proves that this is not just a trend but a mutation in polymer chemistry. Moreover, this industrial revolution should enable agricultural revitalization in certain countries, thanks to the added value of agricultural products. This mutation, which started one decade ago, must be followed by a real strategy concerning the economic constraints of this approach. The best example addresses the peculiar case of lipids, which are currently used for human and animal food and have recently been employed in the production of biodiesel. This continuous growth of lipochemistry activities will promote competition among the different end uses of vegetable oils (in some countries, mainly human nutrition). Nevertheless, some non-edible oil species may be a noncompetitive alternative to this situation. Other biomass deposits, such as algae, lignins, celluloses, polysaccharides and vegetable proteins, are easily affordable precursors of carbon with unlimited deposits and very easy access
thanks to worldwide production. These carbon sources can be extracted from some industrial by-products and wastes (wood, wood pulp, starch, etc.) whose actual valorization is not secured. Developments based on these by-products will undoubtedly be of great interest because they are not competing with raw materials devoted to nutrition. Biosourced materials are rarely used just after harvest or extraction and often need preliminary treatments (purication, chemical or enzymatic modications, etc.) to access reagents usable in the elaboration of polymers and polymeric materials. Linseed oil is a rare oil variety that can be used in its native form, as its polymerization occurs under oxygen and UV irradiation without any preliminary modication. To modify biosourced raw materials to make them usable as reagents in material production will be the great challenge for chemical engineering and biotechnologies during the next decades. Some recent promising results open the way in the eld of vegetable oil modication (epoxidation) and enzymatic degradation of starch to produce various monomers (succinic acid, glycolic acid, etc.). The use and purication of biomass can be satisfying if environmentally friendly processes limiting the production of wastes and the emission of volatile organic compounds (V.O.C.) are involved. In the same way, materials processing should require low temperature and energyefcient processes. For instance, UV radiation is a simple and convenient form of energy and does not require expensive devices. Thanks to its high output, this special polymer processing method is enjoying a new expansion and is applied at the industrial scale for inks, curable resins and also in various high-added-value products such as liquid crystal polymers and non linear optics. Liquid resins can be converted into solid resins in a few tenths of a second, making this process very attractive to the scientic community for the past three decades. The
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Fig. 1. Examples of renewable raw molecules in photochemistry.
photopolymerization mechanism can be achieved either by cycloaddition of photosensitive molecules (chromophore type) or by polyaddition of double bonds under radical or cationic initiation. It is specially adapted to biosourced materials and thermally sensitive molecules, as this technology works at ambient temperature [1]. It can be classied as a green process and its use for biosourced materials may be of practical interest. Thus, this review aims to record the state of knowledge in the area of natural compounds useful for photopolymerization (Fig. 1). In the rst part, we describe compounds from biomass with signicant molecular weights that can be brought together under the designation macromolecules (lipids, polysaccharides. . .). They represent an interesting and important carbon source to be used as the main architectural backbone for materials. Some of them are naturally photosensitive; others require preliminary modications to be reactive under UV irradiation. In the second part, we report the use of biosourced molecules (sugars, amino acids. . .) for their specic properties, such as biocompatibility and pH sensitivity. Their incorporation into functional materials through UV-based methods (grafting or polymerization) are described. In the last part,
we discuss naturally occurring and abundant molecules (coumarin, natural acids. . .) that display photosensitive activities and are used for their photoreactive function. 2. Renewable macromolecules as raw precursors for UV-cured materials 2.1. Lipids Oils and fats from vegetables and animals are historically and currently the most important renewable feedstock of the chemical industry, and their production is growing (Fig. 2) [2]. They are used for the production of surfactants, lubricants and coatings. Vegetable oils are composed of unsaponiable compounds such as terpenes, steroids and fatty acids and saponiable compounds such as phospholipids and glycerides. The latter, and more specically triglycerides (also called triacylglycerols or TAGs), are the most abundant components, and their compositions are specic to the source plant species. Most raw vegetable oils contain various lengths of fatty chains ranging from C10 to C22 and various double bond contents per chain ranging from 0 to 3. Unsaturated oils are much more abundant than saturated ones and are classied into three
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Fig. 2. World production of oils and fats for 19992000 and 20092010.
types depending on the ratio of double bonds measured by iodine value (IV): non-drying oils (IV < 125), semi-drying oils (125 < IV < 140) and drying oils (IV > 140). Rare vegetable oils contain peculiar reactive functional groups, such as an epoxy group (vernonia oil), a hydroxyl group (castor oil with ricinoleic acid) and a keto (oxo) group (Licaniarigida seed oil) (Fig. 3). Otherwise, various chemical pathways to functionalize triglycerides and fatty acids, such as hydroformylation [3,4], thiol-ene reaction (TEC) [5,6] and selective oxidation [7] have already been described. Epoxidation is one of the most widespread functionalizations, thanks to the ease of ring-opening of the epoxy group by various nucleophilic reactants (alcohol, thiol, carboxylic acid, amine, etc.). Some raw oils, such as linseed oil, can be cured under daylight or UV irradiation through a photooxidation mechanism (see Section 2.1.2.1). The photooxidation remains a long process, and metallic salts must be added to enhance the crosslinking rate. For some industrial applications such as coatings, a high drying rate is required. Raw oils are therefore chemically modied with more reactive unsaturations (such as (meth)acrylates [8,9], maleic derivatives [1012] or allyl ethers[13]) that can be cured by radical reaction as illustrated in Fig. 4. Another method has been proposed to enhance curing reactivity by using epoxidized oils or norbornenyl epoxidized oils. In this specic case, crosslinking occurred under cationic polymerization. As previously mentioned, various crosslinking mechanisms are possible depending on the oily reactive compounds. Fig. 5 illustrates photocured vegetable oils obtained by photooxidation, styrenisation, thiol-ene coupling (TEC) or acrylate coupling of fatty chains and the ring-opening of the epoxy group.
Glycerol, the by-product of trans-esterication of vegetable oils in presence of alcohol (methanol and ethanol), is also an interesting derivative for photochemistry. 2.1.1. Glycerol derivatives Glycerol is one of the most important feedstocks in the modern oleochemical industry. It is obtained by the saponication of fats or as a by-product in the production of biodiesel. Due to its competitive cost, worldwide availability, and built-in functionality, glycerin and its derivatives have become useful for numerous commercial applications. As the production of glycerin currently exceeds demand, the valorization of glycerol has emerged as a challenging trend [14]. Thus, glycerol is currently used in industry as an intermediate in the synthesis of various compounds (glycerin carbonate, Solketal , acrylic acid, etc.) [15]. Some of these compounds, bearing a (meth)acrylate group (e.g. glycerin carbonate acrylate (GCA), glycerin carbonate methacrylate (GCMA), Solketal acrylate (SolA), 5-membered ring cyclic acetalglycerin acrylate (5-CAGA), 6-membered ring cyclic acetalglycerin acrylate (6-CAGA) and cyclic carbonate carbamateacrylate (CCCA)) have been studied with respect to photopolymerization [16] (Fig. 6). Kilambi et al. [17,18] have broadly investigated the impact of the glycerol-based group on the rate of the photopolymerization of these (meth)acrylate monomers. They quantied the contribution of intramolecular interactions and steric effects of these monomers to their reactivity. Some of these monomers show very high polymerization rates due to some transfer reactions and the Trommsdorff effect. Additionally, other derivatives of glycerol, such as 1,3-glycerol dimethacrylate (GDM) and glycerol trimethacrylate (GTM) are employed in restorative dental materials to improve their mechanical properties [19,20].
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Fig. 3. Various fatty chains of raw vegetable oils.
Fig. 4. Chemical modications of vegetable oils.
2.1.2. Unsaturated oils 2.1.2.1. Photooxidation. The high rate of unsaturation of some vegetable oils makes them sensitive to autooxidation under air (Fig. 7) [2125]. This reaction is basically used to elaborate Linoleum from linseed oil [2628]. The crosslinking mechanism was largely studied by Paramarta et al. [29], and the formation of the lipidic network was explained by successive reactions: formation of radical species, isomerization, hydroperoxidation and crosslinking. To speed up the oxidation process, different routes such as
thermal treatment or UV irradiation [30] using metal-based catalysts were examined. For instance, metal oxides [31] (zinc, lead, manganese, cobalt) and more recently the association of primary and secondary driers (cobalt combined with zirconium or calcium and zirconium octoates) were investigated. 2.1.2.2. Thiol-ene coupling (TEC) on vegetable oils. Hoyle and Bowman [32] have already presented an overview of thiol-ene coupling (TEC) as a way to make photocurable
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Fig. 5. Vegetable oil-based networks from (a) the photooxidation, (b) the styrenisation, (c) thiol-ene coupling (TEC) or (d) acrylate coupling of fatty chains and (e) ring-opening of epoxy group.
materials using petroleum-alkenes. The polyunsaturated nature of triglycerides makes them good candidates for TEC. Basically, multifunctional thiols are added onto fatty compounds to create a polymeric network as shown in Fig. 5c. The low thermal stability of lipidic compounds justies the use of UV irradiation instead of thermal activation in the TEC reaction. Another benet of UV-induced TEC is its lower sensitivity to oxygen inhibition compared to other typical free radical polymerizations [33]. The structure of both the unsaturated fatty derivatives and the thiol
reagents affects the reactivity [34]. Thus, as mentioned by Hoyle et al. [35] and Hoyle and Bowman [32], the reactivity of unsaturated reagents with SH groups can be classied as conjugated diene < maleimide < (meth)acrylate < vinyl ether < norbornene. Samuelsson et al. [34] showed that coatings could be made by TEC using internal double bonds of fatty esters (methyl oleate and methyl linoleate) and multifunctional thiols. Bexell et al. [36,37] reported the efciency of the TEC reaction for coating aluminum surfaces with vegetable oil-based lms. In this case, linseed oil
