Cellulose alkyl ester/vinyl polymer blends: effects of butyryl substitution and intramolecular copolymer composition on the miscibility

The blend miscibility of cellulose alkyl esters, mainly butyrate (CB) and acetate butyrate (CAB), with synthetic homo- and copolymers comprising N-vinyl pyrrolidone (VP) and/or vinyl acetate (VAc) units, i.e., PVP, PVAc, and P(VP-co-VAc), was examined by differential scanning calorimetry. A miscibility map for the CB/vinyl polymer systems was constructed as a function of the degree of substitution (DS) of CB and the VP fraction of the mixing component. CBs were immiscible with PVAc regardless of the DS used (2.11–2.94), but miscible or immiscible with PVP depending on whether the butyryl DS was <2.5 or >2.5. The critical value of DS≈2.5 is lower than the corresponding one (DS≈2.8) evaluated formally for cellulose acetate (CA)/PVP blend series. This lowering is ascribable to an effect of steric hindrance of the bulky butyryl substituents, leading to suppression of the hydrogen-bonding interactions, as a driving factor for miscibility attainment, between residual hydroxyls of CB and carbonyl groups of PVP. The CB/vinyl copolymer system imparted a ‘miscibility window’ in which the VP/VAc composition participated; viz., CBs of DS≈2.54–2.94 were miscible with some P(VP-co-VAc)s of 30–70Â mol% VP fractions, in spite of the immiscibility with both PVP and PVAc homopolymers. The result was interpreted in terms of another inter-component attraction derived from repulsion between the monomer ingredients constituting the vinyl copolymer component. For CAB/P(VP-co-VAc) blends, it was observed that the VP/VAc range forming such a miscibility window became further expanded, compared with the corresponding series of CB blends. Fourier transform infrared and solid-state ¹³C NMR spectroscopy revealed not only the presence or absence of the intermolecular hydrogen-bonding formation, determined according to the lower or higher DS of the cellulose ester component in the blends considered, but also a difference in the mixing scale between the polymer pairs regarded as miscible by the thermal analysis.     

Interaction and Scale of Mixing in Cellulose Acetate/Poly(<Emphasis Type="Italic">N</Emphasis>-vinyl Pyrrolidone-co-vinyl Acetate) Blends

Binary blends and pseudo complexes of cellulose acetate (CA) with vinyl polymers containing N-vinyl pyrrolidone (VP) units, poly(N-vinyl pyrrolidone) (PVP) and poly(N-vinyl pyrrolidone-co-vinyl acetate) [P(VP-co-VAc)], were prepared, respectively, by casting from mixed polymer solutions in N,N-dimethylformamide as good solvent and by spontaneous co-precipitation from solutions in tetrahydrofuran as comparatively poor solvent. The scale of miscibility and intermolecular interaction were examined for the blends and complexes by solid-state ¹³C-NMR spectroscopy. It was revealed that the formation of complexes was due to a higher frequency of hydrogen-bonding interactions between the residual hydroxyl groups of CA and the carbonyl groups of VP residues in the vinyl polymer component. From measurements of CP/MAS spectra and proton spin-lattice relaxation times (T_1ρ^H) in the NMR study, the existence of the hydrogen-bonding interaction was also confirmed for the miscible blends and the homogeneity of the mixing was estimated to be substantially on a scale within a few nanometers.     

High-performances membranes for pervaporation I. Poly(vinyl alcohol)–poly(N-vinyl pyrrolidone) blends

Dense membranes were prepared from poly(vinyl alcohol)–poly(N-vinyl pyrrolidone) (PVA–PVP) blends of different compositions and studied in swelling and dehydration by pervaporation of three organic solvents contaminated by 5 wt% water. The swelling generally increases with the PVP content. No extraction occurs in water–tetrahydrofuran (THF) and water–methyl ethyl ketone (MEK) mixtures. In ethanol containing 10 wt% of water, there is no extraction for blends containing less than 40 wt% PVP and an increasing extraction beyond this PVP content. The pervaporation flux of the water–ethanol mixture increases drastically at the same threshold whereas the water permselectivity falls to a low level. The values of the diffusion and permeability coefficients determined from transient permeation of the test water–ethanol mixture exhibit a similar sudden increase at the same PVP content threshold. This singular behavior of the blend membranes is interpreted by a strong affinity of the PVP component to ethanol, combined with a disappearance of crystallites in the blend at this threshold. Consequently the amorphous membrane can swell freely according to the affinity of the PVP component, leading to the observed behavior.     

