starch based polyurethanes: a critical review updating recent...

R

Sr

FI

a

ARRAA

KSPAM

C

STvHFdsEH

h0

Carbohydrate Polymers 134 (2015) 784–798

Contents lists available at ScienceDirect

Carbohydrate Polymers

j ourna l ho me pa g e: www.elsev ier .com/ locate /carbpol

eview

tarch based polyurethanes: A critical review updatingecent literature

atima Zia, Khalid Mahmood Zia ∗, Mohammad Zuber, Shagufta Kamal, Nosheen Aslamnstitute of Chemistry, Government College University, Faisalabad 38030, Pakistan

r t i c l e i n f o

rticle history:eceived 20 May 2015eceived in revised form 11 August 2015ccepted 12 August 2015vailable online 18 August 2015

eywords:

a b s t r a c t

Recent advancements in material science and technology made it obvious that use of renewable feedstock is the need of hour. Polymer industry steadily moved to get rid of its dependence on non-renewableresources. Starch, the second largest occurring biomass (renewable) on this planet provides a cheap andeco-friendly way to form huge variety of materials on blending with other biodegradable polymers. Spe-cific structural versatility design for individual application and tailor-made properties have establishedthe polyurethane (PU) as an important and popular class of synthetic biodegradable polymers. Blending

tarcholyurethanedvancesodification of carbohydrates

of starch with polyurethane is relatively a developing area in PU chemistry but with lot of attractionfor researchers. Herein, various starch based polyurethane materials including blends, grafts, copoly-mers, composites and nano-composites, as well as the prospects and latest developments are discussed.Additionally, an overview of starch based polymeric materials, including their potential applications arepresented.

© 2015 Elsevier Ltd. All rights reserved.

ontents

1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7851.1. Starch—A brief overview . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7851.2. Reasons to choose starch for biodegradable blend materials . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7871.3. Applications and developments in starch based materials . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 787

2. Starch based polyurethanes (PUs) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .7872.1. Starch based polyurethane grafts and IPN networks . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7872.2. Starch based PU/WPU films and composites . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 790

2.2.1. Starch–PU/WPU films . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 790
2.2.2. Starch–PU/WPU composites or nano-composites . . . . . . . .
2.3. Starch mixed waterborne polyurethane ionomer dispersions . . . . .2.4. Starch modified polyurethane as biomedical material . . . . . . . . . . . . .

Abbreviations: PLA, Polylactic acid; OSA, Octenyl succinic anhydride; PCL, Polycaprolatarch/cellulose acetate; DMAEMA, Dimethylaminoethyl methacrylate; PLS, Plasticized sthermoplastic starch; PHB-HV, Polyhydroxybutyrate-hydroxyvalerate; PVA, Poly(vinyl

inyl alcohol; TA, Tartaric acid; AgNPs, Silver nano particles; WPU, Waterborne polyureMDI, 1,6- hexamethylene diisocyanate; IPN, Interpenetrating polymer network; SEM, Sourier transform infrared spectroscopy; DSC, Differential scanning calorimetry; DIC, Diffiffraction; NMR, Nuclear magnetic resonance; TGA, Thermogravimetric analysis; ITC, Isocattering; ATR-FTIR, Attentuated total reflectance Fourier transform infrared spectroscopSEM, Environmental scanning electron microscopy; POM, Osiris and Molinspiration (POexamethylene diisocyanate; IPDI, Isophorone diisocyanate.∗ Corresponding author. Tel.: +92 300 6603967; fax: +92 041 9200671.

E-mail address: [email protected] (K.M. Zia).

ttp://dx.doi.org/10.1016/j.carbpol.2015.08.034144-8617/© 2015 Elsevier Ltd. All rights reserved.

. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 791 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 792

. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 793

ctone; ST/St, Starch; KGM, Konjac glucomannan; CMS, Carboxymethyl starch; SCA,arch; PBSA, Poly(butylene succinate co-butylene) adipate; HA, Hydroxyapatite; TPS,alcohol); PBAT, Poly(butylene adipate co-terephthalate); SEVA-C, Starch/ethylenethane; PTD, Polypropyleneoxide toluene diisocyanate; TDI, Toluene diisocyanate;canning electron microscope; DMTA, Dynamic mechanical thermal analysis; FTIR,erential Interference Contrast; TEM, Transmission electron microscopy; XRD, X-raythermal titration calorimetry; AFM, Atomic force microscopy; DLS, Dynamic lighty; DMA, Dynamic mechanical analysis; CLSM, Confocal laser scanning microscopy;M) analyses; MAS-NMR, Magic angle spinning - Nuclear magnetic resonance; HDI,

dx.doi.org/10.1016/j.carbpol.2015.08.034

http://www.sciencedirect.com/science/journal/01448617

http://www.elsevier.com/locate/carbpol

http://crossmark.crossref.org/dialog/?doi=10.1016/j.carbpol.2015.08.034&domain=pdf

mailto:[email protected]

dx.doi.org/10.1016/j.carbpol.2015.08.034

F. Zia et al. / Carbohydrate Polymers 134 (2015) 784–798 785

3. Cyclodextrin based polyurethanes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7934. Conclusion and future perspective . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 795

. . . . . .

1

prboHMIrihcbpG

mitblbp2&

dnacE2tmpctb&M

wteldsL2ahrZpcdafi

References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

. Introduction

From the social and environmental standpoints, the worldwiderobable demands for substituting petroleum derived raw mate-ial by the renewable or bio-based resources in the production ofiodegradable raw materials are of great consequence and centerf public attention for sustainable developments (Cao, Zhang,uang, Yang, & Wang, 2003; Lu, Weng, & Zhang, 2004; Mohanty,isra, & Hinrichsen, 2000; Queiroz & Collares-Queiroz, 2009).

n the last decade, the preparation of novel materials by usingenewable resources (plants, animals, microbes etc.) has appealedncreasing interest. Creation of pollution-free degradable polymersave initiated an advancement of a novel direction in polymerhemistry that is raised during utilization of polymer wastesy burning and recycling, poses many economic and ecologicalroblems (Belgacem & Gandini, 2008; Ermolovich, 2005; Fomin &uzeev, 2001).

Natural polymers are the most promising candidate among theany kinds, and providing polymeric materials which degrades

nto green components after accomplishment of the period ofheir utilization. Natural polymers showed the advantages ofio-degradability, bio-compatibility, non-toxic, high reactivity,

ow cost, easy availability and so on, and therefore they haveeen counted as superb raw chemical substances for conservingetroleum resources and shielding the environment (Ermolovich,005; Fomin & Guzeev, 2001; Kim, Cho, & Park, 2001; Liaw, Huang,

Liaw, 1998; Mecking, 2004; Smith, 2005; Wool & Sun, 2005).Natural polymers (e.g. polysaccharides, proteins, RNA, DNA)

enote a particular class of materials amid the polymers based onatural resources existed from ancient times. These occur in natures macromolecules and may also take in the physically or chemi-ally modified natural polymers into this class (Avella, Buzarovska,rrico, Gentile, & Grozdanov, 2009; Imre & Pukánszky, 2013; Krylov,009; Thomas, Ninan, Mohan, & Francis, 2012). In view of the facthat their bio-compatibility, bio-degradability and resemblance to

acromolecules recognized by the human body, several naturalolymers for example polysaccharides (starch, alginates, chitin,hitosan, cellulose, heparin, chondroitin), proteoglycans and pro-eins (collagen, fibrin, gelatin, silk fibroin, keratin, eggshell mem-rane) are broadly used especially in biomedical field (Mogosanu

Grumezescu, 2014; Sionkowska, 2011; Yoo, Irvine, Discher, &itragotri, 2011; Zia, Zia, Zuber, Rehman, & Ahmad, 2015).An interesting family of synthetic polymer i.e. polyurethanes

ith different type of molecular design (i.e. poly-addition reac-ion among isocyanates, polyols and chain extenders) specific forach application has made it one of the most efficient polymers uti-ized for a variety of products e.g. flexible and rigid foams, medicalevices, sports goods, primer; adhesives, sealants, coatings, tougholids, elastomers etc. (Kim & Kim, 2005; Kim, Seo, & Jeong, 2003;iaw et al., 1998; Li, Vatanparast, & Lemmetyinen, 2000; Prisacariu,011; Zia, Barikani, Zuber, Bhatti, & Sheikh, 2008). New materi-ls produced from blending of polyurethane with native polymersave innovative properties and kept biodegradability hence envi-onmentally safe (Cao & Zhang, 2005a,b; Gao & Zhang, 2001; Lu,hang, Zhang, & Zhou, 2003; Zeng, Zhang, & Zhou, 2004). Variousolysaccharides such as cellulose, starch, alginates, heparin, glu-
omannan, dextrin etc. had been employed with polyurethanes toevelop bio-mimic synthetic materials for biomedical, food pack-ging, plastics, foams, as adsorbents for toxic compounds, textilenishes applications.
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 795

The development in synthetic polymers using constituentsfrom natural resources offers an innovative track to manufac-ture biodegradable polymers from renewable resources (Dang &Yoksan, 2015; Yu, Dean, & Li, 2006a). The object of bio-artificial orbio-synthetic blending is to create man-made blends that presentdistinctive structural and mechanical properties on conserving thebase of the particular properties of natural polymers and syntheticpolymers jointly rather than the single one (Cascone, 1997; Giusti,Lazzeri, Petris, Palla, & Cascone, 1994; Giusti, Lazzeri, & Lelli, 1993;Rogovina & Vikhoreva, 2006; Werkmeister, Edwards, Casagranda,White, & Ramshaw, 1998).

In common, native polymers called biopolymers are moreexpensive (in term of their purification process) than syntheticpolymers, however natural polymers are abundant and some maybe found at a fairly low cost (Vroman & Tighzert, 2009). Starch actu-ally lies among the one of the most abundant polysaccharide andprovides the primary source of carbohydrate in animals while it ispresent in plants as small insoluble granules. Herein, we reviewedstarch based polyurethanes materials such as grafts, composites,copolymers, dispersions, elastomers etc. focusing on their progres-sive developments and applications.

1.1. Starch—A brief overview

Starch, a native, renewable, abundant, low cost and biodegrad-able material is produced as a storage polymer by many granules ofplants, such as corn, wheat grains, cassava, cereal, rice, and potatoother than stems, roots, bulbs or legumes, nuts. Starch is orga-nized in discrete particles ranges from less than 1 �m to morethan 100 �m of varying regular or irregular shapes depending uponthe source. However, according to botanical origin the shapes,size, composition, morphology and superamolecular arrangementof granules may vary (Ahmed, Tiwari, Imam, & Rao, 2012; LeCorre, Bras, & Dufresne, 2010; Tang, Mitsunaga, & Kawamura,2006).

Molecules of starch are consisted of hundreds or thousands ofglucose monomers, are linked to one another through C1 oxygenas glucosidic bond. The starch is essentially composed of two mainpolysaccharide units of amylose and amylopectin linked togetherwith �-d-(1–4) and/or �-d-(1–6) linkages (Fig. 1). Amylose is a lin-ear molecule (Mw = 1–1.5 million) with an extended helical twistcomprises 15–20% of starch whereas amylopectin, a branchedmolecule (Mw = 50–500 million) constitutes the major part ofstarch (Hii, Tan, Ling, & Ariff, 2012; Manners, 1989; Morrision,Miligan, & Azudin, 1984; Sajilata, Singhal, & Kulkarni, 2006;Takerda, Maruta, & Hizukuri, 1992). This unique regular arrange-ment imparts crystallinity to starch granules. The crystallinity isreflected from the assembly of amylopectin while amylose unitsform an amorphous region, arranged irregularly within orderedamylopectin region (Blanshard, 1987).

The physical characteristics of starch, its stability and phasetransformations, say from starch granules to gels (brittle/rawpasta → soft, cooked pasta) are openly linked to this molecularorder. Yet, interpretation of the comprehensive structure of starchneeds precisely advanced research tools and techniques. However,the starch obtained from different plant sources varies in its gelling
ability attributed to the concentration of amylose and amylopectinthat directly control the water holding capacity of starch. Higherthe concentration of amylose more the starch will convert into gelstructure (Fig. 2) (Brown, 2014; Cornuéjols & Pérez, 2010).

786 F. Zia et al. / Carbohydrate Polymers 134 (2015) 784–798

Fig. 1. Structure of amylose and amylopectin unit in starch.

Fig. 2. (a) Schematic of starch gelatinization process based on liquid crystalline approach. (b) Different stages in extrusion processing of thermoplastic starch (Perry & Donald,2002; Waigh, Gidley, Komanshek, & Donald, 2000). Reproduced with permission from Elsevier.

