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ISSN 15600904, Polymer Science, Ser. B, 2015, Vol. 57, No. 4, pp. 292–297. © Pleiades Publishing, Ltd., 2015.

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Novel Applications of Castor Oil Based Polyurethanes: a Short Review1 Amit Shirke, Bharatkumar Dholakiya, and Ketan Kuperkar Applied Chemistry Department, Sardar Vallabhbhai National Institute of Technology (SVNIT), Ichchhanath, Surat—395007, Gujarat, India email: [email protected] Received December 11, 2014; Revised Manuscript Received February 8, 2015

Abstract—Nowadays increasing interest is observed for using of bioderived products replacing petroleum based materials. This may reduce the fuel consumption and result in producing of materials with lower envi ronmental impact. One of such substances is vegetable oil, which possesses unique chemical structure and consists of unsaturation sites, epoxies, hydroxyls, esters and other functional groups along with inherent flu idity characteristics. Such outstanding features enable them to undergo various chemical transformations producing low molecular weight polymeric materials with versatile applications. Our review discusses the synthesis of polyurethane from castor oil and provides an insight of its prominent applications of castor oil based polyurethane as hybrid materials, interpenetrating polymer networks, foams, adhesives, coatings. DOI: 10.1134/S1560090415040132 1

INTRODUCTION Facing challenges in handling and converting the renewable feedstock into applicable industrial materi als as well as tuning the properties of polymers based on desired performance, economic and environmen tal aspects have been of current interest of research. Natural oils, derived from vegetables are triglyceride esters of fatty acids consisting of chains from about 14 to 22 carbon atoms with 1–3 double bonds. These veg etable oils available in abundance constitute the single, largest, relatively cheaper, nontoxic, nondepletable, biodegradable family yielding materials that could effectively replace the traditional petrochemicals, which are used in the synthesis of desired polymer. Varieties of oil seeds as resources viz. linseed, soybean, coconut, palm, sunflower, and canola are few instances of them [1]. Amongst these varieties, castor oil is more com mercially prominent in designing of polymers [2]. In many countries with little or no petrochemical feed stock, castor oil has become handy as versatile renew able resource. Countries like India, China and Brazil supplies world’s largest demand of castor seeds for production of castor oil. Castor oil (botanical name: Ricinuscommunis is a member of purge family of Eurphorbiacae) is not a legume as the name implies. Traditionally, it is a kharif season crop. It comprises of esters of 12hydroxy9 octadecenoic acid (ricinoleic acid, ~89%), linoleic

1 The article is published in the original.

acid (~4.2%), oleic acid (~3.0%), stearic acid (~1%), palmitic acid (~1%), dihydroxystearic acid (~0.7%), linolenic acid (~0.3%), and eicosanoic acid (~0.3%) [3, 4]. Structurally these long pendant chains and fatty acids possess the hydroxyl groups, which impart effec tive thermosetting nature, flexibility, high strength elasticity and hydrolytic resistance to the network, whereas their unsaturation part serves as grafting cen ters during the polymer synthesis [5]. One can utilize such triglycerides to explore the wide area of polymers in foams, coatings, adhesives, elastomers and sealants [6]. Castor oil undergoes familiar organic reactions, i.e. epoxidation, hydrogenation and hydroxylation to form useful derivatives [7]. However, various limita tions of castor oil such as low modulus material due to low hydroxyl number, structural irregularity and low shear strength due to steric hindrances offer an offset to improve nanocomposites, interpenetrating net works [5, 6, 8–10]. Polyols derived from vegetable oils are most wide spread raw materials, which have found many impor tant applications [11]. This short review outlines the uniqueness of castor oil in polymer synthesis and attempts to cover a wider area of its applicability. How ever, the other chemicals that can be produced from castor oil have not been mentioned, because they are not yet produced in commercial quantities.

