Polyether‐segmented nylon hemodialysis membrane. VII. Studies on surface structures of various poly(ethylene oxide)‐segmented nylon membranes

The relationships of the surface morphologies to the surface chemical compositions in poly(ethylene oxide)‐segmented nylon (PEO–Ny) membranes prepared by the phase‐inversion method were studied using scanning electron microscopy (SEM), electron spectroscopy for chemical analysis (ESCA), and static secondary ion mass spectrometry (SSIMS). The PEO–Ny's used were high semicrystalline PEO‐segmented polyiminosebacoyliminohexamethylene (PEO–Ny610), low semicrystalline PEO‐segmented poly(iminosebacoylimino‐m‐xylylene) (PEO–NyM10), and amorphous PEO‐ segmented poly(iminoisophthaloyliminomethylene‐1,3‐cyclohexylenemethylene) (PEO–NyBI). SEM observation showed that the surfaces of the PEO–Ny610 and PEO–NyM10 membranes were composed of crystalline spherulite and that the PEO–NyBI membrane surface had a nodular structure. ESCA analysis exhibited the enrichment of the PEO segment at the surfaces of the PEO–Ny610 and PEO–NyM10 membranes. On the other hand, the enrichment of the Ny segment was observed in the case of the PEO–NyBI membrane. SSIMS analysis revealed that the outermost surfaces of the PEO–Ny membranes except the PEO–NyBI membrane were almost covered with the PEO segment. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 77: 517–528, 2000     

Synthesis and characterization of biodegradable poly(ester‐urethanes) based on bacterial poly(R‐3‐hydroxybutyrate)

A series of poly(R‐3‐hydroxybutyrate)/poly(ε‐caprolactone)/1,6‐hexamethylene diisocyanate‐segmented poly(ester‐urethanes), having different compositions and different block lengths, were synthesized by one‐step solution polymerization. The molecular weight of poly(R‐3‐hydroxybutyrate)‐diol, PHB‐diol, hard segments was in the range of 2100–4400 and poly(ε‐caprolactone)‐diol, PCL‐diol, soft segments in the range of 1080–5800. The materials obtained were investigated by using differential scanning calorimetry, wide angle X‐ray diffraction and mechanical measurements. All poly(ester‐urethanes) investigated were semicrystalline with T_m varying within 126–148°C. DSC results showed that T_g are shifted to higher temperature with increasing content of PHB hard segments and decreasing molecular weight of PCL soft segments. This indicates partial compatibility of the two phases. In poly(ester‐urethanes) made from PCL soft segments of molecular weight (M_n ≥ 2200), a PCL crystalline phase, in addition to the PHB crystalline phase, was observed. As for the mechanical tensile properties of poly(ester‐urethane) cast films, it was found that the ultimate strength and the elongation at the breakpoint decrease with increasing PHB hard segment content. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 83: 703–718, 2002     

Structural investigations of poly(ethylene terephthalate)‐graft‐polystyrene copolymer films

Structural investigations of poly(ethylene terephthalate)‐graft‐polystyrene (PET‐g‐PS) films prepared by radiation‐induced grafting of styrene onto commercial poly(ethylene terephthalate) (PET) films were carried out by FTIR, X‐ray diffraction (XRD), and differential scanning calorimetry (DSC). The variation in the degree of crystallinity and the thermal characteristics of PET films was correlated with the amount of polystyrene grafted therein (i.e., the degree of grafting). The heat of melting was found to be a function of PET crystalline fraction in the grafted films. The grafting is found to take place by incorporation of amorphous polystyrene grafts in the entire noncrystalline (amorphous) region of the PET films and at the surface of the crystallites. This results in a decrease in the degree of crystallinity with the increase in the degree of grafting, attributed to the dilution of PET crystalline structure with the amorphous polystyrene, without almost any disruption in the inherent crystallinity. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 84: 1949–1955, 2002; DOI 10.1002/app.10515     

