The aim of this review is to show the relationships between the structure, the process, and the properties of biodegradable multiphase systems based on plasticized starch (PLS), the so‐called “thermoplastic starch.” These mutiphase materials are obtained when associating association between plasticized starches and other biodegradable materials, such as biodegradable polyesters [polycaprolactone (PCL), polyhydroxyalkanoates (PHAs), polylactic acid (PLA), polyesteramide (PEA), aliphatic, and aromatic copolyesters], or agro‐materials (ligno‐cellulosic fiber, lignin etc.). Depending on materials (soft, rigid) and the plastic processing system used, various structures (blends, composites, multilayers) can be obtained. The compatibility problematic between these hetero‐materials is analyzed. These starchy products show some interesting properties and have some applications in different fields: packaging, sports, catering, agriculture and gardening, or hygiene.

Biodegradable Multiphase Systems Based on Plasticized Starch: A Review

After an introduction reporting the properties and the applications of fluoropolymers, a first part deals with i) the main routes to produce vinylidene fluoride (VDF) monomer, ii) its homopolymerization, and iii) the advantages and uses of polyvinylidene fluoride (PVDF). In a second section, this review, illustrated by numerous examples, extensively reports the synthesis, properties and applications of the copolymers based on VDF with non-halogenated, fluorinated, commercially available or synthesized comonomers. These comonomers exhibit XYC=CZ-Sp-R structures where X, Y, and Z represent H, F, and CF3 groups, Sp a spacer and R a function such as OH, OAc, SAc, CO2R' (R' being a H atom or an alkyl group), CN, P(O)(OR')2 and SO3H. According to the nature and to the amount of the comonomer, the copolymers can be thermoplastic, elastomeric or thermoplastic elastomers. Introducing reactive R side groups brings complementary properties such as hydrophily, ionic exchange or surface properties, or further crosslinking of the resulting copolymers. Then, the kinetics of radical copolymerization of VDF with M comonomers led to the assessment of the reactivity ratios which are compared. Hence, a reactivity series of these M comonomers with respect to a macroradical terminated by VDF is proposed. Usually, these copolymers exhibit random structures but only three comonomers produced alternating copolymers with VDF: hexafluoroisobutylene, F2C=CFCO2CH3, and H2C=C(CF3)CO2R. The controlled radical copolymerizations of VDF with other comonomers (such as chlorotrifluoroethylene, 3,3,3-trifluoropropene, hexafluoropropylene, perfluoromethyl vinyl ether or-trifluoromethacrylic acid) either in the presence of xanthates, borinates or iodo-compounds are also reported. In addition, new VDF-containing copolymers exhibit well-defined architectures, such as block and graft copolymers. They can be synthesized either by conventional techniques or by controlled radical copolymerization. Chemical modifications of PVDF and poly(VDF-co-monomer) copolymers are also presented. Several properties and applications (such as surfactants, dielectrical polymers, thermoplastic elastomers, fuel cell and ultrafiltration membranes, or polycondensates, the fluorinated segments of which bringing softness and thermal stability) of these VDF-containing copolymers will illustrate this review.

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From vinylidene fluoride (VDF) to the applications of VDF-containing polymers and copolymers: recent developments and future trends.

Polymer Blends (or Alloys)

A Binary Interaction Model for Miscibility of Copolymers in Blends

Interpenetrating polymer networks (IPN’s) are a unique type of polyblend, synthesized by swelling a crosslinked polymer (I) with a second monomer (II), together with crosslinking and activating agents, and polymerizing monomer II in situ (Sperling, 1974–1975 ; Sperling and Friedman, 1969). The term IPN was adopted because, in the limiting case of high compatibility between crosslinked polymers I and II, both networks could be visualized as being interpenetrating and continuous throughout the entire macroscopic sample.* As with other types of polyblends, if components I and II consist of chemically distinct polymers, incompatibility and some degree of phase separation usually result (Sperling, 1974–1975; Sperling and Friedman, 1969; Sperling et al., 1970a,b,c; 1971). Even under these conditions, the two components remain intimately mixed, the phase domain dimensions being on the order of hundreds of angstroms. If one polymer is elastomeric and one polymer is plastic at the use temperature, the combination tends to behave synergistically, and either reinforced rubber or impact-resistant plastics result, depending upon which phase predominates (Curtius et al., 1972; Sperling and Mihalakis, 1973; Sperling et al., 1971; Huelck et al., 1972). Among the other kinds of polymer blends discussed in this monograph, the graft-type copolymers are the ones most closely related to the IPN’s.

Interpenetrating Polymer Networks

Melt blends of bisphenol A polycarbonate with poly(butylene terephthalate) were studied by DTA and dynamic mechanical behavior to determine their state of miscibility. Both techniques showed multiple glass transitions indicative of incomplete miscibility in the amorphous phase. However, these transitions in some cases did not correspond to those in the pure components and varied with overall blend composition in some instances. This indicates that there are amorphous phases containing both components, i.e., partial miscibility. This view was supported by the crystallization behavior of the polyester. Two crystallization exotherms were observed for quenched samples, which is interpreted as polyester crystallization from two separate phases, one richer in this component than the other. Other interpretations of these results are discussed.

Polyester–polycarbonate blends. I. Poly(butylene terephthalate)

Melt blends of polycarbonate and poly(ethylene terephthalate) were prepared and examined for their transitional behavior by thermal analysis and dynamic mechanical testing. A single Tg was observed for compositions containing more than 60%–70% PET by weight while compositions below this range showed two glass transitions. From this it is concluded that PC and PET are completely miscible in the amorphous phase for PET-rich compositions, whereas PC-rich blends separate into two amorphous phases which apparently contain both components. Melting point and crystallization behavior are conssistent with these conclusions and suggest that very little if any interchange reactions occur between the ester and carbonate groups during melt mixing.

Polyester–polycarbonate blends. II. Poly(ethylene terephthalate)

Polyester/polycarbonate blends. I. Poly(butylene terephthalate)

The state of thermodynamic miscibility of a polymer blend and its resulting phase behavior and mechanical properties is largely determined by the balance between enthalpic and entropic contributions to the free energy of mixing. Recent applications of this thermodynamic consideration are reviewed for a variety of binary and ternary blends of homopolymers and copolymers. Recent advances in predicting polymer blend miscibility and Lower Critical Solution Temperature behavior from liquid heats of mixing data, through use of a modified Guggenheim quasichemical model combined with the Sanchez lattice fluid model are discussed. Qualitative application of partial miscibility ideas to interfacial adhesion in multiphase polymer blends is also presented.

J. W. Barlow

Papers

Polymer Blends (or Alloys)

Polyester–polycarbonate blends. I. Poly(butylene terephthalate)

Polyester–polycarbonate blends. II. Poly(ethylene terephthalate)

Polyester/polycarbonate blends. I. Poly(butylene terephthalate)

Polymer blends and alloys