Synthesis of Starch-g-Poly(glycidyl methacrylate) and Its Blending with Poly(ϵ-caprolactone) and Nylon 610

Different amounts of glycidyl methacrylate (GMA) were grafted onto corn starch dispersed in water or dimethyl sulfoxide (DMSO) to yield starch-graft-poly(glycidyl methacrylate) (ST-g-PGMA). ST-g-PGMAW, obtained by grafting PGMA onto corn starch that was dispersed in water, showed a higher PGMA grafting content and a lower content of the homopolymerized PGMA than ST-g-PGMAD, which was prepared in DMSO. The modified starches were blended with poly(ϵ-caprolactone) (PCL) and nylon 610, respectively, and the tensile properties of the blends were measured by UTM. Mechanical properties of the biodegradable ST-g-PGMA/PCL blends were dependent on the PGMAD content grafted on starch. Without dramatic loss of the tensile properties of PCL, ST-g-PGMAW was melt blended with PCL. Meanwhile, an increase in the tensile modulus was observed in the ST-g-PGMAW/nylon 610 blend. When nylon 610 was reacted with ST-g-PGMAW in DMSO in the presence of triethylamine, the tensile modulus and strength were much higher than those of the pure nylon 610, and phase-separated domains of starch were not observed microscopically.     

Chitosan-graft-poly(ϵ-caprolactone)s: An optimized chemical approach leading to a controllable structure and enhanced properties

A novel synthetic approach was developed for the controllable modification of chitosan (CS) with poly(ϵ-caprolactone) (PCL). 6-O-Triphenylmethyl-chitosan (TMCS) was synthesized as a highly soluble intermediate in organic solvents to facilitate an efficient grafting reaction of PCL onto CS in a homogeneous reaction medium. Subsequently, the syntheses of CS-g-PCL copolymers with different degrees of substitution (ds) and various chain lengths of PCL (number-average molecular weight = 1200–11,000) were carried out by a coupling reaction between the carboxylic terminal groups of PCL chains and the amino groups of TMCS. The successful grafting reaction was confirmed by GPC measurements, which indicated that the products were graft copolymers rather than physical blends. The ds, defined as the number of PCL chains per saccharide unit, of the graft copolymers could be adjusted simply by changes in the molar feed ratios of PCL to CS, and graft copolymers with different ds values ranging from 0.28 to 0.49 were synthesized, as calculated by ¹H NMR and elemental analysis. DSC and X-ray measurements showed that the melting temperature and enthalpy of the PCL grafts of these graft copolymers could be adjusted by the ds and the chains length of PCL, respectively. Meanwhile, the CS-g-PCL copolymers exhibited better solubility in various solvents, such as in chloroform for some of the resultant graft copolymers, than the original CS. Finally, nanoparticles of 100–200 nm, having hydrophobic PCL domains and cationic hydrophilic surfaces, were obtained through the self-assembly of the copolymers in selective solvents. These types of graft copolymers have great potential in various applications, such as targeted drug and gene delivery as well as tissue engineering. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 2556–2568, 2007     

Synthesis, characterization and self-assemble behavior of chitosan-O-poly(ε-caprolactone)

A facile strategy was proposed for synthesizing chitosan-O-poly(ε-caprolactone) (CS-O-PCL). Stoichiometric sodium dodecyl sulfate-chitosan complex (SCC) which was soluble in common organic solvents was adopted as an intermediate. Regioselective conjugation of PCL onto SCC could be achieved through condensation reaction between isocyanate-terminated PCL and hydroxyl groups of chitosan. The grafting level of PCL could be modulated by varying PCL/SCC weight ratio. SDS was removed from SCC-O-PCL using trihydroxymethylamine (Tris) as a decomplexation agent. The self-assemble behavior of the amphiphilic copolymers was studied by fluorometry, TEM and laser light scattering. The morphology of the CS-O-PCL nanoparticles was found to be dependent on PCL grafting level. Both spherical micelles and vesicle could be formed by dialysis method.     