Porous biodegradable polyesters. II. Physical properties,morphology, and enzymatic and alkaline hydrolysis of porous poly(ϵ‐caprolactone) films

Porous poly(?‐caprolactone) (PCL) films were prepared by water extraction of poly(ethylene oxide) (PEO) from their solution‐cast phase‐separated blend films and the dependence of their blend ratio [X_PCL = PCL/(PEO + PCL)] and molecular weight of PEO on the porosity, pore size, crystallinity, crystalline thickness, mechanical properties, morphology, and enzymatic and alkaline hydrolysis of the porous PCL films were investigated. The film porosity or extracted weight ratio was in good agreement with the expected values, irrespective of X_PCL and molecular weight of PEO. The maximum pore size was larger for the porous films prepared using PEO having a lower molecular weight, compared with films prepared using PEO having a higher molecular weight at the same X_PCL. Differential scanning calorimetry of the porous PCL films revealed that their crystallinity and crystalline thickness were almost constant, regardless of X_PCL and molecular weight of PEO. The Young's modulus and tensile strength of the porous films decreased, whereas the elongation‐at‐break increased with decreasing X_PCL. The enzymatic and alkaline hydrolysis rates of the porous films increased with a decrease in X_PCL and an increase in the molecular weight of PEO. The porous PCL films having Young's modulus in the range of 2–24 kg/mm² and enzymatic hydrolysis rate in the range of one‐ to 20‐fold that of the nonporous PCL film could be prepared by altering X_PCL and the molecular weight of PEO. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 80: 2281–2291, 2001     

The preparation and characterization of high‐performance and thermally stable electroluminescent poly(p‐phenylene‐vinylene‐b‐oligoethylene oxide)

Two luminescent block copolymers (PPVPEO₂₀₀ and PPVPEO₆₀₀), composed of poly(p‐phenylene‐vinylene) (PPV) segments with three phenylene vinylene units and poly(ethylene oxide) (PEO) segments with molecular weight of 200 and 600, respectively, have been successfully synthesized. The structures of the copolymers were verified using FTIR, ¹H‐NMR, and elemental analysis. Single‐layer polymer light‐emitting electrochemical cells (LEC) devices fabricated on the bases of thin films of PPVPEO₆₀₀ and on the bases of thin films of blends of PPVPEO₂₀₀ with additional PEO both demonstrated good electroluminescent (EL) performance with the onset voltage of 2.6 V and EL efficiency of 0.64 cd/A and 0.68 cd/A at 3.2 V, respectively. Thermal analysis shows that the decomposition temperature of PPVPEO₆₀₀ is about 305°C, which is higher than that of PPVPEO₂₀₀ and PEO. AFM studies of PPVPEO₆₀₀ thin films exhibits that the block copolymer self‐assembles to form nanoscale network structures with pseudo‐cross‐linking points, thus accounting for its high thermal stability and good EL performance. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 104: 1118–1125, 2007     

Crystallization and melting behavior of blends comprising poly(3‐hydroxy butyrate‐co‐3‐hydroxy valerate) and poly(ethylene oxide)

Blends of poly(3‐hydroxy butyrate‐co‐3‐hydroxy valerate) (PHBV) and poly(ethylene oxide) (PEO) were prepared by casting from chloroform solutions. Crystallization kinetics and melting behavior of blends have been studied by differential scanning calorimetry and optical polarizing microscopy. Experimental results reveal that the constituents are miscible in the amorphous state. They form separated crystal structures in the solid state. Crystallization behavior of the blends was studied under isothermal and nonisothermal conditions. Owing to the large difference in melting temperatures, the constituents crystallize consecutively in blends; however, the process is affected by the respective second component. PHBV crystallizes from the amorphous mixture of the constituents, at temperatures where the PEO remains in the molten state. PEO, on the other hand, is surrounded during its crystallization process by crystalline PHBV regions. The degree of crystallinity in the blends stays constant for PHBV and decreases slightly for PEO, with ascending PHBV content. The rate of crystallization of PHBV decreases in blends as compared to the neat polymer. The opposite behavior is observed for PEO. Nonisothermal crystallization is discussed in terms of a quasi‐isothermal approach. Qualitatively, the results show the same tendencies as under isothermal conditions. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 2776–2783, 2006     