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higher saponification value than solventextracted oil. Chemically it is viscous, lighter in color, nonvol atile and nondrying oil with a bland taste and is sometimes used as a purgative. It has a slight charac teristic odor and tastes slightly acidic with a nause ating feeling. Relative to the other vegetable oils, it has a good shelf life, and it does not turn rancid unless subjected to excessive heat [4].

Extraction Castor plants grow in tropical and subtropical belts. The oil from castor seed (chemical structure shown in Scheme 1) had been isolated by mechanical pressing, where the seeds were crushed and then adjusted to low moisture content by warming in a steamjacketed vessel. Coldpressed castor oil has low acid value and iodine value and has slightly

O

O C O C

OH

O

O O C

OH OH Scheme 1.

Synthesis Route of Castor Oil Based Polyurethanes The exothermic reaction between isocyanates and alcohols is the most important reaction in polyure thane synthesis leading to the production of urethane [–NH–COO–] linkages. This reaction is catalyzed by tertiary amines with low steric hindrance, such as tri ethylenediamine and N,Ndimethyl cyclohexylamine,

and certain tin, lead, and mercury compounds like stannous octoate (tin 2ethylhexanoate). Scheme 2 presents the possible route of polymer synthesis where castor oil reacts with different kinds of di or polyisocyanates in the presence of catalysts at the temperature range of 60–75°C to give poly urethane. NCO

Castrol oil +

NCO IPDI Isophorone diisocyanate 60–75°C

O O C NCO OCONH

O O C

NCO

O

OCONH

O C

NCO OCONH Polyurethane(PU) Scheme 2.

Novel Applications of Castor Oil Based Polyurethanes Our short review discusses the applications of POLYMER SCIENCE

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polyurethanes as the main raw material synthesized from castor oil as hybrid materials, in interpenetrat

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ing polymer networks, coatings, polyurethane foams, and as adhesives. Hybrid materials. Polymerinorganic filler compos ites have attracted a substantial interest as hybrid mate rials in the field of polymer science. Incorporation of such natural or synthetic inorganic compounds as fillers in the polymer matrices enhances their mechanical properties, electrical conductivity and thermal resis tance [12, 13]. Mostly hybrid materials are synthesized in the absence of catalyst. Earlier polyurethane nano composites were prepared by solvent casting and in situ polymerization techniques. Amongst the various fillers used in this synthesis, clay [14], carbon nanotubes [15], TiO2 [16], silicates [17], zirconium phosphonates [20], fullerene and graphene nanostructures [18] are well known. For instance, R. Zhang et al. synthesized car bon nanotubes as conductive filler to improve the elec trical properties of polymer composites by using perco lation thresholds [15]. B. Finnigan et al. synthesized polyurethane nanocomposites via twinscrew extrusion and solvent casting [17]. Studies have reported few limitations of polyure thane derived from the inorganic fillers as they usually become immiscible, resulting in a serious phase sepa ration, and acquire low interfacial adhesion. However, hydrophobization of the particles adjust their polarity to adapt them to form the stable matrix materials [19, 20]. I. S. Ristic et al. synthesized castor oil based poly urethane hybrid materials with TiO2 nanoparticles as filler with different types of diisocyanates. It was found that aromatic diisocyanate exhibited higher reactivity and more rigidity than aliphatic or cycloaliphatic ones resulting in a more rigid structure. Studies also have revealed that addition of nanofillers, which decrease the glass transition temperature and thereby improve the elastic characteristics, imparts excellent damping properties over a wide range of temperatures. The mechanical properties (tensile strength and hardness) increase with addition of TiO2. However, step increase in elongation break was observed from ~60 to ~110% with the addition of TiO2 [21]. A. Kaushik et al. syn thesized polyurethane nanocomposites using castor oil and with modified clay as filler. It was observed that the interaction between the clay and polymer enhance the thermal and physical stability along with the mechanical properties [5]. B. G. ZanettiRamos et al. synthesized monodisperse polyurethane nanoparticles with average particle diameter ~300 nm using isophor one diisocyanate by miniemulsion technique in the presence of different surfactants and glycols as well as olive oil as the hydrophobic agent [22]. M. A. Corcu era et al. have shown synthesis of polyurethane from castor oil with the different chain extenders, petro chemicalbase butanediol and cornsugar based 1,3 propanediol in the presence of 1,6hexamethylene diisocyanate. It was found that the hydrogen bond for mation between the units is responsible for imparting low crystallinity and strain. Higher hardness was observed from about ~18 to ~52 Shore D (an unit used

