生物基涂料

Progress in Polymer Science 38 (2013) 932– 962 Contents lists available at SciVerse ScienceDirect Progress in Polymer Science j ourna l ho me pag e: www.elsev ier .com/ locate /ppolysc i The use of renewable feedstock in UV-curable materials – A new age for polymers and green chemistry Laurent Fertier, Houria Koleilat, Mylène Stemmelen, Olivia Giani, Christine Joly-Duhamel, Vincent Lapinte, Jean-Jacques Robin ∗ Institut Charles Gerhardt Montpellier UMR5253 CNRS-UM2-ENSCM-UM1 – Equipe Ingénierie et Architectures Macromoléculaires, Université Montpellier II – Bat 17 – cc1702, Place Eugène Bataillon 34095 Montpellier Cedex 5, France a r t i c l e i n f o Article history: Received 18 Ju Received in re 10 December Accepted 19 D Available onlin Keywords: Photopolymerization Renewable resources Vegetable oil Carbohydrates Amino acids Natural rubbe a b s t r a c t This review aims to cover the state of the art of renewable feedstock use in materials produc- tems 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, biodegrad- Contents 1. Introd 2. Renew Abbreviati methacrylate; DMAc, Dimet Dimethylsulfo dimethylamin soybean oil; E HBA, Hyperbr mesenchymal Interpenetrati weight organo phenylisocyan NMA, N-meth Polydimethyls isopropylacryl oil; SIPN, Sem TDI, Toluene d methyl-N-(2-h ∗ Correspon E-mail add 0079-6700/$ – http://dx.doi.o rs ability and finally their end uses. © 2012 Elsevier Ltd. All rights reserved. uction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 933 able macromolecules as raw precursors for UV-cured materials . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 934 ons: 5-CAGA, 5-ring membered cyclic acetalglycerin acrylate; 6-CAGA, 6-ring membered cyclic acetalglycerin acrylate; AEMA, Aminoethyl- API, Acrylatedpolyisoprene; BMA, n-butyl methacrylate; CCCA, Cyclic carbonate carbamateacrylate; DAAm, N,N-dimethylacrylamide; hylacetamide; DMAP, N,N-dimethylamino pyridine; DMF, Dimethylformamide; DMPA, 2,2-dimethoxy-2-phenylacetophenone; DMSO, xide; DS, Substitution degree; ECLO, Epoxidized cyclohexene-derivatized linseed oil; ECM, Extracellular matrix; EDC, 1-ethyl-3-(3- opropyl)-carbodiimidehydrochloride; ENLO, Epoxynorbornene linseed oil; EO, Epoxidized oil; EPI, Epoxypolyisoprene; ESBO, Epoxidized SO, Epoxidized sunflower oil; F, Phenylalanine; GCA, Glycerin carbonateacrylate; GMA, Glycidyl methacrylate; HA, Hyaluronic acid; anched acrylate; HEMA, 2-hydroxyethyl methacrylate; HMPP, 2-hydroxy-2-methylphenyl-1-propanone (Darocur® 1173); hMSC, Human stem cells; HPN, Hybrid polymer network; I, Isoleucine; iBMA, Isobutyl methacrylate; IEMA, 2-isocyanatoethylmethacrylate; IPN, ng polymer network; K, Lysine; L, Leucine; LbL, Layer by layer; LCST, Low critical solution temperature; LMOGs, Low molecular gelators; LO, Linseed oil; M, Methionine; MA, Methacrylic anhydride; MAG, Monoacylglycerol (monoglyceride); MDI, Methylene bis(4- ate); MMA, Methyl methacrylate; NELO, Norbornenylepoxidized linseed oil; NHS, N-hydroxysuccinimide; NIPAAm, N-isopropylacrylamide; ylolacrylamide; NMP, N-methyl-2-pyrrolidone; NR, Natural rubber; NVP, 1-vinyl-2-pyrrolidinone; PBS, Phosphate buffer solution; PDMS, iloxane; PEG, Poly(ethylene glycol); PEGDA, Polyethylene glycol diacrylate; PI, Polyisoprene; PLLA, Poly(L-lactide); PNIPAAm, Poly(N- amide); PUR, Polyurethane; RAFT, Reversible addition-fragmentation chain transfer polymerization; SA, Succinic anhydride; SBO, Soybean i-interpenetrating polymer network; SMCs, Smooth muscle cells; SolA, Solketalacrylate; T, Threonine; TAG, Triacylglycerol (triglyceride); iisocyanate; TEC, Thiol-ene coupling; TEOS, Tetraethylorthosilicate; TPGDA, Tripropylene glycol diacrylate; V, Valine; VA-086, 2,2′-Azobis[2- ydroxyethyl)propionamide]; VAPG, Valine-alanine-proline-glycine; W, Tryptophan. ding author. Tel.: +33 4 67 14 41 57; fax: +33 4 67 14 40 28. ress: Jean-Jacques.Robin@univ-montp2.fr (J.-J. Robin). see front matter © 2012 Elsevier Ltd. All rights reserved. rg/10.1016/j.progpolymsci.2012.12.002 ly 2012 vised form 2012 ecember 2012 e 4 January 2013 tion using photopolymerization processes. This area of investigation is an emerging field 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 natu- rally occurring molecules and macromolecules such as lipids, amino acids, carbohydrates, polyenes, etc. are detailed. The way they are used or integrated in photopolymerizable sys- L. Fertier et al. / Progress in Polymer Science 38 (2013) 932– 962 933 2.1. Lipids . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 934 2.1.1. Glycerol derivatives . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 935 2.1.2. Unsaturated oils . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 936 2.1.3. Epoxidized oils . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 939 2.2. Polysaccharides . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 939 . . . . . . . . . . . . . . 2.3. . . . . . . . 3. Renew . . . . . . . . 3.1. . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3.2. . . . . . . . . . . . . . . . rsors . . 4. Photo . . . . . . . 4.1. . . . . . . . 4.2. . . . . . . . 