Fig. 6. Structures of photocurable glycerol-based monomers.
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Fig. 7. Simplied photooxidation process of drying oils.
reacted with thiol groups of mercaptosilane-treated aluminum. On the other hand, Klaasen and Van der Leeuw [38] prepared a solid alkyl paint based on natural oils by a combination of TEC and oxidative processes. In the rst step, a partial network was created by the reaction between sunower fatty acids and trifunctional thiols. Next, the remaining double bonds were consumed by an oxidation process using a vanadylbipyridyl catalyst. 2.1.2.3. (Meth)acrylated oils. As stated previously, the internal double bonds of vegetable oils have a low reactivity; hence, a wise option is chemical modication to make them more reactive under UV irradiation. Modications of lipids have been extensively described in the literature and can be applied to various oils, such as linseed, rapeseed calendula [9] or soybean [8] oils. One of the most widespread chemical modications of oils is the (meth)acrylation that occurs by the reaction between (meth)acrylate acid and epoxidized oil [8,9,29]. A second pathway consists of the esterication of (meth)acryloyl acid with raw, functional vegetable oil bearing hydroxyl groups (castor oil) [39]. Another strategy to graft (meth)acrylic groups is based on isocyanate derivatives and produces urethane acrylated vegetable oils. Homan et al. [40] also employed an acrylate-bearing isocyanate group to acrylate castor oil. Patel et al. [41] modied monoacylglycerol (also called monoglyceride or MAG) with such diisocyanate reagents as methylene bis(4-phenylisocyanate) (MDI) and toluene diisocyanate (TDI); the free terminal isocyanate groups of MAG reacted with the acrylate monomer-bearing free OH group. A nal route for urethane acrylated vegetable oil synthesis is the reaction of both an acrylate-bearing isocyanate group and fatty chains with a hyperbranched hydroxyl-terminated polyester [42]. These (urethane) (meth)acrylated vegetable oils can be reacted with other co-monomers or directly crosslinked with a thiol reagent. In the rst case, numerous studies have investigated the inuence of acrylate-reactive diluents on the photocuring rate and have shown a relationship between the number of acrylate functional groups on the oil backbone and the hardness of the resulting materials [9,40,41]. Di- and trimethacrylates [41], or acrylated oligomers such as acrylated-PEG or
acrylated-poly(-caprolactone) [43,44], were also associated with the crosslinking process. In this case, the biodegradability properties of the resulting lms were examined, and faster biodegradation was observed for high-density crosslinking as a result of low molecular weight between entanglements that might otherwise block lipase attack sites. The second type of acrylated oil photocuring occurred in the presence of thiol reagents. As mentioned above, even if TEC could occur on triglyceride double bonds, it was shown that reactivity could be enhanced by activating the alkene using acrylate derivatives. Black and Rawlins [45] described the photocuring of vegetable oil-based thermosets using a TEC reaction between acrylated castor oil and a polythiol reagent, trimethylolpropanetris (3-mercaptopropionate). The resulting coating showed high solvent resistance, hardness and exibility. 2.1.2.4. Other unsaturated oils. The dimerization of fatty derivatives by carbon-to-carbon links between unsaturations in separate fatty chains can occur by a thermal process [46] or by a UV process [6], thereby producing fatty diacids. These derivatives, after reduction into fatty diols, were employed as polyols in UV-curable polyurethane dispersions [47]. Polyurethane dispersion technology reduces shrinkage and leads to better adhesion of lms, as the low viscosity of the fatty acid dimer UV formulations for spray application gives them an advantage over competing technologies. Vegetable oils can be modied by reaction with maleic anhydride as illustrated in Fig. 4, and their crosslinks are produced by reactive diluents (e.g. 2-hydroxyethyl methacrylate [48]). Thermosets have been prepared by UV-induced copolymerization between styrene and maleic anhydride-modied oils [11,12]. In the eld of unsaturated polyester resins, Mahmoud et al. [10] used the copolymerization of styrene with an unsaturated polyester based on palm oil MAG. The polyester precursor was synthesized by esterication between the free hydroxyl groups of MAG in the presence of maleic anhydride. Other types of reactive unsaturations can also be involved in photopolymerization. For instance, allylic alcohol can be reacted with epoxidized fatty chains (Fig. 4). In
939
Fig. 8. Photoreactive groups in cationic photopolymerization.
this way, UV-curable coatings insensitive to oxygen were prepared by a thiol-ene process through the reaction of SH groups with allylic derivatives [13]. For instance, soybean oil (SBO) materials were investigated by the combination of polyallylic epoxidized soybean oil (ESBO) and trithiol.
2.1.3. Epoxidized oils The cationic photopolymerization of epoxidized oils is insensitive to oxygen, making it highly attractive for many thin lm applications such as inks and adhesives. Tehfe et al. [49] recently explored the cationic polymerization process of ESO using various photoinitiators under air and solar irradiation. A fundamental research study on photoinitiators was described for the case of cationic photopolymerization of triglycerides. Gu et al. [50] developed original photoinitiators based on salts containing a tetrakis(pentauorophenyl)gallate anion. Another approach was examined by Ortiz et al. [51], who used onium salt to accelerate the photopolymerization of epoxidized natural oils. Other systems were investigated [52] where the effect of the structure of both the cation and anion of diaryliodinium and triarylsulfonium photoinitiators on the polymerization rate were described. Films with a high degree of exibility and impact strength were obtained using this system with vernonia oil as the raw epoxidized oil. This singular oil was also studied by Samuelsson et al. [53], who synthesized UV-curable resin after the esterication of a hydroxyl functional hyperbranched polyester with vernolic acid. The resulting resin polymerized in the presence of vernolic acid methyl ester as the reactive diluent. Several studies focused on nanocomposite coatings, using TiO2 ller and solgel precursors from metal-oxo clusters within epoxidized oil, called ceramers [54]. Organoclays were also incorporated into epoxidized oil to generate coatings, in the presence of an initiator, with low UV-radiation energy consumption during the curing process [55]. Zou and Soucek [56] studied a new generation of epoxidized triglyceride derivatives such as norbornenyl
epoxidized linseed oil (NELO), also termed epoxynorbornene linseed oil (ENLO). Using divinyl ether as a reactive diluent, the curing rate of NELO was halfway between that of linseed oil and that of cycloaliphatic epoxide [57]. Epoxidized cyclohexene-derivatized linseed oil (ECLO) was synthesized at high pressure using the DielsAlder reaction between cyclopentadiene and linseed oil followed by an epoxydation step (Fig. 8) [57]. ECLO was used to prepare organicinorganic hybrid lms with tetraethylorthosilicate (TEOS) [56]. The addition of TEOS enhanced the surface wetting properties, solvent resistance and impact resistance [58]. In sum, numerous strategies for vegetable oil photocuring have been described in the literature. Using radical photopolymerization, raw unsaturated vegetable oils can be easily crosslinked. The modication of triglycerides by (meth)acrylation and the addition of maleic and allylic double bonds lead to higher polymerization rates. Moreover, some natural oils bearing epoxy groups and epoxidized oils can be crosslinked under cationic photopolymerization. These UV-curable lipidic derivatives have mainly been applied in coating technologies.
2.2. Polysaccharides Biomass provides a very important renewable source of molecules as a mixture of polysaccharides (starch, cellulose) and oligosaccharides (sucrose, maltose and fructose). Using chemical or enzymatic processes, polysaccharides can be converted into monosaccharides and simpler molecules (i.e. polyols) [59], unsaturated carboxylic acids [60] and furan derivatives (from hemicelluloses) [61] (Fig. 9). Polysaccharides are the most abundant natural polymers on Earth and are extracted from plants, microorganisms, fungi, marine organisms and animals. These macromolecules are elements of vegetable structures (cellulose, alginate) and play an important role in energy storage (starch). Polysaccharides are in solid state at room
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Fig. 9. Overview of rened molecules obtained from biomass treatment.
temperature, and appear as bers, pellets or gels depending on their chemical structure. Polysaccharides can be either homopolysaccharides (only one type of monosaccharide) or heteropolysaccharides (several monosaccharides), as shown in Fig. 10. Polysaccharides are mainly used in the biomedical eld for their biocompatibility, and they have also been used to design biomaterials that open the way to drug delivery, encapsulation or tissue engineering. These biocompatible and biodegradable polymers exhibit chemically modiable functional groups such as hydroxyls, amines or carboxylates. Moreover, all these polymers have their own specicities in relation to biomedical applications. For instance, chondroitin is a polysaccharide that is present in cartilage and which can help its regeneration. Chitosan [62] and hyaluronic acid [63] accelerate wound healing and have antimicrobial properties, while dextran is mainly used for colonic drug delivery (the presence of dextranase in this organ promotes the hydrogel degradation). Polysaccharides are also used as rheology modiers, but some of them can be applied to photocurable resins [64,65]. Among its other properties, cellulose is also capable of forming a chiral nematic phase in solution if substituents are introduced onto the hydroxyl groups. Recently, new methodologies used polysaccharides and acrylic monomers to form liquid crystal under UV irradiation [6668]. Photocurable materials derived from polysaccharides are called hydrogels, and their denition is more deeply developed in Section 3.2 of this review. Interesting reviews about photopolymerizable hydrogels or photoactive polysaccharides have already been published [6971]. We therefore focus on methods to insert photocrosslinkable functional groups such as (meth)acrylates onto polysaccharide skeletons, on the
