低头-头链含量的聚偏氟乙烯合成

研究了偏氟乙烯的聚合条件与其聚合物的头-头链含量的关系。实验表明聚合物的头-头链的含量与聚合温度有关,而与引发剂的种类无关。因而,可以在较低的聚合温度下聚合制得带有低的头-头结构(约3％)的聚偏氟乙烯。将聚合物链的A结构含量对其熔点作图,得一直线,可表示为方程式A=24.8+0.362T_m(％)。     

The influence of chain structure on the equilibrium melting temperature of poly(vinylidene fluoride)

Three poly(vinylidene fluoride) whole polymers were fractionated according to their head-to-head concentrations. Their melting temperatures and fusion properties were studied. Although small but significant differences were found among the fractions obtained from a given parent polymer, a wide range in chain compositions was not obtained. The equilibrium melting temperatures were determined by extrapolating the dependence of the observed melting temperature on the crystallization temperature. A critical analysis is given of this extrapolation method as applied to poly(vinylidene fluoride) and the results are compared with literature reports. The problems involved in explaining the dependence of the equilibrium melting temperatures on the structural irregularities of the chain are given. Possible reasons for the relatively high level of crystallinity that is observed, for what is essentially a copolymer, are also discussed.     

Calorimetric determination of head-to-head defect in poly(vinylidene fluoride)

Differential scanning calorimetric analyses were conducted on samples of poly(vinylidene fluoride) polymerized in an autoclave by tributylborane-oxygen by free-radical initiation at low temperature (-70-0°C). The peak melting points and the percent head-to-head defect in each polymer sample were determined by a reported calorimetric method. A commercial sample showed a melting temperature in the range 157–162°C and a percent head-to-head defect of 7.7%; whereas two experimental samples showed melting temperatures in the range 172–179°C with a percent head-to-head defect of 4.4 and 4.9%. The calorimetric procedure was modified by reducing annealing times to only 2 h, which saves time and, as shown in this study, avoids thermal polymer degradation.     

Homogeneous phase polymerization of vinylidene fluoride in supercritical carbon dioxide

For the first time, stabilizer‐free vinylidene fluoride (VDF) homopolymerizations were carried out in homogenous phase with supercritical CO₂ using the conventional initiator di‐tert butyl peroxide (DTBP). In‐line FT‐NIR spectroscopy showed that complete monomer conversion may be obtained. Molecular weights were determined via size‐exclusion chromatography and polymer endgroup analysis by ¹H‐NMR spectroscopy. The number average molecular weights were below 10⁴ g mol^?1 and polydispersities ranged from 3.1 to 5.7 depending on DTBP and VDF concentration. For allowing isothermal reaction, high CO₂ contents ranging from 61 to 83 wt % were used. The high‐temperature and high‐pressure conditions required for homogeneous polymerization did not alter the amount of defects in VDF chaining. Scanning electron microscopy indicated that regular stack‐type particles are obtained upon expansion of the homogeneous polymerization mixture. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 5626–5635, 2007     

Antifouling poly(vinylidene fluoride) ultrafiltration membranes containing amphiphilic comb polymer additive

An amphiphilic comb polymer consisting of poly(vinylidene fluoride‐co‐chlorotrifluoroethylene) [P(VDF‐co‐CTFE)] main chains and poly(oxyethylene methacrylate) (POEM) side chains was synthesized using direct initiation of the chlorine atoms in CTFE units through atom transfer radical polymerization, as confirmed by ¹H NMR and FTIR spectroscopy. The P(VDF‐co‐CTFE)‐g‐POEM comb polymer was introduced as an additive to prepare poly(vinylidene fluoride) antifouling ultrafiltration membranes. As the contents of comb polymer increased, the mechanical properties of membranes slightly decreased due to the decreased crystallinity of the membranes, as revealed by universal testing machine and X‐ray diffraction. However, water contact angle measurement and X‐ray photoelectron spectroscopy showed that the hydrophilic POEM segments spontaneously segregated on the membrane surfaces. As a result, the antifouling property of the membranes containing P(VDF‐co‐CTFE)‐g‐POEM comb polymer was considerably improved with a slight change of water flux. © 2009 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 48: 183–189, 2010     