Polym

e(drdtSH22Y2

1

ggasasmvgwpenst1

1

fhtarfi&3EettD2pcr

cmaecp&aF

F. Zia et al. / Carbohydrate

The native starch is not actually thermoplastic in nature, how-ver the addition of water or poly-alcohols de-structured the starchdiminishing the intermolecular H-bonding) and converted it intoegradable thermoplastic starch (TPS) or plasticized starch mate-ial. The TPS have ease of mechanical and chemical modification orerivability along with low cost, abundance and biodegradabilityhus providing alternative to plastic and packaging industry (Ayana,uin, & Khatua, 2014; Bemiller & Whistler, 2009; Cao, Chang, &uneault, 2008; Choi, Kim, & Park, 1999; Galliard, 1987; Halley,005; Le et al., 2010; Mathew & Dufresne, 2002; Mohanty et al.,000; Ratto, Stenhouse, Auerbach, Mitchell, & Farrell, 1999; Wang,ang, & Wang, 2003; Whistler, Bemiller, & Paschall, 1984; Averous,004).

.2. Reasons to choose starch for biodegradable blend materials

After cellulose, starch is one of the most plenteous hetero-eneous polysaccharide formed by plants as water in-solubleranules. Two important features that made starch particularly

versatile and unique material is, firstly, its biodegradability i.e.tarch degrades into organic acids and sugars that acts as renew-ble feedstock for thermoplastics, chemicals and biofuels andecondly, its structural amenability i.e. as a major industrial rawaterial, starch is chemically and/or enzymatically processed into

ariety of products for subsequent use in various industries, ran-ing from food (especially high-fructose and glucose syrups) toashing detergent industries. Being a major contributor to bio-lastic industry with the advantages of less cost, easy availability,nvironmentally benign proved to be a convincing alternative toon-renewable raw material. All these brief points capture thetarch to be used as potential biodegradable material for indus-rial sector (Ahmed et al., 2012; Hobel, 2004; Marchal, 1999; Zobel,992).

.3. Applications and developments in starch based materials

A massive range of natural starches with extremely distinctunctionalities are already on the market (Swinkels, 1985). Starchave been found many uses in non-food sectors, most notably inhe sizing and coating of paper, as a special mulch films, as andhesive, as a green strength additive component to simple mate-ial, for the flushable sanitary product, as a thickener while inood sector its role as gelling agent and stabilizer are also signif-cant (Deis, 1998; Finkenstadt & Tisserat, 2010; Light, 1990; Lu

Xu, 2009; Manek et al., 2005). The chief users of starch i.e.,0% are the paper, cardboard, and corrugating industries in theuropean Union (Frost and Sullivan Report, 2009). Established lit-rature has reported the polymer grafting onto starch nanocrystals,hermoplastic starch modified with PU microparticles using tradi-ional technology and by reactive extrusion (Labet, Thielemans, &ufresne, 2007; Chen, Zhang, Zhang, Fan, & Wu, 2012; Zhang et al.,013a,b). Effects of a novel compatible interface structure on theroperties of starch–PCL composites and preparation and appli-ation of starch nanoparticles for nanocomposites have also beeneported (Liao et al., 2014; Le Corre & Angellier-Coussy, 2014).

Plasticized starch (TPS) blends, nanocomposites and/or viahemical modifications of native starch, materials with adequateechanical strength, flexibility, and water impediment properties

re used for commercial packaging and user products (Mauriziot al., 2005; Ozdemir & Floros, 2004). Possible future applicationsould consist of foam loose-fill packaging and injection-molded
roducts for example ‘take-away’ food containers (Babu, O’Connor,
Seeram, 2013). Antimicrobial features are also imparted in starchnd cellulose by various bio active polymers or metal oxides (Coma,reire, & Silvestre, 2014).

ers 134 (2015) 784–798 787

Starch based materials covered various industrial sectors withtheir enormous properties and ecofriendly nature. Hence Table 1reviewed the potential applications and developments of variousstarch based materials.

2. Starch based polyurethanes (PUs)

It had already been proved that addition of starch granules insynthetic polymers reinforced the polymer’s mechanical propertiesby providing a filler effect. The elongation to break and modulusincreased by increasing starch content whereas the tensile prop-erties decreased due to the stiffening effect of starch. But highwater sensitivity (hydrophilic character) and brittleness of starchlimited its usage (Lim, Lin, Rajagopalan, & Seib, 1992; Santayanon& Wootthikanokkhan, 2003; St-Pierre, Favis, Ramsay, Ramsay, &Verhoogt, 1997; Vaidya, Bhattacharya, & Zhang, 1995).

Several methods have been adopted to overcome these lim-itations in starch based bio-degradable materials including themost effective one preparation of starch blends with hydrophobicsynthetic polymers e.g. PCL, polyurethanes etc. and addition of plas-ticized starch or chemically modified starch to other compounds,and starch-polymer nanocomposites (Elodie, Zheng, Michel, & Luc,2008; Koenig & Huang, 1995; Loubna, Thomas, Amar, & Mustapha,2010; Santayanon & Wootthikanokkhan, 2003).

Ha and Broecker (2002) established that incorporating polyesterbased polyurethane (PCL, BDO and MDI) into potato starch can,somewhat, improved mechanical properties or water resistance ofthe resulting materials. A well dispersion of starch granules in PUwas observed with starch contents up to 20 wt%, above that valuephase separation between components occurred that leads to poormechanical properties (Ha & Broecker, 2002).

2.1. Starch based polyurethane grafts and IPN networks

The brittle nature triggered by the fairly high glass transitiontemperature (Tg) and free volume relaxation and retro-gradationover time along with insufficient beta transition confines the con-sumption of starch in plastics (Wang et al., 2003). Kweon, Cha, Park,and Lim (2000) produced starch-g-polycaprolactone copolymer byreaction of NCO terminated PCL based prepolymer using corn starchat a proportion of starch to NCO/PCL of 2:1. On grafting 35–38 wt%of NCO/PCL prepared with TDI and MDI on to starch, both copoly-mers same have Tg i.e. 238 ◦C. Conversely, when TDI was replacedwith HDI, the value of Tg found to be 195 ◦C. The degradation tem-perature changed on grafting NCO/PCL corresponding to the typeof diisocyanate used. The high stability is related with starch-g-polycaprolactone using MDI intermediates instead of using HDIand TDI. It was established that the Tg values of HDI based starch-g-urethane copolymers (Fig. 3) decreased with rising the ratio ofprepolymer and depended on the crosslinking effect of prepoly-mer either between two starch chains or due to strong H-bondingbetween molecules, which in different ways influenced the mobil-ity of starch modified urethane (Barikani & Mohammadi, 2007).Hydrophobicity of the grafts increased with increasing amount ofurethane prepolymer. Owing to well dispersion and compatibility,these modified starch based grafts could be employed as filler instarch based polyethylene (PE).

A cross-linked starch based polyurethane plastics were obtainedby direct polymerization of corn starch (with 28% of amylosecontents) and oligomeric diisocyanate i.e. PTD. Series of these cross-linked starch based PU was synthesized by varying NCO/OH ratios
i.e. 1.4, 0.75, 0.63, 0.50 and 0.25. The amorphous cross-linkedstructure with elastic properties linked with two glass transitiontemperatures (Tgs) of −60 ◦C and 35 ◦C and showed tremendousreduction in hydrophilicity. The product formed with NCO/OH


Table 1Different techniques used for characterization of starch based materials with their potential applications in various fields.

Sr. no Name Techniques used for characterization Potential applications Reference

1 PLA–starch FT-IR, DSC Potentially used in food packaging García et al. (2012)2 Gelatin–OSA starch DIC Modify food products and to

encapsulate flavor or bioactivecompounds

Wu and McClements (2015)

3 PCL/starch FT-IR, DSC, SEM Promising use in bone tissueengineering applications

Ghavimi, Ebrahimzadeh,Shokrgozar, Solati-Hashjin, andOsman (2015)

4 ST/KGM FT-IR, XRD, SEM, DSC Potentially used as edible foodfilms and coatings

Chen et al. (2008b)

5 CMS & chitosan TGA, FT-IR, SEM, XRD, NMR Used as colon drug carrier Assaad, Wang, Zhu, and Mateescu(2011)

6 Starch/DMAEMA SEM A matrix used for severalproduction processes

Raafat, Araby, and Lotfy (2012)

7 Gelatin–starch SEM Used in production of reasonablygood films and capsules

Zhang et al. (2013a,b)

8 PLS/(PBSA) SEM, CLSM For the design of controlled releaseactive materials

Khalil, Galland, Cottaz, Joly, andDegraeve (2014)

9 Cellulose fiber–starch/PVA FT-IR, SEM, TGA Exceptionally used for foodpackaging

Priya, Gupta, Pathania, and Singha(2014)

10 Starch–clay XRD For preservation of foods especiallybakery products

Barzegar, Azizi, Barzegar, andHamidi-Esfahani (2014)

11 TPS/PLA/Clay SEM, TEM, XRD, DMA, DSC A new green material used inpackaging

Ayana et al. (2014)

12 PHB–HV/maize starch FT-IR, DSC, SEM, XRD Used as packaging material Reis et al. (2008)13 Starch/PVA/cellulose nanofibrils SEM, XRD, AFM Green substitute for application in

food packaging and conservationPanaitescu, Frone, Ghiurea, andChiulan (2015)

14 Starch/PBAT/TA FT-IR, SEM, NMR Suitable for use in food packaging Olivato, Müller, Carvalho,Yamashita, and Grossmann (2014)

15 Starch, polymethacrylic acid &polysorbate 80

FT-IR, TEM, ITC, DLS For the controlled delivery of Doxfor treatment of drug resistantbreast cancer

Shalviri et al. (2012)

16 Chitin & starch ATR-FTIR, TGA, AFM Matrix applied in functional foodcoatings and packaging

Salaberria, Diaz, Labidi, andFernandes (2015)

17 TPS & chitin/chitosan FT-IR, XRD, SEM, DMA Used industrially in food packaging Lopez et al. (2014)18 TPS–chitosan FT-IR, XRD, TGA, DMA Potential application in the food

industry, e.g. as edible filmsDang and Yoksan (2015)

19 Chitosan–starch FT-IR, SEM Drug carrier for the delivery ofbis-desmethoxy curcumin analog

Subramanian, Francis, andDevasena (2014)

20 Alginate/alginate-resistant starch FT-IR, XRD, DSC, SEM As a controlled release carrier forthe food grade peptide, nisin.

Hosseini et al. (2014)

21 Starch–calcium alginate DSC, FT-IR, SEM For encapsulation of antioxidants Lopez-Cordoba, Deladino, andMartino (2014)

22 Starch–alginate FTIR For agrochemical delivery system Singh, Sharma, and Gupta (2009)23 Alginate–sago starch–AgNP TGA, SEM, TEM Potential and economical wound

dressing materialArockianathan, Sekar, Sankar,Kumaran, and Sastry (2012)

24 Starch–chitosan SEM, XRD Used for the electrochemicaldevices

Shukur and Kadir (2015)

25 SEVA-C/SCA SEM Bone plates, screws to drugdelivery carriers, tissueengineering scaffolds

Marques, Reis, and Hunt (2002)

26 Starch/clay ESEM,POM, MAS–NMR Food packaging applications Avella et al. (2005a,b)27 TPS/PCL DSC, DMTA Used as low cost biodegradable

material as environmentallyfriendly material in packaging

Averous et al. (2000)

28 Chitosan/cassava starch/gelatin XRD, FTIR Used for the conservation of freshor minimally processed fruits andvegetables

Zhong and Xia (2008)

29 SEVA-C and SEVA-C/HA SEM Used for Orthopaedic applications,as tissue engineering scaffolds

Gomes, Reis, Cunha, Blitterswijk,and Bruijn (2001)

riwahC

gpa

30 Starch–fluoropolymers SEM, FT-IR, DMA

31 Starch–WPU

32 Castor oil starch–WPU FT-IR, DSC, SEM

atio equal to 1.4 exhibited, in contrast to starch, great reductionn moisture absorption. This factor, at relative humidity of 75%,

as decreased to 72%, and at 43%, by as much as 97% which wasttributed to replacement of polar OH groups by aromatic uret-ane units and less polarity of oligopropylene oxide chains (Da Róz,urvelo, & Gandini, 2009).

Starch modification by chemical derivatisation is anotherood option to improve the TPS based materials. Starch–urethaneolymers via chemical modification of potato starch with urethanend urea derivative of HDI (substitution efficiency 70%) were

For bone implants Pereira et al. (2014)As a sizing agent for paper coating Guo et al. (2011)As a packaging material Lu et al. (2005b)

synthesized. The presence of additional urethane and urea bondsas short chain modifier altered the properties of urethane–starchderivatives rather than the usual mono-alkyl isocyanate modifier.Acceptable bulk hydrophobic properties were associated withstarch polymers of DS ∼ 1.6–1.8, making them suitable candi-date for manufacturing by means of reactive extrusion processes
(Wilpiszewska & Spychaj, 2007). A successful modification of starchby using three different types of poly caprolactone (PCL) polyols-PCL diol, PCL triol and PCL tertol was reported recently (Fig. 4).This work elaborated that with increasing OH numbers of polyols

F. Zia et al. / Carbohydrate Polymers 134 (2015) 784–798 789

Moh

ihttwioc

io�pldhhuct

Fa

Fig. 3. Preparation of starch based polyurethane (Barikani &

n PUP, the compatibility between the hydrophilic starch andydrophobic polyurethane was improved, that actually decreasedhe water sensitivity of starch. The hydrophobicity, toughness andhermal stability of modified starch were simultaneously increasedhile crystallinity decreased due to increased degree of cross link-

ng between starch and PU that actually lowered the interactionf the starch–starch chains. Thus, this modified starch could beonsidered as material of potential applications (Zhang et al., 2012).

