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1.
We observed that modified polyphenylene ether (PPE) was solubilized in thermoplastic styrenic elastomer (TPS) and that a two‐phase lacy structure formed on nanometer scales when the TPS composition was 67 wt % and modified PPE and polystyrene‐block‐poly(styrene‐co‐ethylene‐co‐butylene)‐block‐polystyrene (S‐SEB‐S triblock copolymer) were blended. However, the molecular weight of the outer PS block segments MoutPS and the content of the outer PS block segments ?outPS were <10,000 g/mol and 20 wt %, respectively. The resulting S‐SEB‐S/modified PPE nano‐alloy exhibited both flexibility and flame retardancy, unlike other materials, where a trade‐off exists between these two properties; that is, the flame retardancy was excellent when the phosphorus additive was present. This combination of properties might be attributed to the two‐phase nanometer‐scale structure consisting of flame‐retardant styrene/PPE domains and a continuous soft, lacy SEB matrix. The results for polystyrene‐block‐poly(ethylene‐co‐butylene)‐block‐polystyrene (S‐EB‐S triblock copolymer)/modified PPE blends were presented for comparison. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40446.  相似文献   

2.
In the present work, the effectiveness of five trithiocarbonates (TTCs) as mediating agents in the reversible addition fragmentation chain transfer (RAFT) polymerization and photopolymerization of styrene (St) were investigated. The five TTCs including S,S′‐bis(α, α′‐dimethyl‐α″‐acetic acid) trithiocarbonate (TTC1), bis(2‐oxo‐2‐phenyl‐ethyl) trithiocarbonate (TTC2), 3‐(2‐carboxyethylsulfanylthiocarbonylsulfanyl)‐propionic acid (TTC3), 2‐(2‐carboxyethylsulfanylthiocarbonylsulfanyl)propionic acid (TTC4), and 2‐(2‐carboxyethylsulfanylthiocarbonylsulfanyl)‐2‐methylpropionic acid (TTC5) were synthesized, in which the substitution patterns (groups Z and R) of the TTCs were varied. The dynamic behavior of TTC1, TTC2, TTC4, and TTC5‐mediated polymerization of St was well described by pseudo first‐order kinetics. In the presence of TTC1, TTC2, TTC4, and TTC5, the polydispersity indices changed with increasing conversion in the range of 1.10–1.25 typical for RAFT‐prepared (co)polymers, and were well below the theoretical lower limit of 1.50 for a normal free radical polymerization. Transfer coefficients of TTCs in St polymerization at 70°C were estimated by using the Mayo method. Density functional theory calculations successfully predicted the effect of the structure of TTCs on the activity of RAFT agents in a qualitative manner. The calculated results for RAFT agents agreed well with the experimental results. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2009  相似文献   

3.
Ab initio reversible addition–fragmentation chain transfer (RAFT) emulsion polymerization of styrene/butyl acrylate was investigated with the trithiocarbonate macro‐RAFT agent poly(acrylic acid)‐block‐polystyrene (PAA‐b‐PS) as a stabilizer and a RAFT agent. Influences of the amount of ammonium persulfate (APS), the amount of PAA‐b‐PS and the mass ratio of monomers on emulsion polymerization and film properties are discussed. The particle morphology exhibited spherical‐like structure with particles of about 90 nm in diameter and relatively narrow particle size distribution characterized using transmission electron microscopy and dynamic laser scattering. Fourier transform infrared and 1H NMR spectra showed that the styrene/butyl acrylate emulsion was successfully synthesized. The monomer conversion increased initially with increasing amount of APS, from 0.4 up to 0.8 wt%, and then decreased. The particle size increased and its distribution decreased gradually with increasing amount of APS. The monomer conversion increased from 76.83 to 94.21% as the amount of PAA‐b‐PS increased from 3 to 4 wt%, and then decreased with further increase of PAA‐b‐PS. The particle size decreased and its distribution increased with increasing amount of PAA‐b‐PS. The water resistance and solvent resistance of the polymer films initially increased and then decreased with decreasing mass ratio of butyl acrylate to styrene. © 2014 Society of Chemical Industry  相似文献   

