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1.
Novel fluoride‐teminated hyperbranched poly(ether ether ketone) with 4‐phenoxyphenyl side group (HPEEK‐F) was prepared from 2‐(4‐phenoxyphenyl)‐1,4‐diphenol (A2) and 1,3,5‐tris[4‐(4‐flourobenzoyl) phenoxy]benzene (B3). An end‐capping approach was used to synthesize tertiary amino‐terminated fluorescent (HPEEK‐DMA) and phenyl ethynyl‐terminated self‐crosslinking poly(ether ether ketone)s (HPEEK‐PEP). These three polymers have the same backbone structure and degree of branching (DB=0.67), and different terminal groups. The nature of the terminal group was shown as the influences of the glass transition temperature (Tg) and decomposition temperature (Td) of polymers. The Tg of HPEEK‐F and HPEEK‐DMA are 30°C lower than HPEEK‐PEP, whereas the Td of HPEEK‐F are 90°C and 50°C higher than HPEEK‐DMA and HPEEK‐PEP, respectively. The HPEEK‐DMA fluoresce blue‐green in solid and in solution. This kind of hyperbranched polymer contains a large amount of terminal chromophore groups which can easily lead to the formation of intramolecular excimers. The fluorescence signal was decreased with increasing acidity, furthermore, the two peaks at 466 nm and 507 nm indicated a blue shift occurred. After curing, the HPEEK‐PEP displayed a Tg at 235.5°C, which is 100°C higher than original polymers. Thermally cured samples show good anti‐chemical corrodibility in DMF, THF, DMAc and NMP solvents. 相似文献
2.
Synthesis and Properties of Novel Poly(amine ether)s 总被引:8,自引:0,他引:8
Using aromatic bis(4-bromophenyl) ether and various aromatic diamines as the monomers, a series of novel poly(amine ether)s (PAEs) have been synthesized via palladium-catalyzed aryl amination, which is the Hartwig-Buchwald polycondensation reaction. Their structures were characterized by means of elemental analysis, FT-IR, 1^H NMR and UV-Vis spectroscopy. The results show a good agreement with the proposed structures. Their general properties were studied by DSC and TG and it's obvious that they show high glass transition temperatures (Tg〉200 ℃), good thermal stability with high decomposition temperatures (TD〉500℃) and excellent solubility. The mechanical behavior of these polymers suggested that they could be considered a new class of high-performance polymers. 相似文献
3.
Jianxin Mu Chunling Zhang Zou Wang Jie Chen Zhenhua Jiang 《Frontiers of Chemistry in China》2006,1(2):203-206
Hyperbranched poly(aryl ether ketone)s were prepared by polymerization of hydroquinone (A2) and 1,3,5-tris[4-(4-fluorobenzoyl)phenoxy]benzene (B3). The gelation of hyperbranched poly(aryl ether ketone)s was effectively avoided. Hydroxyl-term inated (HPAEK-OH) and fluoro-terminated
(HPAEK-F) hyperbranched poly(aryl ether ketone)s were prepared by using different A2/B3 mass ratio. The structure of the B3 monomer was confirmed by MS, 1H NMR/IR. The glass transition temperatures of the HPAEK-F and HPAEK-OH are 114°C and 162°C respectively. Thermal stability
of HPAEK-F is higher than HPAEK-OH.
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Translated from Acta Scientianum Naturalium Universitatis Jilinensis, 2005, 5 (in Chinese) 相似文献
4.
Mahalingam Vanjinathan A. Raghavan A. Sultan Nasar 《Journal of polymer science. Part A, Polymer chemistry》2007,45(14):2959-2977
3,5‐bis(4‐aminophenoxy)phenyl phenylcarbamate—a novel AB2‐type blocked isocyanate monomer and 3,5‐bis{ethyleneoxy(4‐aminophenoxy)}phenyl carbonyl azide—a novel AB2‐type azide monomer were synthesized in high yield. Step‐growth polymerization of these monomers were found to give a first example of hyperbranched poly (aryl‐ether‐urea) and poly(aryl‐alkyl‐ether‐urea). Molecular weights (Mw) of the polymer were found to vary from 1,858 to 52,432 depending upon the monomer and experimental conditions used. The polydispersity indexes were relatively narrow due to the controlled regeneration of isocyanate functional groups for the polymerization reaction. The degree of branching (DB) was determined using 1H‐NMR spectroscopy and the values ranged from 87 to 54%. All the polymers underwent two‐stage decomposition and were stable up to 300 °C. Functionalized end‐capping of poly(aryl‐ether‐urea) using phenylchloroformate and di‐t‐butyl dicarbonate (Boc)2O changed the thermal properties and solubility of the polymers. Copolymerization of AB2‐type blocked isocyante monomer with functionally similar AB monomer were also carried out. The molecular weights of copolymers were found to be in the order of 6 × 105 with narrow dispersity. It was found that the Tg's of poly(aryl‐alkyl‐ether‐urea)s were significantly less (46–49 °C) compared to poly(aryl‐ether‐urea)s. Moreover the former showed melting transition at 154 °C, which was not observed in the latter case. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 2959–2977, 2007 相似文献
5.