Fabrication of cationic nanomicelle from chitosan-graft-polycaprolactone as the carrier of 7-ethyl-10-hydroxy-camptothecin

In this research, amphiphilic brush-like polycations were synthesized, and used to fabricate cationic nanomicelle as the carrier of 7-ethyl-10-hydroxy-camptothecin (SN-38), in order to enhance its cellular uptake, solubility and stability in aqueous media. In particular, cationic chitosan-graft-polycaprolactone (CS-g-PCL) copolymers were synthesized with a facile one-pot manner via ring-opening polymerization of ɛ-CL onto the hydroxyl groups of CS by using methanesulfonic acid as solvent and catalyst. The formation of CS-g-PCL nanomicelles was confirmed by fluorescence spectrophotoscopy and particle size measurements. It was found that all the nanomicelles showed spherical shapes with narrow size distributions. Their sizes ranged from 47 to 113 nm, and the zeta potentials ranged from 26.7 to 50.8 mV, depending on the grafting content of PCL in CS-g-PCL, suggesting their passive targeting to tumor tissue and endocytosis potential. Water-insoluble antitumor drug, SN-38, was easily encapsulated into CS-g-PCL nanomicelles by lyophilization method. In comparison with bare CS-g-PCL nanomicelles, the corresponding SN-38-loaded nanomicelles showed increased particle sizes and a little reduced zeta potentials. With an increase of grafting PCL content, the drug encapsulation efficiency (EE) and drug loading (DL) of the nanomicelles increased from 64.3 to 84.6% and 6.43 to 8.66%, respectively, whereas their accumulative drug release showed a tendency to decrease due to the enhanced hydrophobic interaction between hydrophobic drug and hydrophobic PCL segments in CS-g-PCL. Also, the CS-g-PCL nanomicelles effectively protected the active lactone ring of SN-38 from hydrolysis under physiological condition, due to the encapsulation of SN-38 into the hydrophobic cores in the nanomicelles. Compared with free SN-38, the SN-38-loaded nanomicelles showed essential decreased cytotoxicity against L929 cell line, and bare CS-g-PCL nanomicelles almost showed non-toxicity. These results suggested the potential utilization of the CS-g-PCL nanomicelles as the carriers of hydrophobic drugs with improving the delivery and release properties.     

Ceric-initiated polymerization onto polyacrylonitrile with carbohydrate end groups. Graft versus block copolymer formation

Starch-g-polyacrylonitrile (starch-g-PAN) copolymers were prepared by ceric ammonium nitrate initiation, and the major portion of the starch in these graft copolymers was then removed by acid hydrolysis to yield PAN with oligosaccharide end groups. Although these PAN-oligosaccharide samples reacted with methyl methacrylate in the presence of ceric ammonium nitrate, the resulting products were largely graft copolymers rather than the expected PAN-poly(methyl methacrylate) (PMMA) block copolymers. The following evidence is presented for a PAN-g-PMMA structure: (i) PAN without oligosaccharide end groups also produced a copolymer with methyl methacrylate under our reaction conditions. (ii) Starch-g-PAN (51 or 37% add-on) was a less reactive substrate toward ceric-initiated polymerization than PAN with oligosaccharide end groups. (iii) Low-add-on (18%) starch-g-PAN reacted with methyl methacrylate to give a final graft copolymer in which a large percentage of PMMA was grafted to the PAN component rather than to starch.     

The behavior of poly(ε -caprolactone) and poly(ethylene oxide)-b-poly(ε -caprolactone) grafted to a poly(glycerol adipate) backbone at the air/water interface