Vinyl-trimethoxysilane (VTMS) modified starch moleculesncorporated into the waterborne polyurethane to study its effectn biodegradation of WPU (Fig. 5a). The higher weight loss in-amylase solution showed degradation of starch as well asolyurethane segments in the network. Maximum value of weight

oss was consistent with the amount of added starch that pre-ict independent degradation phenomenon. An increase in theardness of blend depended on crosslinking density and strongydrogen bond between starch and WPU while tensile mod-
lus and strength increased with increasing amount of starchontents. Overall, starch molecules seemed to act as a multifunc-ional crosslinks bridging the polyurethane molecules in network
ig. 4. Structure of PCL polyols and preparation of CP2, CP3 and CP4. PU2, PU3 and PU4 rnd CP4 represent starch modified by PU2, PU3 and PU4, respectively (Zhang et al., 2012)

ammadi, 2007) reproduced with permission from Elsevier.

structure (Fig. 5b) that not only increase miscibility but alsobiodegradability of samples (Lee & Kim, 2012).

Although the use of hydrophobic synthetic polymers to over-come the brittleness and water sensitivity is a good way but anotherproblem arises i.e. the lack of miscibility of starch and hydropho-bic polymers during composite formation. Semi interpenetratingnetworks formation is an efficient to enhance the miscibility oftwo components in a composite. Literature already provided thesemi-IPNs of nitrocellulose (Zhang & Zhou, 1999), nito-konjacglucomannan (Gao & Zhang, 2001) and benzyl-konjac glucoman-nan (Lu & Zhang, 2002; Lu et al., 2003) with castor oil derivedpolyurethanes. So here a semi-IPNS of benzyl derivative of starch(BS) with castor oil based polyurethane was reported that showedgood miscibility and mechanical properties. Within 5–70% concen-tration of BS the miscibility and mechanical properties increaseddue to intermolecular interactions between polyurethane andbenzyl-starch, however higher concentration of BS often lead to
phase separation between the components. An increasing BS con-centration in IPNs depicted a morphological change from elastomertoward plastics (Cao & Zhang, 2005a,b).
epresent PUP prepared by PCL diol, PCL triol and PCL tetrol, respectively; CP2, CP3. Reproduced with permission from Elsevier.

790 F. Zia et al. / Carbohydrate Polym

F(

2

vpsacbafb&22

aasDKCLP

mw(

ig. 5. (a) Structure of vinyl modified starch, (b) crosslinked PU/starch compositeLee & Kim, 2012). Reproduced with permission from Elsevier.

.2. Starch based PU/WPU films and composites

Continuous reduction in cost and the control of toxicolatile organic compounds emission have driven the waterborneolyurethanes (WPU) as a chief alternative to conventional organicolvent borne PU. Due to its wide-ranging applications, non-toxicnd non-flammable nature, tunable physical properties, low vis-osity at high molecular weight, high-quality bio-compatibility andio-degradability, good applicability and is very suitable for variouspplications. Waterborne polyurethanes and poly (urethane-urea)ormulations are slowly substituting the typical organic solvent-orne (DMF, MEK, acetone) PU products since 1960s (Ayres, Orefice,

Sousa, 2006; Cao, Li, Bao, Bao, & Dong, 2007; Delpecha & Coutinho,000; Jeon, Jang, Kim, & Kim, 2007; Wicks, Wicks, & Rosthauser,002).

Safety and environmental friendly consideration, WPU can bepplied to leather and textile finishing, floor coverings, primers,dhesives, coatings, pressure sensitive adhesives, ink binder ando on (Brinkman & Vandevoorde, 1997; Coogan, 1997; Duecoffre,iener, Flosbach, & Schubert, 1997; Jung, Kim, Kang, & Kim, 2010;im, Kim, & Jeong, 1994; Kuan et al., 2005; Lamba, Woodhouse, &ooper, 1998; Lei, Zhong, Lin, Li, & Xia, 2014; Lin & Hsieh, 1997;u & Larock, 2008; Meng, Lee, Nah, & Lee, 2009; Park et al., 2009;athak, Sharma, & Khanna, 2009; Petrie, 2000).

Recently, from natural polymers and WPU, a series of compositeaterials have been made using casting and evaporating methodsith the objective of amplifying the properties of both components

Cao et al., 2008; Chen, Liu, Chen, Chen, & Chang, 2008b; Ha &

ers 134 (2015) 784–798

Broecker, 2002; Lu, Tighzert, Berzin, & Rondot, 2005a; Lu, Tighzert,Dole, & Erre, 2005b; Wang & Zhang, 2008; Yu et al., 2006b).

Waterborne polyurethanes have taken an important place ingroup of materials for surface coating industry. Herein, by takingthe advantages of several beneficial properties of WPU, a surfacesizing agent (composite) was prepared by mixing starch with WPUfrom TDI and IPDI following the pre-polymerization method. TheTDI made WPU stronger and hard while IPDI reduced the yellowchange of WPU. Results indicated that the gloss, water resistancean folding resistance of papers sized with starch/WPU compos-ite coating were quite much higher than usual starch sized paper.A definite decrease in ink absorption and a manifold increase inmechanical properties rendered this novel surface sizing agent fordevelopmental prospects in future (Guo, Li, & Wang, 2011).

2.2.1. Starch–PU/WPU filmsA series of compression molded sheets of TPS and water-

borne polyurethanes were obtained from 2,4-tolylene diisocyanate(TDI), poly-1,4-butylene glycol adipate (PBA), and 2,2-bis-(hydroxylmethyl) propionic acid (DMPA). With the contents ofWPU of range 5–30 wt%, the tensile strength of molded blend sheetswere higher than those of starch based PU while the elongationat break is higher than TPS and were between the pure compo-nents, indicating that addition of WPU could efficiently improvethe mechanical characteristics of TPU. Increasing contents of WPUalso led to an increase in water resistance. These upgrading inperformance properties suggested a strong interactions in themolded sheets. The WPU played a vital role in creation of novelmorphology and performance development of blends, offering apromising applications in the area of biodegradable materials (Wu& Zhang, 2001a). Comparable results have also been observed inthe casting blend systems comprising of starch and WPU fromTDI, poly(oxypropylene glycol) and DMPA. Whereas with the addi-tion of 80–90 wt% contents of starch in the blend films increasedthe mechanical properties, water resistivity, thermal stability andlight transmittance as compared to pure starch films (Wu & Zhang,2001b).

Solution casting blend sheets obtained from TPS and polyesterbased waterborne polyurethanes with different molar ratios ofNCO/OH suggested that the thermal and mechanical characteristicsof TPS/WPU blends depend on the starch contents and microstruc-ture of polyurethane. The Tg of the blend with 20 wt% contents ofstarch are higher than corresponding WPU and all other blends(50 wt% starch), indicating that the starch restricted the mobility ofsoft segment in PU matrix due to strong hydrogen bonding inter-actions. The higher molar ratios of NCO/OH (1.75) in WPU2 leadingto the formation of hard segment ordered structure thus exhibitedhigher tensile strength than WPU1 (lower molar ratios of NCO/OH).However, when starch content was lower than 50 wt%, the starchblends from WPU1 (20 wt% of starch and 80 wt% of WPU) showedhigher mechanical properties (tensile strength 27 MPa and elonga-tion at break 949%) than from that of WPU2 because addition ofappropriate starch contents not only provide reinforcement effectto the material by sealing the sot segment matrix but also blockedthe formation of hard segment ordered structure (Cao et al., 2003).

Another breakthrough is the development of vegetable oil basedpolymer materials that have launched the environmentally benignagricultural re-sources as raw material of the polymer industry.Vegetable derived WPU combined all properties such as biodegrad-ability, less toxicity, no emission of VOC, no use of non- renewableresources etc. (Alam, Akram, Sharmin, Zafar, & Ahmad, 2014; Erhan,2005). Usually polyols used in the synthesis of PU or WPU are
basically of petroleum derived resources but Lu et al. synthesizedwaterborne polyurethane dispersions from rapeseed oil (Lu et al.,2005a) and castor oil (Lu et al., 2005b) polyols. Casting films ofWPU (rapeseed oil) dispersions with TPS exhibited higher tensile

Polym

saisioc

su3aocovogbetfMtaca6wdia

atrwyAato

ctph&oactpoeM

wtm%3iWoo


trength (85 to 480%), toughness (1.8 to 7.1 MPa) and elongationt break (2.8 to 4.1 MPa) with lower than 20 wt% of PU, however,ncreasing contents of PU above this value lower the miscibility oftarch and WPU leading to phase separation. The hydrogen bondingnteractions between urethane groups of PU and hydroxyl groupsf starch inclined to lower the interfacial tension between the twoomponents, rendering them more compatible (Lu et al., 2005a).

In case of starch and castor oil derived WPU blends, the tensiletrength first increased and reached to maximum value of 5.1 MPap to 15 wt% contents of WPU then decreased to 2.6 MPa with0 wt% contents of WPU. Same trend is also observed for elongationt break which increased from 116 → 176% with 0–10 wt% contentsf WPU and then decreased to 140% with further increase in WPUontents up to 30 wt%. The toughness displayed the tendency anal-gous to tensile strength with maximum value of 5.2 MPa i.e. thealues are significantly influenced by tensile strength. The strengthf TPU/WPU after 30 days aging was increased attributed to retro-radation of starch in the course of storage while elongation atreak decreased after this period but still exhibited flexibility i.e.longation at break was 92 to 121%. Here an important point ishis trend in mechanical properties of blend was quite differentrom TPS/PCL and TPS/PLA (Averous, Moro, Dole, & Fringant, 2000;

artin & Avérous, 2001) in which elongation at break decreased byhe addition of PLA and PCL in blends. The surface study and waterbsorption analysis of TPS blends with WPU from rapeseed oil orastor oil indicated an increased hydrophobicity (surface or bulk)nd water resistance. The value of water uptake decreased from0% to 25% by 50% addition of rapeseed oil in PU formulation. Itas obvious that from above results that addition of vegetable oilerived WPU and its hydrogen bond interaction with TPS played an

mportant part in enhancing the performance of blends for pack-ging industries (Lu et al., 2005a,b).

In 2007, polyurethane films were obtained by utilizing starchs a core polyol component along with PEG. The starch contents inhese films vary between 30 and 50 wt% while the NCO/OH molaratio ranged from 0.5 to 1.1. The mechanical analysis revealed thatithin an increase in starch constituent the final tensile stress and

oung modulus increased 20 times with 1.1 molar ratio of NCO/OH.dditionally, bending tests results showed a rise in breaking stressnd bending modulus with increasing the above indicated parame-ers. In both tensile and bending tests, strain rate had a major effectn the mechanical characteristics (Kim, Kwon, Yang, & Park, 2007).

All these work did not put the importance of TPS/polyaprolactone blends in shadow. The last decades fully exploredhe attraction of starch and PCL blends which is due to higherformance of PCL in terms of biodegradability, flexibility,ydrophobicity and availability (Carioca, Arora, Selvam, Tavares,

Kennedy, 1996; Koenig & Huang, 1995). Yet, the core drawbackf starch/PCL is owing to a deficiency of adhesion within starchnd PCL due to their changed polarity leading to poor mechani-al properties at higher starch content (Avella et al., 2000). Variousechniques or processes have been exploited to increase the com-atibility either by introducing reactive functional group on the PCLr starch segment or by adding compatibilizers in the blends (Avellat al., 2000; Choi et al., 1999; De Carvalho, Curvelo, & Agnelli, 2001;ani, Tang, & Bhattacharya, 1998).Recently, casting films from thermoplastic starch and PCL-based

aterborne polyurethane blends were reported that interpretedhat tensile strength of the films at first increased and moved to

aximum value of 3.89 MPa with WPU contents of less than 20 wt in blends but then decreased with increase in WPU contents up to0–50 wt% (due to phase separation) whereas elongation at breaks

ncreased regularly with maximum value of 886% with increasingPU contents from 10 to 50 wt% that was in contrast to previ-

us findings (Averous et al., 2000). The water absorbance behaviorf the blend films decreased with an increase in WPU contents

ers 134 (2015) 784–798 791

attributed to waterproof nature of WPU. The water uptake valuesdecreased sharply from 70% to 31% with 50 wt% WPU contents. Soprecisely, this work offered a simple and novel way to overcomethe limitations of PS for its various applications (Cao et al., 2008).

