Jian-Bing Zeng
*a,
Kun-Ang Li
a and
An-Ke Du
b
aCollege of Chemistry and Chemical Engineering, Southwest University, Beibei, Chongqing 400715, China. E-mail: jbzeng@swu.edu.cn; Fax: +86-23-68254000; Tel: +86-23-68254000
bChongqing Academy of Science and Technology, Chongqing 401123, China
First published on 23rd March 2015
Poly(lactic acid) (PLA) is regarded as one of the most promising bio-based and biodegradable polymers, due to its excellent biodegradability, biocompatibility, renewability, high strength, and easy processibility. However, disadvantages such as brittleness and relatively high cost have restricted its applications significantly. Polymer blending provides an economic and efficient way to modify the properties of PLA. Most shortcomings of PLA are theoretically surmountable by blending with abundant polymers with various properties. But, unfortunately, PLA is thermodynamically immiscible with most existing polymers. High-performance PLA-based blends are usually unanticipated by direct blending. In order to obtain PLA-based blends with excellent overall properties, compatibilization is required during polymer blending. Various strategies have been employed or developed to compatibilize PLA blends with different polymers, as reported in recent studies. This article aims to review the development in compatibilization strategies employed in PLA-based blends.
Commercial PLA is often produced by ring-opening polymerization (ROP) of lactide, the dimer of lactic acid, prepared by depolymerization of low molecular weight PLA oligomer,4 as shown in Fig. 1. The purity of lactide is very important for synthesizing high molecular weight PLA. Carothers and coworkers for the first time prepared PLA by ROP of lactide,7 but high molecular weight PLA was only obtained after DuPont developed purification techniques in 1954.4 Recently, Cargill Dow LLC has commercialized PLA under the trade name NatureWorks at a capacity of 140000 tons per year with starch as the starting material in 2002.8 Fermentation of starch gives rise to lactic acid, condensation of lactic acid leads to PLA oligomer, and the catalytic depolymerization of the oligomer under vacuum produces lactide. After purification, high molecular weight PLA could then be synthesized by ROP of lactide in the presence of a catalyst such as Sn(Oct)2.4 Besides ROP, some other techniques such as chain-extension reaction,9–11 azeotropic dehydration condensation,12,13 and melt/solid state polymerization14,15 could also be used to prepare high molecular weight PLA with values of more than 100000 g mol−1. The various synthetic routes for the preparation of high molecular weight PLA are schematically shown in Fig. 1.
Due to the presence of two chiral carbon centers, lactide has three stereoisomers: D,D-lactide (D-LA), L,L-lactide (L-LA), and D,L-lactide (meso-LA), as shown in Fig. 2. The physical properties including melting temperature, crystallization behaviors, and mechanical properties of PLA depend strongly on the stereochemical compositions. PLA homopolymer polymerized from pure L-LA or D-LA has an equilibrium crystalline melting point of 207 °C.8 However, commercially available PLA usually shows a melting point of 170–180 °C due to the slight racemization, imperfect crystallites, and impurities.4 A 1:1 mixture of poly(L-lactide) and poly(D-lactide) presents a higher melting temperature of 230 °C and better mechanical properties than either homopolymer due to the formation of a stereocomplex structure.16,17 The effect of stereochemical composition on the glass transition temperature is much less significant than on the melting temperature as crystalline PLA and amorphous PLA show similar glass transition temperature of 55–63 °C.4 Although there are three types of PLA, commercial PLA is a copolymer of poly(L-lactide) with small amount of poly(D,L-lactide), since the lactic acid derived from biological sources is composed of mostly L-lactic acid and smaller amount of D-lactic acid.13 In the following sections, for brevity, the stereo structure of PLA is not discriminated since the compatibilization techniques in PLA blends are almost the same regardless of the stereo structure.
PLA shows many advantages which make it widely used in many fields. Besides being derived from renewable resources (e.g., corn, sugar, potato), PLA is recyclable,18,19 biodegradable and compostable with the final degradation products of carbon dioxide,20–22 and easily processible to form applicable products with traditional processing equipment.13,23 These characteristics make PLA very attractive to replace non-degradable petroleum-based plastics in commodity plastic applications, such as mulch film, disposable cutlery, shopping bags, trash bags, food containers, and packaging materials.13,23–25 The good biocompatibility and bioresorbability enable PLA to find extensive applications in biomedical and pharmaceutical fields including surgical sutures, tissue engineering materials, and drug delivery systems.26 The high strength and melting temperature help PLA to find potential application in engineering plastics.27 The tensile strength of PLA is usually in the range of 50–70 MPa depending on the molecular weight and stereochemical composition, and the Young's modulus can be as high as 3 GPa.28
However, there are still some drawbacks that restrict the wide application of PLA. For example, PLA is lacking in toughness and has very low impact strength and short extensibility, which are some of the biggest problems that restrict the use of PLA in many areas, where good impact resistance is required. The elongation at break is usually less than 10% and the impact strength is only ∼2.5 kJ m−2.28,29 In addition, the poor crystallizability, slow biodegradation rate, and low heat distortion temperature are the other shortcomings limiting the wide application of PLA.8 In order to extend the application of PLA, modifications have to be done to improve the properties.
The state of miscibility of two polymers is governed by the free energy of mixing, ΔGmix, which is defined as
ΔGmix = ΔHmix − TΔSmix |
Compatibility is a technical term defining the phase morphology and property profile of a blend in view of a certain application.50 If blending of two partially miscible or immiscible polymers generates a fine phase morphology and combines advantageous properties of the blend components, the compatibility between the two polymers is good, while they are incompatible if blending results in coarse phase morphology and poor properties. For the incompatible polymer blends, their compatibility can be improved via an appropriate method, which is usually referred to as compatibilization. We say that the compatibility of an incompatible blend is changed to compatible if the phase morphology transfers from coarse to fine and the properties change from poor to good after compatibilization.