Miscibility and ferroelectric behavior in blends of poly(vinylidene fluoride/trifluoroethylene) and poly(vinyl acetate)

The blend system containing a poly(vinylidene fluoride/trifluoroethylene) [P(VDF/TrFE)] copolymer (68/32 mol %) and poly(vinyl acetate) (PVAc) was miscible from the results of differential scanning calorimetry (DSC) studies that exhibit the presence of a single, composition‐dependent glass transition temperature (T_g) and a strong melting point depression for the semicrystalline P(VDF/TrFE) component. However, differences between the DSC and dielectric measurements, which showed a separate P(VDF/TrFE) T_g peak, suggests that the P(VDF/TrFE)/PVAc blends are actually partially miscible. Because of the lower dielectric constant of PVAc and the reduced sample crystallinity caused by the addition of PVAc, both the dielectric constant and the remanent polarization of the copolymer blends decrease with increasing PVAc content. The presence of a small amount of PVAc stabilized the anomalous ferroelectric behavior of ice–water‐quenched P(VDF/TrFE), and the blend portrayed normal polarization reversal behavior after adding only 1 wt % PVAc. The piezoelectric response suggests small changes with an increasing number of poling cycles. It is believed that PVAc affects the D‐E hysteresis behavior at the interface between crystalline and amorphous phases, although much work remains to be done to confirm this hypothesis. © 2003 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 41: 927–935, 2003     

Effect of poly(vinyl acetate) (PVAc) on thermal behavior and mechanical properties of poly(3-hydroxybutyrate)/poly(propylene carbonate) (PHB/PPC) blends

To assess the compatibility of blends of synthetic poly(propylene carbonate) (PPC), with a natural bacterial poly(3-hydroxybutyrate) (PHB), a simple casting procedure of blend was used. poly(3-hydroxybutyrate)/poly(propylene carbonate) blends are found to be incompatible according to DSC and DMA analysis. In order to improve the compatibility and mechanical properties of PHB/PPC blends, poly(vinyl acetate) (PVAc) was added as a compatibilizer. The effects of PVAc on the thermal behavior, morphology, and mechanical properties of 70PHB/30PPC blend were investigated. The results show that the melting point and the crystallization temperature of PHB in blends decrease with the increase of PVAc content in blends, the loss factor changes from two separate peaks of 70PHB/30PPC blend to one peak of 70PHB/30PPC/12PVAc blend. It is also found that adding PVAc into 70PHB/30PPC blend can decrease the size of dispersed phase from morphology analysis. The result of tensile properties shows that PVAc can increase the tensile strength and Young’s modulus of 70PHB/30PPC blend, and both the elongation at break and the tensile toughness increase significantly with PVAc added into 70PHB/30PPC.     

Lower critical solution temperature and hydrophobic hydration in aqueous polymer solutions

Phase diagrams of aqueous solutions of poly(N-vinyl caprolactam) (PVCL), N-vinyl caprolactam copolymer with vinylamine (3.8 mol%) (CP(VCL-VA)), and poly(N-vinyl propylacetamide) (PVPA) were shown to be binodal curves with lower critical solution temperatures (LCST) in the range 304–313.5 K and critical concentrations in the range of 0.02–0.08 polymer weight fraction. Aqueous solutions of N-vinyl caprolactam copolymer with N-vinyl pyrrolidone (80 mol%) (CP(VCL-VP)) remained homogeneous in the entire region of the liquid state of water. The enthalpy of mixing with water of PVPA and CP(VCL-VP) was negative and the curve was concave over the entire range of composition at 298 and 308 K. The excessive heat capacity and partial heat capacity at infinite dilution of PVPA were positive, proving the hydrophobic character of hydration of this polymer. In contrast, these parameters were negative for CP(VCL-VP), revealing hydrophilic hydration. Hydrophilic hydration was predominant in solutions which were homogeneous over a wide temperature range, whereas hydrophobic hydration predominated in solution of polymers with LCST.     

