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1.
Sulfonated polystyrene (S–PS), which is of considerable scientific and technological interest, has been traditionally prepared by the sulfonation of preformed polystyrene. This report describes the preparation and properties of S–PS prepared by emulsion copolymerization of styrene and sodium styrene sulfonate. S–PS prepared by copolymerization gave solubility, solution behavior and thermal characteristics that are consistent with an ionomeric structure. The solubility characteristics indicated some chain-to-chain sulfonate heterogeneity. Thermal analysis studies indicated that the glass transition does not increase with increasing sulfonate content. This is contrary to what has been observed for S–PS prepared by sulfonation and suggests that the S–PS prepared by copolymerization is fundamentally different in structure than S–PS prepared by sulfonation of polystyrene.  相似文献   

2.
The nonaqueous solution behavior of random copolymers of styrene (ST) with sodium-2-acrylamido-2-methylpropane sulfonate (Na-AMPS) [poly(ST-Na-AMPS)] has been investigated using the transient electric birefringence (TEB) technique. The copolymers with varying high sulfonate contents (about 30–70 mol%), bridging the gap between conventional ionomers and classical polyelectrolytes, were dissolved in the solvent methylformamide (MFA) with a high permittivity ? of ca. 190. The solutions showed a negative birefringence at electric field strength E of the order of kV/cm. A typical Kerr effect was observed at low polymer concentrations C of ca. 10?3g/mL and electric field strengths of the order of kV/cm. However, the detailed, TEB studies demonstrated different behavior at two concentration regimes in dilute solution. At a low concentration regime (e.g., C ≤ 1 × 10?3g/mL for the copolymer with a 66.7 mol % sulfonate content) where the reduced viscosity exhibited a pronounced polyelectrolyte effect, the birefringence signal pattern showed a maximum before reaching a steady value. Additionally, during the rise at an applied electric field strength beyond a threshold value, it was observed that the nonexponential field-free decay was slower than the single exponential field-induced rise. The observed anomalous behavior was similar to those of a polyelectrolyte [sodium poly (styrene sulfonate)] in aqueous solution and might be attributed to the perturbation of the molecular shape by the applied electric field. At the higher concentration regime (e.g., C ≥ 4 × 10?3g/mL for the same copolymer with a 66.7 mol % sulfonate content) where the polyelectrolyte effects started to diminish as indicated by the viscosity study, the birefringence shape showed no variation with an increased electric field strength and the field-free decay turned out to be faster than the single exponential rise. The dissociation of ionic aggregates was tentatively interpreted to be responsible for this observation. It seems that by simply varying the polymer concentration, poly (ST-Na-AMPS) could behave either as a polyelectrolyte or as an ionomer in a single polar organic solvent.  相似文献   

3.
Graft copolymers of benzylcellulose and styrene were prepared by direct irradiation of benzylcellulose–styrene solutions with 60Co γ-radiation. The solutions remained homogeneous during irradiation. The amount of styrene grafted to benzylcellulose increased in dilute solutions and was dose-dependent up to 4.0 MR. The graft copolymer consisted of both branched and linear structures with one in every 140–1020 benzylated anhydroglucose units carrying a grafted polystyrene chain. Grafted polystyrene was isolated from the graft copolymer by hydrolysis of the benzylcellulose substrate. The number-average molecular weight and molecular weight distribution of the grafted polystyrene were the same as those for hompolymer formed in the same solution, indicating that the substrate is fully accessible to the monomer and polymerization conditions are uniform throughout the solution during the grafting procedure. The existence of a true graft copolymer was proved by the solubility behavior, intrinsic viscosity, number-average molecular weight, and density-gradient sedimentation of the product of the grafting procedure. Column elution fractionation of the gross products of the grafting procedure failed to isolate the benzylcellulose–styrene copolymer which was eluted with ungrafted benzylcellulose.  相似文献   