Compatibilization is a technique to improve compatibility and enhance properties of immiscible polymer blends. The most important roles of compatibilization are first to reduce the size of the dispersed phase through the reduction of interfacial tension and second to prevent the dispersed phase from coalescence, thus to stabilize the formed fine phase morphology.41 In addition, compatibilization can improve the interfacial interactions between dispersed phase and matrix as a result of using compatibilizers that are usually macromolecular species showing interfacial activities in heterogeneous blends.50 With formation of fine phase morphology and improved interfacial interaction, useless incompatible blends can be changed to useful compatible materials which combine the excellent properties of the blend components. Taking immiscible poly(lactic acid)/low-density polyethylene (PLLA/LDPE) blend as an example, Fig. 3 shows the morphologies of cryofractured surfaces for immiscible PLLA/LDPE before and after being compatibilized by block copolymer PLLA-b-LDPE, as reported by Wang and Hillmyer.42 The uncompatibilized blend showed coarse morphology with large LDPE dispersed particles and obvious phase boundary, indicating poor compatibility and interfacial adhesion, while the size of dispersed LDPE particles decreased gradually and the phase boundary became less distinct with an increase in the content of compatibilizer. The compatibilized blends showed significantly improved mechanical properties over those of the pristine blend. In addition to the use of block copolymers, there are several other approaches that can compatibilize PLA-based blends, as described in the following section.
Fig. 3 Morphologies for cryofractured surfaces of (a) 80:20 PLLA/LDPE, and (b) 80:20:2, (c) 80:20:5, and (d) 80:20:10 PLLA/LDPE/PE-b-PLLA blends. Reprinted with permission from ref. 42. Copyright 2001 John Wiley. |
Fig. 4 Ideal location of diblock, triblock, and graft copolymers at the interface of an immiscible A/B polymer blend. |
The presence of the block or grafted copolymers at the interface can decrease the interfacial tension of the immiscible blends, thus reducing the size of the droplets of dispersed phase during melt processing.41 Usually, the minor phase exhibits an average particle size in the sub-micrometer range when dispersed in the other polymer matrix. In addition, the existence of the blocky-structured copolymer at the surface could prevent coalescence of the generated dispersed particles during subsequent processing or storage. Therefore, the addition of blocky-structured copolymers as compatibilizers is able to form and stabilize a fine phase morphology in phase-separated polymer blends. It is worth noting that the presence of the blocky-structured copolymers can enhance the interfacial adhesion of the immiscible blends due to the entanglement of each block with the corresponding blend component. Sufficient interfacial adhesion is essential for stress transfer from one phase to the other, which is efficient in stopping the cracks initiated at the interface from growth to catastrophic failure. The formation and stabilization of a fine phase morphology and the improvement in the interfacial adhesion usually change a useless immiscible blend to a useful material in which the advantages of each blend component are combined.41
Bai et al.54 reported the use of poly(D,L-lactide-co-p-dioxanone) (PLADO) random copolymer to compatibilize a poly(p-dioxanone)/poly(D,L-lactide) (PPDO/PLA, 80/20 w/w) blend, and found that the addition of PLADO could obscure the phase boundary between PPDO and PLA phases and increase the compatibility between the two components, although the average number of sequential comonomeric units of PDO unit was only 1.0. Recently, they used poly(p-dioxanone-co-L-lactide) (PDOLLA) to compatibilize a PLLA/PPDO (85/15 w/w) blend, and found that the compatibility and mechanical properties of the blend were much improved with addition of 3.0 wt% PDOLLA.55 In order to improve the compatibility of a poly(D,L-lactic acid)/poly(glycolic acid) (PLA/PGA) blend, Ma et al.56 added poly(D,L-lactic acid-co-glycolic acid) (PLAGA) as a compatibilizer to the mixed solution of PLA and PGA during film preparation, and found that when 5% PLAGA was added the blend showed a smooth and homogeneous morphology which was similar to that of neat PGA film.
PLA–PCL diblock or triblock copolymers have been widely used to compatibilize immiscible PLA/PCL blends. Choi et al.53 synthesized a PLA–PCL diblock copolymer and used it to compatibilize PLA/PCL blends and found that the size of PCL domains in PLA matrix can be reduced upon addition of PLA–PCL diblock copolymer; however, the extent of reduction was less than caused by the addition of PLA–PCL random copolymer. Maglio et al.58–60 and Wu et al.61 used a PLA–PCL–PLA triblock copolymer to compatibilize PLA/PCL blends. The good emulsifying effect was evidenced by the strong reduction in particle size of dispersed PCL phase upon addition of the triblock copolymer. For example, the dimension of dispersed PCL domains in PLA/PCL (70/30, w/w) drastically decreases from about 10–15 μm to about 3–4 μm after adding 4 wt% of the triblock copolymer.59
To improve the compatibility of PLA with natural rubber, Chumeka et al.62 synthesized a diblock copolymer from hydroxyl telechelic natural rubber (NR) oligomers and PLA and used it as a compatibilizer for PLA/NR blend. The results showed that the size of dispersed particles was reduced by the addition of the diblock copolymer.
Na et al.48 have extended this approach to C–B block copolymers, where the C block was miscible with PLA. They blended PLA with PEG-b-PCL block copolymer and found that PLA was miscible with the PEG block while immiscible with the PCL block although it was block-copolymerized with PEG. Then they employed this block copolymer to compatibilize PLA/PCL blends and achieved improved mechanical properties upon addition of the copolymer. Considering that polyoxyethylene (PEO) is miscible with both PLA and PCL, the diblock copolymer PLA-b-PEO of “A–C” type was employed by Maglio et al. to compatibilize PLA/PCL blend and it exhibited similar behavior to PLA-b-PCL-b-PLA triblock copolymer.60 Chang et al.63 improved compatibility between PLLA and soybean oil (SOY) by addition of poly(isoprene-b-lactide) (A–C type) in which polyisoprene is miscible with SOY due to the small Flory–Huggins interaction parameter. With the aid of poly(isoprene-b-lactide), the incorporated content of SOY could be increased from 6 wt% to 20 wt%, and a phase inversion occurred with the minor SOY changing to matrix surrounding PLLA particles to provide improved toughness.