The behavior of crystallizable poly(ε-caprolactone) (PCL) and poly(ε-caprolactone)-b-poly(ethylene oxide) (PCL-b-PEO) is studied at the air/water interface prior and after grafting to an amorphous poly(glycerol adipate) (PGA) backbone (PGA-g-PCL, PGA-g-(PCL-b-PEO)). Langmuir isotherms are measured and the structure formation in the monolayers on the water surface is followed by Brewster angle microscopy (BAM) and in Langmuir–Blodgett films after a transfer to silicon substrates by atomic force microscopy (AFM). It is observed that PGA-g-PCL forms significantly smaller crystals on the water surface and has smaller crystallization rate compared to PCL homopolymers of identical molar masses as the grafted chains. In contrast to crystals formed by linear PCL, the crystals formed by grafted PCL in PGA-g-PCL do not melt (readsorb at the water surface) in an expansion cycle on the Langmuir trough. Additionally, increasing the subphase temperature at constant surface area significantly above the melting point of linear PCL in bulk results in the formation of a mesophase, and it does lead to the disappearance of crystals. The isotherms of PGA-g-(PCL-b-PEO) show a transition at the surface pressure of ～10 mN/m. This is related to the fact that PEO chains leave the water surface and submerge into the subphase and/or the crystallization of PCL chains. The monolayer collapse appears in an extended plateau region starting at π values of ～30 mN/m. AFM images of Langmuir–Blodgett films reveal that PCL chains in PGA-g-PCL and PGA-g-(PCL-b-PEO) form lamellar crystals with a disk-shape and interconnected platelets, respectively.     

Study of hydrogen bonding and thermal properties of polybenzoxazine and poly‐(ε‐caprolactone) blends

The thermal properties of physical blends containing benzoxazine monomer and polycaprolactone (PCL) were monitored by DSC and Fourier transform infrared spectroscopy (FTIR). The ring‐opening reaction and subsequent polymerization reaction of the benzoxazine were facilitated significantly by the presence of a PCL modifier. Hydrogen‐bond formation between the hydroxyl groups of polybenzoxazine and the carbonyl groups of PCL was evident from the FTIR spectra. Only one glass‐transition temperture (T_g) value was found in the composition range investigated, and the T_g value of the resulting blend appeared to be higher in the blend with a greater amount of PCL. © 2001 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 39: 736–749, 2001     

Structure–property relationship in PCL/starch blend compatibilized with starch‐g‐PCL copolymer

The polycaprolactone (PCL)/starch blends were prepared by using the starch‐g‐PCL (SGCL) graft copolymers as compatibilizers, and their mechanical properties were correlated with the compatibilizing effect of the SGCL copolymers having various molecular structures. The modulus and strength of the PCL/starch blend were decreased, whereas the percent elongation and the toughness were increased remarkably with the addition of SGCL having appropriate graft structure. These property changes were analyzed in terms of the PCL crystallinity and the interfacial adhesion between the PCL matrix and starch dispersion phases, which were dominated by the compatibilizing effects of the SGCL copolymers. © 1999 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 37: 2430–2438, 1999     

Biodegradable compositions by reactive processing of aliphatic polyester/polysaccharide blends

Commercially available biodegradable aliphatic polyesters, i.e., high molecular weight poly(ϵ-caprolactone) (PCL) and polylactide (PLA), were melt blended with a well-known natural and biodegradable polysaccharide: starch either as corn starch granules or as thermoplastic corn starch after plasticization with glycerol. Conventional melt blending yielded compositions with poor mechanical performances as a result of lack of interfacial adhesion between the rather hydrophobic polyester matrix and the highly hydrophilic and moisture sensitive starch phase. Interface compatibilization was achieved via two different strategies depending on the nature of the polyester chains. In case of PLA/starch compositions, PLA chains were grafted with maleic anhydride through a free radical reaction conducted by reactive extrusion. The maleic anhydride-grafted PLA chains (MAG-PLA) allowed for reinforcing the interfacial adhesion with granular starch as attested by TEM of cryofracture surface. As far as PCL/starch blends were concerned, the compatibilization was achieved via the interfacial localization of amphiphilic graft copolymers formed by grafting of PCL chains onto a polysaccharide backbone such as dextran. The PCL-grafted polysaccharide copolymers were synthesized by controlled ring-opening polymerization of ϵ-caprolactone proceeding via a coordination-insertion mechanism. These compatibilized PCL/starch compositions displayed much improved mechanical properties as determined by tensile testing as well as a much more rapid biodegradation as measured by composting testing.     

