Syntheses of biodegradable graft copolymers from sodium caseinate and poly ɛ-caprolactone or poly lactic acid. Applications to the compatibilization of sodium caseinate/polyester blends

Casein (and its sodium salt, sodium caseinate, SC) is an inexpensive natural milk protein that is used as a biodegradable biomaterial, especially to produce packaging films. However, to enhance some of its properties, it needs to be blended with other polymers, which should preferably be biodegradable such as poly lactic acid (PLA) and poly ε-caprolactone (PCL). New SC-g-PLA and SC-g-PCL graft copolymers have been prepared and unambiguously characterized, in particular by ¹H and DOSY NMR. The grafting degrees are high (between 24 and 35% by weight) and result in variations of properties, such as hydrophobicity and thermal properties. The microstructures of SC/PLA and SC/PCL blends were studied and compared, with and without the addition of the SC-g-PLA and SC-g-PCL copolymers to test the compatibilization capacity of these new biodegradable copolymers.     

Organizing thermodynamic data obtained from multicomponent polymer electrolytes: Salt‐containing polymer blends and block copolymers

The objective of this review is to organize literature data on the thermodynamic properties of salt‐containing polystyrene/poly(ethylene oxide) (PS/PEO) blends and polystyrene‐b‐poly(ethylene oxide) (SEO) diblock copolymers. These systems are of interest due to their potential to serve as electrolytes in all‐solid rechargeable lithium batteries. Mean‐field theories, developed for pure polymer blends and block copolymers, are used to describe phenomenon seen in salt‐containing systems. An effective Flory–Huggins interaction parameter, χ_eff , that increases linearly with salt concentration is used to describe the effect of salt addition for both blends and block copolymers. Segregation strength, χ_effN , where N is the chain length of the homopolymers or block copolymers, is used to map phase behavior of salty systems as a function of composition. Domain spacing of salt‐containing block copolymers is normalized to account for the effect of copolymer composition using an expression obtained in the weak segregation limit. The phase behavior of salty blends, salty block copolymers, and domain spacings of the latter systems, are presented as a function of chain length, composition and salt concentration on universal plots. While the proposed framework has limitations, the universal plots should serve as a starting point for organizing data from other salt‐containing polymer mixtures. © 2019 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2019 , 57, 1177–1187     

Compatibilization efficiency of styrene–butadiene multiblock copolymers in PS/PP blends

The compatibilizing effect of di‐, tri‐, penta‐, and heptablock (two types) copolymers with styrene and butadiene blocks was studied in polystyrene/polypropylene (PS/PP) 4/1 blends. The structure of PS/PP blends with the addition of 5 or 10 wt % of a block copolymer (BC) was determined on several scale levels by means of transmission electron microscopy (TEM) and small‐angle X‐ray scattering (SAXS). The results of the structure analysis were correlated with measured stress‐transfer properties: elongation at break, impact, and tensile strength. Despite the fact that the molar mass of the PS blocks in all the BCs used was about 10,000, that is, below the critical value M^* (～18,000) necessary for the formation of entanglements of PS chains, all the BCs used were found to be good compatibilizers. According to TEM, a certain amount of a BC is localized at the interface in all the analyzed samples, and this results in a finer dispersion of the PP particles in the PS matrix, the effect being more pronounced with S‐B‐S triblock and S‐B‐S‐B‐S pentablock copolymers. The addition of these two BCs to the PS/PP blend also has the most pronounced effect on the improvement of mechanical properties of these blends. Hence, these two BCs can be assumed to be better compatibilizers for the PS/PP (4/1) blend than the S‐B diblock as well as both S‐B‐S‐B‐S‐B‐S and B‐S‐B‐S‐B‐S‐B heptablock copolymers. In both types of PS/PP/BC blends (5 or 10 wt % BC), the BC added was distributed between both the PS/PP interface and the PS phase, and, according to SAXS, it maintained a more or less ordered supermolecular structure of neat BCs. © 2001 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 39: 931–942, 2001     

Well‐defined PE‐b‐PDMS diblock copolymers via the combination of thiol‐ene click and esterification reactions: Facile synthesis and compatibilization for HDPE/silicone oil blends

Well‐defined diblock copolymers of linear polyethylene (PE) and poly(dimethylsiloxane) (PDMS) have been synthesized through a facile route combining the thiol‐ene click chemistry of vinyl‐terminated polyethylene (PE‐ene) and the sequential esterification reaction. The resulting diblock copolymers are characterized by ¹H NMR, FT‐IR, DSC, TGA, and TEM. In addition, the PE‐b‐PDMS diblock copolymers have been evaluated as compatibilizers in the blends of high‐density polyethylene (HDPE) and silicone oil. The morphological analysis and mechanical properties demonstrate that the compatibilized blends with low loading concentration of PE‐b‐PDMS display significant improvements in modulus of elasticity and elongation at break as compared to the uncompatibilized binary blends. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2014 , 52, 3205–3212     