for measuring higher hardness) in case of butanediol and about ~15 to ~49 Shore D in case of 1,3pro panediol. The tensile modulus ranged from ~12 to ~348 MPa in butanediol while ~9 to ~200 MPa in 1,3 propanediol and tensile strength from ~2.5 to ~6.6 MPa in butanediol and ~2 to ~8.5 MPa in 1,3pro panediol [23]. C. Liu et al. showed the dependence of the organic chain length of polyurethane, layered with zirconium phosphonates in the synthesis of hybrid molecules. They found that the longer organic chain length is the greater availability of the active points to interact with polyurethane molecule will be leading to the stronger interactions between the fillers and the matrix. They also confirmed that the –OH and –NH2 groups on the surface of the hybrid materials interact with polyurethane by the formation of strong hydro gen bonding. This leads to improved mechanical prop erties from ~16 (absence of filler) to ~22 MPa (pres ence of polyurethane/Zr(AE)4P (zirconium 2(2(2 (2aminoethylamino)ethylamino)ethylamino) eth ylphosphonate)), glass transition temperature from ~18 to ~23°C and water resistance, which attributes to better interfacial adhesion between fillers and polyure thane matrix [20]. K. C. Pradhan et al. synthesized hydrophobic polyurethane nanoparticles that were important and versatile biological precursors as potent detoxifiers [24, 25]. However A. Saralegi et al. synthe sized polyurethane bionanocomposites, which showed soft and hard phase transitions that allow using them as smart materials, where thermally activated shape memory properties are required. The tensile strength enhanced from ~240 to ~330 MPa and young’s modulus from ~10 to ~16 MPa [26]. Interpenetrating polymer networks. The thermally stable interpenetrating polymer networks (IPN) syn thesis involves chemical reaction between two poly mers with similar kinetics under controlled conditions and no phase separation [27, 28]. Yenwo et al. were the first to prepare the sequential IPN from castor oil using aromatic diisocyanate to form a polyurethane network [29, 30]. Studies have reported that such syn thesized IPNs may have possible applications in bio medicine, vibration dampening materials, abrasion and thermal resistant coatings [31]. H. Q. Xie et al. showed comparative approach to prepare polyure thane based vinyl/methacrylic polymers as efficient elastomers with better tensile strength [29]. Conduct ing IPNs synthesized by sequential polymerization of castor oil based polyurethane with polymers doped with acid and epoxy resins impart enhanced charac teristics. IPNs prepared from transesterified castor oil show improved dynamic mechanical properties, elec trical properties, tensile strength, storage modulus, thermal stability and damping properties due to more crosslinking density and due to an increase in hydroxyl content [27, 32, 33]. Foams. Foam being colloidal suspension is a matrix of internal phase (air or gases) in the continuous exter nal phase (polymeric material). The gas phase present POLYMER SCIENCE