4.
Block copolymers based on poly(vinylidene fluoride), PVDF, and a series of poly(aromatic sulfonate) sequences were synthesized from controlled radical polymerizations (CRPs). According to the aromatic monomers, appropriate techniques of CRP were chosen: either iodine transfer polymerization (ITP) or atom transfer radical polymerization (ATRP) from PVDF‐I macromolecular chain transfer agents (CTAs) or PVDF‐CCl3 macroinitiator, respectively. These precursors were produced either by ITP of VDF with C6F13I or by radical telomerization of VDF with chloroform, respectively. Poly(vinylidene fluoride)‐b‐poly(sodium styrene sulfonate), PVDF‐b‐PSSS, block copolymers were produced from both techniques via a direct polymerization of sodium styrene sulfonate (SSS) monomer or an indirect way with the use of styrene sulfonate ethyl ester (SSE) as a protected monomer. Although the reaction led to block copolymers, the kinetics of ITP of SSS showed that PVDF‐I macromolecular CTAs were not totally efficient because a limitation of the CTA consumption (56%) was observed. This was probably explained by both the low activity of the CTA (that contained inefficient PVDF‐CF2CH2? I) and a fast propagation rate of the monomer. That behavior was also noted in the ITP of SSE. On the other hand, ATRP of SSS initiated by PVDF‐CCl3 was more controlled up to 50% of conversion leading to PVDF‐b‐PSSS block copolymer with an average number molar mass of 6000 g·mol?1. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011  相似文献   

5.
The solid-state viscoelastic properties of polystyrene containing randomly distributed groups of styrene-p-sodium sulfonate are studied and compared with the corresponding properties of copolymers of styrene and sodium methacrylate (S-NaMA). The viscoelastic behavior in the primary transition region of these two ionomers is very similar. As for the S-NaMA copolymers, it is proposed that sulfonated polystyrene is composed of ion-rich regions (clusters) immersed in a matrix of low ion concentration. Two peaks are observed in the plot of mechanical loss tangent versus temperature for the sulfonated material. The lower peak is assigned to the glass transition of the ion-poor matrix and the upper to the glass transition of the clustered regions. As for some other ionomers, the presence of ions is found to slow down the stress relaxation rate, giving a broad distribution of relaxation times. Above a certain ion concentration, the sulfonated polystyrenes are thermorheologically complex owing to the onset of a secondary relaxation mechanism associated with the ion-rich regions.  相似文献   

6.
ABCBA‐type pentablock copolymers of methyl methacrylate, styrene, and isobutylene (IB) were prepared by the cationic polymerization of IB in the presence of the α,ω‐dichloro‐PS‐b‐PMMA‐b‐PS triblock copolymer [where PS is polystyrene and PMMA is poly(methyl methacrylate)] as a macroinitiator in conjunction with diethylaluminum chloride (Et2AlCl) as a coinitiator. The macroinitiator was prepared by a two‐step copper‐based atom transfer radical polymerization (ATRP). The reaction temperature, ?78 or ?25 °C, significantly affected the IB content in the resulting copolymers; a higher content was obtained at ?78 °C. The formation of the PIB‐b‐PS‐b‐PMMA‐b‐PS‐b‐PIB copolymers (where PIB is polyisobutylene), prepared at ?25 (20.3 mol % IB) or ?78 °C (61.3 mol % IB; rubbery material), with relatively narrow molecular weight distributions provided direct evidence of the presence of labile chlorine atoms at both ends of the macroinitiator capable of initiation of cationic polymerization of IB. One glass‐transition temperature (Tg), 104.5 °C, was observed for the aforementioned triblock copolymer, and the pentablock copolymer containing 61.3 mol % IB showed two well‐defined Tg's: ?73.0 °C for PIB and 95.6 °C for the PS–PMMA blocks. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 3823–3830, 2005  相似文献   

7.
A novel graft-like copolymer of syndiotactic polystyrene (sPS) with polybutadiene (PB) was synthesized by polymerization of styrene in a toluene solution of PB using the cyclopentadiene titanium trichloride (CpTiCl3)/methylaluminoxane (MAO) catalytic system. The effect of PB on the crystallization behavior of the copolymer was investigated by differential scanning calorimetry and wide angle X-ray diffraction. Hydrogenation of the sPS/PB copolymer with p-toluenesulfonyl hydrazide afforded a PE-like copolymer.  相似文献   

8.
The copolymerization of butadiene with sodium styrene sulfonate was studied and the copolymer products characterized. In general these copolymers contain 0.5–4 mole% of sulfonated monomer. The effects of the following reaction variables are described: emulsifier type and concentration, monomers feed ratio, chain transfer agent concentration, and reaction conversion. The products were heterogeneous with regard to composition, molecular weight, and solubility behavior. Copolymers prepared under certain conditions exhibited strong intermolecular interactions derived from associations of the ionic species as observed in other ionomers.  相似文献   