Dynamic rheological behaviors of metallocene-based ethylene-butene copolymers and their blends with low-density polyethylene

The dynamic rheological properties of three metallocene-based ethylene-butene copolymers were examined and were compared with those of some conventional ethylene-butene copolymers and of a low density polyethylene (LDPE). Compared with the conventional ethylene copolymers, the metallocene-based copolymers exhibit the following dynamic rheological features: (1) lower viscoelastic moduli and viscosity at small frequencies, but larger viscoelastic moduli and viscosity at large frequencies, thus a small shear thinning effect; (2) larger values of flow activation energy; (3) a relatively fast relaxation rate. These features are the results of simultaneous absence of high molecular weight tails and low molecular weight tails in the metallocene-based copolymers. The dynamic rheological properties of blends of various ethylene-butene copolymers with LDPE were also investigated. It is found that the addition of LDPE can raise the viscosity at low frequencies but lower the viscosity and elasticity at higher frequencies, and retard the relaxation rate of the metallocene-based ethylene copolymers. However, the improvement in rheological properties by LDPE varies with the polymer samples and there is no improvement for the conventional copolymer G.     

F-C烷基化反应原位增容PS/POE共混物中降解的抑制和增容效果的优化

在聚苯乙烯(PS)/聚烯烃弹性体(POE)/AlCl3共混物中引入苯乙烯(St)单体,增加了共混体系中的不饱和结构,AlCl3催化剂与St反应生成大量的初始碳正离子,这些初始碳正离子进攻POE链生成更多的大碳正离子,进而形成更多的PS-graft-POE共聚物,提高了接枝效率.进而,采用"两次挤出"技术,即先原位增容制成接枝母料,然后接枝母料再与PS和POE二次挤出,可以在一定程度上缓解组份的降解,使共混物的力学性能得到进一步的改善.     

Effects of Electron Beam Irradiation on the Structural Properties of PVA/PAM/CMC Ternary Polymer Blends

Ternary miscible blends based on various ratios of poly(vinyl alcohol) (PVA), poly(acrylamide) (PAM) and carboxymethyl cellulose (CMC) were prepared by solution casting in the form of thin films. The structure‐property behavior of the ternary PVA/PAM/CMC blends, before and after they had been exposed to various doses of electron beam irradiation, was investigated by FT‐IR spectroscopy, SEM, XRD and stress‐strain curves. The visual observation showed that the cast films of the individual polymers PVA, PAM, and CMC and their blends over a wide range of composition are clear and transparent indicating the miscibility of PVA/PAM/CMC ternary blends. The FT‐IR analysis of pure polymers or their ternary blends before or after electron beam irradiation proved the formation of hydrogen bonding. In addition, it was found that the intensity of the different absorption bands depends on the ratio of PAM and CMC in the ternary blend. The XRD patterns showed that the peak position for the ternary blends decreases with increasing the ratio of CMC in the blend. However, the peak position for the ternary blend based on equal ratios of pure polymers was not affected by blending and was found in the same position as in the XRD pattern of pure PVA. The SEM micrographs give support to the visual observation indicating the complete miscibility of PVA/PAM/CMC ternary blends. The improvement in morphology leads to improvement in the tensile mechanical properties of the ternary polymer blends.     

Radiation Vulcanization of Nitrile Butadiene Rubber/Butadiene Rubber Blends

Blends of nitrile butadiene rubber (NBR) with butadiene rubber (BR) with varying ratios have been prepared. Vulcanization of prepared blends has been induced by ionizing radiation of gamma rays with varying dose up to 250 kGy. Physical properties, namely soluble fraction and swelling number have been followed up using toluene as a solvent. Mechanical properties, namely tensile strength, tensile modulus at 100% elongation and elongation at break have been followed up as a function of irradiation dose, as well as blend composition. Thermal stability of blends was studied by TGA. The result indicated that the addition of NBR has improved the properties of NBR/BR blends. Also, NBR/BR blend is thermally stable than BR alone.     