4.3. . . . . . . . 4.4. . . . . . . . 5. Concl . . . . . . . Refer . . . . . . . 1. Introdu The inc to the deve the great p ability to s The constru molecules s tion are a g now, only been availa from castor tion of poly explosion in materials d acrylic acid produced f duction of is not just a Moreover, t tural revital value of agr This mu be followed constraints the peculia human and in the prod lipochemis the differen mainly hum Neverth competitive deposits, su and vegeta of carbon w s to w tracte d, woo t secur undou ompe urced ction a n, chem nts us c mate sed in r oxyg ficatio mod le as re enge f 2.2.1. Acrylate moiety . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2.2.2. Other photocrosslinkable moieties . . . . . . . . . . . . . . . . . . . . . Natural rubbers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . able molecules as functional groups for UV-cured materials. . . . Sugars . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3.1.1. Macromolecules based on (meth)acrylated monomers 3.1.2. Macromolecules based on vinyl/allyl monomers . . . . . . . 3.1.3. Specific use: photoinitiator water-soluble complexes . Amino acids . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3.2.1. Hydrogels based on (meth)acrylate precursors. . . . . . . . 3.2.2. Photoresponsive hydrogels based on cinnamate precu reactive biosourced molecules . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Coumarin-derived compounds . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Cinnamate-derived compounds . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Natural acids . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Furans . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . usion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ences . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ction reasing number of research studies devoted lopment of biosource-based materials reveals otential of renewable raw molecules and their ubstitute for petrochemical-based materials. ction of biorefineries and the availability of uch as glycerin derived from biodiesel produc- reat evolution of the chemical industry. Until a few examples of biosourced polymers have ble, and the famous polyamide 11 is synthesized oil, a vegetable oil also used in the prepara- urethanes. In recent years, there has been a real the number of studies on the development of erived from biomass. Typical monomers such as , epichlorohydrin and acrylonitrile can be now rom biosourced feedstock. The industrial pro- thank be ex (woo is no will not c Bioso extra catio reage meri be u unde modi To usab chall “green” polyethylene in Brazil proves that this trend but a “mutation” in polymer chemistry. his industrial revolution should enable agricul- ization in certain countries, thanks to the added icultural products. tation, which started one decade ago, must by a real strategy concerning the economic of this approach. The best example addresses r case of lipids, which are currently used for animal food and have recently been employed uction of biodiesel. This continuous growth of try activities will promote competition among t end uses of vegetable oils (in some countries, an nutrition). eless, some non-edible oil species may be a non- alternative to this situation. Other biomass ch as algae, lignins, celluloses, polysaccharides ble proteins, are easily affordable precursors ith unlimited deposits and very easy access during the open the w (epoxidatio duce variou The use environmen of wastes pounds (V. processing efficient pr and conve expensive d polymer pr and is app resins and a as liquid c uid resins tenths of a the scientifi . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 940 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 943 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 944 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 946 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 946 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 946 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 947 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 947 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 948 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 948 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 950 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 951 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 951 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 951 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 953 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 955 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 956 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 956 orldwide production. These carbon sources can d from some industrial by-products and wastes d pulp, starch, etc.) whose actual valorization ed. Developments based on these by-products btedly be of great interest because they are ting with raw materials devoted to nutrition. materials are rarely used just after harvest or nd often need preliminary treatments (purifi- ical or enzymatic modifications, etc.) to