2.2.2. Starch–PU/WPU composites or nano-compositesAs it was already mentioned, incorporation of starch reinforced

the properties when blended with synthetic polymer. So, born outof the rising importance of nanocomposites, novel nano materialfrom natural polymers, termed as green bio-nano-composites werereported. Platelet-like nano-crystal of starch obtained from acidhydrolysis (e.g. H2SO4) not only inherited all the benefits of naturalpolymers, but also showed a reinforcing function as filler in com-posites by feature of their rigidity analogous to those customaryinorganic nano-fillers such as ex-foliated layered silicate, addition-ally, optimizing the mechanical, thermal, barrier and absorptionproperties (Angellier, 2005; Kristo & Biliaderis, 2007; Lin, Huang,Chang, Anderson, & Yu, 2011; Zou et al., 2011).

The native starch granules have nano sized semicrystallineblockets and upon acid hydrolysis treatment these blockets can beseparated (Tang et al., 2006). Natural starch have crystalline regionbetween 15 and 45% whereas this percent crystallinity dependsupon the double helixes formed by amylopectin side chains. Thestarch nanocrystals in contrast to cellulose nanocrystals are not100% crystalline. The crystallinity in StNs is 45% depending uponplant source (LeCorre, Bras, & Dufresne, 2011).

Starch and PU micro-particles (liquid–NCO terminated uret-hane oligomer) composite sheets were developed via compressionmolding, consuming water as plasticizer and chain extender for PUprepolymer. The conversion rate of isocyanates units was found tobe almost 100% with the formation of urethane linkages betweenoligourethane units and starch matrix. Mechanical properties of thematerial, particularly, that comprised 10 wt% of PU when comparedto un-modified starch had an increase in breaking stress by 20% andin elongation at break by 62%. A decrease in water absorption ofmaterial by 13% was found by adding PU relative to starch. Mod-ification of water-plasticized starch with PU micro-particles candefinitely be termed an environment-benign product, as it involvedlarge portion made-up of bio-degradable starch without using anyorganic solvents (Wu, Wu, Tian, Zhang, & Cai, 2008).

Using waterborne polyurethane (matrix) and starch nanocrys-tals (nano-filler), bio-nanocomposites material were prepared. Themechanical properties such as elongation, modulus and tensilestrength were simultaneously enhanced from 2 wt% to 5 wt% ofstarch nano crystals (StNs) contents, provided by the uniform dis-persion of StNs and physical interaction between StN nano-fillerand WPU matrix. Conversely, the higher StNs loading level (8 wt%)restricted the mechanical performance because of self-aggregationof StNs. The noticeable progress of mechanical performance wascredited to enduring stress of rigid StN and stress transferringmediated through great interaction on the interface between StNnano-filler and WPU matrix. Besides, chemical grafting was provednot to be in support of enhancing strength and elongation owing tohindering the creation of physical interaction going on the StN sur-face and intensifying the network density of nano-composites. Sothe new green bio-nanocomposite within low level of starch nano-crystals provided superior properties for enormous applications(Chen et al., 2008a).

An advanced methodology in the usage of nanocrystals asfillers is the investigation of a synergistic reinforcement of water-borne polyurethane by both starch nano-crystals and cellulosewhiskers. A system of WPU:1% StN:0.4% CW displayed a far well
reinforcing effect than all other tested WPU/StNs and WPU/CWcomposites. A respective increase by 135%, 252% and 136% of ten-sile strength, Young’s modulus and tensile energy at break of thenano-composites were demonstrated a significant improvement

7 Polym

iceaotnp

imahwppahbitte

acgdtoeasswFbh

p

92 F. Zia et al. / Carbohydrate

n mechanical properties while the elongation at break showedonsistency with pure WPU. Strong hydrogen bonding interactionsxisted both between the nanofillers and between the nanofillersnd the hard segments of WPU matrix, leading to the improvementf the mechanical and thermal properties. This new green approacho prepare polymer nano-composites with great performance viaatural nanocrystals and whiskers collectively were definitely haverospective applications (Wang, Tian, & Zhang, 2010).

Aggregation and sedimentation of starch nanocrystals is anmportant issue during its preparation that results in wastage of

aterial. Zou et al. (2011) elaborated a method that inhibited theggregation and sedimentation of starch nanocrystals even at aigh loading level. Starch nanocrystals (StNs) was incorporated intoaterborne polyurethane (WPU) matrix at high loading levels torepare WPU–StN nano-composites via solution casting. The incor-oration of 10 wt% of StNs enhanced tensile strength i.e. 31.1 MPand modulus than neat WPU. The WPU–StN containing 30 wt% StNsad the highest Young’s modulus (204.6 MPa), which was enhancedy ca. 6720% related to good dispersion of StNs nano-phase and

ts stiffening effect. The active surface and rigidity of StN facili-ated formation of an interface for stress transfer and contributedo higher stress-endurance by strong matrix filler interactions (Zout al., 2011).

Waxy maize starch reinforced WPU nano-composite materi-ls of high strength and elasticity were successfully prepared viaasting and evaporating. Hydrolysis of waxy maize starch granulesenerated the crystalline platelets of the starch nano-crystals withiameter of 25 to 40 nm by treatment with H2SO4. It was detectedhat the pre-dispersing process participated in the well dispersionf starch nano-crystals into the WPU matrix and effective strength-ning of the composites through strong interactions between fillernd matrix as aggregates. The mechanical properties of compositeshowed an improvement in Young’s modulus (0.6–3.2 MPa), ten-ile strength (10.4–24.1 MPa) and having high elongation at breakithin the range of 1148–1136% with only 1 wt% contents of StNs.

inally, these WPU based composites retained good thermal sta-
ility and offered a new environmentally benign way to formulateigh strength WPU based elastomer (Wang & Zhang, 2008).
A series of new oxidised starch cross-linked waterborneolyurethanes (PUs) nanocomposites were made by reaction

Fig. 6. Preparation route of APU/St (Travinskaya et al., 2

ers 134 (2015) 784–798

between PU prepolymer and oxidised corn starch. In the presenceof oxidised starch, a significant difference in the composition andmorphology of PUs and an improvement in mechanical proper-ties of the final products with respect to the unmixed polymerwere observed. The two fold effects of the improved morphologyand inter-molecular cohesion in the system showed that tensilestrength of the modified PU film comprising 10 wt% oxidised starchwas up to 14·9 MPa and water absorption was 4·9% (Yang, Zhang,Rong, & Qiu, 2012).

2.3. Starch mixed waterborne polyurethane ionomer dispersions

Polyurethane ionomers (PUI) made a difference when comparedto traditional polyurethane due to the formation of stable waterdispersion (Travinskaya and Savelyev, 2006). Starch-containingaqueous anionic polyurethane dispersions (APU/St) were pre-pared by the introduction of an aqueous starch solution into ananionic oligo-urethane solution. A comparison of APU/St/15% dis-persions and mechanical mixture of APU and starch (APU + St)suggested a new type of structural elements–polymer–polymermicro-domains existence in APU/St films due to substantial inter-molecular interactions in the system that predetermined thedegradation of the APU/St system as a whole unlike the mixedAPU + St (Fig. 6). Much higher adhesion of micro-organisms B. sub-tilis to the surface of APU/St was observed than APU matrix. TheAPU/St based films displayed higher tensile strength in compari-son with St and are illustrated by increased values of elongation atbreak, hydrophilicity and considerably greater capability to endurean acid/alkaline hydrolysis than that of APU matrix. These novelpolyurethane ionomer–starch based materials have high techno-logical properties with the ability of degradation (Travinskaya,Savelyev, & Mishchuk, 2014).

Knowing the relationship between the rheological behaviorsand the mechanical properties for the development and appli-cation of natural polymer-based composite materials is valuable.Isothermal rheological investigation of glutar-aldehyde cross-
linked WPU/starch aqueous dispersions system was done withsmall-amplitude oscillatory shear flow experiments as a functionof starch concentration. A sudden increase in the elastic storagemodulus (G′), the viscous loss modulus (G′′), the complex dynamic
014). Reproduced with permission from Elsevier.

Polym

vcfutcfa

2

plwapcpimbf2

idmbfTddiPh(

3

raigEo8(s2

iic&crtaec&S&


iscosity (�′′) and the loss tangent (tan ı) was observed during theuring process of the dispersions, as a result of the formation of aractal polymer gel. Using the Winton–Chamber theory, the val-es of the power law exponent (n) and the gel strength (Sg) athe gel point indicated that with an increase of starch content theross-linked WPU/starch gels underwent a transition from weakractal to strong elastic ones, exhibiting increased tensile strengthnd Young’s modulus (Wang, Lue, & Zhang, 2009)

.4. Starch modified polyurethane as biomedical material

By using a multilayer film extrusion technique, a breathableolyurethane membrane was manufactured. The outer support

ayers were of polyethylene-based of the monolithic membraneas unacceptably sticky. Starch being a suitable anti-blocking

gent was outperforming mineral fillers. However, starch incor-oration decreased the membrane permeability toward moisture,onsistent with the results of Maxwell model for randomly dis-ersed impermeable spherical filler. A near-spherical particle shape

ndicated by fitting the Wagner–Sillar model confirmed the imper-eable nature of the starch particles. This unexpected result can

e rationalized by assuming a highly crystalline or glassy natureor the starch domains (Pecku, van der Merwe, Rolfes, & Focke,007).

Polyurethane based asymmetric membranes as wound dress-ng with the use of acetic starch (ASt) was reported in 2013. Theense skin layer supported by a porous sub-layer of PU-based asym-etric membranes was exhibited high adsorption capability (avoid

acterial penetration and de-hydration of the wound bed) and per-ormed drainage of the wound by capillary and tissue regeneration.he porosity and internal sub-structure of PU/ASt membranes wasepending on the ratio of the components i.e., PU and fillers. Fasteregradation behavior of PU/ASt composite membrane was exam-

ned by in vitro degradation test studies when compared to neatU. This PU/ASt based asymmetric membranes made in this studyave ability for application as a perfect wound dressing materialLiu, Hu, Xu, Shou, & Yao, 2013).

. Cyclodextrin based polyurethanes

Cyclodextrins (CDs), belong to class of cyclic oligosaccha-ides, produced from starch degradation by an enzymatic processt a reasonably low price. The degradation of starch involvesntramolecular transglycosylation reaction through cyclodextrinlucanotransferase enzyme (Bilensoy, 2011; Del Valle, 2004;aston & Lincoln, 1999; Tonkova, 1998). These native cyclicligosaccharides (just like crown ethers) are comprised of 6, 7, or

or even from 9 to 19 d(+)-glucose units linked by �-1,4-linkages�-(1 → 4)-linked d-glucopyranose sub-units), and termed corre-pondingly as �-, �-, or �-CD (Li & Loh, 2008; Ritter & Tabatabai,004; Roy, Bajpai, & Bajpai, 2011; Szetjli, 1998).

The main interest of this torus-shaped ring CD lies due tots hydrophilic exterior and a hydrophobic cavity and its abil-ty to produce non-covalent supramolecular complex (inclusionomplexes) with numerous compounds (Del Valle, 2004; Ritter

Tabatabai, 2004; Roy et al., 2011; Szetjli, 1998). Consequently,yclodextrins (CDs) are utilized as drug carriers, additives or toemoval of cholesterol in food, as stabilizer in food, auxiliaries inextile processes, cosmetics elements, encapsulation of fragrancend flavor molecules, separating agents, mass transfer promoters,
nzyme promoters, environmental protection agents (remove toxicompounds) or sensors for organic molecules (Chin, Mohamad,
Bin Abas, 2010; Akcakoca Kumbasara, Akduman, & Cay, 2014;hirasawa, Ueda, Appell, & Goto, 2013; Xiao, Dudal, Corvini, Pieles,

Shahgaldian, 2011; Voncina & Vivod, 2013).

ers 134 (2015) 784–798 793

The usage of CDs is facilitated to produced polymer and copoly-mer material incorporated by cyclodextrins (Harada, Takashima,& Yamaguchi, 2009; Heidel & Schluep, 2012; Mohamed, Wilson,Headley, & Peru, 2011; van de Manakker, Vermonden, van Nostrum,& Hennink, 2009; Zhou & Ritter, 2010).

One approach is fabrication of cyclodextrin based polyurethanematerials by reaction of CDs with diisocyanates to form networkstructure. TDI and HDI based polyurethane and CDs inclusioncomplexes were characterized and used as adsorbent, as binderfor active pharmaceutical ingredients and molecular imprinting(Abbate, Bassindale, Brandstadt, & Taylor, 2012; Chin et al., 2010;Hishiya, Asanuma, & Komiyama, 2002; Khomutov & Donova, 2011;Rohrbach, Zemel, & Koch, 1992; Sreenivasan, 1996; Xiao et al.,2011; Yamasaki, Makihata, & Fukunaga, 2006).