Viscoelastic interfacial properties of compatibilized poly(ε‐caprolactone)/polylactide blend

Poly(ε‐caprolactone)/polylactide blend (PCL/PLA) is an interesting biomaterial because the two component polymers show good complementarity in their physical properties. However, PCL and PLA are incompatible thermodynamically and hence the interfacial properties act as the important roles controlling the final properties of their blends. Thus, in this work, the PCL/PLA blends were prepared by melt mixing using the block copolymers as compatibilizer for the studies of interfacial properties. Several rheological methods and viscoelastic models were used to establish the relations between improved phase morphologies and interfacial properties. The results show that the interfacial behaviors of the PCL/PLA blends highly depend on the interface‐located copolymers. The presence of copolymers reduces the interfacial tension and emulsified the phase interface, leading to stabilization of the interface and retarding both the shape relaxation and the elastic interface relaxation. As a result, besides the relaxation of matrices (τ_m) and the shape relaxation of the dispersed PLA phase (τ_F), a new relaxation behavior (τ_β), which is attribute to the relaxation of Marangoni stresses tangential to the interface between dispersed PLA phase and matrix PCL, is observed on the compatibilized blends. In contrast to that of the diblock copolymers, the triblock copolymers show higher emulsifying level. However, both can improve the overall interfacial properties and enhance the mechanical strength of the PCL/PLA blends as a result. © 2010 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 48: 756–765, 2010     

Dynamic mechanical and gas transport properties of blends and random copolymers of bisphenol-A polycarbonate and tetramethyl bisphenol-A polycarbonate

Dynamic mechanical and gas transport properties for homogeneous homopolymer blends and random copolymers of bisphenol-A and tetramethyl bisphenol-A polycarbonates (PC-TMPC) were determined. The gas transport measurements were performed at 35°C for the gases He, H₂, O₂, Ar, N₂, CH₄, and CO₂. The results show that the copolymers have lower permeability, apparent diffusion, and solubility coefficients than the blends. Permeability coefficients for blends follow a semilogarithmic ideal mixing rule while copolymers exhibit negative deviations from this. Specific volume measurements show that the free volume available for gas transport is slightly larger in copolymers than in blends of the same composition. These apparently contradictory results may relate to the differences in local mode chain motions observed for the copolymer and blend series. The γ relaxation processes in PC and TMPC seem to operate independently in the blends (no intermolecular coupling) while there is clear evidence for intramolecular coupling in the copolymers. © 1992 John Wiley & Sons, Inc.     

Stabilized Polymer Blends

Abstract

Today, producers of plastics are expected to tailor very different properties on request, without much financial and technical effort. But since the costs and the risks of newly developed polymers are high, the interest of industries has turned to combinations of polymers that are already available: 1) In blends [l, 2], different polymers are simply mixed; 2) in copolymers [3], different polymer segments or blocks are chemically tied together. Both principles are combined in blends with copolymer components.     

Optical adhesives based on blends of methylmethacrylate-co-glycidylmethacrylate copolymer and bisphenol-A diglycidyl ether

In pursuit of nonbirefringent optical adhesives, various copolymers of methylmethacrylate and glycidylmethacrylate (MMA-co-GMA) were synthesized and subsequently blended with bisphenol-A diglycidyl ether (EPON-828) epoxy prepolymer using acetone as a common solvent. Miscibility and optical properties of these adhesive blends were investigated by means of differential scanning calorimetry (DSC), dielectric thermal analysis (DETA), and refractive index measurements. The increasing trend of the single glass transition temperatures of the copolymers as well as of their refractive indices with increasing MMA content suggests that these copolymers are probably of a random type. The adhesive blends, after curing with trimellitic anhydride (TMA), remained transparent, suggestive of a single-phase character. The complete miscibility of the adhesive blends made the refractive indices to be adjustable by simply varying the ratio of MMA-co-GMA copolymer in the blends. In addition, the positive and negative dielectric anisotropies (intrinsic birefringence) of the constituent molecules can be compensated fully in their cured states, thereby yielding significant reduction in the net birefringence in the blends of 50–80 wt % copolymer and a zero-birefringent optical adhesive at 60 wt %. © 1997 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 35: 1911–1917, 1997     

Compatibilizing effect of a graft copolymer on bacterial poly(3‐hydroxybutyrate)/poly(methyl methacrylate) blends