Polymerization and copolymerization studies on vinyl fluoride

The polymerization of vinyl fluoride has been studied in the temperature range of 0–50°C. with the aid of different types of initiators. Ziegler-Natta systems based on vanadyl acetylacetonate and AIR(OR)Cl compounds showed good activity. Enhanced reaction rates and higher polymerization degrees were achieved with boron alkyls (and, to a lesser degree, Cd, Zn, and Be alkyls) activated by oxygen. With either types of initiator, the main features and the kinetic parameters of the polymerization were determined. In all cases, the polymerization is considered to be of the free-radical type, though some properties (crystallinity, melting temperature) of the polymer are shown to be markedly improved over the previously described high-pressure polymer. This is chiefly ascribed to an improved degree of chemical regularity of the chains. The copolymerization of vinyl fluoride in the presence of the cited initiators was studied with a number of monomers. The values of the copolymerization parameters allow us to obtain Q (0.010 ± 0.005) and e (?0.8±0.2) values and to discuss the reactivity of vinyl fluoride in radical chain propagation.     

Nuclear magnetic resonance and x-ray determination of the structure of poly(vinylidene fluoride)

In this study, wide-line NMR and x-ray diffraction have been used in conjunction to study the crystal structure of poly(vinylidene fluoride). Drawn poly(vinylidene fluoride) film was found to contain two crystal phases, the relative amounts of each depending on the draw temperature. Drawing at 50°C. yields a single phase, designated as phase I, while drawing at temperatures between 120 and 160°C. yields a mixture of phase I and a second phase (phase II). The fraction of phase II increases with increasing draw temperature, but this phase was never obtained without some phase I. A tentative orthorhombic unit cell is proposed for phase II. The structure of phase I has been determined from x-ray data. The unit cell is orthorhombic, space group Cm2m, having lattice constants a = 8.47, b = 4.90, and c (chain axis) = 2.56 A. There are two polymer chains in this unit cell. The conformation of the polymer chains is planar zigzag. The details of this structure have been confirmed by experimentally determining at ?196°C. the change in the NMR second moment with the angle between the magnetic field and the draw direction of phase I (drawn at 50°C.), and by comparing these results with a theoretical calculation of the second moments, based on the atomic positions obtained from the proposed structure.     

Effects of external donors and hydrogen concentration on oligomer formation and chain end distribution in propylene polymerization with Ziegler‐Natta catalysts

The effect of type and concentration of external donor and hydrogen concentration on oligomer formation and chain end distribution were studied. Bulk polymerization of propylene was carried out with two different Ziegler‐Natta catalysts at 70 °C, one a novel self‐supported catalyst (A) and the other a conventional MgCl₂‐supported catalyst (B) with triethyl aluminum as cocatalyst. The external donors used were dicyclopentyl dimethoxy silane (DCP) and cyclohexylmethyl dimethoxy silane (CHM). The oligomer amount was shown to be strongly dependent on the molecular weight of the polymer. Catalyst A gave approximately 50 % lower oligomer content than catalyst B due to narrower molecular weight distribution in case of catalyst A. More n‐Bu‐terminated chain ends were found for catalyst A indicating more frequent 2,1 insertions. Catalyst A also gave more vinylidene‐terminated oligomers, suggesting that chain transfer to monomer, responsible for the vinylidene chain ends, was a more important chain termination mechanism for this catalyst, especially at low hydrogen concentration. Low site selectivity, due to low external donor concentration or use of a weak external donor (CHM), was also found to increase formation of vinylidene‐terminated oligomers. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 351–358, 2010     