4.
BACKGROUND: The phase behaviour of copolymers and their blends is of great interest due to the phase transitions, self‐assembly and formation of ordered structures. Phenomena associated with the microdomain morphology of parent copolymers and phase behaviour in blends of deuterated block copolymers of polystyrene (PS) and poly(methyl methacrylate) (PMMA), i.e. (dPS‐blockdPMMA)1/(dPS‐block‐PMMA)2, were investigated using small‐angle X‐ray scattering, small‐angle neutron scattering and transmission electron microscopy as a function of molecular weight, concentration of added copolymers and temperature. RESULTS: Binary blends of the diblock copolymers having different molecular weights and different original micromorphology (one copolymer was in a disordered state and the others were of lamellar phase) were prepared by a solution‐cast process. The blends were found to be completely miscible on the molecular level at all compositions, if their molecular weight ratio was smaller than about 5. The domain spacing D of the blends can be scaled with Mn by DMn2/3 as predicted by a previously published postulate (originally suggested and proved for blends of lamellar polystyrene‐block‐polyisoprene copolymers). CONCLUSIONS: The criterion for forming a single‐domain morphology (molecularly mixed blend) taking into account the different solubilization of copolymer blocks has been applied to explain the changes in microdomain morphology during the self‐assembling process in two copolymer blends. Evidently the criterion, suggested originally for blends of lamellar polystyrene‐block‐polyisoprene copolymers, can be employed to a much broader range of block copolymer blends. Copyright © 2008 Society of Chemical Industry  相似文献   

5.
An amphiphilic copolymer poly(acrylic acid)‐block‐poly(styrene) (PAA‐b‐PS) with a trithiocarbonate reactive group was used in the ab initio reversible addition‐fragmentation chain transfer (RAFT) emulsion polymerization of vinylidene chloride (VDC). The fast polymerization and high conversion were achieved. The parameters for a good control over the formation of well‐defined PAA‐b‐PS‐b‐PVDC amphiphilic block copolymers and self‐stabilized latexes were identified. To improve the emulsion stability and prevent the desorption of water‐soluble initiating radicals, the acid groups of PAA‐b‐PS were neutralized by NaOH at the later stage of polymerization. The PAA‐b‐PS‐b‐PVDC block copolymer with a high molar mass of 30 kg mol−1 and the stable latex with 30 wt % solid content was obtained. The kinetics of RAFT emulsion copolymerization of VDC in a living manner was first investigated. The as‐prepared PAA‐b‐PS‐b‐PVDC latex particles were further used as seeds in the emulsion polymerization of styrene, enabling the preparation of novel PAA‐b‐PS‐b‐PVDC‐b‐PS tetra‐block copolymers with a molar mass of 76 kg mol−1 and a relatively low molecular weight distribution of 1.6. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40391.  相似文献   

6.
Core–shell‐type microspheres with microphase‐separated shells of polystyrene (PS) and poly(ethylene glycol) (PEG) (microsphereblock: molar ratio: PS/PEG 49.1/45.9 mol %; Mw: PS chain: 1.07 × 104, PEG chain 1.0 × 104; the ratio of arm numbers of PEG to PS: 1.0; microspheregraft: molar ratio: PS/PEG 33.8/55.9 mol %; Mw: PS chain: 1.54 × 104, PEG chain 1.0 × 104, the ratio of arm numbers of PEG to PS: 2.55) were synthesized by crosslinking of spherical domains of poly(2‐hydroxyethyl methacrylate) (PHEMA) and poly(4‐vinyl pyridine) (P4VP) of the microphase‐separated films of poly(ethylene glycol)‐block‐poly(2‐hydroxyethyl methacrylate)‐block‐polystyrene triblock terpolymer (Mn: 2.18 × 104; molar ratio: PS 49.1 mol %, PHEMA 5.0 mol %, PEG 45.9 mol %) and polystyrene‐block‐[poly(4‐vinyl pyridine)‐graft‐poly(ethylene glycol)] block–graft copolymer (Mn: 4.56 × 104; molar ratio: PS 33.8 mol %, P4VP 10.3 mol %, PEG 55.9 mol %; branch number of PEG: 2.55), respectively. The structures of microphase‐separated films were investigated by transmission electron microscopy and small‐angle X‐ray scattering. The effects of the arm number ratio of PS to PEG and the total arm number on the stability of the water/benzene emulsion were investigated. The emulsion stability of oil in water was improved by using the microsphere synthesized with the microspheregraft. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 91: 321–331, 2004  相似文献   

