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1.
A new monomer, 4,4′‐bis(4‐phenoxybenzoyl)diphenyl (BPOBDP), was prepared by Friedel–Crafts reaction of 4‐bromobenzoyl chloride and diphenyl, followed by condensation with potassium phenoxide. Novel poly(ether ketone ketone) (PEKK)/poly(ether ketone diphenyl ketone ether ketone ketone) (PEKDKEKK) copolymers were synthesized by electrophilic Friedel–Crafts solution copolycondensation of isophthaloyl chloride (IPC) with a mixture of diphenyl ether (DPE) and BPOBDP, in the presence of anhydrous aluminum chloride and N‐methyl‐pyrrolidone (NMP) in 1,2‐dichloroethane (DCE). The copolymers obtained were characterized by various analytical techniques such as FT‐IR, DSC, TGA, and wide‐angle X‐ray diffraction (WAXD). The results showed that the resulting copolymers exhibited excellent thermal stability due to the existence of diphenyl moieties in the main chain. The glass transition temperatures are above 152°C, the melting temperatures are above 276°C, and the temperatures at a 5% weight loss are above 548°C in nitrogen. The copolymers with 50–70 mol% BPOBDP had tensile strengths of 101.5–102.7 MPa, Young's moduli of 3.23–3.41 GPa, and elongations at break of 12–17%. All these copolymers were semicrystalline and insoluble in organic solvents. Copyright © 2008 John Wiley & Sons, Ltd.  相似文献   

2.
A new monomer, 4,4′‐bis(4‐phenoxybenzoyl)diphenyl(BPOBDP), was synthesized via a two‐step synthetic procedure. A series of novel poly(ether sulfone ether ketone ketone)/poly(ether ketone diphenyl ketone ether ketone ketone) copolymers were prepared by electrophilic Friedel–Crafts solution copolycondensation of isophthaloyl chloride (IPC) with a mixture of 4,4′‐diphenoxydiphenylsulfone (DPODPS) and 4,4′‐bis(4‐phenoxybenzoyl)diphenyl (BPOBDP), in the presence of anhydrous aluminum chloride and N‐methylpyrrolidone (NMP) in 1,2‐dichloroethane (DCE). The copolymers with 10–50 mol% DPODPS are semicrystalline and have remarkably increased Tgs over commercially available PEEK and PEKK. The copolymers with 40–50 mol% DPODPS had not only high Tgs of 170–172°C, but also moderate Tms of 326–333°C, which are extremely suitable for melt processing. These copolymers have tensile strengths of 96.5–108.1 MPa, Young's moduli of 1.98–3.05 GPa, and elongations at break of 13–26% and exhibit excellent thermal stability and good resistance to acidity, alkali, and common organic solvents. Copyright © 2009 John Wiley & Sons, Ltd.  相似文献   

3.
Telechelic poly(ether ketone)s (PEKs) and polyisobutylenes (PIBs) were combined to form PIB? PEK? PIB triblock copolymers and (PIB? PEK)n multiblock copolymers via the formation of urea linkages. Monovalent and bivalent amino telechelic PIBs were prepared quantitatively from allyl telechelic PIBs by a newly developed reaction sequence featuring nucleophilic reaction steps. Telechelic PEK? NCO polymers were prepared from the corresponding amino telechelic PEKs via a reaction with diphosgene. The highly reactive PEK? NCO and PIB? NH2 telechelics formed PEK? PIB block copolymers only quantitatively when appropriately reactive primary amino groups were present on the amino telechelic PIBs. The obtained block copolymers were microphase‐separated and featured mostly lamellar structures, as determined by small‐angle X‐ray scattering (SAXS). Temperature‐dependent SAXS measurements revealed ordered polymers in the melt up to 210 °C. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 188–202, 2005  相似文献   

4.
ABA‐type triblock copolymers and AB‐type star diblock copolymers with poly(2‐adamantyl vinyl ether) [poly(2‐AdVE)] hard outer segments and poly(n‐butyl vinyl ether) [poly(NBVE)] soft inner segments were synthesized by sequential living cationic copolymerization. Although both the two polymer segments were composed solely of poly(vinyl ether) backbones and hydrocarbon side chains, they were segregated into microphase‐separated structure, so that the block copolymers formed thermoplastic elastomers. Both the ABA‐type triblock copolymers and the AB‐type star diblock copolymers exhibited rubber elasticity over wide temperature range. For example, the ABA‐type triblock copolymers showed rubber elasticity from about ?53 °C to about 165 °C and the AB‐type star diblock copolymer did from about ?47 °C to 183 °C with a similar composition of poly(2‐AdVE) and poly(NBVE) segments in the dynamic mechanical analysis. The AB‐type star diblock copolymers exhibited higher tensile strength and elongation at break than the ABA‐type triblock copolymers. The thermal decomposition temperatures of both the block copolymers were as high as 321–331 °C, indicating their high thermal stability. © 2013 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2013  相似文献   