different networks obtained by photocrosslinking and on the different photocrosslinkable moieties currently used. 2.2.1. Acrylate moiety The acrylate moiety is commonly used to modify polysaccharides, as illustrated in Fig. 11. (Meth)acrylates are excellent for photopolymerization due to their high photocuring rate and the good mechanical properties of the resulting materials. 2.2.1.1. Synthesis of photocrosslinkable acrylated polysaccharides. Glycidyl methacrylate (GMA) and methacrylic anhydride (MA) are the reagents most often used to modify polysaccharides. The reaction of the hydroxyl groups of polysaccharides with the epoxide ring of GMA is a favorite modication method. Polysaccharides that are modied with GMA include hyaluronan [63,7282], dextran [74,8385], heparin [86], or chondroitin sulfate [87]. The addition of GMA onto polysaccharides usually occurs either in aqueous medium [62,63,72,73,7581] or in a buffer medium (often a phosphate buffer solution) [82,87]. To a certain extent, aqueous medium permits the solubilization of polysaccharide, but GMA is very slightly soluble in this solvent. It can even be degraded in water (via hydrolysis of the epoxy functional group). The esterication of the hydroxyl functional groups of polysaccharides (alginate [8890], hyaluronan [88,91,92], cellulose [93], and chondroitin [94]) with MA is also achieved in aqueous medium. Experimental conditions were deeply explored by Kim and Chu [95] (temperature, time, and amounts of MA and triethylamine). They optimized experimental conditions to control the degree of the substitution, which varied from 1% to 75%.
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Fig. 10. Examples of polysaccharides: heteropolysaccharides (hyaluronan, chitosan, heparin, chondroitin) and homopolysaccharides (starch, cellulose, inulin, dextrin).
Other ways to obtain acrylated polysaccharides have been described, such as the use of acryloyl chloride on chitosan [96], 2-aminoethyl methacrylate (AEMA) on alginate [97], 2-isocyanatoethylmethacrylate (IEMA) on starch [98], and N-methylolacrylamide (NMA) on cellulose [65]. The use of acryloylchloride and NMA is avoided in biomedical applications. Indeed, as previously mentioned, acrylate monomers are more toxic than methacrylate monomers
despite being faster to cure; thus, methacrylate remains the best choice for biomedical applications. Li and Zhang [99] used acryloyl chloride to modify starch, and they photocrosslinked it with a zwitterionic acrylate-based monomer. The nal hydrogel had swelling properties in response to ionic environments as stimuli. Granat et al. [64] also used acryloyl chloride to substitute ethyl-cellulose, which was used in a further step as binder to control the
Fig. 11. (Meth)acrylatedderivatives used for the modication of polysaccharides.
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Fig. 13. Different network structures obtained by UV irradiation. Fig. 12. Modication of chitosan with PEGDA by Michael addition.
viscosity of a UV-radiation-cured ink. Ma et al. proposed an interesting method to insert acrylate functional groups on a polysaccharide: a diacrylate monomer (PEGDA [100] or ethylene glycol acrylate methacrylate [101]) reacted with chitosan according to the well-known Michael-type reaction between the amines of chitosan and the double bonds of the diacrylate, as shown in Fig. 12. Non-toxic segments were introduced on the polymer backbone during the process, and unreacted products like remaining PEGDA were not inconvenient because they were incorporated into the network during the photopolymerization step. The modication of polysaccharides by (meth)acrylate derivatives has been employed by numerous authors. The main differences among published reports concern the experimental conditions (solvent, heterogeneous or homogenous phase reaction depending on the polysaccharide solubility). Indeed, the main drawback of some polysaccharides is their insolubility in common organic solvents. Unfortunately, the acrylated reagents (GMA, MA, AEMA, etc.) used for the modication of polysaccharides are only soluble in organic solvents. Some modications of polysaccharides may improve their solubility by adding lipophilic groups onto the polysaccharide backbone [62,96] or by reducing their molecular weight (mostly by enzymatic digestion) [81]. Tsai et al. [96] improved chitosan solubility in organic solvent by modifying it with phtalic anhydride. Chitosan was then soluble in DMSO, DMAc, DMF, pyridine and NMP. Jeon et al. [97] improved the solubility of alginate by treating it with gamma rays to decrease its molecular weight. 2.2.1.2. UV Irradiation. The experimental conditions for photopolymerization are often similar in the literature, and Irgacure 2959 was most often used as the photoinitiator. Cytotoxicity, cell viability and cytocompatibility are of rst importance for biomedical applications. To avoid cytotoxicity, special care should be given to residual unreacted products, such as acrylates, and to the photoinitiator amount and chemical structure. Baier Leach
et al. [63] studied the inuence on cell viability of the amounts and relative ratios of Irgacure 2959 as the photoinitiator, of N-vinyl-2-pyrrolidone (NVP) as the catalyst and of the co-monomer. Bryant et al. [102] investigated the cytocompatibility of several photoinitiators (Irgacure 651 , Irgacure 184 , Irgacure 907 and Darocur 2959 ) and concluded that Darocur 2959 was the most promising. Polacheck et al. [89,90] used VA-086 as photoinitiator, as it was less cytotoxic for cells (3T3L1) than Irgacure 2959 . Chandler et al. investigated the cytotoxicity of the photopolymerization process, taking into account different parameters such as the photoinitiator, UV irradiation time, and UV radical formation. They demonstrated that a longer UV exposure time could decrease cell viability. 2.2.1.3. Material formation. Polysaccharides can lead to hydrogels, but their properties are often tailored by blending different polysaccharides or one polysaccharide with another polymer (such as PEG, polypeptide, etc.). Such materials can be termed hybrid polymer network (HPN), interpenetrating polymer network (IPN) or semiinterpenetrating polymer network (SIPN), as described in Fig. 13. In the most common network, HPN, the blended polymers are modied with the same photocrosslinkable functional groups. The formation of the 3D network in which both polymers are linked together by covalent bonds occurs under UV irradiation. Han et al. [103] photocrosslinked acrylated chitosan with N-isopropylacrylamide (NIPAAm). A HPN was obtained that combined chitosan hydrogel properties (pH-dependent swelling ratio) with PNIPAAm properties (temperature-sensitive polymer, LCST of 32 C). Leach and Schmidt [77] photocured a hyaluronan polysaccharide with PEG and also a polysaccharide with both PEG and peptide [78]. The PEG, peptides and polysaccharides had been previously modied with acrylate groups and led to a hybrid polymer network under UV irradiation. The use of HPN enabled the tailoring of mechanical
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Fig. 14. Crosslinking of carboxylate functions of polysaccharides with p-diazoniumdiphenyl amine polymer.
properties and the control of swelling ratio for the drug delivery rate, and it improved the biocompatibility and the cytotoxicity of the nal product. In the same way, Pitarresi et al. [84] elaborated a HPN of dextran and polyaspartamine to improve the degradation of the hydrogel in the colon (as polyaspartamine makes the hydrogel permeable to dextranase). An IPNs is a combination of two or more network polymers with no link between the polymers, in contrast to an HPN [104]. An IPN allows additive effects of the mechanical properties of both networks. Weng et al. [73] prepared an IPN with hyaluronan and DAAm (N,N-dimethylacrylamide). Indeed, hyaluronan hydrogels alone are too brittle, but photocrosslinking hyaluronan with a second network of PDAAm (Poly(N,N-dimethylacrylamide)) tremendously improved its mechanical properties. A SIPN consists of a network in which another oligomer or polymer is entangled in as an additive. Pescosolido et al. [105] proposed a SIPN of HEMA-grafted dextran and hyaluronan as additional elements for bioprinting applications. Hyaluronan brought bioactive and viscoelastic properties to the hydrogel. Zhou et al. [106,107] described a SIPN hydrogel of poly(HEMA) as a 3D UV-cured network with N-carboxylethylchitosan inserted as a nonphotocrosslinked ionic additional element that brought pH-dependant behavior to the hydrogel (the swelling ratio is hence directly correlated with pH). Suri and Schmidt [75] photopolymerized methacrylated hyaluronan in a collagen network obtained by brillogenesis; they compared an IPN and a SIPN of hyaluronan and collagen. The IPN exhibited a higher crosslink density, so it had a higher elastic modulus and a lower swelling ratio than the SIPN,
which is a exible gel with a highly porous structure. They obtained a material suitable for regenerative medicinal applications by biomimicry of the extracellular matrix (ECM). 2.2.2. Other photocrosslinkable moieties The acrylate functional group is an interesting reactive group in photocrosslinking processes, but as mentioned above, skin irritation can occur with acrylate derivatives. Thus, some studies found other photocrosslinkable moieties for in vivo applications. Liu et al. [108] developed a hydrogel of heparin and alginic acid sodium salt using a diazonium functional group as photosensitive crosslinker (p-diazoniumdiphenyl amine polymer). The diazonium functional groups reacted with the carboxylate groups of alginate and the sulfate functional groups of heparin without a photoinitiator under UV light, as represented in Fig. 14. The presence of alginate enhanced the hydrophilicity and the stability of the hydrogel and decreased the surface roughness. The diazonium-based polymer, by allowing the construction of a multilayer polymer with successive heparin and alginic acid layers, was an efcient technique for the construction of a layer-by-layer (LbL) self-assembly system. Diazonium functional groups are highly reactive and are good candidates for efcient photocrosslinking, generating only nitrogen as a by-product. Nevertheless, diazonium chemistry is not easy to handle, and the synthesis of the diazonium polymer is complex and requires several synthetic steps [109]. Azide groups (N3 ) are photocrosslinkable agents that, like diazonium groups, release nitrogen gas to yield highly reactive nitrene groups. They interact quickly
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Fig. 15. Photocrosslinking of carboxymethylchitosan thanks to azide functions.
Fig. 16. Maleinated chitosan as macroinitiator of PNIPAAm.
with one other or with amino groups to generate azo groups ( N N ) without any photoinitiator. Thus, chitosan was substituted with lactose and azide moieties to make biological adhesives [110,111]. Lactabionic acid was added to chitosan to enhance its water solubility. According to the author, replacing 2% of the amino groups in chitosan with lactabionate was enough to solubilize it at neutral pH. Jameela et al. [112] improved the process of azide substitution in the polysaccharide. First, 1-chloro-2-hydroxy-3-azidopropane was obtained by reacting epichlorohydrin with sodium azide, and then this was reacted with the amine functional group of chitosan. Yi et al. [113] avoided the lactabionic acid substitution step by using carboxymethyl chitosan, which is water soluble (Fig. 15). The application of this method concerned the controlled release of pesticides in agriculture. Another method was developed by Don and Chen [114]. They used maleic anhydride to substitute chitosan and yield a maleinated chitosan in which the double bond of maleic groups reacted with NIPAAm by free radical polymerization under UV irradiation in the presence of photoinitiator, as shown in Fig. 16. Zhong et al. [115] designed a similar technique, using maleinated chitosan and PEGDA as the crosslinker (Fig. 17). The swelling ratios, mechanical properties and pore size were easily controlled by varying the ratio of maleinated chitosan to PEGDA. Cytotoxicity assays showed that maleinated chitosan and its copolymer with PEGDA were only slightly cytotoxic at high doses, making it safe for use in biomedical applications. The grafting of maleic functional groups results in free carboxyl groups that are useful in biomedical applications (e.g. to couple biologically active agents or promote the deposition of inorganic minerals). Monier et al. [116] introduced an -cyano-4-hydroxycinnamic acid moiety on chitosan to create a pH-responsive hydrogel. This cinnamic acid derivative is photosensitive and requires no photoinitiator. Thus, Nakamura et al.