Another type of copolymer (C–D type) such as polyethylene oxide–polypropylene oxide–polyethylene oxide (PEO–PPO–PEO) triblock copolymer is sometimes used to compatibilize PLLA blends. For example, PEO–PPO–PEO was employed as a compatibilizer in PLLA/PCL64 and PLLA/PBSL65 blends. In those systems, PEO–PPO–PEO worked like a third homopolymer such as PEG which was miscible with both blend components and thus could emulsify the phase interface to improve compatibility. Real C–D type block copolymers, of which one block (C block) is miscible with A component and the other block (D block) is miscible with B component, have seldom been used in compatibilization of PLLA blends, possibly due to the difficulty of finding such specific block copolymers.
From the above description, we can see that addition of premade copolymers is an efficient way to compatibilize PLA blends with various polymers. Besides the powerful compatibilization efficiency, the best advantage of this technique is its universality. Theoretically, this method can be used to compatibilize various immiscible blends by careful design and synthesis of suitable copolymers. The literature that focuses on the use of this method to compatibilize immiscible blends grows rapidly. However, this technique seems not to be suitable in large-scale production due to the commercial unavailability and high cost of the specific copolymers.
There are many advantages of addition of reactive polymers over addition of premade copolymers. Firstly, the reactive polymers only give rise to block or graft copolymers at the location where they are needed, always at the interface of immiscible blends, which should be more efficient in compatibilization than the addition of premade copolymers. Secondly, reactive polymers usually show lower melt viscosity than premade copolymers, at least if the blocks of premade copolymer possess similar molecular weight to the reactive “blocks”, which makes the reactive polymer diffuse towards the interface of immiscible blends much faster than the premade copolymer. This is extremely important with respect to the short processing time during reactive blending which is usually of the order of a minute or even less. In some cases, the reactive polymers may not be miscible with either component of the blend, but they can also be used as compatibilizers if they are reactive towards the functional groups of both blend components. Copolymers, working as compatibilizers, could also be formed at the interface of immiscible blends through the reaction between the components in the presence of the reactive polymers.68
In order to successfully compatibilize immiscible blends with reactive polymers, they must have a suitable reactivity with the functional groups of the blend components so as to accomplish reaction to form block or graft copolymers during the short blending time. Furthermore, the formed covalent bonds must be stable enough to remain intact under the subsequent processing conditions. PLA is an aliphatic polyester with terminal groups of carboxyl and hydroxyl, which are reactive with many functional groups such as epoxy, anhydride, isocyanate, and oxazoline groups. Fig. 6 shows the reactions between terminal groups of PLA and reactive polymers with those functional groups.
Addition of reactive polymers to compatibilize immiscible blends also has some other advantages. Compared to graft and block copolymers, reactive polymers with various functional groups are easier to produce with simple techniques and some reactive polymers even have been commercialized. However, this technique also has some disadvantages. The reactive polymers with functional groups may be poisonous, which would cause some potential injuries to operators. The inevitable residue of some poisonous functional groups if remaining would cause some safety problems to the resulting blends. Nevertheless, this method has been widely used in PLA-based blends. Many reactive polymers with various functional groups that were used in compatibilization of PLA-based blends are described in the following text.
Poly(butylene adipate-co-terephthalate) (PBAT) is a flexible biodegradable polyester that can be used to toughen PLA without compromising the biodegradability. Zhang et al.68 improved the compatibility between PLA and PBAT by adding a polymer containing 8% GMA, which, containing epoxy groups, can react with both PLA and PBAT to form copolymers of PLA and PBAT and thus to compatibilize the blends. Al-Itry et al.72 also compatibilized PLA/PBAT blends with a reactive polymer named Joncryl containing nine GMA functions.
Natural rubber (NR) is a biobased polymer with high resilience and high elongation at break and thus can be used as an impact modifier for PLA without sacrificing sustainability. But NR is also immiscible with PLA. The compatibility of PLA/NR blends was improved by the addition of glycidyl methacrylate-grafted natural rubber (NR-g-GMA), and the impact strength and elongation at break of PLA/NR blend increased about 2.5 times and 2 times, respectively, when 1 wt% NG-g-GMA was introduced, as reported by Punmanee et al.73 Polyamide 610 (PA610) is also a biobased polymer and not miscible with PLA. In order to obtain fully biobased blends with improved mechanical properties, Pai et al.74 compatibilized PLA/PA610 blends with a low molecular weight bisphenol-A type epoxy resin, and found that PA610 could toughen PLA and no-break untorched impact products were obtainable with a suitable content of epoxy resin, due to the formation of copolymers at the interface of the blends via reaction of PLA and PA610 in the presence of the epoxy resin. Shi et al.75 compatibilized blends of PLA and thermoplastic starch (TPS) with addition of GMA-grafted poly(ethylene octane), which is able to react with both PLA and TPS. Wu et al.76 compatibilized a blend of PLA and olefin block copolymer (OBC) with a random terpolymer of ethylene, methyl acrylate and GMA. The compatibilization was evidenced from the reduced particle size of dispersed OBC and the narrowed particle size distribution.