Blends of isotactic (natural) poly(3‐hydroxybutyrate) (PHB) and poly(methyl methacrylate) (PMMA) are partially miscible, and PHB in excess of 20 wt % segregates as a partially crystalline pure phase. Copolymers containing atactic PHB chains grafted onto a PMMA backbone are used to compatibilize phase‐separated PHB/PMMA blends. Two poly(methyl methacrylate‐g‐hydroxybutyrate) [P(MMA‐g‐HB)] copolymers with different grafting densities and the same length of the grafted chain have been investigated. The copolymer with higher grafting density, containing 67 mol % hydroxybutyrate units, has a beneficial effect on the mechanical properties of PHB/PMMA blends with 30–50% PHB content, which show a remarkable increase in ductility. The main effect of copolymer addition is the inhibition of PHB crystallization. No compatibilizing effect on PHB/PMMA blends with PHB contents higher than 50% is observed with various amounts of P(MMA‐g‐HB) copolymer. In these blends, the graft copolymer is not able to prevent PHB crystallization, and the ternary PHB/PMMA/P(MMA‐g‐HB) blends remain crystalline and brittle. © 2002 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 40: 1390–1399, 2002     

Influence of chain architecture on phase behaviour of styrene-(styrene/butadiene)-styrene triblock copolymers and their binary blends

The phase behaviour of symmetric (LN4) and asymmetric (LN3) triblock copolymers based on styrene-b-(styrene-co-butadiene)-b-styrene (S-SB-S) and their blends have been studied using transmission electron microscopy (TEM) and small-angle X-ray scattering (SAXS) and were correlated with rheological properties. A direct control over the final morphology and segregation strength for the block copolymer blends was achieved by blending of LN3 and LN4. The interaction parameter (χ) for LN4 is extracted by fitting the SAXS patterns at temperatures well above the ODT in consistency with Leibler mean-field structure-function for ABA triblock copolymers. A weak temperature dependency of χ has been observed which revealed that the phase behaviour in LN4 is mainly controlled by the entropic term. In the low frequency regime a non-terminal flow behaviour was observed in LN3 revealing the persistence of ordered structure within the experimental temperature range whereas a terminal flow behaviour with composition fluctuation was observed in LN4. G′ vs. G″ plots indicated a solid-like elastic melt behaviour for LN3 whereas presence of ODT over a broad temperature range was observed for LN4. ODT is observed to increase non-linearly with increase in LN3 content in the blends. ODT behaviour of the blends further reveals that the blends shift from weak-segregation to intermediate-segregation strength with the increase in LN3 content. The improvement in the state of ordering along with the change in morphology with the increase of LN3 content is attributed to co-surfactant effect between the PS end-blocks of LN3 and LN4 inside PS-rich phase.     

Miscibility of polycarbonates with copolymers containing cyclohexylmethacrylate

We prepared various copolymers containing styrene and methacrylates to examine their miscibility with polycarbonates such as bisphenol A polycarbonate (PC), dimethylpolycarbonate (DMPC), and tetramethylpolycarbonate (TMPC). Among the various copolymers examined, poly(methyl methacrylate‐co‐cyclohexylmethacrylate) [P(MMA–CHMA)] copolymers containing proper amounts of cyclohexylmethacrylate (CHMA) formed miscible blends with PC and DMPC, whereas TMPC did not form a miscible blend with P(MMA–CHMA). However, TMPC was miscible with poly(styrene‐co‐cyclohexylmethacrylate) [P(S–CHMA)] copolymers containing less than about 40 wt % CHMA, whereas PC and DMPC were always immiscible with P(S–CHMA). Miscible blends exhibited lower critical solution temperature (LCST)‐type phase behavior. Binary interaction energies were calculated from the observed phase boundaries with lattice–fluid theory combined with a binary interaction model. The quantitative interaction energy of each binary pair indicated that the phenyl ring substitution of polycarbonate with methyl groups did not lead to interactions that were favorable for miscibility with methyl methacrylate (MMA) and CHMA, but it did lead to favorable interactions with styrene. The addition of CHMA to MMA initially increased the LCST but ultimately led to immiscibility with PC and DMPC; however, addition of CHMA to styrene always decreased the LCST with TMPC. The increased LCST of PC or DMPC blends stemmed from intramolecular repulsion between MMA and CHMA, whereas the decreased LCST of TMPC/P(S–CHMA) blends with CHMA content came from negative interaction energy between styrene and CHMA. © 2001 John Wiley & Sons, Inc. J Polym Sci Part B: Polym Phys 39: 1948–1955, 2001     

Miscibility of polysulfone blends with poly(1‐vinylpyrrolidone‐co‐styrene) copolymers and their interaction energies