[117] prepared cinnamate-modied heparin, producing a photocrosslinked hydrogel for biomedical applications. The use of a cinnamate group as a photocrosslinkable moiety has two major advantages in that it is biosourced and it is naturally photosensitive. This cinnamate chemistry will be more thoroughly explained in Section 4.2. Shen et al. [118] inserted allylic moieties onto carboxymethyl cellulose sodium salt to form hydrogels after UV irradiation. Kumar et al. modied cellulose [119] or starch [120] thanks to the radical copolymerization of GMA; free glycidyl functional groups were then used as photocrosslinkers in the presence of cationic photoinitiator, thereby generating a nal lm that was perfectly suitable for coating applications. Delville et al. [121] photocrosslinked starch in bulk with no crosslinking agent, using benzoic acid sodium salt as a photoadditive. They showed that addition of this salt allowed the formation of a biodegradable and waterresistant lm with properties similar to those of typical plastic materials. A similar process was described by Zhou et al. [122], who used sodium benzoate to modify the surface of starch sheets. Currently, photocrosslinkable polysaccharides are mainly used in biomedical applications. Medical applications require a very low cytotoxicity, and materials based on polysaccharides modied with acrylate or other photocrosslinkable moieties can be harmless and useful for applications such as drug delivery or tissue engineering. 2.3. Natural rubbers Natural rubbers (NR) are renewable raw materials extracted from the latex products of Hevea brasilieusis, the rubber tree. The crosslinking of polyisoprene (PI) by UV irradiation and without degradation is difcult to achieve because of the poor reactivity of the amylene double bonds.
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Fig. 17. Photocrosslinking of maleinated chitosan with PEGDA as photocrosslinker.
The conversion of this functional group into an epoxy group or an acrylate double bond allows efcient crosslinking with short exposure time in the presence of adequate photoinitiator. Epoxidized polyisoprene (EPI) was obtained by the treatment of natural rubber with peracetic acid for 6 h at 5 C [123]. The ring-opening polymerization of the epoxy group efciently proceeds upon UV irradiation in the presence of triarylsulfonium salt, with the formation of ether links [124126]. The cationic photoinitiated polymerization has the advantage of proceeding in the dark after an initiating exposure, in contrast to radicalbased polymerization. Thus, all the epoxy groups reacted after 0.5-s UV exposure and one day of storage in the dark. Decker et al. [124126] have extensively studied UV curing using cationic and free radical photoinitiators of both epoxydized liquid natural rubber and their acrylated derivatives. Acrylated polyisoprene (API) was transformed into a hard and insoluble material with a photoinitiator [125]. The intra-chain amylene double bonds of polyisoprene were shown to copolymerize with the acrylate double bonds, thus leading to the formation of a relatively tight polymer network [127]. Polyisoprene can also be readily photocrosslinked by introducing pendant acrylate double bonds onto the polymer backbone by reacting EPI with acrylic acid. The curing of a cationic photoinitiator-induced system comprising epoxydized natural rubber, cycloaliphatic diepoxyde and glycidyl methacrylate was studied by Kumar et al. [128]. The epoxy groups attached to the rubber particles rapidly and efciently reacted both under UV exposure and during the postcuring process. In these experimental conditions, the chain extension and crosslinking reactions occurred
simultaneously, leading to the formation of an interpenetrating polymer network. NR exhibited good properties (i.e. tensile strength, exibility and resistance to impacts and tears) but also had some drawbacks. NR had low ame resistance, limited resistance to chemical solvents, and poor ozone aging, mainly owing to its unsaturated hydrocarbon chain structure. Consequently, the chemical modication of NR has widely been considered as a solution to compensate for these disadvantages. The synthesis of graft copolymers from NR has been conducted in solution [129,130], in solid state [131] or in latex media [132136]. Derouet et al. [137] prepared N,Ndiethyldithiocarbamate-functionalized 1,4-polyisoprenes to synthesize thermoplastic-grafted polyisoprene by the photopolymerization of vinyl monomers initiated according to the principle of the grafting from route. Two different methods of grafting N,N-diethyldithiocarbamate function in the lateral position of 1,4-polyisoprene chains have been considered (Fig. 18). Derouet et al. [137] grafted N,N-diethyldithiocarbamate initer groups onto rubber chains, and these groups were used to initiate the photopolymerization of acrylate or methacrylate phosphorus-containing monomers [138]. Under UV irradiation, the rubbery macroiniters dissociated to form stable N,N-diethyldithiocarbamate radicals capable of initiating monomer polymerization. To improve NR properties (i.e. ame-retardancy and oil resistance), the grafting of polymers bearing phosphonate groups was performed. Graft copolymers [139] of NR poly(dimethyl(acryloyloxymethyl)phosphonate) with (NR-g-PDMAMP) and of NR with poly(dimethyl(NR-g-PDMMEP) (methacryloyloxyethyl)phosphonate) were prepared [140] in latex medium with a UV lamp to
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Fig. 18. Various ways considered to synthesize N,N-diethyldithiocarbamate-functionalized PI.
initiate the grafting reaction. Various graft copolymers derived from NR were synthesized with well-controlled structure and size by this technique. Photopolymerization of vinyl monomers such as alkylacrylates and methylacrylates, styrene, acrylonitrile and acrylamide, initiated by N,N-diethyldithiocarbamate-functionalized NR, was successfully conducted in bulk in toluene solution or in latex media [139]. In summary, few studies have focused on the photopolymerization of NR; rather, they have mainly focused on the modication of the amylene bond to obtain functionalized PI that could be crosslinked by UV irradiation. 3. Renewable molecules as functional groups for UV-cured materials 3.1. Sugars 3.1.1. Macromolecules based on (meth)acrylated monomers Primary and secondary hydroxyl groups are easily modied, mainly using carboxylic acid or acyl chloride reagents, to form (meth)acrylate-based precursors. Considering the toxicity of the reagents, most acrylate-based experiments described in the literature are for coatings and
related applications. The methacrylate-based formulations are more widely used in the biomedical eld because of their lower cytotoxicity and biocompatibility [141143]. Rios and Bertorello [144] showed an example of the surface modication of industrial poly(vinyl chloride) (PVC) substrates with photocrosslinked acrylated sucrose. They incorporated sucrose onto the PVC surfaces to increase the hydrophilic character of the polymer surface. Kim and Peppas [145] highlighted the role of glucose bearing a methacrylate functional group in the construction of a copolymer network (Fig. 19). The incorporation of glucose units provided a water-swelling property to the copolymer, and the use of methacrylate acid as a co-monomer yielded pH sensitivity for oral drug delivery systems. Drug-loading systems have been engineered using polymers based on -cyclodextrin molecules and hyaluronic acid hydrogels [72]. A hydrogel was obtained by the photopolymerization of a mixture of methacrylated cyclodextrin and methacrylated hyaluronic acid; this new complex showed better interaction with hydrocortisone drugs. Recently, Yang et al. [146] used methacrylatederivitized galactose to functionalize polypropylene membranes and mimic glycol receptors on cell surfaces. This modication conferred selective bacterial recognition
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Fig. 19. UV copolymerization of methacrylated-based glucose, methacrylic acid and tetraethylene glycol dimethacrylate.
Fig. 20. Glucose-terminal brushes immobilized on polystyrene core.
(Enterococcus faecalis) to the membranes. d-glucose methacrylate was used to form polymeric brushes from spherical polystyrene cores for the specic recognition of wheat germ agglutinin lectins [147] (Fig. 20). The authors observed higher binding ability for the glycopolymer-based nanospheres than for the well-known N-acetylglucosamine-based systems. Further applications based on (meth)acrylated molecules with pendant saccharides have been investigated (e.g. human cornea substitutes based on a collagenglucose matrix [148] and an antifouling coating based on new glyco-membrane bioreactors [149]). For example, Patel et al. [150] formulated an acrylate-based glycoside with polyurethane pendant chains. They converted cellulose from sugar cane to glycoside and prepared a UV-curable coating with pendant acrylate-polyurethane chains. They succeeded in the deposition of microlms with good adhesion to mild steel substrates with no liberation of volatiles. Recently, Stefer [151] found cosmetic applications of photopolymerizable compositions for preparing human ngernails. They used methacrylated derivatives of sucrose and sefose (a sucrose fully modied with fatty acid chains).
of donoracceptor type copolymerization applied to vinylribose and allyl-ribose was evaluated with maleate and fumarate derivatives. Sugar-derived monomers showed an interesting reactivity compared to commercial oil-sourced ether derivatives. The sugar-based vinyloxy monomers exhibited a higher reactivity with maleate and fumarate monomers than oil-sourced ether. They also showed that the H-bonding due to the free hydroxyl groups in the sugar structure provided better access to the functional groups. Another method to form copolymers from unsaturated monomers was reported by Acosta Ortiz et al. [155,156] using a thiol-ene process between polyallylbased sucrose and thiol-based derivatives, as illustrated in Fig. 21. They noticed that photopolymerization could proceed in the absence of photoinitiator, but addition of 1% (by weight) photoinitiator permitted a complete reaction. The use of polyfunctional monomers gave a exible polythioether network (Tg = 30 C). This method has also been employed with pentaerythritol-based compounds for medical research [157,158].
3.1.2. Macromolecules based on vinyl/allyl monomers Few examples of vinyl/allyl-based saccharides involved in photopolymerization have been reported. Yang et al. [152] studied the interaction processes between carbohydrates and proteins. They reported for the rst time the UV grafting of -d-allyl-glycoside on polypropylene membranes. They demonstrated that the immobilized sugars could interact with the protein Con A when the surface density did not exceed 90 g cm2 . They highlighted that a weak interaction (Ka = 103 104 M1 ) occurred between glycoside structures and Con A. Pichavant et al. investigated the photopolymerization of unsaturated monomers derived from renewable feedstock [153,154]. The potential