Pyrolysis of polyphenylenes with PCL or/and PSt side chains

Thermal degradation characteristic of polyphenylenes is an important issue for developing a rational technology of polymer processing and applications. In this study, we discussed thermal degradation of polyphenylenes (PP) with poly(-caprolactone) (PCL) and/or PCL/polystyrene copolymers (PSt) prepared by combined controlled polymerization and cross-coupling processes via direct pyrolysis mass spectrometry. When PP-graft-PCL/PSt copolymers were considered, thermally less stabile PCL side chains decomposed in the first step. In the second stage of pyrolysis, the decomposition of the polystyrene chains has taken place. A slight increase in thermal stability of PCL chains for PP-graft-PCL/PSt copolymers was noted compared to copolymer PP-graft-PCL due to the interaction between PSt and PCL chains. This interaction was stronger when PSt chains were linked to the 2-position of the 1,4-phenylene ring.     

Starch/Polycaprolactone Blends Compatibilized with Starch Modified Polyurethane

Starch modified polyurethane(St-PCL) was synthesized via chemical modification of corn starch with hexamethylene diisocyanate terminated polycaprolactone. The obtained St-PCL with different grafting rates was used as compatibilizer of starch/polycaprolactone(St/PCL) blend. The structure of St-PCL was confirmed by FTIR, and the grafting rate could reach as high as 64%. In addition, a lower St-PCL amount can effectively improve the compatibility of St/PCL blends. And the thermal, mechanical and hydrophobic properties of St/PCL blends could be tailored by the amount of St-PCL.     

Epoxy resin/poly(ϵ‐caprolactone) blends cured with 2,2‐bis[4‐(4‐aminophenoxy)phenyl]propane. I. Miscibility and crystallization kinetics

Crystalline thermosetting blends composed of 2,2′‐bis[4‐(4‐aminophenoxy)phenyl]propane (BAPP)‐cured epoxy resin (ER) and poly(?‐caprolactone) (PCL) were prepared via the in situ curing reaction of epoxy monomers in the presence of PCL, which started from initially homogeneous mixtures of diglycidyl ether of bisphenol A (DGEBA), BAPP, and PCL. The miscibility of the blends after and before the curing reaction was established with differential scanning calorimetry and dynamic mechanical analysis. Single and composition‐dependent glass‐transition temperatures (T_g's) were observed in the entire blend composition after and before the crosslinking reaction. The experimental T_g's were in good agreement with the prediction by the Fox and Gordon–Taylor equations. The curing reaction caused a considerable increase in the overall crystallization rate and dramatically influenced the mechanism of nucleation and the growth of the PCL crystals. The equilibrium melting point depression was observed for the blends. An analysis of the kinetic data according to the Hoffman–Lauritzen crystallization kinetic theory showed that with an increasing amorphous content, the surface energy of the extremity surfaces increased dramatically for DGEBA/PCL blends but decreased for ER/PCL blends. © 2003 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 41: 1085–1098, 2003     

Thermal characterization of polycarbonate/polycaprolactone blends

In this work, we prepared blends of bisphenol A polycarbonate (PC) and poly(ϵ‐caprolactone) (PCL) in a wide composition range by melt mixing and solution mixing. Two different molecular weights of PCL were used (nominally, 10.000 g/mol, PCL10, and 80.000 g/mol, PCL80). The thermal behavior of both systems was studied via differential scanning calorimetry under dynamic and isothermal conditions. The blends were miscible in the entire composition range in the liquid and amorphous states, as indicated by the single glass‐transition temperature (T_g) exhibited by both the PC/PCL10 and PC/PCL80 blends. The compositional variation of the T_g was accurately described by the Fox equation for the PC/PCL80 blends, whereas slight deviations from this equation were exhibited by the PC/PCL10 blends. For blend compositions containing 40% or more PCL, either one or both blend components crystallized. Crystallization occurred during cooling from the melt or during subsequent heating in the form of cold crystallization. Although PCL crystallization was reduced and its crystallization rate decreased with the addition of PC, PCL was a very effective macromolecular plasticizer for PC, to the extent that crystallization during the scan was detected for some blend compositions. Isothermal crystallization experiments allowed the determination of equilibrium melting points (T) by the Hoffman–Weeks extrapolation method. A T depression was found for both PCL and PC components as the content of the other blend component was increased. The Avrami equation was closely obeyed by both blend components during the isothermal overall crystallization kinetics up to crystalline conversion degrees of 60–70% and with values of Avrami indices ranging from 3 to 4, depending on the crystallization temperature employed. © 2001 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 39: 771–785, 2001     