7.
Polystyrene‐block‐poly(4‐vinylpyridine) (PS‐b‐P4VP) was synthesized by two steps of reversible addition‐fragmentation transfer (RAFT) polymerization of styrene (St) and 4‐vinylpyridine (4VP) successively. After P4VP block was quaternized with CH3I, PS‐b‐quaternized P4VP/montmorillonite (PS‐b‐QP4VP/MMT) nanocomposites were prepared by cationic exchange reactions of quaternary ammonium ion in the PS‐b‐QP4VP with ions in MMT. The results obtained from X‐ray diffraction (XRD) and transmission electron microscopy (TEM) images demonstrate that the block copolymer/MMT nanocomposites are of intercalated and exfoliated structures, and also a small amount of silicates' layers remained in the original structure; differential scanning calorimetry (DSC) and thermal gravimetric analysis (TGA) results show that the nanocomposites displayed higher glass transition temperature (Tg) and higher thermal stability than that of the corresponding copolymers. The blending of PS‐b‐QP4VP/MMT with commercial PS makes MMT to be further separated, and the MMT was homogeneously dispersed in the polymer matrix. The enhancement of thermal stability of PS/PS‐b‐QP4VP/MMT is about 20°C in comparison with commercial PS. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102:1950–1958, 2006  相似文献   

8.
Reversible addition–fragmentation chain transfer polymerization (RAFT) was developed for the controlled preparation of polystyrene (PS)/poly(4‐vinylpyridine) (P4VP) triblock copolymers. First, PS and P4VP homopolymers were prepared using dibenzyl trithiocarbonate as the chain transfer agent (CTA). Then, PS‐b‐P4VP‐b‐PS and P4VP‐b‐PS‐b‐P4VP triblock copolymers were synthesized using as macro‐CTA the obtained homopolymers PS and P4VP, respectively. The synthesized polymers had relatively narrower molecular weight distributions (Mw/Mn < 1.25), and the polymerization was controlled/living. Furthermore, the polymerization rate appeared to be lower when styrene was polymerized using P4VP as the macro‐CTA, compared with polymerizing 4‐vinylpyridine using PS as the macro‐CTA. This was attributed to the different transfer constants of the P4VP and PS macro‐CTAs to the styrene and the 4‐vinylpyridine, respectively. The aggregates of the triblock copolymers with different compositions and chain architectures in water also were investigated, and the results are presented. Reducing the P4VP block length and keeping the PS block constant favored the formation of rod aggregates. Moreover, the chain architecture in which the P4VP block was in the middle of the copolymer chain was rather favorable to the rod assembly because of the entropic penalty associated with the looping of the middle‐block P4VP to form the aggregate corona and tailing of the end‐block PS into the core of the aggregates. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 1017–1025, 2003  相似文献   

9.
In this contribution, we reported to utilize polystyrene‐block‐polybutadiene‐block‐polystyrene (PS‐b‐PB‐b‐PS), a commercial triblock copolymer to toughen epoxy thermosets. First, a PS‐b‐PB‐b‐PS triblock copolymer was chemically modified with hydroboration‐oxidation reaction, with which the midblock was hydroxylated whereas the endblocks remained unaffected. It was found that the degree of hydroxylation was well controlled. One of the hydroxylated PS‐b‐PB‐b‐PS samples was then used as the macromolecular initiator to synthesize a poly(ε‐caprolactone)‐grafted PS‐b‐PB‐b‐PS via the ring‐opening polymerization. It was found that the PS‐b‐PB‐b‐PS with poly(ε‐caprolactone) grafts can be successfully employed to nanostructure epoxy thermosets; the “core‐shell” microdomains composed of PB and PS were generated in the nanostructured thermosets. The nanostructured thermosets displayed improved fracture toughness. POLYM. ENG. SCI., 59:2387–2396, 2019. © 2019 Society of Plastics Engineers  相似文献   