3.1.3. Specic use: photoinitiator water-soluble complexes Due to the pollution of organic volatile compounds used in conventional photopolymerization, water-soluble complexes represent a very promising alternative for pollutant-free processes. In 1976, Kubota et al. [159] reported the use of saccharides (e.g. glucose, cellobiose, and maltose) to initiate the photopolymerization of methyl methacrylate (MMA). They highlighted that the saccharides were able to form radicals under UV radiation between 220 and 300 nm and could stabilize the MMA radicals formed during irradiation. These radicals were able to initiate the polymerization of acrylamide in aqueous solution [160]. The conversion increased with the solubility of the saccharides in water (e.g. sucrose (2000 g/L) d-glucose (900 g/L)). To the best of our knowledge, few studies have
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Fig. 21. UV copolymerization of sucrose-based allylic derivatives using thiol-ene process.
been published in this eld. The water-soluble property of saccharides has been applied mainly to the modication of hydrophobic photoinitiators to make them usable for photopolymerization in aqueous media [161,162]. For this purpose, cyclic oligosaccharides such as cyclodextrin have been employed for their hydrophobic cavity and hydrophilic corona [163,164]. The -cyclodextrin is a seven-glucose ring that has been widely used as watersoluble host/guest complex. Enmanji [165] showed that the -cyclodextrin/benzoin ethyl-ether complex was more efcient for the inclusion of photoinitiator in cyclodextrin due to the electron delocalization in the structure. Lougnot et al. [166] and Balta et al. [167,168] showed the efciency of a thioxanthone-based encapsulated photoinitiator in -cyclodextrin for the photopolymerization of acrylamide or MMA. More recent papers describe the use of methyl--cyclodextrin [169172], which is more soluble than -cyclodextrin in water (2000 g/L). Sugars from renewable resources are a good alternative to the use of fossil feedstock. Using environmentally friendly reactions such as those induced by UV, these molecules have been employed as precursors to prepare materials for coatings or biomedical applications, with consideration to their biocompatibility, water solubility, and pH-responsiveness. Sugars were mainly functionalized with UV-reactive functional groups such as (meth)acrylate and allyl/vinyl groups on the hydroxyl groups. 3.2. Amino acids Vegetables, legumes and grains contain the essential amino acids in various proportions. Approximately 80
amino acids exist in nature, but only 2029 are required for human growth. Among the 20 amino acids included in proteins, only eight are known as the essential amino acids: isoleucine (I), leucine (L), lysine (K), methionine (M), threonine (T), phenylalanine (F), tryptophan (W) and valine (V). The photopolymerization of this type of compound is limited to the preparation of hydrogels for medical applications. The synthesis of hydrogels by photopolymerization does not use amino acids as monomers. The amino acids are grafted or introduced along the backbone of the polymer to synthesize precursors. Next, the UV crosslinking reaction takes place in water, as required for biomedical applications. Therefore, the synthesis of hydrogels based on (meth)acrylated precursors and of photoresponsive hydrogels based on cinnamate precursors will be described. 3.2.1. Hydrogels based on (meth)acrylate precursors Radical photoinitiated polymerization is largely used for the formation of biological hydrogels. Such products have been extensively employed for a number of biomedical applications, such as scaffolds for tissue engineering and controlled-release systems for drug delivery [173,174]. Hydrogels produced by photopolymerization provide a highly swollen three-dimensional structure similar to soft tissues and allow diffusion of nutrients and cellular waste through the elastic network. Additionally, these materials, generally deposited on living tissues as a liquid, are polymerized in situ. Amino acid sequences can be introduced along the backbone or can be grafted into synthetic hydrogels during polymerization. Among synthetic polymers that
Fig. 22. Incorporation of polyamino acids without and with a PEG spacer arm.
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can form hydrogels via crosslinking, poly(ethyleneglycol) (PEG) is the most-investigated polymer backbone. PEGbased hydrogels have many advantages in comparison with natural hydrogels: they can be photopolymerized into various shapes or injected for tissue repair, and their mechanical properties can be adjusted to t nal application requirements [70]. Incorporation of amino acids has been explored with [175] and without [176] a PEG spacer, as indicated in Fig. 22, to provide a biological activity. Using this amino acid incorporation technique, PEG hydrogels containing amino acid sequences such as IKLLI, IKVAVA, LRE, YIGSR, PDSGR, DGEA and different combinations have been synthesized. These polymerization conditions have been shown to be cytocompatible with various cell types, providing matrixcell interactions responsible for the attachment of broblasts [175,177], aortic smooth muscle cells [178], osteoblasts [179,180], and mesenchymal stem cells [181]. However, a major limitation of this synthetic route is the heterogeneity of PEG-based gels, appearing during the polymerization process, which inuences the nal material properties. Synthesis by click chemistry of hydrogels with controlled architectures was developed by Polizzotti et al. [182]. Thanks to this technique, the authors improved the mechanical properties of the nal materials. The integration of multifunctional photoreactive polyamino acid sequences into the network was performed. A tetrazide-multiarm PEG and a diacetylenefunctionalized allyl ester containing amino acids were used to generate well-dened PEG-amino acid hydrogels, as shown in Fig. 23.
A new method for attaching biological molecules to hydrogels was developed by Elbert et al. [183]. They used a Michael-type addition between a thiol-peptide and a PEG diacrylamide so that amino acids could be attached in 2 h in aqueous solution at room temperature. The photopolymerization step can be performed in contact with living cells. The irradiation conditions and precursor composition greatly affects the stiffness of the materials, which subsequently affects cell spreading. The interest in the use of Michael-type addition between a thiol-containing peptide and an acrylate functional group is the high selectivity of this reaction [174]. When proteins are modied exclusively via their free thiols, primary amine-dependent protein properties and functions may therefore be preserved. Although the primary amines of proteins can also react with acrylate groups by Michael-type conjugate addition, under physiological conditions this reaction is very slow (hours) whereas thiols react quickly (minutes) [183,184]. Free radicals generated by the dissociation of photoinitiator during photopolymerization can have side effects and cause damage on cell membranes, proteins and DNA. Consequently, intensive research has been focused on the development of cytocompatible photoinitiator; the best-established initiator system for photo-encapsulation was Irgacure 2959 (I2959). However, in the case of amino acids, the aromatic amino acids also absorb at 285 nm, thus competing with I2959 during photoinitiation. Thus, Bahney et al. [185] developed non-toxic experimental conditions for the photo-encapsulation of human mesenchymal stem cells (hMSC) using a visible light
Fig. 23. Synthesis of hydrogels via the [3 + 2] cycloaddition reaction. (AA)n: polyamino acids.
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Fig. 24. Schematic representation of the photoresponse of an amino acid-based dendron functionalized with p-nitrocinnamate and its dimer.
photoinitiator system, composed of eosin Y, triethanolamine and 1-vinyl-2 pyrrolidone, with a peak absorbance close to 510 nm. This visible light photoinitiator produced hydrogel scaffolds with a more tightly crosslinked network in one-third the UV polymerization time of I2959. These synthetic hydrogels are difcult to synthesize and expensive to obtain. An easier and less expensive strategy was reported in 2010 by Miller et al. [186], who synthesized PEG precursors. Step growth polymerization via a Michael-type reaction was performed to create high-molecular-weight photoactive macromonomers of the form of acrylate-PEG-(peptide-PEG)m -acrylate. The macromonomers were then crosslinked into hydrogels during a second radical-mediated photopolymerization. This system was used to develop materials to promote angiogenesis in an ex vivo aortic arch assay. The formation and invasion of new sprouts in the hydrogels, mediated by endothelial cells from embedded embryonic chick aortic arch, were demonstrated. Thanks to this method, the gel swelling was improved and the cost of the materials was reduced compared to previous synthesis methods. Recently, Zhou et al. [187] developed antimicrobial hydrogel lms and coatings based on photopolymerizable -poly-l-Lysine-graft-methacrylamide (EPL-MA). Because of the polymerization difculty of the oligomeric EPL-MA (Mn = 3000 g mol1 ), dimethylacrylamide and polyethylene glycol diacrylate (PEGDA) crosslinkers were added to copolymerize and to improve the mechanical properties (Youngs modulus) of the hydrogels. These hydrogels were able to inhibit the growth of both bacteria and fungi; they showed in vitro biocompatibility with human epidermal keratinocytes. Cai et al. [176] used another type of peptide-based precursor. Poly-l-lysine with one end-capped allyl group was synthesized by the
ring-opening polymerization of carbobenzyloxy-l-LysineN-carboxyanhydride initiated by allylamine. Next, the poly-l-lysine obtained (Mn = 3060 g mol1 , I = 1.23) was covalently linked into PEGDA networks via photocrosslinking. This covalent immobilization of poly-l-lysine in PEGDA hydrogels has great potential for the development of injectable materials for nerve repair and regeneration. 3.2.2. Photoresponsive hydrogels based on cinnamate precursors Organogels from low molecular weight organogelators (LMOGs, Mw 3000 g mol1 ) are considered stimulusresponsive materials. They can therefore be used as sensor materials, chemical valves, catalysts, mechanical transducers, controlled-release systems, and articial muscles for biomedical purposes. The morphology of these materials changes reversibly by the action of light, temperature [188], pH [189], coordination function [190], redox stimuli [191] and even ultrasound [192]. Iwaura and Shimizu [193] reported a thymine-containing bolaamphiphile showing a reversible photochemical conversion of self-assembled helical nanobers. They described for the rst time the reversible conversion by UV light of the helicity of the thymine moiety between helical and non-helical nanobers. Ji et al. [194] described an efcient photo-reversible gelator based on azo-modied poly(GlyAsp) dendron and demonstrated that dendrons could represent a new candidate for the elaboration of smart gels. Kuang et al. [195] created a photoresponsive organogel from the amino acid-based dendron functionalized with p-nitrocinnamate. This dendron could self-assemble into a brous network in common organic solvents at low concentrations. This remarkable gel was photoresponsive and thermoresponsive. The solgel transition in response to