Hydroxypropyl-�-cyclodextrin (HP-�-CD) based polyurethanemembranes were synthesized and the effect of CD addition onsorption performance of PU membrane was tested to separatedbenzene/cyclohexane (Bz/Cx) mixture. The HP-�-CD acts not onlyto enhance the sorption selectivity but also enhancing the per-meation flux on Bz/Cx mixtures. The hybrid membranes areactually benzene selective so the sorption rate for benzene washigh, however, membranes with lower molecular weight polyolshowed better absorption than higher one (Lue & Peng, 2003).Recently blending of �-CDs-PU polymer with polysulfone wasdone to synthesize composite membranes. Addition of low �-CD-PU concentration improved the flux and sorption capacitywithout disturbing rejection ability of polysulfone membranes.This was attributed to fewer surface pores and chemical link-ing between OH or NH and sulfonyl backbone of polysulfone(Adams, Nxumalo, Krause, Hoek, & Mamba, 2012).

�-Cyclodextrin based polyurethane polymer was effectivelyused to extract aromatic amines from water. The CD ability to forminclusion complex facilitate the better performance of solid phaseextraction process so high recovery rate was observed (Bhaskar,Aruna, Jeevan, & Radhakrishnan, 2004).

Nebulized spray pyrolysis (NSP) derived MWNTs based CD poly-mer were successfully synthesized by polymerizing HMDI/TDI with�-CD and functionalized NSP–MWNTs. The spongy structure ofresultant polymer improved thermal stability with less than 5% ofMWNTs contents while the spongy surface diminishes by increas-ing the content of NSP-MWNT from 1 to 5%. FTIR, SEM, DSC, and TGAconfirmed the polymerization and crosslinking between MWNTand CD. This novel polymer could efficiently be used to removeorganic pollutants from water bodies (Salipira et al., 2008).

It was found that �-CD based PU copolymer sorbents showedtunable heterogeneous sorption properties toward phenolic dyesand naphthenates (NAs) in aqueous solution under the specificconditions. Various mole ratio of �-CD/diisocyanate i.e. 1:1, 1:2,1:3 were used to synthesize different copolymer sorbents. Thepresence of �-CD inclusion sites in the copolymer structure aredetermined to be the core sorption point for phenols and naph-thenates over the formation of defined inclusion complexes. Resultsshowed that the diisocyante domains in copolymer adsorbent sig-nificantly absorb p-nitrophenol (PNP) rather than phenolphthalein,and NAs (Mohamed et al., 2011).

A new category of hybrid organic/inorganic molecular catalystwas developed with �-CDs-polyurethane polymer. The excellentcomplexing properties of �-CDs-PU along with good stability andgreat catalytic activity, was proved to be a suitable alternativeas solid–liquid phase-transfer catalyst (solid–liquid PTC) to themore complicated crown ethers (Kiasat & Nazari, 2012a,b). Thisnovel hybrid polymer was coated successfully over Fe3O4 magnetic
nanoparticle and assessed being solid–liquid PTC and molecularhost system for SN reactions of benzyl halides (C6H5CH2X) withazide, thiocyanate, acetate anions, and cyanide in water. Character-ization and testing results demonstrated the successful synthesis


F e polyr

onbbC

HCrTm(

bgtTicTTd

ig. 7. Schematics of the adsorption interaction of phthalates with the polyurethaneproduced with permission from Elsevier.

f the polymer catalyst and showed that this water insolubleanomagnetic polymer catalyst offered good stability, easy accessi-ility, and excellent catalytic activity without the formation of anyyproduct thus provide an effective substitute to the water solubleD (Kiasat & Nazari, 2012a,b).

A novel lipopolysaccharide (LPS) adsorbent was prepared fromMDI based polyurethane and �-CD copolymerization. This �-D-PU copolymer showed higher adsorption capacity against LPSemoval from DNA than usual hydrophobic and cationic adsorbent.he 99% recovery of DNA established that the �-CD-PU copoly-er restrained the adsorption of DNA thus showed high selectivity

Sakata, Uezono, Kimura, & Todokoro, 2013).Electrospun thermoplastic polyurethane (TPU) nanofibers

ased �-CD membrane material was developed in order to investi-ate the subsequent effects of �-CD on fiber properties. This study ishe key incentive behind being an initial step of the advancement ofPU based textile materials functionalized by CDs for possible usesn medical textiles industry. The phenolphthalein test method indi-
ated higher phenolphthalein absorbance for 8% TPU-CD than 10%PU-CD due to their greater surface area as they retain finer fibers.hese outcomes prove that �-CD within nanofibers of TPU canevelop inclusion complexes (Akcakoca Kumbasara et al., 2014).
mer on (a) interfacial and (b) inclusion spaces of the adsorbents (Okoli et al., 2014)

Recently starch based polyurethane polymers along with �-cyclodextrin were used as adsorbent for phthalate removali.e. a toxic pollutant from plastic industry. The materialshowed excellent adsorption that could be linked to multipleadsorbent–adsorbent interactions e.g. hydrogen bonding, �–�stacking, and pore-filling. The ease of synthesis, low cost of rawmaterial and effective adsorption capacity made it excellent choicefor phthalate removal (Fig. 7) from aqueous environment (Okoli,Adewuyi, Zhang, Diagboya, & Guo, 2014).

Polyurethane crosslinked �-CD materials were synthesizedusing two different diisocyanate i.e. HDI, CDI. It was observed thatproperties and texture of the resultant material changed by therapid or drop wise addition of diisocyanate. The characterizationof material established that higher crosslinking was attained viadrop wise addition of diisocyanate, however, higher crosslinkinglower the inclusion sites of CDs. Thus rapid or drop-wise additionof cross-linker provided materials with tunable physico-chemicalproperties for diverse sorptive uses (Mohamed, Wilson, & Headley,
2015).
A series of CDs based polyurethanes were developed in avery short time using microwave heat assistance technique. Threemostly used dissocyanates i.e. TDI, MDI and HDI were employed

Polym

wmaocrohmm

4

wimmciwtPtpfeiwbDwpa

R

A

A

A

A

A

A

A

A

A

A

A

A

A


ith all three forms of CDs (�, �, �). The resultant CD-polyurethaneaterials are characterized and categorized as organic-soluble

nd water-insoluble depending upon appropriate stoichiometryf CDs and diisocyanates. Whereas, the greater contents of diiso-yanates resulted in organic-insoluble polymers. This novel andapid way to synthesize microwave assisted series of CDs-PUffered materials with high adsorbent capacity than conventionaleating process with possible applications to remove undesirableaterials, toxic compounds and encapsulation of fragrance/colorolecules (Biswas, Appell, Liu, & Cheng, 2015).

. Conclusion and future perspective

Biological polymers are closer to the reality of discovering aorld without conventional synthetic polymers that was never

magined ever before. Currently bio-based polymer industry isainly focusing on manufacturing bio-versions of prevailing poly-er products. Starch being an abundant, biodegradable, low

ost, non-toxic etc. natural polymer was desirable for develop-ng eco-friendly material industry. A huge variety of starch blends

ith different polymers, organic, inorganic compounds coveringhe major industrial sectors e.g. paper and packaging industry.olyurethane from synthetic origin diversified the industrial sec-or with its inherent biodegradability, superior mechanical andhysical properties. So to made independency on non-renewableeed stock and to fill up the individual drawbacks associated withach class of materials, joint adventure of these materials aremportant. Advanced trend of utilization of nano-reinforcements

as also bloomed in biopolymer based synthetic polymers i.e.io-nanocomposites. Nano fillers CNT, graphene, nano-clays, 2-

layered materials, starch nano crystals and cellulose whiskersith bio-based polymers matrix could boost a large number ofroperties leading to a way functional bio-material for enormouspplications.

eferences

bbate, V., Bassindale, A. R., Brandstadt, K. F., & Taylor, P. G. (2012). Anartificialorganosilicon receptor. Polymer Chemistry, 3, 2018–2027.

dams, F. V., Nxumalo, E. N., Krause, R. W. M., Hoek, E. M. V., & Mamba, B. B. (2012).Preparation and characterization of polysulfone/�-cyclodextrin polyurethanecomposite nanofiltration membranes. Journal of Membrane Science, 405–406,291–299.

hmed, J., Tiwari, B. K., Imam, S. H., & Rao, M. A. (2012). Starch-based polymericmaterials and nanocomposites: Chemistry, processing, and applications (1st ed.).Boca Raton, FL: CRC Press (Chapter 1 & 2).

kcakoca Kumbasara, E. P., Akduman, C., & Cay, A. (2014). Effects of �-cyclodextrinon selected properties of electrospun thermoplastic polyurethane nanofibers.Carbohydrate Polymers, 104, 42–49.

lam, M., Akram, D., Sharmin, E., Zafar, F., & Ahmad, S. (2014). Vegetable oil basedeco-friendly coating materials: A review article. Arabian Journal of Chemistry,7(4), 469–479.

ngellier, H. (2005). Nanocristaux d’amidon de maïs cireux pour applicationscomposites. In Material sciences. Grenoble, France: University Joseph Fourier(PhD thesis).

rockianathan, P. M., Sekar, S., Sankar, S., Kumaran, B., & Sastry, T. P. (2012).Evaluation of biocomposite films containing alginate and sago starchimpregnated with silver nano particles. Carbohydrate Polymers, 90, 717–724.

ssaad, E., Wang, Y. J., Zhu, X. X., & Mateescu, M. A. (2011). Polyelectrolyte complexof carboxymethyl starch and chitosan as drug carrier for oral administration.Carbohydrate Polymers, 84, 1399–1407.

vella, M., Buzarovska, A., Errico, M. E., Gentile, G., & Grozdanov, A. (2009).Eco-challenges of bio-based polymer composites. Materials, 2, 911–925.

vella, M., De Vlieger, J. J., Errico, M. E., Fischer, S., Vacca, P., & Volpe, M. G. (2005).Biodegradable starch/clay nanocomposite films for food packagingapplications. Food Chemistry, 93(3), 467–474.

vella, M., Errico, M. E., Laurienzo, P., Martuscelli, E., Raimo, M., & Rimedio, R.(2000). Preparation and characterisation of compatibilisedpolycaprolactone/starch composites. Polymer, 41(10), 3875–3881.

vella, M., Vlieger, J. J. D., Errico, M. E., Fischer, S., Vacca, P., & Volpe, M. G. (2005).
Biodegradable starch/clay nanocomposite films for food packagingapplications. Food Chemistry, 93, 467–474.
verous, L. (2004). Biodegradable multiphase systems based on plasticized starch:A review. Journal of Macromolecular Science—Polymer Reviews C, 44(3),231–274.

ers 134 (2015) 784–798 795

Averous, L., Moro, L., Dole, P., & Fringant, C. (2000). Properties of thermoplasticblends: Starch–polycaprolactone. Polymer, 41, 4157–4167.

Ayana, B., Suin, S., & Khatua, B. B. (2014). Highly exfoliated eco-friendlythermoplastic starch (TPS)/poly (lacticacid)(PLA)/clay nanocomposites usingunmodified nanoclay. Carbohydrate Polymers, 110, 430–439.

Ayres, E., Orefice, R. L., & Sousa, D. (2006). Influence of bentonite type inwaterborne polyurethane nanocomposite mechanical properties.Macromolecular Symposia, 245–246, 330–336.

Babu, R. P., O’Connor, K., & Seeram, R. (2013). Current progress on bio-basedpolymers and their future trends. Progress in Biomaterials, 2(8), 1–16.

Barikani, M., & Mohammadi, M. (2007). Synthesis and characterization ofstarch-modified polyurethane. Carbohydrate Polymers, 68, 773–780.

Barzegar, H., Azizi, M. H., Barzegar, M., & Hamidi-Esfahani, Z. (2014). Effect ofpotassium sorbate on antimicrobial and physical propertiesof starch–claynanocomposite films. Carbohydrate Polymers, 110, 26–31.

Belgacem, M. N., & Gandini, A. (2008). Monomers, polymers and composites fromrenewable resources (1st ed.). Amsterdam: Elsevier (Chapter 3).

Bemiller, J. N., & Whistler, R. L. (2009). Starch: Chemistry and technology (3rd ed.).New York/Whistler: Academic Press.

Bhaskar, M., Aruna, P., Jeevan, R. J. G., & Radhakrishnan, G. (2004).�-Cyclodextrin–polyurethane polymer as solid phase extraction material forthe analysis of carcinogenic aromatic amines. Analytica Chimica Acta, 509,39–45.

Bilensoy, E. (2011). Cyclodextrins in pharmaceutics, cosmetics and biomedicine:Currentand future industrial applications. Hoboken, NJ: Wiley.

Biswas, A., Appell, M., Liu, Z., & Cheng, H. N. (2015). Microwave-assisted synthesisof cyclodextrin polyurethanes. Carbohydrate Polymers, 133, 74–79.

Blanshard, J. M. V. (1987). In T. Galliard (Ed.), Starch granule structure and function:A physicochemical approach in starch properties, and potential (pp. 16–54). UK:John Wiley.

Brinkman, E., & Vandevoorde, P. (1997). Waterborne two-pack isocyanate-freesystems for industrial coatings. Progress in Organic Coatings, 34, 21–25.