5.
Thermoresponsive block copolymers are of interest for delivery vehicles in the body. Often an interior domain is designed for the active agent and the exterior domain provides stability in the bloodstream, and may carry a targeting ligand. There is still much to learn about how block sequence and chain end identity affect micelle structure, size, and cloud points. Here, hydrophilic oligo(ethylene glycol) methyl ether acrylate and more hydrophobic di(ethylene glycol) methyl ether methacrylate monomers were polymerized to give amphiphilic block copolymers with amphiphilic chain ends. The block sequence and chain end identity were both controlled by appropriate choice of RAFT chain transfer agents to study the effect of ‘matched’ and ‘mismatched’ chain end polarity with amphiphilic block sequence. The affect of matching or mismatching chain end polarity and block sequence was studied on the hydrodynamic diameter, cloud point, and temperature range of the chain collapse on linear di‐ and triblock copolymers and star diblock polymers. The affects of matching or mismatching chain end polarity were significant with linear diblock copolymers but more complex with triblock and star copolymers. Explanations of these results may help guide others in designing thermoresponsive block copolymers. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2015 , 53, 2838–2848  相似文献   

6.
Aromatic tetracarboxylic dianhydride having crank and twisted noncoplanar structure, 2,2′-bis(3,4-dicarboxyphenoxy)-1,1′-binaphthyl dianhydride, was synthesized by the reaction of 4-nitrophthalonitrile with 2,2′-dihydroxy-1,1′-binaphthyl, followed by alkaline hydrolysis of the intermediate bis(ether dinitrile) and subsequent dehydration of the resulting bis(ether diacid). Binaphthyl-2,2′-diyl–containing novel aromatic polyimides having inherent viscosities up to 0.67 dL/g were obtained by the one-step polymerization process starting from the bis(ether anhydride) and various aromatic diamines. All the polyimides showed typical amorphous diffraction patterns. Most of the polyimides were readily soluble in common organic solvents such as N,N-dimethylacetamide (DMAc), N-methyl-2-pyrrolidone (NMP), and pyridine. These aromatic polyimides had glass transition temperatures in the range of 280–350°C, depending on the nature of the diamine moiety. All polymers were stable up to 400°C, with 10% weight loss being recorded above 485°C in air. © 1998 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 36: 1937–1943, 1998  相似文献   

7.
Rod‐coil‐rod triblock copolymers, poly[4′‐(methoxy)‐2‐vinylbiphenyl‐4‐methyl ether] ‐blockpolydimethylsiloxane‐block‐poly[4′‐(methoxy)‐2‐vinylbiphenyl‐4‐methyl ether] (PMVBP‐b‐PDMS‐b‐PMVBP), were synthesized by nitroxide‐mediated radical polymerization, and their hierarchically ordered structures were studied. A difunctional TEMPO macroinitiator was first synthesized by the hydrosilylation reaction between hydride‐endcapped PDMS and allylic alkoxyamine. The polymerization of the monomer MVBP was triggered by the macroinitiator, resulting in a series of triblock copolymers. The molecular weights and polydispersity indexes were determined by gel permeation chromatography. Differential scanning calorimetry results demonstrate that the triblock copolymers exhibit two glass transition temperatures (?120 °C and 160 °C) that are markedly different. As revealed by small‐angle X‐ray scattering and transmission electron microscopy experiments, the triblock copolymers self‐assemble into hierarchical structures with the liquid crystalline phase of PMVBP in the lamellar structures. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2014 , 52, 1737–1744  相似文献   