Intercalated clay structures and amorphous behavior of solution cast and melt pressed poly(ethylene oxide)–clay nanocomposites

The polymer nanocomposite (PNC) films consisted of poly(ethylene oxide) (PEO) and sodium cations montmorillonite (MMT) clay were prepared by aqueous solution casting and direct melt press compounding techniques, whereas the films of PEO with trimethyl octadecyl ammonium cations organo‐modified montmorillonite (OMMT) clay were formed by melt pressed technique. The clay concentrations in the nanocomposites used are 1, 2, 3, 5, 10, and 20 wt % of the PEO weight. The X‐ray diffraction patterns of these nanocomposites were measured in the angular range (2θ) of 3.8–30°. The values of basal spacing d₀₀₁ of MMT/OMMT, clay gallery width W_cg, d‐spacings of PEO crystal reflections d₁₂₀ and d₁₁₂, and their corresponding crystallite size L, and the peaks intensity I (counts) were determined for these nanocomposites. Results reveal that the nanocomposites have intercalated clay structures and the amount of intercalation increases with the increase of clay concentration. As compared to melt pressed PEO–MMT nanocomposites, the amount of clay intercalation is higher in aqueous solution cast nanocomposites. At 20 wt % MMT dispersion in PEO matrix, the solution cast PEO–MMT nanocomposite almost changes into amorphous phase. The melt press compounded PEO–OMMT films show more intercalation as compared to the PEO–MMT nanocomposites prepared by same technique. In melt pressed nanocomposites, the PEO crystalline phase significantly reduces when clay concentration exceeds 3 wt %, which is evidenced by the decrease in relative intensity of PEO principal crystalline peaks. The effect of interactions between the functional group (ethylene oxide) of PEO and layered sheets of clay on both the main crystalline peaks of PEO was separately analyzed using their XRD parameters in relation to structural conformations of these nanocomposites. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 39898.     

Novel gas sensor from polymer‐grafted carbon black: Vapor response of electric resistance of conducting composites prepared from poly(ethylene‐block‐ethylene oxide)‐grafted carbon black

A crystalline block copolymer of poly(ethylene‐block‐ethylene oxide) (PE‐b‐PEO) was successfully grafted onto a carbon black surface by direct condensation of its terminal hydroxyl groups with carboxyl groups on the surface using N,N′‐dicyclohexylcarbodiimide as a condensing agent. The electric resistance of the composite from PE‐b‐PEO (PEO content is above 50 wt %)‐grafted carbon black drastically increased to 10⁴–10⁶ times of the initial resistance in a vapor of dichloromethane, chloroform, tetrahydrofuran, and carbon tetrachloride, which are good solvents for PE‐b‐PEO, and returned immediately to the initial resistance when the composite was transferred in dry air. However, the change of the electric resistance of these composites was less than one‐tenth in a poor solvent vapor at the same condition. The response of the electric resistance was reproducible and stable even after exposure to a good solvent vapor and dry air with 30 cycles or exposure to the vapor over 24 h. The effect of PEO content on the vapor response was also investigated. The composite from PE‐b‐PEO‐grafted carbon black responded to the low vapor concentration with a linear relationship between the electric resistance and the concentration of the vapor in dry air. This indicates that the composite can be applied as a novel gas sensor. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 77: 2437–2447, 2000     

Porous biodegradable polyesters. I. Preparation of porous poly(L‐lactide) films by extraction of poly(ethylene oxide) from their blends