Brown, A. (2014). Understanding food: Principles and preparations (5th ed., pp.31–57). USA: Cengage Learning.

Cao, X., & Zhang, L. (2005a). Miscibility and properties of polyurethane/benzylstarch semi interpenetrating polymer networks. Journal of Polymer Science, B:Polymer Physics, 43, 603–615.

Cao, X., & Zhang, L. (2005b). Effects of molecular weight on the miscibility andproperties of polyurethane/benzyl starch semi-interpenetrating polymernetworks. Biomacromolecules, 6(2), 671–677.

Cao, X., Chang, P. R., & Huneault, M. A. (2008). Preparation and properties ofplasticized starch modified with poly(caprolactone) based waterbornepolyurethane. Carbohydrate Polymers, 71, 119–125.

Cao, X., Li, C., Bao, H., Bao, Q., & Dong, H. (2007). Fabrication of strongly fluorescentquantum dot-polymercomposite in aqueous solution. Chemistry of Materials,19(15), 3773–3779.

Cao, X., Zhang, L., Huang, J., Yang, G., & Wang, Y. (2003). Structure propertiesrelationship of starch/waterborne polyurethane composites. Journal of AppliedPolymer Science, 90, 3325–3332.

Carioca, J. O., Arora, H. L., Selvam, P. V. P., Tavares, F. C. A., & Kennedy, J. F. (1996).Industrial utilization of starch and its derived products in Brazil. Starch/Starke,48(9), 322–326.

Cascone, M. G. (1997). Dynamic–mechanical properties of bioartificial polymericmaterials. Polymer International, 43, 55–69.

Chen, G., Wei, M., Chen, J., Huang, J., Dufresne, A., & Chang, P. R. (2008).Simultaneous reinforcing and toughening: New nanocomposites ofwaterborne polyurethane filled with low loading level of starch nanocrystals.Polymer, 49, 1860–1870.

Chen, J., Liu, C., Chen, Y., Chen, Y., & Chang, P. R. (2008). Structural characterizationand properties of starch/konjac glucomannan blend films. CarbohydratePolymers, 74, 946–952.

Chen, X., Zhang, Y., Zhang, P., Fan, B., & Wu, Q. (2012). Thermoplastic starchmodified with polyurethane microparticles: Effects of hydrophilicity ofpolyurethane prepolymer. Starch—Stärke, 64(4), 255–262.

Chin, Y. P., Mohamad, S., & Bin Abas, M. R. (2010). Removal of parabens fromaqueous solution using �-cyclodextrin crosslinked polymer. InternationalJournal of Molecular Sciences, 11, 3459–3471.

Choi, E., Kim, C., & Park, J. J. (1999). Structure–property relationship in PCL/starchblend compatibilized with starch-g-PCL copolymer. Journal of Polymer Science,B: Polymer Physics, 37(17), 2430–2438.

Coma, V., Freire, C. S. R., & Silvestre, A. J. D. (2014). Recent advances on thedevelopment of antibacterial polysaccharide-based materials. Polysaccharides,2014, 1–46.

Coogan, R. G. (1997). Post-crosslinking of water-borne urethanes. Progress inOrganic Coatings, 32, 51–63.

Cornuéjols, D., & Pérez, S. (2010). Starch: A structural mystery. Science in School, 14,22–27.

Da Róz, A. L., Curvelo, A. A. S., & Gandini, A. (2009). Preparation and characterizationof cross-linked starch polyurethanes. Carbohydrate Polymers, 77, 526–529.

Dang, K. M., & Yoksan, R. (2015). Development of thermoplastic starch blown filmby incorporatingplasticized chitosan. Carbohydrate Polymers, 115,
575–581.
De Carvalho, A. J. F., Curvelo, A. A. S., & Agnelli, J. A. M. (2001). A first insight oncomposites of thermoplastic starch and kaolin. Carbohydrate Polymers, 45,189–194.

Deis, R. C. (1998). The new starches. Food Product Design, 7, 34–56.

http://refhub.elsevier.com/S0144-8617(15)00775-4/sbref0005























































































































































































































































































































































































































































































































































































































































































































































































































































7 Polym

D

D

D

E

E

EE

F

F

F

GG

G

G

G

G

G

G

H

H

H

H

H

H

H

H

I

J

J

K

K


el Valle, E. M. M. (2004). Cyclodextrins and their uses: A review. ProcessBiochemistry, 39(9), 1033–1046.

elpecha, M. C., & Coutinho, F. M. B. (2000). Waterborne anionic polyurethanesand poly(urethane-urea)s: Influence of the chain extender on mechanical andadhesive properties. Polymer Testing, 19, 939–952.

uecoffre, V., Diener, W., Flosbach, C., & Schubert, W. (1997). Emulsifiers with highchemical resistance: A key to high performance waterborne coatings. Progressin Organic Coatings, 34, 200–205.

aston, C. J., & Lincoln, S. F. (1999). Modified cyclodextrins. Scaffolds and templatesfor supramolecular chemistry. Singapore: World Scientific Publishing.

lodie, H., Zheng, D., Michel, B., & Luc, A. (2008). Polyurethanes based on castor oil:Kinetics, chemical, mechanical and thermal properties. MacromolecularMaterials and Engineering, 293, 922–929.

rhan, S. Z. (2005). Industrial uses of vegetable oil. Champaign, IL: AOCS Press.rmolovich, O. A. (2005). Structure and properties of biodegradable film materials

based on compatibilized polyethylene/starch compositions. PolimernyjZhurnal, 27(3), 174–180.

inkenstadt, V. L., & Tisserat, B. (2010). Poly(lactic acid) and Osage Orange woodfiber composites for agricultural mulch films. Industrial Crops and Products, 31,316–320.

omin, V. A., & Guzeev, V. V. (2001). Biologically degradable polymers. PlasticheskieMassy, 2, 2–46.

rost & Sullivan Report. (2009). Global bio-based plastic market, M4AI-39 (Chapter5).

alliard, T. (1987). Starch properties and potential. New York, NY: Wiley.ao, S., & Zhang, L. (2001). Molecular weight effects on properties of

polyurethane/nitrokonjac glucomannan semi-interpenetrating polymernetworks. Macromolecules, 34(7), 2202–2207.

arcía, N. L., Lamanna, M., D’Accorso, N., Dufresne, A., Aranguren, M., & Goyanes, S.(2012). Iodegradable materials from grafting of modified PLA onto starchnanocrystals. Polymer Degradation and Stability, 97, 2021–2026.

havimi, S. A. A., Ebrahimzadeh, M. H., Shokrgozar, M. A., Solati-Hashjin, M., &Osman, N. A. A. (2015). Effect of starch content on the biodegradation ofpolycaprolactone/starch composite for fabricating in situ pore-formingscaffolds. Polymer Testing, 43, 94–102.

iusti, P., Lazzeri, L., & Lelli, L. (1993). Bioartificial polymeric materials: A newmethod to design biomaterials by using both biological and syntheticpolymers. TRIP, 1, 261–270.

iusti, P., Lazzeri, L., Petris, S., Palla, M., & Cascone, M. G. (1994). Collagen basednew bioartificial polymeric materials. Biomaterials, 15, 1229–1233.

omes, M. E., Reis, R. L., Cunha, A. M., Blitterswijk, C. A., & Bruijn, J. D. D. (2001).Cytocompatibility and response of osteoblastic-like cells to starch-basedpolymers: Effect of several additives and processing conditions. Biomaterials,22, 1911–1917.

uo, Y., Li, S., & Wang, G. (2011). Properties of waterborne polyurethane/starchcomposite surface sizing agent. Advanced Materials Research, 317/319,15–18.

a, S. K., & Broecker, H. C. (2002). The crosslinking of polyurethane incorporatedwith starch granules and their rheological properties: Influence of starchcontents and reaction conditions. Macromolecular Materials Engineering, 288,569–577.

alley, P. J. (2005). Thermoplastic starch biodegradable polymers. In R. Smith (Ed.),Biodegradable polymer for industrial applications (pp. 140–162). Cambridge/UK:Woodhead.

arada, A., Takashima, Y., & Yamaguchi, H. (2009). Cyclodextrin-basedsupramolecular polymers. Chemical Society Reviews, 38(4), 875–882.

eidel, J. D., & Schluep, T. (2012). Cyclodextrin-containing polymers: Versatileplatforms of drug delivery materials. Journal of Drug Delivery, 2012, 17.

ii, S. L., Tan, J. S., Ling, T. C., & Ariff, A. B. (2012). Pullulanase: Role in starchhydrolysis and potential industrial applications. Enzyme Research, 12,1–14.

ishiya, T., Asanuma, H., & Komiyama, M. (2002). Spectroscopic anatomy ofmolecularly-imprinting of cyclodextrin. Evidence for preferential formationofordered cyclodextrin assemblies. Journal of the American Chemical Society,124, 570–575.

obel, C. F. V. (2004). Access to biodiversity and new genes from thermophiles byspecial enrichment methods. Iceland: University of Iceland (Ph.D. thesis).

osseini, S. M., Hosseini, H., Mohammadifar, M. A., German, J. B., Mortazavian, A.M., Mohammadi, A., et al. (2014). Preparation and characterization of alginateand alginate-resistant starch microparticles containing nisin. CarbohydratePolymers, 103, 573–580.

mre, B., & Pukánszky, B. (2013). Compatibilization in bio-based and biodegradablepolymer blends. European Polymer Journal, 49, 1215–1233.

eon, H. T., Jang, M. K., Kim, B. K., & Kim, K. H. (2007). Synthesis andcharacterizations of waterborne polyurethane–silica hybrids using sol–gelprocess. Colloids and Surfaces A: Physicochemical and Engineering Aspects, 302,559–567.

ung, D. H., Kim, E. Y., Kang, Y. S., & Kim, B. K. (2010). High solid and highperformance UV cured waterborne polyurethanes. Colloids and Surfaces A:Physicochemical and Engineering Aspects, 370, 58–63.

halil, F., Galland, S., Cottaz, A., Joly, C., & Degraeve, P. (2014). Polybutylene
succinate adipate/starch blends: A morphological studyfor the design ofcontrolled release films. Carbohydrate Polymers, 108, 272–280.
homutov, S., & Donova, M. V. (2011). Nanodimer cyclodextrin ligands withhighaffinity to steroids. The Journal of Inclusion Phenomena and MacrocyclicChemistry, 70, 353–357.

ers 134 (2015) 784–798

Kiasat, A. R., & Nazari, S. (2012a). Application of �-cyclodextrin–polyurethane as astationary microvessel and solid–liquid phase-transfer catalyst: Preparation ofbenzyl cyanides and azides in water. Catalysis Communications, 18, 102–105.

Kiasat, A. R., & Nazari, S. (2012b). Magnetic nanoparticles grafted with�-cyclodextrin–polyurethane polymer as a novel nanomagnetic polymerbrush catalyst for nucleophilic substitution reactions of benzyl halides inwater. Journal of Molecular Catalysis A: Chemical, 365, 80–86.

Kim, B. K., Kim, T. K., & Jeong, H. M. (1994). Aqueous dispersion of polyurethaneanionomers from H12MDI/IPDI, PCL, BD, and DMPA. Journal of Applied PolymerScience, 53, 371–378.

Kim, B. K., Seo, J. W., & Jeong, H. M. (2003). Morphology and properties ofwaterborne polyurethane/clay nanocomposites. European Polymer Journal, 39,85–91.

Kim, B. S., & Kim, B. K. (2005). Enhancement of hydrolytic stability and adhesion ofwaterborne polyurethanes. Journal of Applied Polymer Science, 97, 1961–1969.

Kim, C. H., Cho, K. Y., & Park, J. K. (2001). Grafting of glycidyl methacrylate ontopolycaprolactone: Preparation and characterization. Polymer, 42, 5135–5142.

Kim, D. H., Kwon, O. J., Yang, S. R., & Park, J. S. (2007). Preparation of starch-basedpolyurethane films and their mechanical properties. Fibers and Polymers, 8,249–256.

Koenig, M. F., & Huang, S. J. (1995). Biodegradable blends and composites ofpolycaprolactone and starch derivatives. Polymer, 36, 1877–1882.

Kristo, E., & Biliaderis, C. G. (2007). Physical properties of starch nanocrystalsreinforced pullulan films. Carbohydrate Polymers, 68, 146–158.

Krylov, S. N. (2009). Book review of probes and tags to study biomolecular functionfor proteins, RNA, and membranes. Journal of the American Chemical Society,131, 1621–1622.

Kuan, H., Ma, M., Chang, W., Yuen, S., Wu, H., & Lee, T. (2005). Synthesis, thermal,mechanical and rheological properties of multiwall carbonnanotube/waterborne polyurethane nanocomposite. Composites Science andTechnology, 65, 1703–1710.

Kweon, D. K., Cha, D. S., Park, H. J., & Lim, S. T. (2000). Starch graftedpolycaprolactone copolymerization using diisocyanate intermediate andthermal characteristics of copolymer. Journal of Applied Polymer Science, 78,986–993.