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Fig. 25. Cyclodimerization of coumarins under UV radiation.
external photostimuli was attributed to the cycloaddition and cleavage of the cinnamate groups, as shown in Fig. 24. Such materials led to the fabrication of cinnamate-based devices but also provided a novel path to design smart materials. This cinnamate chemistry will be described in more detail in Section 4.2. In summary, the use of amino acids in photopolymerization is very limited; they have mainly been used as precursors to synthesize hydrogels for biomedical applications because of their biocompatibility. UV crosslinking reactions with amino acids require the attachment of reactive functional groups such as (meth)acrylate, methylacrylamide, allyl and cinnamate groups onto peptide sequences. 4. Photoreactive biosourced molecules 4.1. Coumarin-derived compounds Coumarins are a class of molecules comprising several hundred derivatives, among which 7-hydroxycoumarin is the most famous structure. These molecules are naturally present in many plants but have also been synthesized by different routes [196,197]. They are used in various applications, including fragrances, medicines, drug delivery, and liquid crystalline polymers. Their ability to photodimerize was discovered one century ago [198]. This coupling reaction is achieved by photoactivation but not by thermal processes, making this reaction very interesting for its specicity of activation. The reaction occurs in the solid state for some derivatives, and can also occur in solution at > 300 nm, leading to different isomers with the formation of a cyclobutane ring by a (2+2) cycloaddition. These isomers exhibit good thermal stability, depending on the structure of the dimers (Fig. 25) [199202]. Because of the peculiar behavior of this natural pseudolactone, the crosslinking of polymers became possible and different applications emerged [203]. Interestingly, the reversibility of this crosslinking under short-wavelength irradiation (<290 nm) was demonstrated in the 1960s by Krauch et al. (Fig. 26) [200]. As a consequence, a new class of thermosetting materials was obtained for applications such as uorescent coatings, laser dyes, printing formulations, polymeric liquid crystals [204208]; they could be recycled by simple UV irradiation. Chujo et al. [209] investigated this property by gelifying water-soluble poly(2-methyl 2-oxazolines) that were partially hydrolyzed and functionalized with coumarin moieties. They observed a reversible crosslinking, which is typical for hydrogen-bonded systems. This strategy was applied to different classes of polymers,
Fig. 26. Crosslinking coumarins.
of
polymers
through
cyclodimerization
of
including polyacrylates [210,211] and polyamides [212]. Chain extension of oligomers was also explored [213216]. As an example, hydroxytelechelic oligomers of polyethers were modied by converting OH groups by simple esterication before the reversible chain extension, offering chemists a versatile method to prepare highmolecular-weight polymers (Fig. 27) [214]. It must be mentioned here that the dimer of coumarin can also be used to couple diamino-terminated molecules, thereby acting as a uorescent probe for kinetics studies, as shown in Fig. 28 [217]. The dimerization ability of coumarin derivatives has recently become fashionable thanks to the advent of controlled radical polymerization. Thus, Chen et al. and Feng et al. used RAFT polymerization to prepare polyacrylates and polystyrenes bearing pendant coumarin moieties that were subsequently dimerized [218,219]. In the same way, Tian et al. used atom transfer radical polymerization to produce liquid crystalline homopolymers and di- or triblock copolymers with polystyrene segments (Fig. 29) [220]. It should be noted that there were some attempts to modify well-known biodegradable polymers, such as polypeptides [221,222], -caprolactone and poly(trimethylene carbonate) [223226], for application in biomaterials. The literature on the use of coumarins and coupling mechanisms is extensively described in the excellent review of Trenor et al. [227]. 4.2. Cinnamate-derived compounds Cinnamic acid is synthesized by numerous plants by the action of phenylalanine ammonia-lyase on lphenylalanine, yielding phenylpropanoid compounds. The intra-cyclization of cinnamic acid leads to the formation of coumarins (described above). The synthesis of cinnamic ester-derived polymers is a wide area of investigation, and studies over many years have focused on the polymerization of related monomers or on the modication of pre-formed polymers by cinnamate groups [228]. Cinnamate groups can be (2 + 2) dimerized under UV light (270310 nm) or isomerized
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from trans to cis form in a reversible equilibrium, as illustrated in Fig. 30 [213,229]. The design of new monomers bearing cinnamate groups has been widely investigated, and many syntheses of (meth)acrylates bearing lateral cinnamoyl groups have been proposed. These functionalized polymers exhibit good reactivity with or without photosensitizer, making them suitable in the area of photoactivable polymers [230,231] and patterned polymers [232]. The presence of substituents on the aromatic ring can slightly modify the reactivity of the ,-unsaturated ketone [233,234]. Laschewsky and Rekai [235] synthesized a cinnamoylmodied methacrylamide combining the cloud point of the methacrylamide moiety, the crosslinking property of the cinnamoyl entity and a free OH group for further grafting (of a drug, for instance). Styrenic derivatives containing cinnamate groups were prepared by chemical modication of 4-chloromethylstyrene and copolymerized with
a styrenic monomer bearing an azobenzene moiety. The properties of the obtained statistic copolymer were studied in the eld of photoalignment materials [236]. Linear or cyclic polysiloxanes such as polydimethylsiloxane (PDMS) were designed, and the competition between dimerization and isomerization was studied in detail for liquid PDMS [237,238]. Similarly, linear and cyclic polyphosphazenes were synthesized either by the modication of the hexachlorocyclotriphosphazene monomer before its ring-opening polymerization or by the modication of poly(dichlorophosphazene) and its crosslinking [239,240]. Polyvinyl cinnamates were mainly obtained by modication of PVA with cinnamoyl chloride [241,242] and were used for compartmentalized reactions in microparticles and microbers [243]. These polyvinyl cinnamates could also be synthesized by the amidication of polyvinyl amine with cinnamoyl chloride, giving hydrophilic networks with potential applications in the biomedical eld [244].
Fig. 27. Chain extension of polymers using cyclodimerization of coumarins.
Fig. 28. Coupling of polymers using dimers of coumarins.
Fig. 29. Block copolymers synthesized from controlled radical polymerization.
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Fig. 30. Reversibility of the cinnamate cyclodimerization.
The recent interest in natural materials opened the way to the design of materials bearing functionalities. As a result, modications of natural materials to make them photoresponsive were investigated. Epoxidized natural oils [245], cellulose [246], chitosan [247] and starch [248] were modied using cinnamoyl chloride to give materials exhibiting gel properties (for example) or to modify the physical or mechanical properties of the starting natural products. The modication of biodegradable polymers was also studied, and some authors crosslinked poly(l-lactide). This polymer was extended to produce high-molecular-weight polymers before irradiation; the resulting polymer gels were less sensitive to enzymatic degradation [249]. The copolymerization of l-lactide with a cyclic carbonate bearing a pendant cinnamate group was also described. The resulting poly(ester-carbonate) copolymer with a statistical distribution of the two monomers was shown to be photocrosslinkable at > 365 nm [250]. Finally, the bio-based nanoparticles of poly(3,4-dihydroxycinnamic acid-co-4-hydroxycinnamic acid) were shown to be sensitive to dimensional size changes under UV irradiation at >280 nm. Thus, the diameter of the particles halved under irradiation and partially recovered their dimensions after a second exposure at 254 nm, making them interesting as size-controlled carriers for environmental and biomedical applications [251]. Finally, besides the design of new monomers with cinnamate moieties, it must be mentioned that some monomers with two cinnamate groups were developed. These monomers were investigated in step growth polymerization of PET to make it photosensitive. Thus, PET-based copolymers were spun after melt extrusion before their irradiation under UV light, yielding PET with improved mechanical and thermal properties (Fig. 31) [252].
Otherwise, many attempts focused on the area of liquid crystalline polymers, where cinnamoyl groups are good candidates for mesogenic derivatives. Thus, the nature and the inuence of the substituents of the aromatic ring, and the length of the spacer between the polymer backbone and the cinnamoyl group, were studied in detail by many teams [253262]. Several authors, such as Boutevin et al. [263,264] and Hernandez et al. [265], studied various nonlinear optical polymers with cinnamate as the crosslinker. In summary, cinnamic and coumarin moieties are promising biosourced functional groups enabling the crosslinking of polymers under UV irradiation. The reversibility of the reaction makes them useful in technical polymers, paving the way for high technologies such as liquid crystalline polymers and optical applications such as nonlinear optics. 4.3. Natural acids Owing to their high biocompatibility and their pHdependent behavior, natural acids have great potential for biomedical applications. These molecules are naturally available in the biomass (e.g. tartaric acid and caffeic acid) or obtained by chemical or enzymatic processes (e.g. citric acid, succinic acid, itaconic acid, and lactic acid). The literature describes natural acids as pH-dependent agents, reagents for the synthesis of polymers (e.g. polyester and polyamide) [266], photopolymerizable groups for photochemical processes and precursors of diols after reduction. Some biosourced acids showing a native UV reactivity have been used as functional groups and were grafted onto prepolymers using their carboxylic acid group. As shown in Fig. 32, they exhibit similar chemical structures, with a double bond close to that of carboxylic acid, which is a highly reactive functional group under UV exposure.
Fig. 31. Crosslinking of PET modied with cinnamates moieties.
Fig. 32. Chemical structures of natural acids. From the left to the right: acrylic acid, itaconic acid, cinnamic acid and caffeic acid.