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in voids or cells is referred to as the blowing or foaming agent. Depending on the chemical composition and the rigidity of the resin, it is used as a matrix. Also con sidering the type of crosslinking that exist between the molecules, the polymeric foams are classified as flexi ble, semiflexible (or semirigid) and rigid. L. Zhang et al. synthesized flameretarded polyure thane foams and found that the fire retardant incorpo rated in the castor oil molecule chain increased the thermal stability, compression strength and limiting oxygen index value of polyurethane foam by +5% [34]. M. Spontón et al. synthesized flexible polyurethane foams based on castor oil, which exhibited a consider able degradation rate [35]. X. Cao et al. synthesized polyurethane/montmorillonite nanocomposites with organically modified layered silicates (organoclays). Dispersion of montmorillonite in polyurethane has been found to improve the properties of polyurethane elastomers nanocomposites. It enhances the mechani cal properties, thermal stability and gas permeability [36]. The use of 100% castor oil in foam synthesis pro duces a semirigid material. D. S. Ogunniyi and W. R. O. Fakayejo prepared polyurethane foams with gradual high density, tensile strengths and low elonga tionatbreak due to the rigid crosslinks produced between aromatic diisocyanate and castor oil. In vary ing ratio of polyol and castor oil, as castor oil ratio increase the tensile strength rises from ~83 to ~140 KN/m2, compression set rises from 5 to 50%, while elongation at break decrease from 216 to 100% [37]. Coatings. Corrosion being surface phenomena causes structural deformation of object. Corrosion of metals leads to a huge adverse effects on the environ ment. Coating on metals provide a protective measure against oxygen, which reduces the rate of corrosion by lowering the availability of oxygen, H+ ion and water by metal surfaces [38–41]. Polyurethane based coat ings derived from oilbased polyols have proven good anticorrosion ability due to long aliphatic fatty triester chain of oils and the hydrophobicity of the constituent triglycerides further enhancing their physical and chemical properties. R. Gharibi et al. have shown that such polyure thane based compounds improve corrosion protection properties and showed excellent anticorrosive efficacy with a substantial lower corrosion current and higher corrosion potential [38]. D. Akram et al. developed a novel use of boron incorporation in polyester and polyurethane as modifier that enhanced structural and physicochemical characteristics, thermal stability as well as coating properties [41]. C.W. Chang et al. have synthesized 2package waterborne PU polyurethane (2KWPU) from Modified castor oil using different hardeners diisocyanates and found that addition of hardener diisocyanate impart excellent gloss, hardness and Tg [42]. S. Thakur et al. carried out comparative study of castor oil based hyperbranched polyurethane and monoglyceride based hyperbranched polyure thane and found that branching provides higher tensile POLYMER SCIENCE

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strength and scratch hardness comparing to linear polyurethane [1]. D. P. Patel et al. synthesized alkyd CEsICOPU blends on the mild steel panels and found excellent structural compatibility of the compo nents and chemical resistance in the blend, which formed a crosslinked polymer. They observed a signif icant improvement in hardness in blends. As the con centration of resin increases, the hydroxyl value is 113 KOH/gm, which gave maximum impact resis tance up to 197 lb (libra, the unit of weight), pencil hardness up to 9 H and scratch hardness up to 2.8 kg [43]. Another group report about preparing of surface coat ing formulations by blending of rosinified phenolic resin with castor oil. It was found that scratch hard ness, pencil hardness and resistance against chemicals are higher by almost two times than in case of polyure thane films prepared from 4,4'diphenylmethane diisocyanate as compared from 1,6hexamethylene diisocyanate due to its aromaticity and higher reac tivity [44]. Adhesives. Polyurethane based adhesives have found wide range of versatile applications depending on the different compositions of various polyols and isocyanate adducts. It was M.R. Patel et al. who synthesized castor oil based novel polyurethane adhesive for wood to wood and metal to metal bonding by using polyester polyols transesterified with castor oil to give castor oilpolyes ter polyols. These adhesives were reported to give lap shear strength in metal to metal up to 10 × 105 N/m2 and same adhesive gave up to 40 × 105 N/m2 in wood to wood [45]. K. P. Somania et al. prepared adhesives from different polyols with different isocyanate adducts. These glycols have higher hydroxyl value, which give excellent lap shear strength. They observed that the adhesive containing an aromatic isocyanate adducts cured faster almost twice than the aliphatic isocyanate adducts [46]. B. B. R. Silva et al. prepared polyurethane solventfree adhesives using only castor oil and TDI with or without catalysts. The solventfree castor oilbased polyurethane adhesives were more suitable for synthesizing foam in the mattress industry than for wood substrates due to their chemical nature similarity [47]. S. D. Desai et al. used polyester polyols in the preparation of polyurethane adhesives from potato starch and natural oils. Group found that castor oil based polyurethane adhesive give superior bonding properties compare to commercially available adhe sives used for wood joints. As NCO/OH ratio increase, curing time decreases, while bond length, leap strength and hardness of adhesives increases as higher NCO concentration provide a higher crosslinking degree. Increasing hydroxyl value is also responsible for these properties. Studies revealed that beyond cer tain limit of NCO/OH ratio reversible effects were observed in adhesive performance [48].