The miscibility of polysulfone (PSf) with various hydrophilic copolymers was explored. Among these blends, PSf gave homogeneous mixtures with poly(1‐vinylpyrrolidone‐co‐styrene) [P(VP–S)] copolymers when these copolymers contained 68–88 wt % 1‐vinylpyrrolidone (VP). Miscible PSf blends with P(VP–S) copolymers underwent phase separation on heating caused by lower critical solution temperature (LCST)‐type phase behavior. The phase behavior depended on the copolymer composition. Changes in the VP content of P(VP–S) copolymers from 65 to 68 wt % shifted the phase behavior from immiscibility to miscibility and the LCST behavior. The phase‐separation temperatures of the miscible blends first increased gradually with the VP content, then went through a broad maximum centered at about 80 wt % VP, and finally decreased just before the limiting content of VP for miscibility with PSf. The interaction energies of binary pairs involved in PSf/P(VP–S) blends were evaluated from the phase‐separation temperatures of PSf/P(VP–S) blends with lattice‐fluid theory combined with a binary interaction model. The decrease in the contact angle between water and the membrane surface with increasing VP content in P(VP–S) copolymers indicated that the hydrophobic properties of PSf could be improved via blending with hydrophilic P(VP–S) copolymers. © 2003 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 41: 1401–1411, 2003     

Synthesis of polyvinyltrimethylsilane-graft-poly(ethylene glycol) copolymers and properties of gas-separating membranes formed on their basis

A method is developed for the synthesis of the graft copolymer polyvinyltrimethylsilane-graft-poly(ethylene glycol) via the interaction of a brominated polymer with the methyl ether of a low-molecular-mass poly(ethylene glycol). Graft copolymer samples containing up to 79 wt % poly(ethylene glycol) are synthesized through this method. The properties of the graft copolymers and blends formed on their basis with a specially synthesized low-molecular-mass PEG derivative with a terminal trimethylsilyl group are investigated. Physical blends are prepared in order to increase the content of ethylene oxide groups while the film-forming properties of the composite materials are preserved. As shown by structural studies, the graft copolymers are amorphous single-phase systems, while the related blends are two-phase disperse systems, in which one phase is enriched in polytrimethylvinylsilane and the other is enriched in PEG. Studies of the gas-transport behavior of the samples reveal that the introduction of PEG, in contrast to the nonselective initial polymer, results in the formation of PVTMS-based materials that are selective for CO₂ in mixtures with H₂.     

Phase behavior in mixtures of a homopolymer and a block copolymer 1. FTIR and DSC studies

Miscibility in blends of three styrene-butadiene-styrene and one styrene-isoprene-styrene triblock copolymers containing 28%, 30%, 48%, and 14% by weight of polystyrene, respectively, with poly(vinyl methyl ether) (PVME) were investigated by FTIR spectroscopy and differential scanning calorimetry (DSC). It was found from the optical clarity and the glass transition temperature behavior that the blends show miscibility for each kind of triblock copolymers below a certain concentration of PVME. The concentration range to show miscibility becomes wider as the polystyrene content and molecular weight of PS segment in the triblock copolymers increase. From the FTIR results, the relative peak intensity of the 1100 cm^-1 region due to COCH₃ band of PVME and peak position of 698 cm^-1 region due to phenyl ring are sensitive to the miscibility of SBS(SIS)/PVME blends. The results show that the miscibility in SBS(SIS)/PVME blends is greatly affected by the composition of the copolymers and the polystyrene content in the triblock copolymers. Molecular weights of polystyrene segments have also affected the miscibility of the blends. ©1995 John Wiley & Sons, Inc.     

Tensile properties of blends of copolymers of n-butyl methacrylate with ethyl acrylate and chlorinated rubber

Solution blending of n-butyl methacrylate-ethyl acrylate copolymers with chlorinated rubber was investigated. The tensile properties of the blends were studied; it was concluded that the blends serve as good film forming materials.     

Molecular design of multicomponent polymer systems. X. Emulsifying effect of poly(styrene-b-methyl methacrylate) in poly(vinylidene fluoride)/noryl blends

The emulsifying activity of block copolymers is investigated in blends of incompatible engineering polymers such as polyvinyldene fluoride (PVF₂) and Noryl (high impact polystyrene-poly-2,6-dimethyl-1,4-phenylene oxide mixture). When the blends are modified by a poly(styrene-b-methyl methacrylate) copolymer, (PS-PMMA) each block of which being selectively miscible with Noryl and PVF₂ respectively, Phase dispersion, interfacial adhesion and ultimate mechanical properties are significantly improved; major effect is observed upon addition of 12 percent copolymer, resulting in intermingled and firmly adherent phases and a rough additivity of both tensile strength and elongation at break. All these features clearly demonstrate the important emulsifying effect of PS-PMMA in these very attractive PVF₂/Noryl blends.