Labet, M., Thielemans, W., & Dufresne, A. (2007). Polymer grafting onto starchnanocrystals. Biomacromolecules, 8, 2916–2927.

Lamba, N. M. K., Woodhouse, K. A., & Cooper, S. L. (1998). Polyurethanes inbiomedical applications. Boca Raton, FL: CRC Press.

Le Corre, D., & Angellier-Coussy, H. (2014). Preparation and application of starchnanoparticles for nanocomposites: A review. Reactive & Functional Polymers, 8,97–120.

Le Corre, D., Bras, J., & Dufresne, A. (2010). Starch nanoparticles: A review.Biomacromolecules, 11, 1139–1153.

LeCorre, D., Bras, J., & Dufresne, A. (2011). Influence of botanic origin and amylosecontent on the morphology of starch nanocrystals. Journal of NanoparticleResearch, 13, 7193–7208.

Lee, S. J., & Kim, B. K. (2012). Covalent incorporation of starch derivative intowaterborne polyurethane for biodegradability. Carbohydrate Polymers, 87,1803–1809.

Lei, L., Zhong, L., Lin, X., Li, Y., & Xia, Z. (2014). Synthesis and characterization ofwaterborne polyurethane dispersions with different chain extenders forpotential application in waterborne ink. Chemical Engineering Journal, 253,518–525.

Li, J., & Loh, X. J. (2008). Cyclodextrin-based supramolecular architectures:Syntheses, structures, and applications for drug and gene delivery. AdvancedDrug Delivery Reviews, 60(9), 1000–1017.

Li, S., Vatanparast, R., & Lemmetyinen, H. (2000). Cross-linking kinetics andswelling behavior of aliphatic polyurethane. Polymer, 41, 5571–5576.

Liao, J., Luo, Z., Zhang, Y., Zhang, X., Cheng, J., & Wu, Q. (2014). Effects of a novelcompatible interface structure on the properties of starch–PCL composites.New Journal of Chemistry, 38, 2522–2529.

Liaw, D., Huang, C., & Liaw, B. (1998). Synthesis and properties of polyurethanesbased on bisphenol-S derivatives. Polymer, 39(15), 3529–3535.

Light, J. M. (1990). Modified food starches: Why, what, where and how. CerealFoods World, 35, 1081–1092.

Lim, S.-T., Lin, J. J., Rajagopalan, S., & Seib, P. A. (1992). Effect of starch granule sizeon physical properties of starch-filled polyethylene film. BiotechnologyProgress, 8, 51–57.

Lin, N., Huang, J., Chang, P. R., Anderson, D. P., & Yu, J. (2011). Preparation,modification and application of starch nanocrystals in nanomaterials: Areview. Journal of Nanomaterials, 2011, 13.

Lin, Y., & Hsieh, F. (1997). Water-blown flexible polyurethane foam extender withbiomass materials. Journal of Applied Polymer Science, 65, 695–703.

Liu, L., Hu, D. D., Xu, G. K., Shou, L. W., & Yao, J. M. (2013). Fabrication andevaluation of polyurethane based assymetrical membranes. Journal of MaterialsScience, 48(5), 1902–1910.

Lopez, O., Garcia, M. A., Villar, M. A., Gentili, A., Rodriguez, M. S., & Albertengo, L.(2014). Thermo-compression of biodegradable thermoplastic corn starch filmscontaining chitin and chitosan. LWT—Food Science and Technology, 57, 106–115.

Lopez-Cordoba, A., Deladino, L., & Martino, M. (2014). Corn starch–calcium alginate
matrices for the simultaneous carrying of zinc and yerba mate antioxidants.LWT—Food Science and Technology, 59, 641–648.
Loubna, N., Thomas, J., Amar, Z., & Mustapha, R. (2010). Isocyanate-free route tostarch–graft-p polycaprolactone via carbonyldiimidazole (CDI)-mediated endgroup conversion. Starch/Stärke, 62, 90–101.



















































































































































































































































































































































































































































































































































































































































































































































































































































































































































































































































































































































































































































Polym

L

L

L

L

L

L

L

L

M

M

M

M

M

M

M

M

M

M

M

M

M

M

O

O

O

P

P

P

P

P


u, D. R., & Xu, S. J. (2009). Starch-based completely biodegradable polymermaterials. Express Polymer Letters, 3, 366–375.

u, Y. S., Weng, L. H., & Zhang, L. N. (2004). Morphology and properties of soyprotein isolate thermoplastics reinforced with chitin whiskers.Biomacromolecules, 5, 1046–1051.

u, Y., & Larock, R. C. (2008). Soybean-oil-based waterborne polyurethanedispersions: Effects of polyol functionality and hard segment content onproperties. Macromolecules, 9, 3332–3340.

u, Y., & Zhang, L. (2002). Morphology and mechanical properties ofsemi-interpenetrating polymer networks from polyurethane and benzylkonjac glucomannan. Polymer, 43, 3979–3986.

u, Y., Tighzert, L., Berzin, F., & Rondot, S. (2005). Innovative plasticized starch filmsmodified with waterborne polyurethane from renewable resources.Carbohydrate Polymers, 61, 174–182.

u, Y., Tighzert, L., Dole, P., & Erre, D. (2005). Preparation and properties of starchthermoplastics modified with waterborne polyurethane from renewableresources. Polymer, 46, 9863–9870.

u, Y., Zhang, L., Zhang, X., & Zhou, Y. (2003). Effects of secondary structure onmiscibility and properties of semi-IPN from polyurethane and benzyl konjacglucomannan. Polymer, 44(21), 6689–6696.

ue, S. J., & Peng, S. H. (2003). Polyurethane (PU) membrane preparation with andwithout hydroxypropyl-�-cyclodextrin and their pervaporationcharacteristics. Journal of Membrane Science, 222, 203–217.

anek, R. V., Kunle, O. O., Emeje, M. O., Builders, P., Rao, G. V. R., Lopez, G. P., &Kolling, W. M. (2005). Physical, thermal and sorption profile of starch obtainedfrom Tacca leontopetaloides. Starch—Starke, 57(2), 55–61.

ani, R., Tang, J., & Bhattacharya, M. (1998). Synthesis and characterization ofstarch–graft-polycaprolactone as compatibilizer for starch/polycaprolactoneblends. Macromolecular Rapid Communications, 19, 283–286.

anners, D. J. (1989). Recent developments in our understanding of amylopectinstructure. Carbohydrate Polymers, 11, 87–112.

archal, L. M. (1999). Towards a rational design of commercial maltodextrines: Amechanistic approach,. 〈http://library.wur.nl/WebQuery/wurpubs/62312〉.

arques, A. P., Reis, R. L., & Hunt, J. A. (2002). The biocompatibility of novelstarch-based polymers and composites: In vitro studies. Biomaterials, 23,1471–1478.

artin, O., & Avérous, L. (2001). Poly(lactic acid): Plasticization and properties ofbiodegradable multiphase systems. Polymer, 42, 6209–6219.

athew, A. P., & Dufresne, A. (2002). Morphological investigation ofnanocomposites from sorbitol plasticized starch and tunicin whiskers.Biomacromolecules, 3, 609–617.

ecking, S. (2004). Nature or petrochemistry?—Biologically degradable materials.Angewandte Chemie International, 43, 1078–1085.

eng, Q., Lee, B., Nah, S.-I., & Lee, C. Y.-S. (2009). Preparation of waterbornepolyurethanes using an amphiphilic diol for breathable waterproof textilecoatings. Progress in Organic Coatings, 66, 382–386.

ogosanu, G. D., & Grumezescu, A. M. (2014). Natural and synthetic polymers forwounds and burns dressing. International Journal of Pharmaceutics, 463,127–136.

ohamed, M. H., Wilson, L. D., & Headley, J. V. (2015). Tuning the physicochemicalproperties of �-cyclodextrin based polyurethanes via cross-linking conditions.Microporous and Mesoporous Materials, 214, 23–31.

ohamed, M. H., Wilson, L. D., Headley, J. V., & Peru, K. M. (2011). Investigation ofthe sorption properties of �-cyclodextrin-based polyurethanes with phenolicdyes and naphthenates. Journal of Colloid and Interface Science, 356,217–226.

ohanty, A. K., Misra, M., & Hinrichsen, G. (2000). Biofibres, bidegradablepolymers and biocomposites: An overview. Macromolecular Materials andEngineering, 276/277, 1–26.

orrision, W. R., Miligan, T. P., & Azudin, M. N. (1984). A relationship between theamylose and lipid contents of starches from diploid cereal and other starches.Journal of Cereal Science, 2, 257–271.

koli, C. P., Adewuyi, G. O., Zhang, Q., Diagboya, P. N., & Guo, Q. (2014). Mechanismof dialkyl phthalates removal from aqueous solution using �-cyclodextrin andstarch based polyurethane polymer adsorbents. Carbohydrate Polymers, 114,440–449.

livato, J. B., Müller, C. M. O., Carvalho, G. M., Yamashita, F., & Grossmann, M. V. E.(2014). Physical and structural characterisation of starch/polyester blends withtartaric acid. Materials Science and Engineering C, 39, 35–39.

zdemir, M., & Floros, J. D. (2004). Active food packaging technologies. CriticalReviews in Food Science and Nutrition, 44, 185–193.

anaitescu, D. M., Frone, A. N., Ghiurea, M., & Chiulan, I. (2015). Influence of storageconditions on starch/PVA films containingcellulose nanofibers. Industrial Cropsand Products, 70, 170–177.

ark, S. H., Lee, S. K., Choi, H. Y., Lee, E. M., Kim, E. Y., & Kim, B. K. (2009).Mechanical and surface properties and hydrolytic stability of cycloaliphaticpolyester-based waterborne polyurethanes modified with fluoro oligomer.Journal of Applied Polymer Science, 111, 1828–1834.

athak, S. S., Sharma, A., & Khanna, A. S. (2009). Value addition to waterbornepolyurethane resin by silicone modification for developing high performancecoating on aluminum alloy. Progress in Organic Coatings, 65, 206–216.

ecku, S., van der Merwe, T. L., Rolfes, H., & Focke, W. W. (2007). Starch asantiblocking agent in breathable polyurethane membranes. Journal of Vinyl andAdditive Technology, 13, 215–220.

ereira, J. D. S. A., Camargo, R. C. T., Filho, J. C. S. C., Alves, N., Rodriguez-Perez, M. A.,& Constantino, C. J. L. (2014). Biomaterials from blends of fluoropolymers and

ers 134 (2015) 784–798 797

corn starch—Implant and structural aspects. Materials Science and Engineering,C, 36, 226–236.

Perry, P. A., & Donald, A. M. (2002). The effect of sugar on gelatinisation of starch.Carbohydrate Polymers, 49, 155–165.

Petrie, E. M. (2000). Handbook of adhesives and sealants. New York, NY:McGraw-Hill.

Prisacariu, C. (2011). Polyurethane elastomers from morphology to mechanicalaspects. Wien/New York: Springer.

Priya, B., Gupta, V. K., Pathania, D., & Singha, A. S. (2014). Synthesis, characterizationand antibacterial activity of biodegradablestarch/PVA composite filmsreinforced with cellulosic fibre. Carbohydrate Polymers, 109, 171–179.

Queiroz, A. U. B., & Collares-Queiroz, F. P. (2009). Innovation and industrial trendsin bioplastics. Polymer Reviews, 49(2), 65–78.

Raafat, A. I., Araby, E., & Lotfy, S. (2012). Enhancement of fibrinolytic enzymeproduction from Bacillus subtilis via immobilization process onto radiationsynthesized starch/dimethylaminoethyl methacrylate hydrogel. CarbohydratePolymers, 87, 1369–1374.

Ratto, J. A., Stenhouse, P. J., Auerbach, M., Mitchell, J., & Farrell, R. (1999).Processing, performance and biodegradability of a thermoplastic aliphaticpolyester/starch system. Polymer, 40, 6777–6788.

Reis, K. C., Pereira, J., Smith, A. C., Carvalho, C. W. P., Wellner, N., & Yakimets, I.(2008). Characterization of polyhydroxybutyrate–hydroxyvalerate(PHB–HV)/maize starch blend films. Journal of Food Engineering, 89,361–369.

Ritter, H., & Tabatabai, M. (2004). Encyclopedia of polymer science and technology(3rd ed.). New York: John Wiley & Sons, Inc.

Rogovina, S. Z., & Vikhoreva, G. A. (2006). Polysaccharide-based polymer blends:Methods of their production. Glycoconjugate Journal, 23, 611–618.

Rohrbach, R. P., Zemel, H., & Koch, M. B. (1992). Cyclodextrin films on solidsubstrates. U.S. Patent 5, 098, 793.

Roy, A., Bajpai, J., & Bajpai, A. K. (2011). Carbohydrate polymers as versatilematerialsin controlled release technologies. In C. E. Jones (Ed.), Encyclopedia ofpolymerresearch (pp. 1195–1225). New York, NY: Nova Science Publishers.