9.
A polyimide‐graft‐polystyrene (PI‐g‐PS) copolymer with a polyimide backbone and polystyrene side chains was synthesized by the “grafting from” method using styrene polymerization on a polyimide multicenter macroinitiator via ATRP mechanism. The side chain grafting density z = 0.86 of PI‐g‐PS is rather high for graft‐copolymers synthesized by the ATRP method. Molecular characteristics and solution behavior of PI‐g‐PS were studied in selective solvents using light scattering and viscometry methods. In all solvents, the backbone tends to avoid contact with a poor solvent. To describe the conformation and hydrodynamic properties of PI‐g‐PS macromolecules in thermodynamically good solvents for side chains and PI‐g‐PS, the wormlike spherocylinder model is used. Macromolecules of the studied graft‐copolymer are characterized by high equilibrium rigidities (Kuhn segment length >20 nm). In Θ‐conditions, PI‐g‐PS macromolecules may be modeled by a rigid prolate ellipsoid of revolution with a low asymmetry form and a collapsed backbone as the ellipsoid core. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2014 , 52, 1539–1546  相似文献   

10.
Bead copolymers of styrene crosslinked with 1,2,4- and 1,3,5-trivinylbenzene (TVB) are sulfonated at different rates. The copolymer beads with 4% 1,3,5-TVB sulfonate more slowly than do those with 8% 1,2,4-TVB. The 8% 1,2,4-TVB crosslinked polystyrene beads sulfonate at about the same rate as do the beads prepared with 8% p-DVB crosslinkage.  相似文献   

11.
The behavior of sulfonated PS containing 0.5, 1.35, 2.6, and 5.8 mol % of sodium sulfonate groups in chloroform solutions has been studied by static and dynamic light scattering, viscometry, and electric birefringence. The molecular mass of ionomers is measured, and their translational diffusion coefficient, intrinsic viscosity, and free relaxation times are estimated. It has been shown that association in solutions of ionomers containing more than 1.35 mol % of sodium sulfonate groups proceeds according to the open association model. Analysis of autocorrelation functions of scattered light intensity and electric birefringence decay makes it possible to determine translational diffusion coefficients and relaxation times for individual ionomer molecules, their pair associates, and higher multiplicity associates. With an increase in the fraction of sodium sulfonate groups, the hydrodynamic radius of individual ionomer molecules decreases from 8 to 5.8 nm, while the ratio between the hydrodynamic radius of pair associates and individual sulfonated PS molecules increases.  相似文献   

12.
A commercial elastomeric block copolymer of butadiene (B) with styrene (A) is studied. A single chain of the material has the formula A-B-A. Differential thermal analysis studies show the presence of two transitions. The lower transformation temperature corresponds to the Tg of the butadiene chain segments, and the upper transformation temperature corresponds to the Tg of the styrene chain segments. The upper transition of the material is also studied by following the variation of the torsional modulus with temperature. This transition is found to be quite unusual. Our experiments show that the upper transformation of unstressed block copolymer samples is broad. The transition sharpens for samples which, prior to the modulus–temperature experiments, are stress-relaxed at high elongations. These observations (and those of the literature) suggest that the styrene and butadiene chain segments in the block copolymer aggregate in the solid state and give rise to two distinct transition phenomena. Our studies of the upper transformation suggest that stretching of the bulk material enhances the aggregation of the styrene chain segments. Pure polystyrene (A) blocks of the material are recovered by selective cleavage and fractionation experiments. The Tg of the pure polystyrene blocks is found to be similar to the value of the upper transition temperature of the copolymer. The ABA blocks copolymer is found also to undergo a stress-softening phenomenon analogous to that of reinforced rubber.  相似文献   

13.
A novel linked‐half‐sandwich lutetium–bis(allyl) complex [(C5Me4? C5H4N)Lu(η3‐C3H5)2] ( 1 ) attached by a pyridyl‐functionalized cyclopentadienyl ligand was synthesized and fully characterized. Complex 1 in combination with [Ph3C][B(C6F5)4] exhibited unprecedented dual catalysis with outstanding activities in highly syndiotactic (rrrr>99 %) styrene polymerization and distinguished cis‐1,4‐selective (99 %) butadiene polymerization, respectively. Strikingly, this catalyst system exhibited remarkable activity (396 kg copolymer (molLu h)?1) for the copolymerization of butadiene and styrene. Irrespective of whether the monomers were fed in concurrent mode or sequential addition of butadiene followed by styrene, diblock copolymers were obtained exclusively, which was confirmed by a kinetics investigation of monomer conversion of copolymerization with time. In the copolymers, the styrene incorporation rate varied from 4.7 to 85.4 mol %, whereas the polybutadiene (PBD) block was highly cis‐1,4‐regulated (95 %) and the polystyrene segment remained purely syndiotactic (rrrr>99 %). Correspondingly, the copolymers exhibited glass transition temperatures (Tg) around ?107 °C and melting points (Tm) around 268 °C; typical values for diblock microstructures. Such copolymers cannot be accessed by any other methods known to date. X‐ray powder diffraction analysis of these diblock copolymers showed that the crystallizable syndiotactic polystyrene (syn‐PS) block was in the toluene δ clathrate form. The AFM micrographs of diblock copolymer showed a remarkable phase‐separation morphology of the cis‐1,4‐PBD block and syn‐PS block. This represents the first example of a lutetium‐based catalyst showing both high activity and selectivity for the (co)polymerization of styrene and butadiene.  相似文献   