Singh et al.83 enhanced the compatibility of a blend containing major LDPE (80 wt%) and minor PLA (20 wt%) with MA-grafted LDPE. When 4 phr MA-grafted LDPE was added, PLA dispersed uniformly in the LDPE matrix, and optimum mechanical properties were obtained. Yoo et al.84 compatibilized an immiscible blend containing major polypropylene (PP) and minor PLA with PP-g-MAH, and found that the maximum tensile strength and minimum interfacial tension were obtained when 3 phr PP-g-MAH was added for a PP/PLA (80/20, w/w) blend. In a PP/PLA blend consisting of major PLA and minor PP, PP-g-MAH could also be used as a reactive compatibilizer, as reported by Choudhary et al.85 The mechanical properties, especially the toughness, of PP/PLA blends may be improved if ethylene-propylene-diene monomer rubber (EPDM) is added and proper compatibilization occurs for the PP/EPDM/PLA ternary blends. PP-g-MAH alone could not successfully compatibilize the blends in this case, since PP is not miscible with EPDM. While if EPDM-g-MAH was used as a mixing compatibilizer with PP-g-MAH, PP/EPDM/PLA ternary blends with good compatibilization and excellent mechanical properties were obtained, as reported by Park et al.86 Since PP-g-MAH can only react with hydroxyl groups of PLA, the carboxyl groups remained after processing. The compatibilization could be further improved if a co-compatibilizer, which is able to react with carboxyl groups of PLA, was added in the PP/PLA blends. In this regard, Lee et al.87 evaluated the use of PP-g-MAH and PE-g-GMA as a hybrid compatibilizer for PP/PLA blends containing a toughening modifier and compared it with using PP-g-MAH or PE-g-GMA as a single compatibilizer. They found that the hybrid compatibilizer has much better compatibilization efficiency than either PP-g-MAH or PE-g-GMA. In addition, PP-g-MAH was also used as an efficient compatibilizer for PLA/PP/sepiolite nanocomposites as reported by Nunez et al.88 Polycarbonate (PC) is an important engineering plastic with excellent comprehensive performance. To blend with the renewable PLA could endow PC with sustainability. However, PLA and PC are immiscible. In order to improve the compatibility of PLA/PC blends, Lee et al.89 employed three types of maleic anhydride-containing reactive polymers, i.e., poly(styrene-g-acrylonitrile)-maleic anhydride (SAN-g-MAH), poly(ethylene-co-octene) rubber-maleic anhydride (EOR-MAH) and poly(ethylene-co-glycidyl methacrylate) (EGMA), to compatibilize PC/PLA blends. They found that SAN-g-MAH was the most efficient compatibilizer for the blends since the maximum impact and tensile strengths and the minimum interfacial tension were achieved for a PC/PLA (70/30, w/w) blend when 5 phr SAN-g-MAH was added. The best compatibilization efficiency of SAN-g-MAH in PC/PLA blends was ascribed to the partial miscibility between SAN and PC90 and the reaction between MAH and hydroxyl groups of PLA. Teamsinsungvon et al.91 prepared maleic anhydride-grafted PLA (PLA-g-MA) and evaluated the effect of PLA-g-MA on the compatibility of PLA/PBAT blends, and found that the tensile properties of PLA/PBAT with incorporation of PLA-g-MA were much better than those of the uncompatibilized PLA/PBAT blends. Jiang et al.92 also prepared PLA-g-MAH and used it as a compatibilizer in another immiscible blend containing PLA and poly(ethylene terephthalate glycol) (PETG), and found that the phase morphology of the blends became finer with addition of PLA-g-MAH. The optimum content of PLA-g-MAH was 3 phr for a PLA/PETG (80/20, w/w) blend, because it produced the finest phase morphology and the largest elongation at break.
The main advantage of this method would be the high reactivity of the low molecular weight chemicals, which would react with the blend components quickly during melt blending. The fast reaction makes the method very suitable to be used in the preparation polymer blends through extrusion, which usually occurs in several minutes. One of the challenges of this method is the unmatched viscosity between the low molecular weight chemicals and blend components. It is hard to mix them uniformly due to the rather low viscosity of the low molecular weight chemicals. In addition, the volatility of some low molecular weight chemicals could result in greater harm to operators.
Poly(butylene succinate) (PBS) is another biodegradable polyester can be obtained from renewable resources and shows excellent mechanical properties with good flexibility. It can be used to toughen PLA without sacrificing both sustainability and biodegradability if their compatibility can be improved. Isocyanates should be good reactive compatibilizers for PLA/PBS blends, since the two components contain hydroxyl groups. Harada et al.94 reported the use of LTI to compatibilize PLA/PBS blends during melt extrusion, and found that the impact strength of a PLA/PBS (90/10, w/w) blend was significantly increased from 18 kJ m−2 to 50–70 kJ m−2 when only 0.5 wt% LTI was added, indicating an improvement in compatibility. LTI also succeeded in compatibilizing immiscible blends of PLA and poly(butylene succinate-co-L-lactate) (PBSL) or poly(butylene succinate-co-ε-caprolactone), as evidenced by the changed phase morphologies reported by Vannaladsaysy et al.95,96 Harada et al.97 compared the compatibilization efficiency of four isocyanates, i.e., LTI, LDI, Duranate TPA-100, and Duranate 24A-100, towards immiscible PLLA/PCL blends, and found that the highest impact strength was obtained when LTI was used, but the authors did not explain the reason for the result. The reason might be that the isocyanate group of LTI is more reactive than that of other isocyanates, and thus could react with both blend components sufficiently to compatibilize the blends.
Fang et al.98 compatibilized immiscible blends of PLA and soy protein isolate (SPI) with MDI. The PLA/SPI blends showed a more uniform morphology in the presence of MDI, due to the formation of block or grafted copolymers of PLA and SPI through urethane linkages generated by reaction of isocyanate group of MDI and hydroxyls of blend components. Phetwarotai et al.99,100 investigated the effect of MDI on the properties of PLA/gelatinized starch blends, and found that the interfacial adhesion between the two phases and the tensile properties were improved by addition of 1.25 wt% MDI. Karagoz et al.101 enhanced compatibility and improved mechanical properties of immiscible blends of PLA and citric acid-modified TPS with MDI, both the tensile and impact strengths of the blends being apparently improved by compatibilization with only 1 wt% MDI. MDI was also reported to be efficient in compatibilization of PLA/chitosan blends.102
With the aim of toughening PLA without significant loss in modulus and ultimate tensile strength, Zaman et al.103 blended PLA with a thermoplastic polyester elastomer (TPEE) in the presence of MDI as a reactive compatibilizer, and investigated the effect of MDI content on the mechanical properties and morphologies of PLA/TPEE blends. The results suggested that the dispersed TPEE particle size decreased with increasing MDI content, and the elongation at break of PLA/TPEE (80/20, w/w) increased to more than 200% with only 1 wt% MDI compared to 80% of the control blend, and the tensile strength was also improved slightly by the addition of MDI.