Porous poly(L ‐lactide) (PLLA) films were prepared by water extraction of poly(ethylene oxide) (PEO) from solution‐cast PLLA and PEO blend films. The dependence of blend ratio and molecular weight of PEO on the porosity and pore size of films was investigated by gravimetry and scanning electron microscopy. The film porosity and extracted weight ratio were in good agreement with the expected for porous films prepared using PEO of low molecular weight (M_w = 1 × 10³), but shifted to lower values than expected when high molecular weight PEO (M_w = 1 × 10⁵) was utilized. The maximum pore size was larger for porous films prepared from PEO having higher molecular weight, when compared at the same blending ratio of PLLA and PEO before water extraction. Differential scanning calorimetry of as‐cast PLLA and PEO blend films revealed that PLLA and PEO were phase‐separated at least after solvent evaporation. On the other hand, comparison of blend films before and after extraction suggested that a small amount of PEO was trapped in the amorphous region between PLLA crystallites even after water extraction and hindered PLLA crystallization during solvent evaporation. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 75: 629–637, 2000     

Thermal properties and crystalline structure of liquid crystalline poly(ethylene terephthalate‐co‐2(3)‐chloro‐1,4‐phenylene terephthalate)

Thermal properties and crystalline structure of liquid crystalline (LC) poly(ethylene terephthalate‐co‐2(3)‐chloro‐1,4‐phenylene terephthalate) [copoly(ET/CPT)] were investigated using differential scanning calorimetry (DSC), thermogravimetry (TGA), limiting oxygen index (LOI) measurement, electron dispersive X‐ray analysis (EDX), X‐ray diffractometry, and infrared spectrometry (IR). The thermal transition temperatures of copoly(ET/CPT) were changed with the composition. Copoly(ET/CPT) showed two thermal decomposition steps and the residues at 700°C and LOI values of copoly(ET/CPT) were almost proportional to its chlorine content. The activation energy of thermal decomposition of LC units was very low compared to that of poly(ethylene terephthalate)(PET) units. Crystal structure of copoly(ET/CPT) (20/80) was of triclinic system with the lattice constants of a = 9.98 A?, b = 8.78 A?, c = 12.93 A?, α = 97.4°, β = 96.1°, and γ = 90.8°, which is very close to that of poly(chloro‐p‐phenylene terephthlate) (PCPT) with the lattice constants of a = 9.51 A?, b = 8.61 A?, c = 12.73 A?, α = 96.8°, β = 95.4°, and γ = 90.8°. When copoly(ET/CPT)(50/50) was annealed at 220°C in vacuum, crystallization induced sequential reordering (CISR) was not observed but the heat of fusion was slightly increased due to the increase of the trans isomer content in PET units. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 84: 1286–1294, 2002; DOI 10.1002/app.10451     

Synthesis and characterization of thermo‐ and pH‐sensitive block copolymers bearing a biotin group at the poly(ethylene oxide) chain end

A poly(ethylene oxide)‐block‐poly(dimethylamino ethyl methacrylate) block copolymer (PEO‐b‐PDMAEMA) bearing an amino moiety at the PEO chain end was synthesized by a one‐pot sequential oxyanionic polymerization of ethylene oxide (EO) and dimethylamino ethyl methacrylate (DMAEMA), followed by a coupling reaction between its PEO amino and a biotin derivative. The polymers were charac terized with ¹H NMR spectroscopy and gel permeation chromatography. Activated biotin, biotin‐NHS (N‐hydroxysuccinimide), was used to synthesize biotin‐PEO‐PDMAEMA. In aqueous media, the solubility of the copolymer was temperature‐ and pH‐sensitive. The particle size of the micelle formed from functionalized block copolymers was determined by dynamic light scattering. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 3552–3558, 2006     

Synthesis and properties of poly(amide–imide)s based on N,N′‐bis(4‐carboxyphenyl)‐4,4′‐oxydiphthalimide,p‐aminobenzoic acid and various aromatic diamines