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Natural acids have been widely used for the production of coatings and for biomedical applications. For instance, fumaric, maleic and itaconic acids have been employed for the production of contact lenses [267] because of their hydrophilic character. From the large range of UV-sensitive bio-based acids, acrylic acid is one of the most frequently used molecules. Over the last three decades, thousands of publications and patents have reported the use of acrylic acid in UV-radiation processes. In many instances, this molecule has been used as a UV-sensitive functional group grafted onto prepolymers. Decker [268271] described in several papers the potential of acrylic-based monomers as precursors involved in the photopolymerization process. Today, acrylic acid can be obtained from biomass by several methods. The Arkema company uses the catalytic conversion of glycerol to acrolein and acrylic acid or catalytic dehydration of lactic acid [272,273]. Cargill and Novozymes developed an enzymatic route that could produce acrylic acid from 3-hydroxypropionic acid using sugars as raw material. Johnson and Landin [274] claimed that unsaturated polyesters based on acrylic acid could be useful as protective coating materials using UV polymerization. Recently, pressure-sensitive adhesives based on acrylic derivatives were prepared, representing a promising route for electronic coatings in applications such as touch screens. Kajtna and Krajnc [275] illustrated this application using an acrylic prepolymer resulting from a 2-ethylhexyl acrylate, acrylic acid and t-butyl acrylate mixture. Bag and Rao [276] studied the potential of difunctional silane monomers as precursors of hybrid materials (based on methacryloxyacryloxy-silane) and for coating applications because of the thermal stability of these UV-cured objects. Derivatives of acrylic acid, such as cinnamic-based molecules (also called trans-3-phenylacrylic), are mainly involved in reversible dimerization processes to form a cyclobutane ring under UV light. Nagata and Inaki [249] photocrosslinked a poly(lactide) skeleton functionalized with cinnamic groups. Similar studies were conducted using caffeic acid (also called trans-3,4-dihydroxycinnamic
acid or trans-3,4-dihydroxy-3-phenylacrylic acid). This analog of cinnamic acid, mainly found in lignin biomass, is composed of a benzenic ring disubstituted with hydroxyl groups that can easily be modied [277]. The use of cinnamic acid and its derivatives is described in Section 4.2 of this review. Rosin is obtained from pines and other plants (such as conifers) by heating fresh resins to eliminate volatile terpene components. All rosins are made up of 90% diterpenic monocarboxylic acids, also called resin acids (Fig. 33). Abietic acid is the major constituent of resin acids, and it represents the major portion of rosin. Resin acids have been extensively used in paper sizing, printing inks and adhesives. Kwak et al. [278] applied methacrylate-based abietic acid to photolithographic applications. In a similar way, Kim et al. [279] showed that abietic acid-based styrene monomers were efcient precursors in the photocrosslinking of polymers with methyl methacrylate. Tannin compounds are widely distributed in plants and are made of polyphenolic molecules. Digallic acid (a polyphenolic acid fragment of tannic acid) has been employed as a precursor of photoactive lms for coating materials [280]. Digallic acid was also combined with isocyanate and methacrylate molecules to form a UV-sensitive urethane, and the reactivity of the formulation was compared under thermal and photochemical curing. Polyacids are useful for biomedical applications such as drug delivery agents thanks to their pH-responsive behavior. Itaconic acid, obtained by distillation of citric acid, is composed of one photosensitive double bond and two carboxylic acids (pKa 3.8, 5.5) [281]. Chen et al. [282] copolymerized itaconic acid with N-vinyl-2-pyrrolidone monomer to prepare pH-sensitive hydrogels using UV induced methods. Other research was performed by Tomic et al. [283] and Betancourt et al. [284]. They demonstrated the ability of itaconic acid to photocopolymerize with methacrylate monomers and to generate pH-responsive hydrogels. Malic acid, another well-known biosourced monomer, was studied for its pH-responsive property and
Fig. 33. Examples of resin acids: (from the left to the right) abietic acid, neoabietic acid, dehydroabietic acid, pimaric acid; digallic acid (from tannin).
Fig. 34. Formation of hydrogel using methacrylated malic acid.
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Fig. 35. Synthesis of furfural and its conversion into furfuryl alcohol and furfuryl methacrylate.
Fig. 36. Photochemistry of copolyester bearing furan chromophore under near-UV irradiation.
its biocompatibility (Fig. 34). This hydroxyl-diacid (pKa 3.4, 5.2) is produced from the metabolism of carbohydrates. He et al. [285] developed the synthesis of biodegradable hydrogels using a poly(,-malic acid) prepolymer functionalized by methacryloyl-based functions, with the aim of nding biocompatible materials. In summary, the use of natural unsaturated acids allows the functionalization of molecules or polymers and provides photosensitive properties. Biosourced acids represent a promising route for preparing materials for industrial coating and medical applications. The carboxylic acid function gives a pH-dependant character, and this property is being exploited mainly in the biomedical eld for drug delivery systems. 4.4. Furans Most furans and their related derivatives come from the acid-catalyzed hydrolytic depolymerization of hemicelluloses [61,286]. Two different aldopentoses were described: xylose and rhamnose. Their dehydration leads to furfural and methylfurfural compounds after purication by distillation, as illustrated in Fig. 35. Most furfural is converted into furfuryl alcohol, but other molecules acting as building blocks for polymers can be obtained from it, such as dialdehydes, diacids, diisocyanates, and diamines. Furan is most often involved in DielsAlder reactions with maleimide derivatives. This typical reaction was extensively described by the Gandini group [287]. It is thermally reversible and was the basis of novel smart materials. This group also described the photochemistry of conjugated furanic structures [288,289]. To do so, the authors grafted this aromatic chromophore onto polymers before photoinitiator-free crosslinking, involving a (2+2) cycloaddition, under UV irradiation. This reactive chromophore was also engaged in linear polyesters using chain end functionalizations, as shown in Fig. 36. Fang et al. [290] investigated the grafting of conjugated furan chromophores on polyvinyl alcohol (PVA) (Fig. 37). According to the range of substitutions, the glass transition temperatures of the modied PVAs were lower than that of the starting PVA due to the decrease of intermolecular hydrogen bonding. By dimerization, these modied
materials were converted into insoluble thin lms by irradiation. Potential applications of this strategy have been devoted to photoresist technology, particularly in offset printing plates. Another furanic derivative, furan-2-carboxylic acid, was employed in the elaboration of nanoparticles by photocrosslinking in the presence of dextran after a dialysis process [291]. Lange et al. [292] exploited the high reactivity of acrylate or methacrylate functional groups in the area of furfurylic compounds, modeling the kinetic parameters at different temperatures. Using this method, they showed that the dominant step of the successive reactions (primary initiation, propagation, cross-termination, etc.) changed with respect to temperature. Moreover, the crosslink density of acrylated furanic polymers was predicted by this method. In summary, furans and theirs derivatives are usually used as building blocks in the preparation of initiator-free photocrosslinkable prepolymers. We have mentioned here that these compounds come from renewable resources but that they require numerous chemical transformation steps, in contrast to some other natural raw materials such as polysaccharides and oils. Moreover, some studies reported the toxicity of furans and their derivatives as food contaminants [293,294].
Fig. 37. Photocyclodimerization of PVA grafted.
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5. Conclusion The aim of this review was to describe the macromolecules and the variety of reactive species derived from biomass that can lead to materials through a photopolymerization process. Biodiversity allows chemists to screen a large number of backbone structures and properties. For instance, oils are hydrophobic while polysaccharides are hydrophilic. These biosourced macromolecules can be easily modied to obtain UV-reactive macromolecules. Otherwise, bio-based compounds can be introduced into polymeric materials to obtain specic properties or, when they are photosensitive, can be used as reactive functional groups to induce the UV polymerization process. Consequently, bio-based materials have a large variety of applications such as coatings, biomaterials and electronic devices, which generally are high-added-value products. Some natural elements can be used for the construction of linear or ramied polymers and networks. The use of UV irradiation a clean process without pollutant emission such as volatile organic compounds (VOC) allows the conversion of the liquid formulation to networked material in a few seconds. It is more adapted to thin-layer applications such as coatings (with a thickness from 1 to 100 m), as it has penetration limitations. The UV process exhibits many advantages in comparison to thermal curing. It can be conducted at room temperature without any degradation of sensitive molecules and without any modication of thermosensitive substrates (e.g. wood and plastics). It is classied as a green process, and the emergence of new applications for UV-responsive biosourced materials will take place in the next decade. It is true that we are at the beginning of a new age for the chemical industry, and it is obvious that the industry is now slowly converting its processes by replacing fossil-based chemicals with biosourced ones. For instance, new bio-based surfactants, solvents or monomers are used in the chemical industry, progressively changing old habits. However, a number of challenges still remain in terms of the purity and chemical reactivity of some compounds. Moreover, one must take into account economic aspects to make these natural products attractive for users. Finally, the extraction and purication steps of materials must involve ecological processes with low energy consumption and no pollutant emissions to make them acceptable for a sustainable development strategy. Recent regulations have favored the growth of radiation-curing technologies, as they are VOCfree and lead to materials with good properties. Obviously, these technologies have some limits. First, the oxygen inhibition of radical polymerization has given birth to a great eld of research. Moreover, the question of the photoinitiators present in cured materials and their migration is a key area of further research. The development of nonhazardous photoinitiators usable in medicinal applications and in food contact coatings is a new opportunity for researchers. For industrial applications, the new trends in future papers will concern the development of ultra-fast reactive monomers with low toxicity as opposed to irritant and allergenic acrylate-derived compounds. Finally, more
eco-friendly formulations will result in the emergence of UV water-borne systems.
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The Use of Renewable Feedstock in UV-curable Materials - A New Age For Polymers and Green Chemistry