聚甲基丙烯酸甲酯与聚醋酸乙烯酯共混的红外光谱研究

用红外光谱(FTIR)研究了聚甲基丙烯酸甲酯(PMMA)与聚醋酸乙烯酯(PVAc)共混体系相容性,在160℃以上共混体系发生相分离;分相体系与非分相体系的FTIR谱明显不同;共混体系的FTIR谱不能从两统组分红外光谱简单加和得到;结果表明大分子构象发生了变化,PMMA/PVAc体系相容可能是大分子构象熵变所致。     

聚乙烯醇/聚乙烯基吡咯烷酮共混体系相容性研究

用DSC、FTIR、SAXS和测定Flory-Huggins相互作用参数等方法对聚乙二醇(PVA1)/聚乙烯基吡咯烷酮(PVP)共混体系的研究。结果表明,该体系具有完全互容的性质。共混物只有一个玻璃化转变温度。用DMSO作溶剂浇铸的膜光学透明。PVA1的长周期和片晶厚度均随PVP含量增加而增大,但后者增大的幅度比前者小得多,表明PVP和PVA1的非晶部分形成均相并夹入到球晶内部。共混物中PVP羰基吸收峰和PVA1的羟基吸收峰与相应均聚物相比,在红外光谱图中皆向低频方向迁移,迁移波数随第二组分含量的增加而增大。表明二者间有氢键生成。用平衡熔点计算的Flory-Huggins相互作用参数为-0.88。     

COMPATIBILITY IN POLYMER BLENDS OF POLY (VINYL ACETATE) AND POLY (METHYL METHACRYLATE)STUDIED BY NMR

Compatibility of poly (vinyl acetate) (PVAc) with poly (methyl methacrylate) (PMMA) mixtures has been studied by using nuclear magnetic relaxation, differential scanning calorimeter and small-angle X-ray scattering techniques. The nuclear magnetic relaxation time T_1's were measured as a function of composition in blends of PMMA and PVAc prepared from chloroform solution. The results show that the system is miscible for casting from chloroform solution.     

Study of the miscibility of poly(vinyl pyridines) with poly(vinyl acetate), poly(vinyl alcohol) and their copolymers

Miscibility of poly(4-vinyl pyridine) (P4VP) and poly(2-vinyl pyridine) (P2VP) with poly(viny acetate) (PVAc), poly(vinyl alcohol) PVA and poly(vinyl acetate-co-alcohol) (ACA copolymers) has been investigated over a wide composition range. Differentiaal scanning calorimetry (DSC) results indicate that P2VP is immiscible with PVAC, PVA, and their copolymers over the whole composition range. In turn, P4VP appears to be immiscible with PVAC and PVA, but miscible with some ACA copolymers in certain range of composition. The P4VP-ACA phase diagram for different copolymer compositions has been determined. The variation of the glass transition temperature with composition for miscible mixtures was found to follow the Gordon-Taylor equation, with the parameter κ dependent upon copolymer composition. FTIR analysis of blends reveal the existence of specific interactions via hydrogen bonding between hydroxyl groups and the nitrogen of the pyridinic ring, which appear to be decisive for miscibility. © 1994 John Wiley & Sons, Inc.     

Pyrolysis mass spectrometry analysis of polycarbonate/poly(methyl methacrylate)/poly(vinyl acetate) ternary blends

Direct insertion probe pyrolysis mass spectrometry (DIP-MS) analyses of polycarbonate/poly(methyl methacrylate)/poly(vinyl acetate), (PC/PMMA/PVAc), ternary blends have been performed. The PC/PMMA/PVAc ternary blends were obtained by coalescing from their common γ-cyclodextrin-inclusion compounds (CD-ICs), through the removal of the γ-CD host (coalesced blend), and by a co-precipitation method (physical blend). The coalesced ternary blend showed different thermal behaviors compared to the co-precipitated physical blend. The stability of PC chains decreased due to the reactions of CH₃COOH formed by deacetylation of PVAc above 300 °C, for both coalesced and physical blends. This process was more effective for the physical blend most likely due to the enhanced diffusion of CH₃COOH into the amorphous PC domains, where it can further react producing low molecular weight PC fragments bearing methyl carbonate chain ends. The decrease in thermal stability of PC chains was less significant for the coalesced ternary blend indicating that the diffusion of CH₃COOH was either somewhat limited or competed with intermolecular reactions between PMMA and PC and between PMMA and PVAc, which were detected and were associated with their close proximity in the intimately mixed coalesced PC/PMMA/PVAc ternary blend.     