Effect of acetylene on the γ-radiation-induced polymerization of ethylene

The effects of acetylene on the γ-radiation-induced polymerization of ethylene were studied from the viewpoint of the gaseous products and polymer structure. The experiments were carried out under a pressure of 400 kg/cm²; the temperature was 30°C; the does rate was 1.1 × 10⁵ rad/hr; and the acetylene content was 0–20%. The solid polymer was obtained in the polymerization of ethylene containing 2.2% acetylene, while the monomer containing 19.7% acetylene gave a yellowish viscous oil. The polymer yield and molecular weight decreased remarkably with acetylene content. The main gaseous product was hydrogen, and trace amounts of butane, butene-1, butadiene-1,3, and benzene and its derivatives were also observed. The rate of formation of hydrogen was almost independent of acetylene content and there was no difference in acetylene contents before and after the irradiation was found. The infrared spectra of the polymers showed the presence of vinylidene, trans-vinylene, and terminal vinyl unsaturations, 1,4-disubstituted benzene, and carbonyl groups. The contents of trans-vinylene, terminal vinyl, and methyl groups increased with acetylene content, and that of vinylidene was independent of acetylene content. The monomer reactivity ratios of ethylene and acetylene were evaluated as 45.5 and 66.0, respectively. On the basis of the results, the effects of acetylene on the γ-radiation-induced polymerization of ethylene were discussed.     

Continuous precipitation polymerization of vinylidene fluoride in supercritical carbon dioxide: molecular weight distribution

The surfactant-free precipitation polymerization of vinylidene fluoride (VF2) in supercritical carbon dioxide was studied in a continuous stirred autoclave. The polymerization temperature ranged from 65 to 85°C, the average residence time in the reactor varied from 10 to 50 min., and the pressure was between 210 and 305 bar. Diethyl peroxydicarbonate was used as the initiator. The fractional conversion of monomer varied from 7 to 26%, the number-average molecular weight of the polymer was between about 14,000 and 79,000, and the weight-average molecular weight was between about 21,000 and 700,000. In many cases, the polymer exhibited a bimodal molecular-weight distribution, especially at high monomer concentrations.     

Effect of polymerization conditions on the morphology of as-polymerized poly(vinylidene chloride)

Poly(vinylidene chloride) (PVDC) separates from the reaction mixture during the free-radical polymerization of vinylidene chloride. The morphology of the “as-polymerized” powder is determined by the degree of undercooling existing in the reaction medium at the time of crystallization. Crystallization occurs simultaneously in the process of polymerization and subsequently by the precipitation of polymer which formed in solution. As the medium becomes more favorable, an increasing portion of the polymer forms in solution and then crystallizes. The morphology developed by polymerization in borderline solvents such as dioxane can be nearly duplicated by recrystallization under similar conditions. The simultaneous occurrence of solution and solid phase polymerization leads to a double DTA endotherm. The upper peak at ca. 200°C represents the melting point of PVDC. The size and temperature of the lower peak vary with polymerization conditions. The results can be correlated with the degree of under-cooling as estimated by the difference between the polymerization temperature and the temperature at which the crystalline polymer dissolves in the reaction mixture.     

The crystal structure of the alternating copolymer of hexafluoroisobutylene and vinylidene fluoride

The crystal structure of the alternating copolymer of hexafluoroisobutylene and vinylidene fluoride, P(HFIB/VF₂), was determined using x-ray diffraction techniques. Oriented specimens of the copolymer were produced by drawing melt-pressed film at 300°C. The unit cell of P(HFIB/VF₂) is orthorhombic with dimensions at a = 1.064, b = 1.837, and c = 0.783 nm. The chain conformation is a 2₁ helix with an approximate trans-trans-gauche-gauche backbone dihedral-angle sequence. Severe intrachain steric crowding exists; as a consequence, the chain is quite rigid and some of the backbone bond angles are highly extended. The unit cell contains four such chains packed according to the symmetry of space group Iba2. Neighboring chains in a crystal are mechanically interlocked; in combination with the rigidity of the chains, this is the basis for the superior mechanical properties of the copolymer compared to PTFE. A structure containing up to 20-30% of head-to-head residues was found to be statistically indistinguishable from a completely head-to-tail structure.     