10.
Polystyrene (PS)/polyolefin (PO) blends in various mixing ratios compatibilized by a triblock copolymer polystyrene‐block‐poly(ethene‐co‐butylene)‐block‐polystyrene (SEBS) and a diblock copolymer polystyrene‐block‐poly(ethene‐co‐propene) (SEP) and subsequently γ‐irradiated were prepared. The blends have been subjected to extraction in different solvents (chloroform or toluene) for various periods of time to obtain porous films. The efficiency of the extraction and the morphology of the films have been assessed by infrared spectrometry (IR), optical and electronic microscopy, differential scanning calorimetry (DSC) and thermogravimetry (TG); glass transition, melting heat, thermal stability, overall kinetic parameters and weight losses have been evaluated. The extraction behavior is close related to compatibility of the components, so on the base of the obtained results optima compatibility ratios have been established.  相似文献   

11.
Well‐defined polydimethylsiloxane‐block‐polystyrene (PDMS‐b‐PS) diblock copolymers were prepared by reversible addition‐fragmentation chain transfer (RAFT) polymerization using a functional PDMS‐macro RAFT agent. The RAFT polymerization kinetics was simulated by a mathematical model for the RAFT polymerization in a batch reactor based on the method of moments. The model described molecular weight, monomer conversion, and polydispersity index as a function of polymerization time. Good agreements in the polymerization kinetics were achieved for fitting the kinetic profiles with the developed model. In addition, the model was used to predict the effects of initiator concentration, chain transfer agent concentration, and monomer concentration on the RAFT polymerization kinetics. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011  相似文献   

12.
γ‐Radiation vulcanized natural rubber (RVNR)/phase transfer/suspension polymerization technique was used to prepare high‐impact polystyrene (HIPS) in bead form. The high notched Izod impact resistance of HIPS based on RVNR was observed and compared with that of unmodified PS. The impact resistance of HIPS based on RVNR was further enhanced by addition of 10% of polystyrene‐block‐polyisoprene‐block‐polystyrene copolymer. A mesh structure of all crosslinked rubber particles containing polystyrene and long crazes in HIPS were observed under electron microscopy. Copyright © 2003 Society of Chemical Industry  相似文献   

13.
Mono‐ and bifunctional poly(phenylene oxide) (PPO) macroinitiators for atom transfer radical polymerization (ATRP) were prepared by esterification of mono‐ and bishydroxy telechelic PPO with 2‐bromoisobutyryl bromide. The macroinitiators were used for ATRP of styrene to give block copolymers with PPO and polystyrene (PS) segments, namely PPO‐block‐PS and PS‐block‐PPO‐block‐PS. Various ligands were studied in combination with CuBr as ATRP catalysts. Kinetic investigations revealed controlled polymerization processes for certain ligands and temperature ranges. Thermal analysis of the block copolymers by means of DSC revealed only one glass transition temperature as a result of the compatibility of the PS and PPO chain segments and the formation of a single phase; this glass transition temperature can be adjusted over a wide temperature range (ca 100–199 °C), depending on the composition of the block copolymer. Copyright © 2005 Society of Chemical Industry  相似文献   

14.
Summary: In the previous study, we observed compatibilizing effects of low density polyethylene (LDPE)/polystyrene (PS) with polystyrene‐block‐poly(ethylene‐co‐butylene)‐block‐polystyrene (SEBS), a triblock copolymer. Blends consisting of 70 wt.‐% LDPE and 30 wt.‐% PS were prepared with a SEBS concentration of up to 10 wt.‐%. This study examined the electrical properties such as the electrical breakdown, water tree length, permittivity and tan δ in the blends. The possibility of using these blends as insulating material substitutes for LDPE was investigated. The electrical breakdown strength reached a maximum of 66.67 kV/mm, which is superior to 50.27 kV/mm of the LDPE used as electrical insulators for cables. In addition, the water tree length decreased with increasing SEBS concentration. The water tree lengths of the blends containing SEBS were shorter than that of the LDPE. The permittivity of the blends was 2.28–2.48 F/m, and decreased with increasing SEBS concentration with the exception of S‐0. Tan δ of the blends increased smoothly with increasing SEBS content.