14.
D -Lactose-O-(vinylbenzyl)oxime (LVO), prepared from α-D -lactose and [O-(vinylbenzyl)oxy]amine ( 1 ) was copolymerized with styrene (ST) in dimethylsulfoxide (DMSO)-toluene (1 : 1, v/v) at 65°C using 2,2′-azobisisobutyronitrile (AIBN) as a free radical initiator. The polymerization was rapid when using AIBN as the initiator. The resultant copolymers were characterized by elemental analyses, infrared, viscometry, TGA, DSC, and 1H-NMR spectroscopy. The poly(ST-co-LVO) had an intrinsic viscosity in the range of 0.11–0.51 dL/g in DMSO at 30°C. The molecular weight was determined by gel permeation chromatography (GPC), and the molecular weight of the resulting polymers ranged from 2.11 × 104 to 6.53 × 107 with low polydispersities. The solubility of the copolymers with different monomer compositions in solvents of varied polarities was also studied. Incorporation of up to 65% (mol %) of lactose-based monomer onto polystyrene backbone led to a water-soluble polymer. Thermal behavior of the synthesized copolymers was evaluated by thermogravimetric analysis (TGA) and correlated very well with the polymer composition. Introduction of a pendant disaccharide compromised the thermal stability of the copolymer. The synthetic approach described in this report provides a route to prepare a novel disaccharide surfactant polymer with well-defined structures and hydrophilic/hydrophobic balances, by adjusting feed ratio of the lactose-based monomer ( 1 ) to styrene. © 1998 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 36: 2971–2978, 1998  相似文献   

15.
Blends of two or more ethylene–styrene (ES) copolymers that differed primarily in the comonomer composition of the copolymers were studied. Available thermodynamic models for copolymer–copolymer blends were utilized to determine the criteria for miscibility between two ES copolymers differing in styrene content and also between ES copolymers and the respective homopolymers, polystyrene and linear polyethylene. Model estimations were compared with experimental observations based primarily on melt‐blended ES/ES systems, particularly via the analysis of the glass‐transition (Tg ) behavior from differential scanning calorimetry (DSC) and solid‐state dynamic mechanical spectroscopy. The critical comonomer difference in the styrene content at which phase separation occurred was estimated to be about 10 wt % for ES copolymers with a molecular weight of about 105 and was in general agreement with the experimental observations. The range of ES copolymers that could be produced by the variation of the comonomer content allowed the study of blends with amorphous and semicrystalline components. Crystallinity differences for the blends, as determined by DSC, appeared to be related to the overlapping of the Tg of the amorphous component with the melting range of the semicrystalline component and/or the reduction in the mobility of the amorphous phase due to the presence of the higher Tg of the amorphous blend component. © 2000 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 38: 2976–2987, 2000  相似文献   

16.
Polymers of various structures, namely, the model PS with pentafluorophenyl groups, the linear-dendrite perfluorinated polyphenylenegermane-polystyrene, and diblock copolymer polystyrene-Ge(C6F5)2-polystyrene, have been prepared by radical polymerization and activated copolycondensation. The polymers have been studied in dilute solutions by GPC, static and dynamic light scattering, and viscometry. The addition of a bis(pentafluorophenyl group) to the ends of a PS chain facilitates the development of supramolecular structures in solutions of hybrid systems. If the fluorinated group is incorporated at the center of the polymer chain, no associative phenomena are observed, because of its screening by the molecular coil.  相似文献   

17.
In the preparation of the ABC star triblock copolymer of ethylene oxide, styrene and methyl methacrylate (MMA), the photo-induced charge-transfer complex (CTC) was used to initiate the polymerization of the third monomer MMA. The CTC was composed of the diblock copolymer of poly(ethylene oxide) (PEO) and polystyrene (PS), PEO-b i -PS, with an aromatic imino group at the conjunction point and benzophenone (BP). It was confirmed that the kinetic behavior of this macromolecular initiation system is nearly the same with a general small radical initiator: the polymerization rate R p ∝ [PEO-b i -PS]0.48[BP]0.45[MMA]0.97. Moreover, if the molecular weight of the PEO block is fixed, R p is independent of the molecular weight of the PS block.  By means of measurements of viscosity and fluorescence, it was found that the micelles of the diblock copolymer PEO-b i -PS were formed in benzene. The aromatic imino groups were located on the boundary surfaces of the micelles and were fully exposed, and so the BP and MMA molecules easily approached them and affected the charge-transfer polymerization of MMA. Received: 18 August 1998 Accepted in revised form: 25 November 1998  相似文献   