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Progress in Polymer Science 38 (2013) 932962

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Progress in Polymer Science

L. Fertier et al. / Progress in Polymer Science 38 (2013) 932962

L. Fertier et al. / Progress in Polymer Science 38 (2013) 932962

Fig. 1. Examples of renewable raw molecules in photochemistry.

L. Fertier et al. / Progress in Polymer Science 38 (2013) 932962

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Fig. 3. Various fatty chains of raw vegetable oils.

Fig. 4. Chemical modications of vegetable oils.

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Fig. 6. Structures of photocurable glycerol-based monomers.

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Fig. 7. Simplied photooxidation process of drying oils.

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Fig. 8. Photoreactive groups in cationic photopolymerization.

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Fig. 9. Overview of rened molecules obtained from biomass treatment.

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Fig. 11. (Meth)acrylatedderivatives used for the modication of polysaccharides.

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Fig. 15. Photocrosslinking of carboxymethylchitosan thanks to azide functions.

Fig. 16. Maleinated chitosan as macroinitiator of PNIPAAm.

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Fig. 17. Photocrosslinking of maleinated chitosan with PEGDA as photocrosslinker.

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Fig. 18. Various ways considered to synthesize N,N-diethyldithiocarbamate-functionalized PI.

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Fig. 20. Glucose-terminal brushes immobilized on polystyrene core.

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Fig. 21. UV copolymerization of sucrose-based allylic derivatives using thiol-ene process.

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Fig. 25. Cyclodimerization of coumarins under UV radiation.

Fig. 26. Crosslinking coumarins.

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Fig. 27. Chain extension of polymers using cyclodimerization of coumarins.

Fig. 28. Coupling of polymers using dimers of coumarins.

Fig. 29. Block copolymers synthesized from controlled radical polymerization.

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Fig. 30. Reversibility of the cinnamate cyclodimerization.

Fig. 31. Crosslinking of PET modied with cinnamates moieties.

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Fig. 34. Formation of hydrogel using methacrylated malic acid.

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Fig. 37. Photocyclodimerization of PVA grafted.

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eco-friendly formulations will result in the emergence of UV water-borne systems.

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