Effect of nanoclay on relaxation of poly(vinylidene fluoride) nanocomposites

The effect of Lucentite™ STN nanoclay on the relaxation behavior of poly(vinylidene fluoride) (PVDF) nanocomposites was investigated using dielectric relaxation spectroscopy (DRS) and wide- and small-angle X-ray scattering. Lucentite™ STN is a synthetic nanoclay based on hectorite structure containing an organic modifier between the hectorite layers. The addition of this nanoclay to PVDF results in preferential formation of the beta-crystallographic phase. When the STN content increased to 5% and 10%, only the beta-phase was observed. Bragg long period and lamellar thickness both decrease with STN addition. The relaxation rates for processes termed α_a (glass transition, related to polymer chain motions in the amorphous regions) and α_c (related to polymer chain motions in the crystalline regions and fold surfaces) can be described either with the Vogel-Fulcher-Tamman equation or with Arrhenius behavior, respectively. DRS shows that the α_a relaxation rate increases with the concentration of STN because of the reduction of intermolecular correlations between the polymer chains, caused by the presence of layered silicate nanoclay particles, which serve to segregate polymer chains in the amorphous regions. Comparing samples with beta-crystal phase dominant, the relaxation rate for the α_c relaxation also increases with concentration of STN in all nanocomposite samples. Dielectric properties at low frequencies are dominated by the dc conductivity, and as more STN is added, the conductivity increases rapidly. The addition of 10% STN makes the dc conductivity increase by almost four decades when compared with neat PVDF. © 2009 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 47: 2520–2532, 2009     

Vibrational analysis for the all-trans ferroelectric phase conformation of P (VDF) homopolymer and of P(VDF/TrFE) copolymer: A cluster-lattice calculation

Green's functions formalism and transfer matrix method have been used to predict the spectra of all-trans poly(vinylidene fluoride) and the expected changes for poly(vinylidene fluoride/trifluoroethylene) copolymers with the same chain conformation. We find that the use of a simple cluster-lattice calculation, where the impurity cluster is a trifluoroethylene (TrFE) unit immersed in a poly(vinylidene fluoride) [P(VDF)] regular chain, can explain the main features observed by infrared and Raman spectroscopy in the frequency range 800 to 1450 cm^?1. The bands associated to vibration modes of regular VDF sequences, like the 880, 1070, 1280, and 1430 cm^?1 ones, are predicted to decrease or even to disappear with increasing TrFE content. The appearance of new peaks at 970, 1300, 1330, and 1410 cm^?1 is also discussed.     

聚偏氟乙烯凝胶电解质组成间相互作用及其凝胶化研究

通过冷却聚偏氟乙烯 (PVDF) 丙烯碳酸酯 (PC)或PVDF PC LiClO4的溶液 ,制备了数个聚合物凝胶 .实验表明 ,聚合物凝胶的凝胶化时间 (tgel)与凝胶温度、聚合物浓度有关 ,且强烈地依赖于体系中盐的浓度 ,因为盐会缩短体系的tgel.凝胶体系中LiClO4的存在提高了其凝胶熔融温度 (Tgm) ,LiClO4的含量越大 ,相应凝胶的Tgm 越高 .用DSC和落球法所测凝胶的Tgm 有较大的差别 .这说明凝胶中可能存在热稳定性好和热稳定性相对较差的两种不同结构部分 .FT IR的研究结果表明 ,凝胶电解质的各组成 (LiClO4,PC和PVDF)间存在较强的相互作用 .对含盐和不含盐的两类凝胶体系的对比研究表明 ,两者不同的凝胶化现象和Tgm 归因于盐与聚合物或溶剂间的络合作用     

Anomalous solubility of polyacrylamide prepared by dispersion (precipitation) polymerization in aqueous tert‐butyl alcohol