A new diimide–diacid monomer, N,N′‐bis(4‐carboxyphenyl)‐4,4′‐oxydiphthalimide (I), was prepared by azeotropic condensation of 4,4′‐oxydiphthalic anhydride (ODPA) and p‐aminobenzoic acid (p‐ABA) at a 1:2 molar ratio in a polar solvent mixed with toluene. A series of poly(amide–imide)s (PAI, III_a–m) was synthesized from the diimide–diacid I (or I′, diacid chloride of I) and various aromatic diamines by direct polycondensation (or low temperature polycondensation) using triphenyl phosphite and pyridine as condensing agents. It was found that only III_k–m having a meta‐structure at two terminals of the diamine could afford good quality, creasable films by solution‐casting; other PAIs III using diamine with para‐linkage at terminals were insoluble and crystalline; though III_g–i contained the soluble group of the diamine moieties, their solvent‐cast films were brittle. In order to improve their to solubility and film quality, copoly(amide–imide)s (Co‐PAIs) based on I and mixtures of p‐ABA and aromatic diamines were synthesized. When on equimolar of p‐ABA (m = 1) was mixed, most of Co‐PAIs IV had improved solubility and high inherent viscosities in the range 0.9–1.5 dl g^?1; however, their films were still brittle. With m = 3, series V was obtained, and all members exhibited high toughness. The solubility, film‐forming ability, crystallinity, and thermal properties of the resultant poly(amide–imide)s were investigated. © 2002 Society of Chemical Industry     

Modification of poly(octadecene‐alt‐maleic anhydride) films by reaction with functional amines

Thin films of poly(octadecene‐alt‐maleic anhydride) on top of Si wafers and glass plates were modified by reactions with different functional amines to be used in future studies on the relevance of certain molecular surface properties for the covalent immobilization of proteins. For that aim, a strategy was developed and applied to convert the anhydride moieties of the copolymer by functional amines into side chains bearing hydrophilic groups of acidic (carboxylic acid, sulfonic acid), basic (amines), or neutral (poly(ethylene oxide) (PEO), glucose) character. The modification of the copolymer films was achieved through the two‐step formation of a cyclic imide, which was very stable in aqueous solution. Depending on the reactivity of the applied amine, the adjustment of the reaction time was suitable for the preparation of partially converted surfaces of the polymer film. Degrees of modification between 5 and 30% (according to X‐ray photoelectron spectroscopy data) were obtained. Annealing the modified polymer films induced efficient back‐formation of the anhydride groups. By reaction of the layered polyanhydrides with highly crosslinked diamines, amine‐functionalized polymer films were produced that were capable of binding secondary polyanhydride layers. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 87: 1255–1266, 2003     

Nonfouling biomaterials based on polyethylene oxide‐containing amphiphilic triblock copolymers as surface modifying additives: Synthesis and characterization of copolymers and surface properties of copolymer–polyurethane blends

The objective of this work is to develop nonfouling biomaterials by blending polyethylene oxide (PEO)‐containing block copolymers with a polyurethane (PU) matrix; it is expected that the PEO component will migrate to the tissue‐material interface. Three amphiphilic triblock copolymers, PEO‐PU‐PEO, in which the PEO MW was 550 (copolymer 1), 2000 (copolymer 2), and 5000 (copolymer 3), respectively, were synthesized. XPS data showed that the polymer/vacuum interfaces of copolymers 2 and 3 were enriched in the PU block, whereas that of copolymer 1 was enriched in the PEO block. In contact with water, the PEO blocks for all three copolymers migrated to the surface as indicated by water contact angles. Blends of the copolymers with a segmented polyurethane were investigated. Surface enrichment of the copolymers occurred and increased over time up to a limit; the degree of enrichment was dependent on PEO block size and copolymer content. At copolymer content <10%, enrichment decreased with increasing PEO block size. For the copolymer 2 and copolymer 3 blends, enrichment increased with increasing copolymer content; at 20% copolymer the surfaces consisted essentially of pure copolymer. For the copolymer 1 blends, the surface was completely covered by copolymer at content ≥ 1%. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Preparation and characterization of PSt‐b‐PHEMA metal hybrids