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NonIsocyanate Based Polyurethanes To prepare the crosslinked polyurethanes, polyols or isocyanates with functionality higher than two are used. However, the use of such diisocyanates should be avoided for several reasons as they are very harmful for human health due to acute poisoning [49–53]. Many efforts have thus been dedicated to minimize the amount of diisocyanates involved in the preparation of polyurethane or even better to develop nonphosgene

and nonisocyanate approaches to polyurethane syn thesis in order to improve their biodegradation and chemical recycling. According to one such proposed nonisocyanate methods oligomers terminated with five membered cyclic carbonate groups react with diamines (Scheme 3). The reaction product thus obtained con tains additional, hydroxyl groups in βpositions [49].

R1

OH

O O

O+ O

O Cyclic carbonate

O

R2 H2N

O

NH2

O

Diamines

OH

H N

O

1

R

H N

2

R

O A—with secondary hydroxyl groups + O

R1

H N

O

2

n

H N

R O

O HO

n

OH

B—with primary hydroxyl groups Scheme 3.

Alternatively, aliphatic polyurethane can also be prepared according to a chain growth polymerization method, employing ringopening polymerization of aliphatic cyclic urethanes. These polymers were obtained employing copolymerization of tetramethyl ene urea with six or five membered cyclic carbonate. Cyclic derivatives of carbonic acid (cyclic carbonates) are used for preparation of aliphatic polyurethanes. A. R. Mahendran et al. reported nonisocyanate urethane from a modified linseed oil and an alkylated phenolic polyamine from cashew nut shell liquid [50], while G. Rokicki and A. Piotrowska reported the syn thesis of polyurethane from diamines and diols using ethylene carbonate as a substitute for phosgene. V. Besse et al. [49] synthesized polyurethanes using new cyclocarbonate from isosorbide by carbonation to form better controlled and polydispersed linear and branched polymer with varying glass transition tem perature values meant for suitable applications [51]. B. Nohra reported the influence of medium engineer ing on the reaction of glycerol carbonate with dimethyl carbonate for the preparation of cyclic glycerylic car bonate bearing exocyclic urethane functions. Kinetic investigation was achieved by HPLC to determine the ratio of the products formed in the medium during the course of the reaction [52]. Halogenbased flame retardants have disadvantages of corroding the metal components and eluting toxic corrosive fumes of hydrogen halides during the combustion. Therefore halogenfree flameretardants containing phospho rous have attracted more attention for polymer syn

thesis in recent years. Z. Hosgöra et al. synthesised a novel carbonatemodified bis (4glycidyloxy phenyl) phenyl phosphine oxide according to Stöber method of preparation of phosphine oxide based spherical polyurethane/silica nanocomposites [53]. CONCLUSIONS Vegetable oils have already shown their versatility as vital source for polymers. Research in this arena is focused on improving such derived chemicals to the engineering and materials fields. Interdisciplinary efforts are necessary to improve the processing condi tions and materials performance. Uncertainty in terms of price and availability of petroleum, in addition to global, political and institutional tendencies toward the principles of sustainable development, urge chem ical industry to use a renewable resource in order to synthesize biobased chemicals and products. This review covers the synthesis of such versatile polymer as polyurethanes and highlights its perfor mance in environmentfriendly coatings, adhesives, paper coatings, and textile sizing. This is a very chal lenging field of research with unlimited future pros pects. However, researchers have focused their atten tion on agricultural products for manufacturing monomers and polymers to keep the environment cleaner and greener. POLYMER SCIENCE

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