8.
This study reports a method to prepare fully aromatic poly(ether ketone) thermosets. The cyclization of 2′,5′‐dimethoxy[1,1′‐biphenyl]‐2,5‐diol and a difluoro monomer was carried out under pseudo high dilution condition. Two types of fully aromatic poly(ether ketone)s with macrocycle were successfully prepared by copolymerization of macrocycle of aryl ether ketone containing hydroxyphenyl groups, 4,4′‐(hexafluoroisopropylidene)diphenol (HFBPA), and 4,4‐difluorobenzophenone. The obtained copolymers have high molecular mass, good solubility, and high glass transition temperatures in the presence of CsF, the crosslinking reaction of copolymers occurred and afforded fully aromatic thermoset poly(aryl ether ketone)s by ring‐opening reaction driven by entropy. After crosslinking, these copolymers show much higher glass transition temperatures, excellent thermal stability, and better mechanical strength. © Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 7002–7010, 2008  相似文献   

9.
New phenolic hydroxyl‐pendant aromatic polyimides were synthesized with the N‐silylated diamine method in two steps: the ring‐opening polyaddition of tetrakis(trimethylsilyl)‐substituted 4,4′‐diamino‐3,3′‐dihydroxybiphenyl to various aromatic tetracarboxylic dianhydrides, giving trimethylsiloxy‐pendant poly(amic acid) trimethylsilyl esters, and thermal imidization. The hydroxyl‐bearing polyimides were amorphous but insoluble in organic solvents. They had glass‐transition temperatures greater than 370 °C and temperatures of 10% weight loss greater than 415 °C in nitrogen. The hydroxyl‐pendant polypyromellitimide film had a high tensile strength and a high modulus of 310 MPa and 10 GPa, respectively. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 1790–1795, 2002  相似文献   

10.
Stimuli‐responsive ABC triblock copolymers with three segments with different phase‐separation temperatures were synthesized via sequential living cationic copolymerization. The triblock copolymers exhibited sensitive thermally induced physical gelation (open association) through the formation of micelles. For example, an aqueous solution of EOVE200b‐MOVE200b‐EOEOVE200 [where EOVE is 2‐ethoxyethyl vinyl ether, MOVE is 2‐methoxethyl vinyl ether and EOEOVE is 2‐(2‐ethoxy)ethoxyethyl vinyl ether; the order of the phase‐separation temperatures was poly(EOVE) (20 °C) < poly(EOEOVE) (41 °C) < poly(MOVE) (70 °C)] underwent multiple reversible transitions from sol (<20 °C) to micellization (20–41 °C) to physical gelation (physical crosslinking, 41–64 °C) and, finally, to precipitation (>64 °C). At 41–64 °C, the physical gel became stiffer than similar diblock or ABA triblock copolymers of the same molecular weight. Furthermore, the ABC triblock copolymers exhibited Weissenberg effects in semidilute aqueous solutions. In sharp contrast, another ABC triblock copolymer with a different arrangement, EOVE200b‐EOEOVE200b‐MOVE200, scarcely exhibited any increase in viscosity above 41 °C. The temperatures of micelle formation and physical gelation corresponded to the phase‐separation temperatures of the segment types in the ABC triblock copolymer. No second‐stage association was observed for AB and ABA block copolymers with the same thermosensitive segments found in their ABC counterparts. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 2601–2611, 2004  相似文献   

11.
A series of block copoly(arylene ether)s containing pendant superacid groups were synthesized, and their properties were investigated for fuel cell applications. Two series of telechelic oligomers, iodo‐substituted oligo(arylene ether ketone)s and oligo(arylene ether sulfone)s, were synthesized. The degree of oligomerization and the end groups were controlled by changing the feed ratio of the monomers. The nucleophilic substitution polymerization of the two oligomers provided iodo‐substituted precursor block copolymers. The iodo groups were converted to perfluorosulfonic acid groups via the Ullmann coupling reaction. The high degree of perfluorosulfonation (up to 83%) was achieved by optimizing the reaction conditions. Tough and bendable membranes were prepared by solution casting. The ionomer membranes exhibited characteristic hydrophilic/hydrophobic phase separation with large hydrophilic clusters (ca. 10 nm), which were different from that of our previous random copolymers with similar molecular structure. The block copolymer structure was found to be effective in improving the proton‐conducting behavior of the superacid‐modified poly(arylene ether) ionomer membranes without increasing the ion exchange capacity (IEC). The highest proton conductivity was 0.13 S/cm at 80 °C, 90% relative humidity, for the block copolymer ionomer membrane with IEC = 1.29 mequiv/g. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011  相似文献   