The block copolymer polystyrene‐b‐poly[2‐(trimethylsilyloxy)ethylene methacrylate] (PSt‐b‐PTMSEMA) was synthesized using atom‐transfer radical polymerization (ATRP). The hydrolysis of PSt‐b‐PTMSEMA led to the formation of an amphiphilic block copolymer, polystyrene‐b‐poly(2‐hydroxylethyl methacrylate) (PSt‐b‐PHEMA), which was characterized by GPC and ¹H‐NMR. TEM showed that the PSt‐b‐PHEMA formed a micelle, which is PSt as the core and PHEMA as the shell. Under appropriate conditions, the nickel or cobalt ion cause chemical reactions in these micelles and could be reduced easily. ESCA analysis showed that before reduction the metal existed as a hydroxide; after reduction, the metal existed as an oxide, and the metal content of these materials on the surface is more than that on the surface of the copolymer metal ion. XRD analysis showed that the metal existed as a hydroxide before reduction and existed as a metal after reduction. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 83: 2883–2891, 2002; DOI 10.1002/app.10278     

Synthesis and characterization of polystyrene‐b‐poly(ethylene oxide)‐b‐polystyrene triblock copolymers by atom‐transfer radical polymerization

Well‐defined polystyrene (PS)‐b‐poly(ethylene oxide) (PEO)‐b‐PS triblock copolymers were synthesized by atom‐transfer radical polymerization (ATRP), using C—X‐end‐group PEO as macroinitiators. The triblock copolymers were characterized by infrared spectroscopy, nuclear magnetic resonance spectroscopy, and gel permeation chromatography. The experimental results showed that the polymerization was controlled/living. It was found that when the number‐average molecular weight of the macroinititors increased from 2000 to 10,000, the molecular weight distribution of the triblock copolymers decreased roughly from 1.49 to 1.07 and the rate of polymerization became much slower. The possible polymerization mechanism is discussed. According to the Cu content measured with atomic absorption spectrometry, the removal of catalysts, with CHCl₃ as the solvent and kaolin as the in situ absorption agent, was effective. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 77: 2882–2888, 2000     

Study on a water‐swellable rubber compatibilized by amphiphilic block polymer based on poly(ethylene oxide) and poly(butyl acrylate)

A water‐swellable rubber (WSR), compatibilized by the amphiphilic block copolymer, has been prepared by blending a natural rubber (NR) matrix with crosslinked sodium polyacrylate (CSP), poly(ethylene oxide)‐b‐poly(butyl acrylate) (PEO‐b‐PBA), poly(ethylene glycol) (PEG), reinforced filler, and vulcanizing agents. The preparation process was described. The microphase structure of WSR was characterized by a scanning electron microscopy (SEM) photograph. The dependence of the degree of the water‐absorbing and the water‐swelling, the water‐absorbing and water‐swelling rates on CSP, PEG, and PEO‐b‐PBA contents were investigated. The compatibilizing mechanism of PEO‐b‐PBA on WSR was studied. And the optimum composition range was identified: CSP (30–60 phr), PEG (10–20 phr) PEO‐b‐PBA (PEO/PBA = 0.36, 5 phr). © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 3120–3125, 2002     

Synthesis and properties of hydrophilic segmented block copolymers based on poly(ethylene oxide)‐ran‐poly(propylene oxide)