Interactions and prediction of phase diagrams in ternary blends comprising poly(vinyl acetate), poly(vinyl p‐phenol), and poly(methyl methacrylate)

This study investigated and discovered a new miscible ternary blend system comprising three amorphous polymers: poly(vinyl acetate) (PVAc), poly(vinyl p‐phenol) (PVPh), and poly(methyl methacrylate) (PMMA) using thermal analysis and optical and scanning electron microscopies. The ternary compositions are largely miscible except for a small region of borderline ternary miscibility near the side, where the binary blends of PVAc/PMMA are originally of a borderline miscibility with broad T_g. In addition to the discovering miscibility in a new ternary blend, another objective of this study was to investigate whether the introduction of a third polymer component (PVPh) with hydrogen bonding capacity might disrupt or enhance the metastable miscibility between PVAc and PMMA. The PVPh component does not seem to exert any “bridging effect” to bring the mixture of PVAc and PMMA to a better state of miscibility; neither does the Δχ effect seem to disrupt the borderline miscible PVAc/PMMA blend into a phase‐separated system by introducing PVPh. Apparently, the ternary is able to remain in as a miscible state as the binary systems owing to the fact that PVPh is capable of maintaining roughly equal H‐bonding interactions with either PVAc or PMMA in the ternary mixtures to maintain balanced interactions among the ternary mixtures. © 2006 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 44: 1147–1160, 2006     

醋酸纤维素／聚乙烯基吡咯烷酮共混体系的相容性研究（Ⅰ）

用ＤＳＣ，ＤＭＴＡ研究了醋酸纤维素（ＣＤＡ），聚乙烯基吮咯烷酮（ＰＶＰ）及ＣＤＡ／ＰＶＰ共混体系的玻璃化转变行为．用精密量热法测定了该体系的混合热焓．结果表明：共混体系只存在一个玻璃化转变温度（Ｔｇ），其值随共混组成的变化而改变；共混体系的混合热焓为负值，其绝对值随组成中ＰＶＰ含量的增加而减少．力学性能研究表明，共混体系具有协同效应．上述试验结果证明，ＣＤＡ和ＰＶＰ是一对相容性高聚物．     

可光交联的共聚物肉桂酰化的聚(N-乙烯基吡咯烷酮-丙烯酸-2-羟基乙酯)的合成及其水溶液的温敏性

可光交联的共聚物肉桂酰化的聚(N-乙烯基吡咯烷酮-丙烯酸-2-羟基乙酯)的合成及其水溶液的温敏性     

Miscibility and crystallinity of poly(3-hydroxybutyrate)/poly(3-hydroxybutyrate-co-3-hydroxyvalerate) blends

With the objective of developing new biodegradable materials, the miscibility and the crystallinity of blends of poly(3-hydroxybutyrate), P(3HB), and poly(3-hydroxybutyrate-co-3-hydroxyvalerate), P(3HB-co-3HV), have been studied. P(3HB) (300 kg mol⁻¹)/P(3HB-co-3HV)–10% 3HV (340 kg mol⁻¹) blends were prepared by casting in a wide range of proportions, and characterized by differential scanning calorimetry (DSC) and Fourier transform infrared spectroscopy (FT-IR). The experimental values for the glass transition temperatures (T_g) are in good agreement with the values provided by the Fox equation, showing that the blends are miscible. It was observed that the T_g and the melting temperature (T_m) decreases with the increase in the P(3HB-co-3HV)–10% 3HV content, while the crystallization temperature (T_c) increases. FT-IR analyses confirmed the decrease on the crystallinity of P(3HB)/P(3HB-co-3HV)–10% 3HV blends with higher copolymer contents. Bands related to the crystallinity were changed, due to the copolymer content that produced miscible and less crystalline blends.     

Interaction of collagen and poly(vinyl pyrrolidone) in blends

The interaction between collagen and poly(vinyl pyrrolidone) (PVP) in blends has been studied by viscometry, differential scanning calorimetry (DSC) and by Fourier transform infrared spectroscopy (FTIR). It was found that the amide A and amide I bands position in FTIR spectra of collagen were shifted after blending with PVP to higher wavenumbers. DSC measurements showed different melting temperature, glass transition temperature and enthalpy for the blends and for the single components. Viscosity measurements showed interaction between collagen and PVP also in a dilute water solution.The results have shown, that the interactions between collagen and PVP exist due to the strong interactions between the synthetic and biological component, mainly by hydrogen bonds. These interactions caused that collagen and PVP are miscible at molecular level. The blending of collagen with PVP may give the possibility of producing new materials for potential biomedical applications.     