Breakdown strength , water tree length, permittivity and tan δ of the LDPE/PS/SEBS blends and raw materials.  相似文献   


15.
Junwei Fu 《Polymer》2008,49(25):5431-5438
Two novel reversible addition-fragmentation chain transfer (RAFT) reagents bearing functional groups, S,S′-bis(9-anthrylmethyl) trithiocarbonate (BATTC) and S,S′-bis(1-naphthylmethyl) trithiocarbonate (BNTTC) were synthesized and used for the RAFT polymerizations of styrene (St). The polymerization results showed that the RAFT polymerizations could be well controlled using BNTTC or BATTC as the RAFT agents. For example, the polymerization rates were of first-order with respect to the monomer concentration, and the molecular weights of the obtained polystyrenes (PS) with narrow molecular weight distributions increased linearly with the monomer conversions and were close to their theoretical values in the presence of BNTTC or BATTC. The successful reaction of chain extension and analysis of 1H NMR spectra confirmed the existence of the functional anthracene or naphthalene groups at the chain end of the correspondingly obtained PS. Optical properties of the obtained PS were characterized by fluorescence and UV absorption. Photochemical properties of the obtained PS end capped with anthracene were also described under irradiation of UV light.  相似文献   

16.
Weidong Zhang 《Polymer》2008,49(21):4569-4575
The novel trifunctional reversible addition-fragmentation chain transfer (RAFT) agent, tris(1-phenylethyl) 1,3,5-triazine-2,4,6-triyl trithiocarbonate (TTA), was synthesized and used to prepare the three-armed polystyrene (PS3) via RAFT polymerization of styrene (St) in bulk with thermal initiation. The polymerization kinetic plot was first order and the molecular weights of polymers increased with the monomer conversions with narrow molecular weight distributions (Mw/Mn ≤ 1.23). The number of arms of the star PS was analyzed by gel permeation chromatography (GPC), ultraviolet visible (UV-vis) and fluorescence spectra. Furthermore, poly(styrene-b-N-isopropylacrylamide)3 (PS-b-PNIPAAM)3, the three-armed amphiphilic thermosensitive block copolymer, with controlled molecular weight and well-defined structure was also successfully prepared via RAFT chain extension method using the three-armed PS obtained as the macro-RAFT agent and N-isopropylacrylamide as the second monomer. The copolymers obtained were characterized by GPC and 1H nuclear magnetic resonance (NMR) spectra. The self-assembly behaviors of the three-armed amphiphilic block copolymers (PS-b-PNIPAAM)3 in mixed solution (DMF/CH3OH) were also investigated by high performance particle sizer (HPPS) and transmission electron microscopy (TEM). Interestingly, the lower critical solution temperature (LCST) of aqueous solutions of the three-armed amphiphilic block copolymers (PS-b-PNIPAAM)3 decreased with the increase of relative length of PS in the block copolymers.  相似文献   

17.
A new graft copolymers poly(aryl ether sulfone)‐graft‐polystyrene (PSF‐g‐PS) and poly(aryl ether sulfone)‐graft‐[polystyrene‐block‐poly(methyl methacrylate)] (PSF‐g‐(PS‐b‐PMMA)) were successfully prepared via atom transfer radical polymerisation (ATRP) catalyzed by FeCl2/isophthalic acid in N,N‐dimethyl formamide. The products were characterized by GPC, DSC, IR, TGA and NMR. The characterization data indicated that the graft copolymerization was accomplished via conventional ATRP mechanism. The effect of chloride content of the macroinitiator on the graft copolymerization was investigated. Only one glass transition temperature (Tg) was detected by DSC for the graft copolymer PSF‐g‐PS and two glass transition temperatures were observed in the DSC curve of PSF‐g‐(PS‐b‐PMMA). The presence of PSF in PSF‐b‐PS or PSF‐g‐(PS‐b‐PMMA) was found to improve thermal stabilities. © 2002 Society of Chemical Industry  相似文献   