Solid-State NMR Studies of Polysaccharide Systems

Summary: Two polysaccharide systems were studied by solid-state NMR methods: (i) Chitin/glucan complexes. The ¹³C NMR spectra have shown that in samples isolated from the mushroom Pleurotus sp., the glucan content was always higher in stems than in pilei. While carbonyl lineshape in complex isolated from Aspergillus niger mycelium shows similar hydrogen bonding as in neat chitin, a significantly higher amounts of hydrogen bonding between carbonyl groups of chitin and hydroxy groups of glucan was found in complexes isolated from Pleurotus sp. (ii) Biodegradable starch/polycaprolactone (PCL) blends. From the relaxation times T₁(H) and T_1ρ(H) it follows that blends starch/PCL, starch/ester oligomers and starch formate/ester oligomers are phase-separated even on the scale 20–110 nm. On the contrary, starch formate/PCL blend is phase-separated on the scale 1–9 nm but homogeneously mixed on the scale 20–90 nm. Therefore formylation of starch significantly improves its miscibility with PCL.     

PLA maleation: an easy and effective method to modify the properties of PLA/PCL immiscible blends

In this study, maleic-anhydride-grafted polylactide (PLA-g-MA) was investigated as a potential compatibilizing agent for the polylactide (PLA)/poly(ε-caprolactone) (PCL) system, with the aim of enhancing the final properties of the two polymer blends. Indeed, PLA-g-MA was prepared via reactive blending through a free radical process and characterized by means of ¹H-NMR and titration measurements, which demonstrated that the employed procedure allows grafting 0.7 wt% of MA onto the polymer backbone, while avoiding a dramatic reduction of PLA molecular mass. The specific effect of the MA-grafted PLA on the features of the PLA/PCL system was highlighted by adding different amounts of PLA-g-MA to 70:30 (w/w) PLA/PCL blends, where the 70 % PLA component was progressively substituted by its maleated modification. The efficiency of PLA-g-MA as a compatibilizer for the PLA/PCL blends was assessed through SEM analysis, which showed that the dimensions of PCL domains decrease and their adhesion to PLA improves by increasing the amount of PLA-g-MA in the blends. The peculiar microstructure promoted by the presence of PLA-g-MA was found to enhance the mechanical properties of the blend, improving the elongation at break without decreasing its Young’s modulus. Our study demonstrated that not only the microstructure but also the thermal properties of the blends were significantly affected by the replacement of PLA with PLA-g-MA.     

Blends of polycarbonate and poly(ϵ‐caprolactone) and the determination of the polymer–polymer interaction parameter of the two polymers

The thermal properties of blends of polycarbonate (PC) and poly(ε‐caprolactone) (PCL) were investigated by differential scanning calorimetry (DSC). From the thermal analysis of PC‐PCL blends, a single glass‐transition temperature (T_g) was observed for all the blend compositions. These results indicate that there is miscibility between the two components. From the modified Lu and Weiss equation, the polymer–polymer interaction parameter (χ₁₂) of the PC‐PCL blends was calculated and found to range from −0.012 to −0.040 with the compositions. The χ₁₂ values calculated from the T_g method decreased with the increase of PC weight fraction. By taking PC‐PCL blend as a model system, the values of χ₁₂ were compared with two different methods, the T_g method and melting point depression method. The two methods are in reasonably good agreement for the χ₁₂ values of the PC‐PCL blends. © 2000 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 38: 2072–2076, 2000     