Thermoplastic polyurethane (TPU) with good flexibility can be used to toughen PLA if their immiscibility issue can be resolved. To improve compatibility of immiscible PLA/TPU blends, Dogan et al.104 introduced PDI into PLA/TPU blends during thermal processing, where reactive compatibilization occurred through reactions between isocyanate groups of PDI and hydroxyl/carboxyl groups of PLA and hydroxyl or urethane groups of TPU. The particle size of TPU in a PLA/TPU (80/20, w/w) blend reduced from 1–2 μm to 0.4–1 μm on average with the addition of 1 wt% PDI, and the optimum PDI content for mechanical properties was only 0.5 wt%.
Wang et al.105 improved compatibility of PLA/PBS blends via an in situ compatibilization procedure in the presence of DCP, and found that when only 0.1 wt% DCP was added, the particle size of dispersed PBS reduced significantly to 0.2–1.0 μm and the blend showed a uniform morphology, which were very beneficial for obtaining excellent mechanical properties. The notched impact strength of a PLA/PBS (80/20, w/w) blend with addition of 0.1 wt% DCP showed the highest value of 30 kJ m−2, compared to 3.7 kJ m−2 for the blend without DCP. Ji et al.106 also studied the effect of DCP on the morphology and properties of PLA/PBS blends, and found that the compatibility of PLA/PBS was increased significantly as evidenced by the decreased dispersed PBS particle size and the finer phase morphology with increasing DCP content, which resulted in significant improvement in mechanical properties. Also, the addition of DCP could cause branched and crosslinked structure, which could work as a nucleation site to accelerate the crystallization rate of PLA. DCP was also applied in compatibilization of PLA/PBAT blends, as reported by Ma et al.107 They found that the introduction of DCP during thermal blending of PLA and PBAT could lead to a reduction in PBAT domain size and an enhancement in interfacial adhesion. The elongation at break and impact strength of the PLA were increased to 300% and 110 J m−1, respectively, after blending with PBAT in the presence of DCP. Branched/crosslinked structure also formed as evidenced by the solid-like behavior in the low-frequency zone. Another peroxide, 2,5-dimethyl-2,5-di(tert-butylperoxy)hexane, was also reported to improve the compatibility of PLA/PBAT blends by Coltelli et al.108 The best compatibilization efficiency was obtained by the addition of 0.2 wt% peroxide for a PLA/PBAT (75/25, w/w) blend, which showed the largest elongation at break and the best phase morphology with smallest PBAT particles dispersed uniformly in PLA matrix. The compatibilization mechanism was proposed as the formation of copolymers consisting of PLA and PBAT through the reaction of macro-radicals PBAT˙ or PBAT–O–O˙ with PLA˙ or PLA–O–O˙ generated in the presence of the peroxide. Dong et al.109 investigated the effect of DCP on the morphology and properties of fully biobased polymer blends of PLA and PHB, and found that the size of dispersed PLA phase was reduced obviously and the phase boundary became unclear on addition of DCP. The mechanical properties of PLA/PHB blends were significantly improved, indicating improved compatibility, which was ascribed to the formation of PHB-g-PLA copolymers and/or PHB-crosslink-PLA network at the interfaces. The compatibility of immiscible PLA/NR blends could be also significantly enhanced by addition of DCP through the formation of crosslinking copolymers containing both PLA and NR, as reported by Huang et al.110
Shin et al.112 compatibilized PLA/PCL blends through addition of GMA monomer with the help of electron-beam irradiation. Two steps were involved in this technique. In the first step, melt blending of PLA, PCL and GMA was carried out in a twin-screw co-rotating extruder, which caused the formation of PLA/PCL blends with GMA located at the interface. The existence of GMA could result in a fine dispersion of minor PCL in the PLA matrix. In the second step, electron-beam irradiation was used to initiate the cross-copolymerization of GMA at the interface to enhance interfacial adhesion between PLA and PCL phases. The combination of the two steps could result in a significant improvement in compatibility between PLA and PCL.
Xiong et al.113 compatibilized immiscible PLA/starch blends with epoxidized soybean oil (ESO), which is usually used as an eco-friendly plasticizer for PVC and chlorinated rubber and contains several epoxy groups available for the reaction with carboxyl and hydroxyl groups of polymers. Limited improvement in compatibility was obtained by direct blending of PLA with starch and ESO, due to the relatively low reactivity of hydroxyl towards epoxy groups of ESO, while sufficient compatibilization occurred if MA-grafted native starch (MGST) was used to replace native starch to blend with PLA and ESO, owning to the increased reaction possibility between ESO and MGAT. The formation of the actual compatibilizer, i.e., copolymer of starch and PLA, is shown in Fig. 9.
Fig. 9 Possible reaction in PLA/MGST blends compatibilized by ESO during melt blending process. Reprinted with permission from ref. 113. Copyright 2014 Elsevier. |
Jariyasakoolroj et al.114 reported the compatibilization of PLA and starch by the use of chloropropyltrimethoxysilane (CPMS), which was first grafted onto the surface of the starch through formation of covalent bonds to modify the starch. The CPMS-grafted starch would then react with PLA during blending to generate copolymers of PLA and starch, which provided compatibility between PLA and starch and also worked as a nucleating agent to significantly increase the degree of crystallinity.