12.
Benzyl 6-(2′-pentamethyldisiloxanyl ethyl)-ortho-tolyl ketone (I) was prepared by a ruthenium-catalyzed Murai reaction of benzyl ortho-tolyl ketone with vinyl pentamethyldisiloxane. The reaction of I with a mixture of styrene and a catalytic amount of picoline Cu(II) acetate yielded the telechelic polystyrene α,ω-bis(2-pentamethyl-disiloxanyl ethyl)polystyrene (III). The acid-catalyzed equilibration polymerization of octamethylcyclotetrasiloxane into the Si O Si bonds of telechelic III yielded the polydimethylsiloxane-polystyrene-polydimethylsiloxane triblock soft–hard–soft copolymer. The molecular weights of the copolymers were studied by 1H NMR end-group analysis and gel permeation chromatography. The thermal properties and morphology of IV were examined by differential scanning calorimetry and transmission electron microscopy (TEM). © 2000 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 38: 482–488, 2000  相似文献   

13.
A new series of sulfonated poly(benzoxazole ether ketone)s (SPAEKBO-X) were prepared by the aromatic nucleophilic polycondensation of 4,4′-(hexafluoroisopropylidene)-diphenol with 2,2′-bis[2-(4-fluorophenyl)benzoxazol-6-yl]hexafluoropropane and sodium 5,5′-carbonylbis-2-fluorobenzenesulfonate in various ratios. Fourier transform infrared and 1H NMR were used to characterize the structures and sulfonic acid contents of the copolymers. The copolymers were soluble in N-methyl-2-pyrrolidinone, N,N-dimethylacetamide, and N,N-dimethylformamide and could form tough and flexible membranes. The protonated membranes were thermally stable up to 320 °C in air. The water uptake, hydrolytic and oxidative stability, and mechanical properties were evaluated. At 30–90 °C and 95% relative humidity, the proton conductivities of the membranes increased with the sulfonic acid content and temperature and almost reached that of Nafion 112. At 90–130 °C, without external humidification, the conductivities increased with the temperature and benzoxazole content and reached above 10−2 S/cm. The SPAEKBO-X membranes, especially those with high benzoxazole compositions, possessed a large amount of strongly bound water (>50%). The experimental results indicate that SPAEKBO-X copolymers are promising for proton-exchange membranes in fuel cells, and their properties might be tailored by the adjustment of the copolymer composition for low temperatures and high humidity or for high temperatures and low humidity; they are especially promising for high-temperature applications. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 2273–2286, 2007  相似文献   

14.
Statistical copolymers of (±)2-ethylhexyl acrylate and 3-[3,3,3-trimethyl- 1,1-bis (trimethylsiloxy) disiloxanyl] propyl methacrylate were synthesized and the reactivity ratios and the Q and e values were calculated. The glass transition temperatures of the copolymers were in good agreement with the predictions of Fox's equation and Wood's formula. © 1997 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 35 : 3571–3574, 1997  相似文献   

15.
ABSTRACT

1,1,1-Tris(4-hydroxyphenyl)ethane, THPE, was silylated with chlorotrimethylsilane and the silylated THPE was polycondensed with 1,4-bis(4-fluorobenzoyl)benzene, BFBB, in dry N-methylpyrrolidone. The resulting poly(ether ketone) had a moderate molecular weight and contained a significant fraction of cyclic oligomers and polymers. The pendant trimethylsiloxy group allowed an in situ alkylation with chloropropionitrile, allylbromide, 3,4-dichlorobenzyl chloride, 4-nitrobenzyl bromide, 1,3-propane sultone and 1,4-butane sultone. The latter alkylating agents yielded poly(ether ketone)s having pendant sulfonic acid groups. Further functional groups were introduced by acylation of the pendant free OH-group (resulting from the hydrolysis of the Me3SiO group) with acetic anhydride, methacrylic anhydride, cinnamoyl chloride and undecenoyl chloride.  相似文献   

16.
Novel elastomeric A‐B‐A triblock copolymers were successfully synthesized in a new two‐step process: controlled ring‐opening polymerization of the cyclic ether–ester 1,5‐dioxepan‐2‐one as the amorphous middle block (B‐block) followed by addition and polymerization of the two semicrystalline L ‐lactide blocks (A‐block). A 1,1,6,6‐tetra‐n‐butyl‐1,6‐distanna‐2,5,7,10‐tetraoxacyclodecane initiator system was utilized and the reaction was performed in chloroform at 60 °C. A good control of the synthesis was obtained, resulting in well defined triblock copolymers. The molecular weight and chemical composition were easily adjusted by the monomer‐to‐initiator ratio. The triblock copolymers formed exhibited semicrystallinity up to a content of 1,5‐dioxepan‐2‐one as high as 89% as determined by differential scanning calorimetry. WAXS investigation of the triblock copolymers showed a crystal structure similar to that of the pure poly(L ‐lactide). © 2000 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 38: 1774–1784, 2000  相似文献   