Reactive compatibilization of blends of PET and PP modified by GMA grafting

The melt radical grafting of glycidyl methacrylate (GMA) onto isotactic polypropylene (PP) was carried out in Brabender internal mixer and the influence of reaction procedure, radical initiator concentration and addition of co-monomer (styrene) on the grafting efficiency was examined. The viscosity, the thermal behaviour and melt rheology of PP-g-GMA samples was then analysed as a function of grafted GMA content. Blends of poly(ethylene terephthalate) (PET) with PP and PP-g-GMA (5.2 wt% GMA), prepared in internal mixer, were characterised by SEM, DSC and melt viscosimetry. The morphological analysis of PET/PP-g-GMA blends (80/20, 50/50 w/w) pointed out a marked improvement of phase dispersion (with particle size of about 0.6 μm for 80/20 blend) and interfacial adhesion, as compared to non-compatibilized PET/PP blend. The results of mixing torque and thermal analysis supported the occurrence of in-situ compatibilization reaction between epoxy groups of GMA modified PP and carboxyl end-groups of PET in the melt.     

二醋酸纤维素接枝聚己内酯的核磁共振表征

用^1H-NMR和^13C-NMR研究了二醋酸纤维素(CDA)和聚己内酯(PCL)的接枝共聚反应,确定了^1H-NMR和^13C-NMR谱中各谱峰的归属,为证明二醋酸纤维素和己内酯的接枝共聚反应提供了依据。     

Crystallization and melting of poly(glycerol adipate)‐based graft copolymers with single and double crystallizable side chains

The crystallization and melting behavior of a series of poly(glycerol adipate) (PGA) based graft copolymers with either poly(ε‐caprolactone) (PCL), poly(ethylene oxide) (PEO), or PCL‐b‐PEO diblock copolymer side chains (i.e., PGA‐g‐PCL, PGA‐g‐PEO, and PGA‐g‐(PCL‐b‐PEO)) was studied using polarized light optical microscopy (POM), differential scanning calorimetry (DSC), small‐angle X‐ray scattering (SAXS), and wide‐angle X‐ray diffraction (WAXD). These results were compared with the behavior of the corresponding linear analogs (PEO, PCL, and PCL‐b‐PEO). POM revealed that spherulitic morphology was retained after grafting. However, spherulite radius as well as radial growth rate was significantly smaller in the graft copolymers. Evaluation of isothermal crystallization kinetics by means of the Avrami theory revealed that the nucleation density was much higher in the graft copolymers. The DSC results indicated that the degree of crystallinity decreased strongly upon grafting while the melting temperatures of PGA‐g‐PCL and PGA‐g‐PEO were found to be close to the values of neat PCL and PEO, respectively. This was attributed to the absence of specific thermodynamic interactions, and, additionally, to lamella thicknesses being similar to those of the homopolymers. The latter point was confirmed by SAXS measurements. In case of PCL‐b‐PEO diblock copolymers and PGA‐g‐(PCL‐b‐PEO) graft copolymers, the crystallization behavior and thus the resulting lamellar morphology is more complex, and a suitable model was developed based on a combination of DSC, WAXD, and SAXS data. © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2013 , 51, 1581–1591     

Pyrolysis of polyphenylenes with PCL or/and PSt side chains

Thermal degradation characteristic of polyphenylenes is an important issue for developing a rational technology of polymer processing and applications. In this study, we discussed thermal degradation of polyphenylenes (PP) with poly(ɛ-caprolactone) (PCL) and/or PCL/polystyrene copolymers (PSt) prepared by combined controlled polymerization and cross-coupling processes via direct pyrolysis mass spectrometry. When PP-graft-PCL/PSt copolymers were considered, thermally less stabile PCL side chains decomposed in the first step. In the second stage of pyrolysis, the decomposition of the polystyrene chains has taken place. A slight increase in thermal stability of PCL chains for PP-graft-PCL/PSt copolymers was noted compared to copolymer PP-graft-PCL due to the interaction between PSt and PCL chains. This interaction was stronger when PSt chains were linked to the 2-position of the 1,4-phenylene ring.