Epoxy is one of the most widely reported reactive groups incorporated into polymers to prepare compatible PLA blends, which should be ascribed to the high reactivity towards terminal groups of PLA and easy introduction of epoxy to polymers through copolymerization of GMA with other vinyl monomers. In order to improve the compatibility between liquid natural rubber and PLA, Nghia et al.115 modified the liquid natural rubber by incorporation of epoxy groups, which would react with the terminal carboxyl groups of PLA to form covalent bonding at the interface to enhance the interfacial adhesion and improve the compatibility. Oyama116 prepared a super-tough PLA blend by reactive blending of PLA with an ethylene copolymer, EGMA, which contains 3 wt% GMA. The epoxy groups could react with the terminal carboxyl and hydroxyl groups of PLA leading to sufficient compatibility between the two components. Super-tough PLA/EGMA blends with impact strength of 72 kJ m−2 could be obtained when the dispersed EGMA particle size was reduced to 100–300 nm under suitable processing conditions. Su et al.117 prepared compatibilized PLA binary blends by blending with a GMA-grafted poly(ethylene octane) (GMA-g-POE). The good compatibility was also ascribed to the reaction between epoxy groups of GMA-g-POE and terminal groups of PLA. In order to toughen PLA with ABS and improve compatibility of PLA/ABS blends, Su et al.118 prepared GMA-functionalized ABS (ABS-g-GMA) and used it as a component to blend with PLA. They found that compatibilization and crosslinking took place simultaneously between the epoxy groups of ABS-g-GMA and the end carboxyl or hydroxyl groups of PLA. Super toughness of the blend was obtained, as evidenced by an impact strength of 540 J m−1 when only 1 wt% GMA was grafted to ABS. When some other polymers such as poly(butyl acrylate-co-ethyl acrylate) and poly(methyl methacrylate-co-butadiene) were modified by GMA, they also showed good compatibility with PLA, and their blends showed excellent mechanical properties, as reported by Hao et al.119,120
Anhydride groups can be incorporated into polymer chains with the aid of free radicals, and thus are sometimes introduced into the blending component of PLA-based blends to improve compatibility. Orozco et al.121 prepared PLA-g-MAH and used it as a component to blend with starch so as to obtain a PLA/starch blend with improved compatibility and mechanical properties. The compatibilization happened by the reaction between anhydride groups of PLA and the side hydroxyl groups of starch.
Yoon et al.122 studied the effects of blend composition and blending time on the interchange reaction and tensile properties of PLA blends with low and high molecular weight PCL (PLA/LPCL/HPCL), and found that a copolymer of PLA and PCL was formed by the ester interchange reaction at 220 °C for 30–60 minutes, and the tensile strength and modulus of blends increased with increasing HPCL content, while the elongation at break of the blend increased with increasing LPCL content.
Coltelli et al.123 investigated the interchange reaction between PLA and PBAT in a discontinuous mixer with tetrabutyl titanate, Ti(OBu)4, as a catalyst, and found that the dispersed PBAT particle size decreased and interfacial adhesion increased with increasing blending time, and that good compatibility could be obtained when the blending was performed at 200 °C for more than 20 min with a Ti(OBu)4 content of 0.07 wt%. Lin et al.124 carried out interchange esterification between PLA and PBAT at 165–175 °C through melt extrusion at a screw speed of 90 rpm. They studied the effect of the added content of the catalyst Ti(OBu)4 on the compatibility and mechanical properties of PLA/PBAT blends, and found that large PBAT particles dispersed non-uniformly in the PLA matrix in pristine PLA/PBAT blend and a distinct interface can be observed, while when Ti(OBu)4 was added, the size of PBAT particles decreased and the interface became obscure, indicating improved compatibility. The particle size of PBAT was reduced to 0.5 μm when 0.5 wt% Ti(OBu)4 was added and the blends showed tensile strength, elongation at break and impact strength of 45 MPa, 298% and 9 kJ m−2, respectively, compared to 35 MPa, 46% and 5 kJ m−2 for the pristine PLA/PBAT blend.
Sadik et al.125 studied the interchange reaction between PLA and poly(ethylene-co-vinylalcohol) (EVOH) in the absence and presence of different catalysts, i.e., 1,5,7-triazabicyclo[4.4.0]dec-5-ene (TBD) and tin(II) bis(2-ethylhexanoate) (Sn(Oct)2). The reaction was accelerated by the addition of both catalysts, but Sn(Oct)2 showed higher catalytic efficiency than TBD. The reaction finished in only a few minutes if Sn(Oct)2 was used as the catalyst at 200 °C. PLA-grafted EVOH was formed through the reaction as confirmed by thermal, thermomechanical and 1H NMR analyses.
To improve compatibility and physical properties of PLA blends with PC, Phuong et al.126 added tetrabutylammonium tetraphenylborate (TBATPB) and triacetin (TA) into the blends during melt processing. Interchange reaction between PLA and PC occurred when TBATPB and TA were used as catalysts, and thus PLA–PC copolymers were formed in the blends. Consequently, the compatibility between PLA and PC was improved significantly with co-continuous phase morphology formed, and mechanical strength of the compatibilized blends was improved significantly.
Recently, Thurber et al.127 improved the compatibility of PLA/PE blends by addition of interfacially localized catalysts. In the study, the compatibilization occurred through interchange reaction between telechelic hydroxyl functional PE and PLA. Interfacially localized catalyst (stannous octoate) accelerated the interchange reaction and resulted in improved compatibility. The size of dispersed PLA domain decreased while the number of dispersed PLA particles increased considerably.
Interchange reaction is a simple, efficient, and eco-friendly method to compatibilize PLA-based blends. However, the method has some limitations, as it is only applicable when the blend components have exchangeable functional groups. Such reaction could not happen between PLA and some vinyl polymers. In addition, interchange reaction usually occurs at high temperatures, where thermal degradation of the components cannot be avoided, which would lead to deterioration of properties, and undesirable color and appearance.