17.
We demonstrate, in this article, the facile synthesis of a broad class of low‐polydispersity ethylene–norbornene (E–NB) copolymers having various controllable comonomer composition distributions, including gradient, alternating, diblock, triblock, and block–gradient, through “living”/quasiliving E–NB copolymerization facilitated with a single Pd – diimine catalyst ( 1 ). This synthesis benefits from two remarkable features of catalyst 1 , its high capability in NB incorporation and high versatility in rendering E–NB “living” copolymerization at various NB feed concentrations ([NB]0) while under an ethylene pressure of 1 atm and at 15 °C. At higher [NB]0 values between 0.42 and 0.64 M, E–NB copolymerization with 1 renders nearly perfect alternating copolymers. At lower [NB]0 values (0.11–0.22 M), gradient copolymers yield due to gradual reduction in NB concentration, with the starting chain end containing primarily alternating segments and the finishing end being hyperbranched polyethylene segments. Through two‐stage or three‐stage “living” copolymerization with sequential NB feeding, diblock or triblock copolymers containing gradient block(s) have been designed. This work thus greatly expands the family of E–NB copolymers. All the copolymers have controllable molecular weight and relatively low polydispersity (with polydispersity index below 1.20). Most notably, some of the gradient and block–gradient copolymers have been found to exhibit the characteristic broad glass transitions as a result of their possession of broad composition distribution. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2013  相似文献   

18.
ABA triblock copolymers were synthesized using two polymerization techniques, polycondensation, and atom transfer radical polymerization (ATRP). A telechelic polymer was synthesized via polycondensation, which was then functionalized into a difunctional ATRP initiator. Under ATRP conditions, outer blocks were polymerized to form the ABA triblock copolymer. Six types of samples were prepared based on a poly(ether ether ketone) or poly(arylene ether sulfone) center block with either poly(methyl methacrylate), poly(pentafluorostyrene), or poly(ionic liquid) outer blocks. As polycondensation results in polymers with broad molecular weight distribution (MWD), the center of these triblock copolymers are disperse, while the outside blocks have narrow MWD due to the control afforded from ATRP. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2015 , 53, 228–238  相似文献   

19.
New ABC triblock copolymers that contain lipophilic, hydrophilic, and fluorophilic blocks are reported. These new block copolymers were synthesized via sequential controlled/living atom transfer radical polymerization. The formation of block copolymers was confirmed by size exclusion chromatography, 1H, and 19F NMR. In direct comparison to the ABC copolymer, the corresponding ABA′ polymer did not produce a gel up to 45 wt % polymer. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 2601–2608, 2007  相似文献   

20.
A novel polymer-forming diimide–diacid, 2,6-bis(4-trimellitimidophenoxy)naphthalene, was prepared by the condensation reaction of 2,6-bis(4-aminophenoxy)naphthalene with trimellitic anhydride (TMA). A series of novel aromatic poly(amide–imide)s containing 2,6-bis(phenoxy)naphthalene units were prepared by the direct polycondensation of the diimide–diacid with various aromatic diamines using triphenyl phosphite (TPP) in N-methyl-2-pyrrolidone (NMP)/pyridine solution containing dissolved calcium chloride. Thirteen of the obtained polymers had inherent viscosities above 1.01 dL/g and up to 2.30 dL/g. Most of polymers were soluble in polar solvents such as DMAc and could be cast from their DMAc solutions into transparent, flexible, and tough films. These films had tensile strengths of 79–117 MPa, elongation-at-break of 7–61%, and initial moduli of 2.2–3.0 GPa. The wide-angle X-ray diffraction revealed that some polymers are partially crystalline. The glass transition temperatures of some polymers could be determined with the help of differential scanning calorimetry (DSC) traces, which were recorded in the range 232–300°C. All the poly(amide–imide)s exhibited no appreciable decomposition below 450°C, and their 10% weight loss temperatures were recorded in the range 511–577°C in nitrogen and 497–601°C in air. © 1998 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 36: 919–927, 1998  相似文献   

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