access able in the elaboration of polymers and poly- rials. Linseed oil is a rare oil variety that can its native form, as its polymerization occurs en and UV irradiation without any preliminary n. ify biosourced raw materials to make them agents in material production will be the great or chemical engineering and biotechnologies next decades. Some recent promising results ay in the field of vegetable oil modification n) and enzymatic degradation of starch to pro- s monomers (succinic acid, glycolic acid, etc.). and purification of biomass can be satisfying if tally friendly processes limiting the production and the emission of volatile organic com- O.C.) are involved. In the same way, materials should require low temperature and energy- ocesses. For instance, UV radiation is a simple nient form of energy and does not require evices. Thanks to its high output, this special ocessing method is enjoying a new expansion lied at the industrial scale for inks, curable lso in various high-added-value products such rystal polymers and non linear optics. Liq- can be converted into solid resins in a few second, making this process very attractive to c community for the past three decades. The 934 L. Fertier et al. / Progress in Polymer Science 38 (2013) 932– 962 photopolym cycloadditio type) or by or cationic materials a nology wo classified a materials m Thus, th in the area o ization (Fig In the fir with signifi together un polysacchar important c tural backb photosensit to be react we report t acids. . .) fo patibility a functional ing or poly Fig. 1. Examples of renewable raw molecules in ph erization mechanism can be achieved either by n of photosensitive molecules (chromophore polyaddition of double bonds under radical initiation. It is specially adapted to biosourced nd thermally sensitive molecules, as this tech- rks at ambient temperature [1]. It can be s a “green” process and its use for biosourced ay be of practical interest. is review aims to record the state of knowledge f natural compounds useful for photopolymer- . 1). st part, we describe compounds from biomass cant molecular weights that can be brought der the designation macromolecules (lipids, ides. . .). They represent an interesting and arbon source to be used as the main architec- one for materials. Some of them are naturally ive; others require preliminary modifications ive under UV irradiation. In the second part, he use of biosourced molecules (sugars, amino r their specific properties, such as biocom- nd pH sensitivity. Their incorporation into materials through UV-based methods (graft- merization) are described. In the last part, we discuss (coumarin, activities an 2. Renewa for UV-cur 2.1. Lipids Oils and torically an feedstock o is growing tion of surf are compos penes, stero such as pho specifically TAGs), are t positions ar vegetable o ging from C chain rangi abundant th otochemistry. naturally occurring and abundant molecules natural acids. . .) that display photosensitive d are used for their photoreactive function. ble macromolecules as raw precursors ed materials fats from vegetables and animals are his- d currently the most important renewable f the chemical industry, and their production (Fig. 2) [2]. They are used for the produc- actants, lubricants and coatings. Vegetable oils ed of unsaponifiable compounds such as ter- ids and fatty acids and saponifiable compounds spholipids and glycerides. The latter, and more triglycerides (also called triacylglycerols or he most abundant components, and their com- e specific to the source plant species. Most raw ils contain various lengths of fatty chains ran- 10 to C22 and various double bond contents per ng from 0 to 3. Unsaturated oils are much more an saturated ones and are classified into three L. Fertier et al. / Progress in Polymer Science 38 (2013) 932– 962 935 99–200 types depen iodine valu oils (125 < I Rare veg groups, suc group (cast group (Lica chemical pa acids, such (TEC) [5,6] described. E tionalizatio epoxy grou thiol, carbo Some ra daylight or anism (see a long pro enhance th cations suc Raw oils a reactive un maleic deri cured by ra method ha by using ep In this spec polymeriza As prev anisms are compounds obtained by pling (TEC) ring-openin lycerol e oils o an in Glyce lycerol rn ole on of esel. D nd bui becom Fig. 2. World production of oils and fats for 19 ding on the ratio of double bonds measured by e (IV): non-drying oils (IV < 125), semi-drying V < 140) and drying oils (IV > 140). etable oils contain peculiar reactive functional h as an epoxy group (vernonia oil), a hydroxyl or oil with ricinoleic acid) and a keto (oxo) niarigida seed oil) (Fig. 3). Otherwise, various thways to functionalize triglycerides and fatty as hydroformylation [3,4], thiol-ene reaction and selective oxidation [7] have already been poxidation is one of the most widespread func- G etabl is als 2.1.1. G mode ficati biodi ity, a have ns, thanks to the ease of ring-opening of the p by various nucleophilic reactants (alcohol, xylic acid, amine, etc.). w oils, such as linseed oil, can be cure