The dispersed phase in this technique is a rubber, which is a very efficient toughening agent for brittle polymers. Therefore, this technique is very powerful for toughening of PLA. Liu et al.128–130 for the first time employed this technique to prepare PLA-based materials with super toughness. The rubber phase that they used is an ethylene-butyl acrylate-glycidyl methacrylate (EBA-GMA) terpolymer, and a zinc ionomer of ethylene methyacrylic acid copolymer (EMAA-Zn) was used as a catalyst, of which the carboxyl group initiated the crosslinking of epoxy groups in the EBA-GMA phase, and zinc ions catalyzed the reaction between the epoxy groups of EBA-GMA and the terminal groups of PLA to improve interfacial adhesion between the dispersed rubber phase and the PLA matrix. Morphological analysis indicated that the binary blend of PLA/EBA-GMA (80/20, w/w) showed very fine morphology with EBA-GMA dispersed uniformly in the PLA matrix at the size of ∼0.3 μm due to the good compatibility of the blend resulting from the reaction of epoxy of EBA-GMA and hydroxyl of PLA; the vulcanization of EBA-GMA after introduction of EMAA-Zn led to an increase in the size of dispersed phase in the PLA/EBA-GMA/EMAA-Zn (80/10/10, w/w/w) to ∼0.83 μm, which is in the optimum range for high toughening efficiency in rubber-toughened PLLA blends. Through dynamic vulcanization and interfacial compatibilization, the ternary blends showed elongation at break and notched impact strength of 229.1% and 777.2 J m−1, respectively, compared to 10.2% and 101.9 J m−1 for the binary PLA/EBA-GMA blend.
Chen et al.131 employed dynamic vulcanization and interfacial compatibilization to improve compatibility between PLA and NR by melt blending in the presence of DCP as an initiator. The thermal decomposition of DCP led to the formation of free radicals, which then initiated vulcanization of NR and also caused the formation of PLA macroradicals that reacted with NR to generate copolymers to enhance interfacial adhesion between PLA and vulcanized NR. A super-tough blend with notched impact strength of 58.3 kJ m−2 was obtained when 35 wt% NR was blended with 65 wt% PLA. It is interesting that in such a system, the minor phase of NR changed to the continuous phase while the major PLA phase became the dispersed phase after dynamic vulcanization and interfacial compatibilization. But the mechanism for the formation of continuous vulcanized NR phase was unclear.
Fang et al.132 reported super-tough PLA blends with poly(ethylene glycol) diacylate (PEGDA) monomer via dynamic vulcanization and interfacial compatibilization without additional radical initiators. Rheological measurement suggested that thermally induced crosslinking of PEGDA occurred when the temperature was increased to higher than 116 °C in the absence of additional initiator. They thought that the polymerization may be initiated by free radical species such as radical impurities, peroxides, and oxygen plasma. When PEGDA was melt blended with PLA, the crosslinking of PEGDA finished within the blending period of 10 min, as evidenced by the change of melt torque of the blend. FT-IR analysis indicated that in situ compatibilization took place by interchange esterification of PLA and PEGDA during melt blending. The blends after dynamic vulcanization and interfacial compatibilization showed notched impact strength up to 50 kJ m−2 when 15 wt% PEGDA was introduced.
Recently, we have introduced two different crosslinked polyurethanes (CPUs), which were obtained via in situ polymerization, as the rubber phases to toughen PLA through dynamic vulcanization and interfacial compatibilization.133,134 In one case, the CPU was composed of poly(ethylene glycol) (PEG) and polymeric methylenediphenylene diisocyanate (PMDI). During blend preparation, PLA was first premixed with PEG in an internal mixer at 190 °C for 4 min, the blending being finished when the melt torque leveled off after the addition of PMDI. The CPU was in situ formed through polymerization of PEG with PMDI, and interfacial compatibilization occurred by the reaction of isocyanate groups with the terminal groups of PLA, as evidenced by FT-IR analysis. A super-tough PLA blend was obtained when the content of the incorporated CPU was 30% with elongation at break and notched impact strength of ∼250% and 546 J m−1, respectively. In order to further investigate the effect of crosslinking density of CPU on the properties of CPU-toughened PLA blends, PMDI was replaced by MDI and glycerol in the other system. The crosslinking density, which was proved to be very important in determining phase morphology and mechanical properties of PLA/CPU blends, could be tuned by the content of the tri-functional monomer glycerol. The particle size of CPU in PLA matrix increased gradually while the notched impact strength increased first and then decreased with increasing CPU crosslinking density. The highest notched impact strength of 407.6 J m−1 was achieved for a PLA/CPU (80/20, w/w) blend that contained 10 wt% glycerol (based on PEG weight), and the particle size of CPU in this blend was ∼0.76 μm, which was just in the optimum range for rubber-toughened PLA blends.
In order to produce super-tough PLA materials without compromising sustainability, we prepared an unsaturated aliphatic polyester elastomer (UPE) from biobased monomers and melt blended it with PLA in the presence of DCP as a free radical initiator via a dynamic vulcanization and interfacial compatibilization technique.135 During melt processing, dynamic vulcanization of UPE occurred by the initiation of free radicals formed via thermal decomposition of DCP. Meanwhile free radicals could abstract hydrogen from PLA polymer chains to generate PLA macroradicals, which then grafted onto the vulcanized UPE dispersed phases via attacking the double bonds of the UPE to form grafting copolymers, which located at the interface to significantly improve the interfacial adhesion between the two phases. Fig. 11 shows the proposed reactions for the preparation of PLA blends with UPE through dynamic vulcanization and interfacial compatibilization. The blend was named thermoplastic vulcanizate (TPV) which refers to a polymer blend with a crosslinked rubber phase dispersed finely in a thermoplastic matrix. Super-tough TPV with elongation at break and notched impact strength of 259.9% and 586.6 J m−1 was obtained by blending PLA with 20 wt% UPE in the presence of 0.2 phr DCP at 180 °C and 50 rpm for about 10 min.