FT‐IR Investigation into the miscible interactions in new materials for optical devices

In this article we determine the miscibility of azobenzene derivative (poly(4‐(N‐(2‐methacryloyloxyethyl)‐N‐ethylamino)‐4′‐nitroazobenzene)₉₀‐co‐(methyl methacrylate)₁₀)/poly(vinyl acetate) (PVAc) and azobenzene derivative/poly(vinyl chloride) (PVC) blends using Fourier Transform infrared (FT‐IR) spectroscopy. With this method we can clearly identify the exact interactions responsible for miscibility. In the azobenzene derivative 50:50PVAc blend new peaks were evident at 2960, 2890, 1237 and 959 cm^?1, these peaks depict miscible interactions. These wavenumbers indicate that the miscible interactions occurring are from the C? H stretching band, the vinyl acetate C?O, conjugated to the ester carbonyl, the cis‐transformation N?N stretch frequency and the acetate ester weak doublet. The azobenzene derivative 80:20PVC blend display peaks identical in profile to the blend homopolymers, indicating no miscible interactions. However, this could be due to overlapping of peaks within the same wavenumber region, making resolution difficult. This research demonstrates FT‐IR can deduce favorable interactions for miscibility and therefore numerous miscible blends can successfully be calculated if possessing the same groups responsible for miscibility. This paves the way for a new generation of designer optical materials with the desired properties. Copyright © 2003 John Wiley & Sons, Ltd.     

Viscometric study of poly(vinyl chloride)/poly(vinyl acetate) blends in various solvents

The intermolecular interactions between poly(vinyl chloride) (PVC) and poly(vinyl acetate) (PVAc) in tetrahydrofuran (THF), methyl ethyl ketone (MEK) and N,N^′-dimethylformamide (DMF) were thoroughly investigated by the viscosity measurement. It has been found that the solvent selected has a great influence upon the polymer-polymer interactions in solution. If using PVAc and THF, or PVAc and DMF to form polymer solvent, the intrinsic viscosity of PVC in polymer solvent of (PVAc+THF) or (PVAc+DMF) is less than in corresponding pure solvent of THF or DMF. On the contrary, if using PVAc and MEK to form polymer solvent, the intrinsic viscosity of PVC in polymer solvent of (PVAc+MEK) is larger than in pure solvent of MEK. The influence of solvent upon the polymer-polymer interactions also comes from the interaction parameter term Δb, developed from modified Krigbaum and Wall theory. If PVC/PVAc blends with the weight ratio of 1/1 was dissolved in THF or DMF, Δb<0. On the contrary, if PVC/PVAc blends with the same weight ratio was dissolved in MEK, Δb>0. These experimental results show that the compatibility of PVC/PVAc blends is greatly associated with the solvent from which polymer mixtures were cast. The agreement of these results with differential scanning calorimetry measurements of PVC/PVAc blends casting from different solvents is good.     

Mechanical properties and morphology of epoxy/poly(vinyl acetate)/poly(4-vinyl phenol) brominated system

Diglycidyl ether of bisfenol-A (DGEBA)/poly(vinyl acetate) (PVAc)/poly(4-vinyl phenol) brominated (PVPhBr) ternary blends cured with 4,4’-diaminodiphenylmethane (DDM) were investigated by differential scanning calorimetry (DSC), dynamic mechanical thermal analysis (DMTA) and scanning electron microscopy (SEM). Homogeneous (DGEBA+DDM)/PVPhBr networks with a unique T _g are generated. Ternary blends (DGEBA+DDM)/PVAc/PVPhBr are initially miscible and phase separate upon curing arising two T _gs that correspond to a PVAc-rich phase and to epoxy network phase. Increasing the PVPhBr content the T _gof the PVAc phase move to higher temperatures as a consequence of the PVAc-PVPhBr interactions. Different morphologies are generated as a function of the blend composition.     

聚乙烯醇/聚乙烯基吡咯烷酮共混体系的结晶行为

用DSC、WAXD和SAXS研究了聚乙烯醇(PVAl)/聚乙烯基吡咯烷酮(PVP)共混体系的结晶行为.PVAl的结晶度随PVP含量增加而减少,并存在结晶度为零的组成(PVAl)的重量分数约为50％.与纯PVAl相比,共混物的温度区间T_m-T_g减小,表明PVP对PVAl的结晶起抑制作用.共混物中PVAl的结晶速度下降,具体表现为PVAl过冷区随PVP含量增加而扩大,动力学速度常数减小,球晶增长速度下降.纯PVAl和共混体系的等温结晶速率均遵循Avrami方程.退火样品的长周期、片晶厚度和过渡层厚度大于相同组成未退火样品.两者长周期随PVP含量增长加显著增大,片晶厚度增长次之,过渡层厚度变化不大.