Sajilata, M. G., Singhal, R. S., & Kulkarni, P. R. (2006). Resistant starch—A review.Comprehensive Reviews in Food Science and Food Safety, 5(1), 1–17.

Sakata, M., Uezono, K., Kimura, K., & Todokoro, M. (2013).�-Cyclodextrin–polyurethane copolymer adsorbent for selective removal ofendotoxin from DNA solution. Analytical Biochemistry, 443, 41–45.

Salaberria, A. M., Diaz, R. H., Labidi, J., & Fernandes, S. C. M. (2015). Role of chitinnanocrystals and nanofibers on physical, mechanical and functional propertiesin thermoplastic starch films. Food Hydrocolloids, 46, 93–102.

Salipira, K. L., Krausea, R. W., Mamba, B. B., Malefetse, T. J., Cele, L. M., & Durbach, S.H. (2008). Cyclodextrin polyurethanes polymerized with multi-walled carbonnanotubes: Synthesis and characterization. Materials Chemistry and Physics,111(2–3), 218–224.

Santayanon, R., & Wootthikanokkhan, J. (2003). Modification of cassava starch byusing propionic anhydride and properties of the starch–blended polyesterpolyurethane. Carbohydrate Polymers, 51, 17–24.

Shalviri, A., Raval, G., Prasad, P., Chan, C., Liu, Q., Heerklotz, H., et al. (2012).pH-dependent doxorubicin release from terpolymer of starch, polymethacrylicacid and polysorbate 80 nanoparticles for overcoming multi-drug resistance inhuman breast cancer cells. European Journal of Pharmaceutics andBiopharmaceutics, 82, 587–597.

Shirasawa, T., Ueda, M., Appell, M., & Goto, T. (2013). Use of cyclodextrin-basedpolymer for patulin analysis in apple juice. Mycotoxin, 63(1), 1–8.

Shukur, M. F., & Kadir, M. F. Z. (2015). Hydrogen ion conducting starch–chitosanblend based electrolyte for application in electrochemical devices.Electrochimica Acta, 158, 152–165.

Singh, B., Sharma, D. K., & Gupta, A. (2009). A study towards release dynamics ofthiram fungicide from starch–alginate beads to control environmental andhealth hazards. Journal of Hazardous Materials, 161(1), 208–216.

Sionkowska, A. (2011). Current research on the blends of natural and syntheticpolymers as new biomaterials: Review. Progress in Polymer Science, 36,1254–1276.

Smith, R. (2005). Biodegradable polymers for industrial applications. USA: CRC Press.Sreenivasan, K. (1996). Studies on polyurethane-�-cyclodextrin copolymers. 1.

Syn-thesis and characterization. New Polymeric Materials, 5, 73–79.St-Pierre, N., Favis, B. D., Ramsay, B. A., Ramsay, J. A., & Verhoogt, H. (1997).

Processing and characterisation of starch/polyethylene blends. Polymer, 38,647–656.

Subramanian, S. B., Francis, A. P., & Devasena, T. (2014). Chitosan–starchnanocomposite particles as a drug carrier for thedelivery of bis-desmethoxycurcumin analog. Carbohydrate Polymers, 114, 170–178.

Swinkels, J. J. M. (1985). Composition and properties of commercial nativestarches. Starch/Stärke, 37, 1–5.

Szetjli, J. (1998). Introduction and general overview of cyclodextrin chemistry.Chemical Reviews, 98, 1743–1753.

Takerda, Y., Maruta, N., & Hizukuri, S. (1992). Structure of amylose surfactants withdifferent molecular sizes. Carbohydrate Research, 226, 279–285.

Tang, H., Mitsunaga, T., & Kawamura, Y. (2006). Molecular arrangement inblocklets and starch granule architecture. Carbohydrate Polymers, 63, 555–560.

Thomas, S., Ninan, N., Mohan, S., & Francis, E. (2012). . Natural polymers,biopolymers, biomaterials, and their composites, blends, and IPNs advances inmaterials science (2) USA: CRC.

Tonkova, A. (1998). Bacterial cyclodextrin glucanotransferase. Enzyme andMicrobial Technology, 22(8), 678–686.

















































































































































































































































































































































































































































































































































































































































































































































































































































































































































































































































































































































































































































7 Polym

T

T

V

v

V

VW

W

W

W

W

W

W

W

W

W

W

W

W

W

R. E. Hebeda (Eds.), Starch hydrolysis products (pp. 23–44). New York, NY, USA:VCH.


ravinskaya, T. V., & Savelyev, Yu. V. (2006). Aqueous polyurethane–alginatecompositions: Peculiarities of behavior and performance. European PolymerJournal, 42, 388–394.

ravinskaya, T., Savelyev, Yu., & Mishchuk, E. (2014). Waterborne polyurethanebased starch containing materials: Preparation, properties and study ofdegradability. Polymer Degradation and Stability, 101, 102–108.

aidya, U. R., Bhattacharya, M., & Zhang, D. (1995). Effect of processing conditionson the dynamic-mechanical properties of starch and anhydride functionalpolymer blends. Polymer, 36, 1179–1188.

an de Manakker, F., Vermonden, T., van Nostrum, C. F., & Hennink, W. E. (2009).Cyclodextrin-based polymeric materials: Synthesis, properties, andpharmaceutical/biomedical applications. Biomacromolecules, 10(12),3157–3175.

oncina, B., & Vivod, V. (2013). Cyclodextrins in textile finishing. In M. Günay (Ed.),Eco-friendly textile dyeing and finishing (pp. 53–75). Croatia: InTech.

roman, I., & Tighzert, L. (2009). Biodegradable polymers. Materials, 2, 307–344.aigh, T. A., Gidley, M. J., Komanshek, B. U., & Donald, A. M. (2000). The phase

transformation in starch during gelatinisation: A liquid crystalline approach.Carbohydrate Research, 328, 165–176.

ang, X., Yang, K., & Wang, Y. (2003). Properties of starch blend withbiodegradable polymer. Journal of Macromolecular Science, C: Polymer Reviews,43, 385–409.

ang, Y., & Zhang, L. (2008). High-strength waterborne polyurethane reinforcedwith waxy maize starch nanocrystals. Journal of Nanoscience Nanotechnology,8(11), 5831–5838.

ang, Y., Lue, A., & Zhang, L. (2009). Rheological behavior of waterbornepolyurethane/starch aqueous dispersions during cure. Polymer, 50, 5474–5481.

ang, Y., Tian, H., & Zhang, L. (2010). Role of starch nanocrystals and cellulosewhiskers in synergistic reinforcement of waterborne polyurethane.Carbohydrate Polymers, 80, 665–671.

erkmeister, J. A., Edwards, G. A., Casagranda, F., White, J. F., & Ramshaw, J. A. M.(1998). Evaluation of a collagen-based biosynthetic materials for the repair ofabdominal wall defects. Journal of Biomedical Materials and Research, 39,429–436.

histler, R. L., Bemiller, J. N., & Paschall, E. F. (1984). Starch: Chemistry andtechnology (2nd ed.). New York, NY: Academic Press.

icks, Z. W., Wicks, D. A., & Rosthauser, J. W. (2002). Two package waterborneurethane systems. Progress in Organic Coatings, 44, 161–183.

ilpiszewska, K., & Spychaj, T. (2007). Chemical modification of starch byhexamethylene diisocyanate derivatives. Carbohydrate Polymers, 70, 334–340.

ool, R., & Sun, X. S. (2005). Bio-based polymers and composites. Burlington, MA:Elsevier Inc.

u, B.-C., & McClements, D. J. (2015). Microgels formed by electrostaticcomplexation of gelatin and OSA starch: Potential fat or starch mimetics. FoodHydrocolloids, 47, 87–93.

u, Q., & Zhang, L. (2001a). Preparation and characterization of thermoplasticstarch mixed with waterborne polyurethane. Industrial and EngineeringChemistry Research, 40(2), 558–564.

u, Q., & Zhang, L. (2001b). Structure and properties of casting films blended with
starch and waterborne polyurethane. Journal of Applied Polymer Science, 79(11),2006–2013.
u, Q., Wu, Z., Tian, H., Zhang, Y., & Cai, S. (2008). Structure and properties oftough thermoplastic starch modified with polyurethane microparticles.Industrial and Engineering Chemistry Research, 47, 9896–9902.

ers 134 (2015) 784–798

Xiao, P., Dudal, Y., Corvini, P. F.-X., Pieles, U., & Shahgaldian, P. (2011).Cyclodextrin-based polyurethanes act as selective molecular recognitionmaterials of activepharmaceutical ingredients (APIs). Polymer Chemistry, 2,1264–1266.

Yamasaki, H., Makihata, Y., & Fukunaga, K. (2006). Efficient phenol removal ofwastewater from phenolic resin plants using crosslinked cyclodextrinparticles. Journal of Chemical Technology and Biotechnology, 81,1271–1276.

Yang, D. Y., Zhang, H. Q., Rong, S. C., & Qiu, F. X. (2012). Investigation on oxidizedstarch based waterborne polyurethane nanocomposites. Plastics Rubbers andComposites, 41, 425–429.

Yoo, J.-W., Irvine, D. J., Discher, D. E., & Mitragotri, S. (2011). Bio-inspired,bioengineered and biomimetic drug delivery carriers. Nature Reviews DrugDiscovery, 10, 521–535.

Yu, L., Dean, K., & Li, L. (2006). Polymer blends and composites from renewableresources. Progress in Polymer Science, 31, 576–602.

Yu, S., Mi, F., Shyu, S., Tsai, C., Peng, C., & Lai, J. (2006). Misciability, mechanicalcharacteristics and platelet adhesion of6-O-carboxymethylchitosan/polyurethane semi-IPN membrane. Journal ofMembrane Science, 276(1–2), 68–80.

Zeng, M., Zhang, L., & Zhou, Y. (2004). Effects of solid substrate on structure andproperties of casting waterborne polyurethane/carboxymethyl chitin films.Polymer, 45(10), 3535–3545.

Zhang, L., & Zhou, Q. (1999). Structure and properties of semi-interpenetratingpolymer networks based on polyurethane and nitrocellulose. Journal ofPolymer Science, B: Polymer Physics, 37, 1623–1631.

Zhang, N., Liu, H., Yu, L., Liu, X., Zhang, L., Chen, L., et al. (2013). Developinggelatin–starch blends for use as capsule materials. Carbohydrate Polymers, 92,455–461.

Zhang, Y., Huang, L., Zhou, H., Zhang, P., Zhu, M., Fan, B., et al. (2013). Toughthermoplastic starch modified with polyurethane microparticles by reactiveextrusion. Starch—Stärke, 65(5–6), 425–432.

Zhang, Y., Leng, Y., Zhu, M., Fan, B., Yan, R., & Wu, Q. (2012). Starches modified withpolyurethane microparticles: Effects of hydroxyl numbers of polyols inpolyurethane. Carbohydrate Polymers, 88, 1208–1213.

Zhong, Q. P., & Xia, W. S. (2008). Physicochemical properties of edible andpreservative films from chitosan/cassava starch/gelatin blend plasticized withglycerol. Food Technology and Biotechnology, 46(3), 262–269.

Zhou, J., & Ritter, H. (2010). Cyclodextrin functionalized polymers as drug deliverysystems. Polymer Chemistry, 1(10), 1552–1559.

Zia, K. M., Barikani, M., Zuber, M., Bhatti, I. A., & Sheikh, M. A. (2008). Molecularengineering of chitin based polyurethane elastomers. Carbohydrate Polymers,74, 149–158.

Zia, K. M., Zia, F., Zuber, M., Rehman, S., & Ahmad, M. N. (2015). Alginate basedpolyurethanes: A review of recent advances and perspective. InternationalJournal of Biological Macromolecules, 79, 377–387.

Zobel, H. F. (1992). Starch: Sources, production, and properties. In F. W. Schenck, &

Zou, J., Zhang, F., Huang, J., Chang, P. R., Su, Z., & Yu, J. (2011). Effects of starchnanocrystals on structure and properties of waterborne polyurethane-basedcomposites. Carbohydrate Polymers, 85, 824–831.











































































































































































































































































































































































































































































































































































































































































































































本文献由“学霸图书馆-文献云下载”收集自网络，仅供学习交流使用。

学霸图书馆（www.xuebalib.com）是一个“整合众多图书馆数据库资源，

提供一站式文献检索和下载服务”的24 小时在线不限IP

图书馆。

图书馆致力于便利、促进学习与科研，提供最强文献下载服务。

图书馆导航：

图书馆首页文献云下载图书馆入口外文数据库大全疑难文献辅助工具

http://www.xuebalib.com/cloud/

http://www.xuebalib.com/

http://www.xuebalib.com/cloud/


http://www.xuebalib.com/vip.html

http://www.xuebalib.com/db.php

http://www.xuebalib.com/zixun/2014-08-15/44.html


starch based polyurethanes: a critical review updating recent...

Documents