Fig. 11 Possible reactions in preparation of super-tough PLA blends with unsaturated aliphatic polyester elastomer (UPE) through dynamic vulcanization and interfacial compatibilization. Reprinted with permission from ref. 135. Copyright 2014 American Chemical Society. |
Chen et al.47 evaluated the effect of twice-functionalized organoclay (TFC) on the compatibility between PLA and PBS, and found that the content of TFC played an important role in the morphology of the blend. TFC exfoliated fully and dispersed almost exclusively in the PLA matrix and the domain size of dispersed PBS did not change considerably when the content of TFC was less than 0.5 wt%; while as the TFC content increased, the clay layers dispersed in both PLA and PBS phases and the domain size of PBS became much smaller and increased gradually with further increasing TFC content. This change with increasing TFC content was attributed to two factors. On the one hand, TFC with functional groups could react with both PLA and PBS, thus acting like a reactive compatibilizer. On the other hand, some clay layers that located at the interface of PLA/PBS blend could prevent coalescence of the dispersed domains and contribute to the reduction in the domain size. Hoidy et al.136 compatibilized PLA/PCL blends with organoclay (OMMT), and found that the presence of OMMT as a filler not only enhanced the dispersion and interfacial adhesion of the polymer matrix but also improved mechanical properties and thermal stability of PLA/PCL blends. Ojijo et al.137 compatibilized PLA/PBSA blends with organoclay (C20A) and investigated the effect of the content of C20A on the properties of the blends. They found that the optimum properties for a PLA/PBSA (70/30, w/w) blend was obtained when the content of C20A was 2 wt%. Risse et al.138 tailored the morphology and properties of PLA/PBS blend by addition of an organoclay (Cl30B). They found that Cl30B exfoliated partially in the blend and its content played an important role in the morphology and properties of the blend. Co-continuous morphology of a PLA/PBS (50/50, w/w) blend with a ductile behavior was achieved when 3 wt% Cl30B was added, while lamellar morphology accompanied by brittleness was obtained with further increasing Cl30B content. A recent study by Ferreira et al.139 suggested that the addition of Cloisite® 30B (C30B) into TPS/PLA blends would improve adhesion between the two phases, compared to the unmodified binary blends.
Carbon nanotubes are a new type of anisotropic one-dimensional nanoparticles, which have attracted considerable attention in terms of reinforcing physical properties of polymer matrices through nanocomposite technology, due to their extraordinarily high elastic modulus, strength, and resilience. They could also be used in improving the compatibility of immiscible blends via selective localization, as reported by Wu et al.140 They functionalized multiwalled carbon nanotubes (MWCNT) with carboxyl groups, and added the functionalized MWCNT into melts of immiscible PCL/PLA blend during mixing with a rheometer. The compatibility between PCL and PLA was improved obviously by the addition of functionalized MWCNT, as evidenced by the significant reduction of dispersed PLA domain size and the enhanced interfacial adhesion. The dispersed PLA particle size in a PCL/PLA (70/30, w/w) blend decreased apparently from 21.5 to 6.3 μm as the MWCNT loadings increased up to 1 phr. The improved compatibility was attributed to the special morphological structure that was formed in which carboxylic MWCNTs mainly dispersed in the PCL matrix and at the phase interface. The compatibilized PCL/PLA blends then showed highly improved performance with respect to rheological, conductive, and mechanical properties as compared with those of unmodified PCL/PLA blend.
Another nanoparticle that has been used to compatibilize immiscible PLA blends is silica, as reported by Odent et al.141 in PLA blend with a rubbery ε-caprolactone-based copolyester, P[CL-co-LA]. They found that P[CL-co-LA] with sphere-like nodules dispersed regularly in the PLA matrix in a blank blend containing 10 wt% P[CL-co-LA], while the spherical nodules disappeared when 5 wt% hexamethyldisilazane surface-treated fumed silica nanoparticles were added and oblong microstructures began to appear, and more interestingly co-continuous morphology was observed with further increasing silica nanoparticle content up to 10 wt%, as shown in Fig. 12. Such a morphological change was ascribed to the presence of large-surface silica nanoparticles at the interface of the blend components. The impact strength of the blend by addition of silica was significantly increased from 11.4 kJ m−2 for the blank blend to 27.3 and 39.7 kJ m−2 for blends containing 5 and 10 wt% silica, respectively.
Fig. 12 TEM images of room-temperature notched surfaces of PLA-based materials containing 10 wt% of P[CL-co-LA] copolyester without silica nanoparticles (a), and with 5 wt% (b and b′) and 10 wt% of silica nanoparticles (c and c′). Reprinted with permission from ref. 141. Copyright 2013 Elsevier. |
Recently, Monticelli et al.142 evaluated the effects of different types of modified polyhedral oligomeric silsesquioxane (POSS) on the compatibility of PLA/PCL blends. Addition of unmodified POSS reduced the size of PCL domains; addition of hydroxyl group-functionalized POSS (POSS–OH) increased the adhesion between PLA and PCL; and addition of poly(ε-caprolactone)-b-poly(L-lactide) diblock copolymer-grafted POSS (POSS-PCL-b-PLLA) led to the formation of an almost homogeneous microstructure. All the characteristics indicated the improved compatibility of the blends.
Introducing some special interactions such as hydrogen bonding between PLA and the other blend component is also able to improve compatibility. The work by Kuo et al.145 indicated that addition of bisphenol A (BPA) was able to improve compatibility between PLA and PCL since both polymers are miscible with BPA. In order to improve compatibility between PLA and polystyrene (PS), Zuza et al.44 incorporated hydroxyl groups into PS by copolymerization of styrene with hydroxystyrene (HS) and then blended the modified PS with PLA. The introduction of hydroxyl groups to PS led to the formation of hydrogen bonding with carbonyl groups of PLA, resulting in significant improvement in compatibility between the two polymers. A completely miscible blend was even achieved when the molar content of HS was increased to 16%.
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