18.
The novel C60–styrene copolymers with different C60 contents were prepared in sodium naphthalene-initiated anionic polymerization reactions. Like the pure polystyrene, these copolymers exhibited the high solvency in many common organic solvents, even for the copolymer with high C60 content. In the polymerization process of C60 with styrene an important side reaction, i.e., reaction of C60 with sodium naphthalene, would occur simultaneously, whereas crosslinking reaction may be negligible. 13C-NMR results provided an evidence that C60 was incorporated covalently into the polystyrene backbone. In contrast to pure polystyrene, the TGA spectrum of copolymer containing ∼ 13% of C60 shows two plateaus. The polystyrene chain segment in copolymer decomposed first at 300–400°C. Then the fullerene units reptured from the corresponding polystyrene fragments attached directly to the C60 cores at 500–638°C. XRD evidence indicates that the degree of order of polymers increases with the fullerene content increased in terms of crystallography. Incorporation of C60 into polystyrene results in the formation of new crystal gratings or crystallization phases. In addition, it was also found that [60]fullerene and its polyanion salts [C60n(M+)n, M = Li, Na] cannot be used to initiate the anionic polymerization of some monomers such as acrylonitrile and styrene, etc.© 1998 John Wiley & Sons, Inc. J. Polym. Sci. B Polym. Phys. 36: 2653–2663, 1998  相似文献   

19.
A novel aromatic block–graft copolymer of sulfonated poly(styrene–isobutylene–styrene)‐graft‐poly(vinyl phosphonic acid) (SIBS‐g‐PVPA SO3H) was synthetized for direct methanol fuel cell (DMFC) and chemical and biological protective clothing (CBPC) applications. The polystyrene (PS) blocks of SIBS were chloromethylated via a Friedel–Crafts reaction to obtain the macroinitiator SIBS‐CH2Cl. Atom transfer radical polymerization (ATRP) was performed to graft VPA to the chloromethylated groups of the macroinitiator and yield SIBS‐g‐PVPA, which was subsequently sulfonated using acetyl sulfate as the sulfonating agent. After each functionalization step, a membrane was prepared by using the solvent casting technique. The final membrane was composed of triblock SIBS as the backbone, PVPA grafts attached to the chloromethylated PS end blocks and sulfonic groups in the non‐chloromethylated PS units. A comprehensive materials characterization study (e.g., GPC, FTIR, TGA, EA) was performed to confirm proper functionalization of each material. Unique ionic interactions (i.e., crosslinking via formation of sulfonate–phosphonium complexes) arose between the phosphonic and sulfonic groups (i.e., PO3H2 and SO3H, respectively) that enhanced the water absorption capabilities, thermal and oxidative stability, and the transport properties of SIBS. The SIBS‐g‐PVPA SO3H membrane presented high Nafion ® normalized selectivity and separation efficiency, indicating that this ionomer adequately functions for both applications. © 2018 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2018 , 56, 1424–1435  相似文献   

20.
The synthesis of arborescent styrenic homopolymers and copolymers was achieved by anionic polymerization and grafting. Styrene and p‐(3‐butenyl)styrene were first copolymerized using sec‐butyllithium in toluene, to generate a linear copolymer with a weight‐average molecular weight Mw = 4000 and Mw/Mn = 1.05. The pendant double bonds of the copolymer were then epoxidized with m‐chloroperbenzoic acid. A comb‐branched (or arborescent generation G0) copolymer was obtained by coupling the epoxidized substrate with living styrene‐p‐(3‐butenyl)styrene copolymer chains with Mw ≈ 5000 in a toluene/tetrahydrofuran mixture. Further cycles of epoxidation and coupling reactions while maintaining Mw ≈ 5000 for the side chains yielded arborescent copolymers of generations G1–G3. A series of arborescent styrene homopolymers was also obtained by grafting Mw ≈ 5000 polystyrene side chains onto the linear and G0–G2 copolymer substrates. Size exclusion chromatography measurements showed that the graft polymers have low polydispersity indices (Mw/Mn = 1.02–1.15) and molecular weights increasing geometrically over successive generations. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012  相似文献   

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