18.
Different polymers containing sulfonic groups attached to the phenyl rings were prepared by sulfonation of polystyrene (PS) and styrene‐block‐(ethylene‐co‐1‐butene)‐block‐styrene (SEBS). The sulfonation degree (SD) was varied between 1 and 20 mol% of the styrene units. Polyphase materials containing sulfonated units were prepared by blending styrene‐block‐butadiene‐block‐styrene (SBS), with both sulfonated PS and sulfonated SEBS in a Brabender mixer. Such a procedure was performed as an alternative route to direct sulfonation of SBS which is actually not selective towards benzene rings because of the great reactivity of the double bonds in polybutadiene (PB) blocks to sulfonation agents. Thermal and dynamic‐mechanic analysis, together with morphology characterization of the blends, is consistent with obtaining partially compatible blends characterized by higher Tg of the polystyrene domains and improved thermal stability. © 2001 Society of Chemical Industry  相似文献   

19.
An approach to achieve confined crystallization of ferroelectric semicrystalline poly(vinylidene fluoride) (PVDF) was investigated. A novel polydimethylsiloxane‐block‐poly(methyl methacrylate)‐block‐polystyrene (PDMS‐b‐PMMA‐b‐PS) triblock copolymer was synthesized by the atom‐transfer radical polymerization method and blended with PVDF. Miscibility, crystallization and morphology of the PVDF/PDMS‐b‐PMMA‐b‐PS blends were studied within the whole range of concentration. In this A‐b‐B‐b‐C/D type of triblock copolymer/homopolymer system, crystallizable PVDF (D) and PMMA (B) middle block are miscible because of specific intermolecular interactions while A block (PDMS) and C block (PS) are immiscible with PVDF. Nanostructured morphology is formed via self‐assembly, displaying a variety of phase structures and semicrystalline morphologies. Crystallization at 145 °C reveals that both α and β crystalline phases of PVDF are present in PVDF/PDMS‐b‐PMMA‐b‐PS blends. Incorporation of the triblock copolymer decreases the degree of crystallization and enhances the proportion of β to α phase of semicrystalline PVDF. Introduction of PDMS‐b‐PMMA‐b‐PS triblock copolymer to PVDF makes the crystalline structures compact and confines the crystal size. Moreover, small‐angle X‐ray scattering results indicate that the immiscible PDMS as a soft block and PS as a hard block are localized in PVDF crystalline structures. © 2019 Society of Chemical Industry  相似文献   

20.
A novel photodegradable TiO2‐Fe(St)3‐polystyrene (TiO2‐Fe(St)3‐PS) nanocomposite was prepared by embedding TiO2 and Fe(St)3 into the commercial polystyrene. Ferric stearate was added into polymer as cocatalyst in order to improve the dispersion in polystyrene and photocatalytic efficiency of TiO2 nanoparticles. Solid‐phase photocatalytic degradation of the TiO2‐Fe(St)3‐PS nanocomposite was carried out in an ambient air at room temperature under ultraviolet lamp. The properties of TiO2‐Fe(St)3‐PS composite film were compared with that of the pure PS film and the TiO2‐PS composite film, through weight loss monitoring, scanning electron microscope, gel permeation chromatogram, and FTIR spectroscopy. The photodegradation efficiency of TiO2‐Fe(St)3‐PS composite film was higher than that of the pure PS film and the TiO2‐PS composite film under the UV light irradiation. The average molecular weight (Mw) of TiO2‐Fe(St)3‐PS composite film decreased 63.08%, and the number of average molecular weight (Mn) decreased 79.49% after UV light irradiation for 480 h. Photo‐oxidation leads to an increase in the low molecular weight fraction by chain scission, thereby facilitating biodegradation. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013  相似文献   

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