Polyacrylamide prepared by dispersion (precipitation) polymerization in an aqueous t‐butyl alcohol (TBA) medium is only partially soluble when the TBA concentrations in the polymerization media are in the range 82 vol % < TBA < 95 vol %. Independent experiments with a soluble (linear) sample of polyacrylamide show that the polymer swells sufficiently in the aforementioned media to lower the glass‐transition temperature of the polymer below the polymerization temperature (50 °C). The anomalous solubility has been attributed to the crosslinking of polymer chains that occurs during the solid‐phase polymerization of acrylamide in the swollen polymer particles. It is postulated that some of the radical centers shift from the chain end to the chain backbone during solid‐phase polymerization by chain transfer to neighboring polymer molecules, and when pairs of such radicals come into close vicinity, crosslinking occurs. However, dispersion (precipitation) polymerization in other media such as aqueous methanol and aqueous acetone yields polymers that are soluble. This result has been attributed to the fact that the polymer radical undergoes a chain‐transfer reaction with these solvents at a much faster rate than with TBA, which overcomes the effect of the polymer‐transfer reaction. Even the addition of as little as 5% methanol to a TBA–water mixture (TBA:water = 85:10) gives rise to a soluble polymer. The chain‐transfer constants for acetone, methanol, and TBA have been determined to be 9.0 × 10^?6, 6.9 × 10^?6, and 1.48 × 10^?6, respectively, at 50 °C. © 2001 John Wiley & Sons, Inc. J Polym Sci Part A: Polym Chem 39: 3434–3442, 2001     

Well‐defined copolymers based on poly(vinylidene fluoride): From preparation and phase separation to application

Poly(vinylidene fluoride) (PVDF) has reached the second largest production volume of fluoropolymers in recent years, and its popularity can be ascribed to high thermal stability and chemical inertness combined with its ferroelectric behavior. Copolymerization of vinylidene fluoride with other monomers leads to a wide variety of products with modified or improved properties. Besides commercially available fluorinated random copolymers, well‐defined block‐, graft, and alternating copolymers based on PVDF received more attention in recent years. PVDF‐containing block copolymers that may self‐assemble into well‐ordered morphologies are of particular interest, being potential precursors for functional nanostructured materials applicable in membranes and electronics. This Highlight provides an overview of the routes developed towards these materials via conventional and controlled polymerization techniques. In addition, it discusses their nanoscopic phase behavior and current and potential applications. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2014 , 52, 2861–2877     

RHEOLOGICAL PROPERTIES OF POLY(VINYLIDENE FLUORIDE) IN MOLTEN STATE

The theological behavior of poly(vinylidene fluoride)(PVDF)samples of different molecular weights was investigated by means of high pressure capillary rheometer and rotational rheometer.Information on the rheological properties of such materials above melt temperatures is of interest as this can lead to an improved understanding of polymer behavior in processing and fabrication technologies.Shift factors derived from time-temperature superposition showed good fit to the Arrhenius equation with a flow act...     

Polyaniline-poly(vinylidene fluoride) blend microfiltration membrane and its spontaneous gold recovery application

Structural regular polyaniline was synthesized via a modified-chemical oxidative polymerization reaction. Highly hydrophilic polyaniline (PANi) and polyaniline-poly(vinylidene fluoride) blend (PANi-PVDF) membranes were prepared by solution casting and phase inversion techniques. Both of the mechanical and filtration properties of the membranes depend on the polymer composition and doping level of the blends. The elasticity of the membrane is greatly improved upon introducing poly(vinylidene fluoride) into the blend. The water permeability of the blend membranes is further enhanced when the membranes are doped with hydrochloric acid. The PANi-PVDF blend membranes are capable of recovering metallic gold from the acid/halide leaching streams spontaneous and sustainably, and are promising candidates for wastewater treatments in electronic industries.     

Computational analysis of bending strain in single chains of β‐PVDF

Hartree–Fock calculations on 20 carbon atom chains of β‐phase poly(vinylidene fluoride) (PVDF) were done as a function of bending strain. The results can be modeled in terms of a classical energy versus strain curve resulting in a pseudomodulus (310 GPa) comparable to the Young's modulus calculated for stretching along carbon atom chain (199 GPa). The model also shows that the minimum energy state of a single chain of the polymer is not linear in the all‐trans geometry and that a significant strain energy is stored in natural thin films. This suggests that energy can be captured from bending motions in β‐PVDF. © 2011 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 49: 1493–1495, 2011