The present article discusses the synthesis and various properties of segmented block copolymers with random copolymer segments of poly(ethylene oxide) and poly(propylene oxide) (PEO‐r‐PPO) together with monodisperse amide segments. The PEO‐r‐PPO contained 25 wt % PPO units and the segment presented a molecular weight of 2500 g/mol. The synthesized copolymers were analyzed by differential scanning calorimetry, Fourier transform infra‐red spectroscopy, atomic force microscopy and dynamic mechanical thermal analysis. In addition, the hydrophilicity and the contact angles (CAs) were studied. The PEO‐r‐PPO segments displayed a single low glass transition temperature, as well as a low PEO crystallinity and melting temperature, which gave enhanced low‐temperature properties of the copolymer. The water absorption values remained high. In comparison to mixtures of PEO/PPO segments, the random dispersion of PPO units in the PEO segments was more effective in reducing the PEO crystallinity and melting temperature, without affecting the hydrophilicity. Increasing the polyether segment length with terephthalic groups from 2500 to 10,000 g/mol increased the hydrophilicity and the room temperature elasticity. Furthermore, the CAs were found to be low 22–39° and changed with the crosslink density. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci 117:1394–1404, 2010     

Highly enhanced accelerating effect of melt‐recrystallized stereocomplex crystallites on poly(L‐lactic acid) crystallization: effects of molecular weight of poly(D‐lactic acid)

The effects of the molecular weight of poly(D ‐lactic acid) (PDLA), which forms stereocomplex (SC) crystallites with poly(L ‐lactic acid) (PLLA), and those of processing temperature T_p on the acceleration (or nucleation) of PLLA homocrystallization were investigated using PLLA films containing 10 wt% PDLA with number‐average molecular weight (M_n) values of 5.47 × 10⁵, 9.67 × 10⁴ and 3.67 × 10⁴ g mol^–1 (PDLA‐H, PDLA‐M and PDLA‐L, respectively). For the PLLA/PDLA‐H and PLLA/PDLA‐M films, the SC crystallites that were ‘non’‐melted and those that were ‘completely’ melted at T_p values just above their endset melting temperature and recrystallized during cooling were found to act as effective accelerating (or nucleation) agents for PLLA homocrystallization. In contrast, SC crystallites formed from PDLA‐L, having the lowest M_n, were effective accelerating agents without any restrictions on T_p. In this case, the accelerating effects can be attributed to the plasticizer effect of PDLA‐L with the lowest M_n. The accelerating effects of SC crystallites in the PLLA/PDLA‐H and PLLA/PDLA‐M films was dependent on crystalline thickness for T_p values below the melting peak temperature of SC crystallites, whereas for T_p values above the melting peak temperature the accelerating effects are suggested to be affected by the interaction between the SC crystalline regions and PLLA amorphous regions.     

Enzymatic degradation of blends of poly(ε‐caprolactone) and poly(styrene‐co‐acrylonitrile) by Pseudomonas lipase

In polymer blends, the composition and microcrystalline structure of the blend near surfaces can be markedly different from the bulk properties. In this study, the enzymatic degradation of poly(ε‐caprolactone) (PCL) and its blends with poly(styrene‐co‐acrylonitrile) (SAN) was conducted in a phosphate buffer solution containing Pseudomonas lipase, and the degradation behavior was correlated with the surface properties and crystalline microstructure of the blends. The enzymatic degradation preferentially took place at the amorphous part of PCL film. The melt‐quenched PCL film with low crystallinity and small lamellar thickness showed a higher degradation rate compared with isothermally crystallized (at 36, 40, and 44°C) PCL films. Also, there was a vast difference in the enzymatic degradation behavior of pure PCL and PCL/SAN blends. The pure PCL showed 100% weight loss in a very short time (i.e., 72 h), whereas the PCL/SAN blend containing just 1% SAN showed ～50% weight loss and the degradation ceased, and the blend containing 40% SAN showed almost no weight loss. These results suggest that as degradation proceeds, the nondegradable SAN content increases at the surface of PCL/SAN films and prevents the lipase from attacking the biodegradable PCL chains. This phenomenon was observed even for a very high PCL content in the blend samples. In the blend with low PCL content, the inaccessibility of the amorphous interphase with high SAN content prevented the attack of lipase on the lamellae of PCL. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 83: 868–879, 2002