Kazuhiro Morita Tamotsu Hashimoto Michio Urushisaki Toshikazu Sakaguchi 《Journal of polymer science. Part A, Polymer chemistry》2013,51(11):2445-2454
Cationic cyclopolymerizations of 2,2‐bis(vinyloxymethyl)bicyclo[2.2.1]heptane ( 1 ), 5,5‐bis(vinyloxymethyl)‐2‐bicyclo[2.2.1]heptene ( 2 ), and 2,2‐bis(vinyloxymethyl)tricyclo[3.3.1.1]3, 7decane ( 3 ), divinyl ethers with a norbornane, norbornene, or adamantane unit, respectively, were investigated with the HCl/ZnCl2 initiating system in toluene and methylene chloride at ?30 °C. All the reactions proceeded quantitatively to give gel‐free, soluble polymers in organic solvents. The number‐average molecular weight (Mn) of the polymers increased in direct proportion to monomer conversion and further increased on addition of a fresh monomer feed to the almost completely polymerized reaction mixture. The contents of the unreacted vinyl groups in the produced soluble polymers were less than ~10 mol %, and therefore, the degree of cyclization of the polymers was determined to be over ~90%. These facts show that cyclopolymerization of 1 , 2 , and 3 exclusively occurred and the poly(vinyl ether)s with the cyclized repeating units and polycyclic pendants were obtained with their molecular weights being regulated. BF3OEt2 initiator also caused cyclopolymerization of 1 , 2 , and 3 to give the corresponding high‐molecular‐weight cyclopolymers quantitatively. Glass transition temperatures (Tg's) of poly( 1 ) and poly( 2 ) were 165–180 °C, and Tg's of poly( 3 ) were 211–231 °C; these values are very high as vinyl ether polymers. © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2013, 51, 2445–2454 相似文献
6.
Four novel perfluoroalkylated poly(arylene ether)s have been synthesized successfully using four perfluoroalkyl‐activated bisfluoro monomers. These polymers are synthesized through nucleophilic displacement of the fluorine atoms on the benzene ring with 4,4′‐thiodiphenol and are named as 1a, 1b, 1c and 1d, respectively. The polymers obtained by displacement of the fluorine atoms exhibit weight‐average molar masses up to 3.9×104 g · mol?1 in Gel permeation chromatography. These poly(arylene ether)s showed very high thermal stability up to 548°C for 10% weight loss in TGA under nitrogen and high glass transition temperature (Tg) up to 178°C in DSC depending on the repeat unit structures. The glass transition temperatures taken as peak in tan δ in DMA measurements are in good agreement with the DSC Tg values. All the polymers synthesized are soluble in a wide range of organic solvent such as CHCl3, CHCl2, THF, NMP, DMF and toluene. Transparent thin films of these polymers cast from THF exhibited tensile strengths up to 72 MPa, modulus up to 1.69 GPa with low elongation at break depending on their exact repeating unit structures. Rheological properties showed ease of processability of these polymers with no change in melt viscosity with temperature. 相似文献
7.
A new monomer, N,N′‐bis(4‐phenoxybenzoyl)‐p‐phenylenediamine (BPBPPD), was prepared by the condensation of p‐phenylenediamine with 4‐phenoxybenzoyl chloride in N,N‐dimethylacetamide (DMAc). Novel aromatic poly(ether amide amide ether ketone ketone)s (PEAAEKKs) were synthesized by electrophilic Friedel–Crafts solution copolycondensation of BPBPPD with a mixture of terephthaloyl chloride (TPC) and isophthaloyl chloride (IPC), over a wide range of TPC/IPC molar ratios, in the presence of anhydrous aluminum chloride and N‐methylpyrrolidone (NMP) in 1,2‐dichloroethane (DCE). The influences of reaction conditions on the preparation of polymers were examined. The polymers obtained were characterized by different physico–chemical techniques such as FT‐IR, Differential scanning calorimetry (DSC), Thermogravimetric analysis (TGA), and wide angle X‐ray diffraction (WAXD). The polymers with 70–100 mol% IPC are semicrystalline and have remarkably increased Tgs over commercially available poly(ether ether ketone) (PEEK) and poly(ether ketone ketone) (PEKK) due to the incorporation of amide groups in the main chain. The polymers with 70–80 mol% IPC had not only high Tgs of 209–213°C, but also moderate Tms of 339–348°C, which are suitable for melt processing. The polymers with 70–80 mol% IPC had tensile strengths of 107.5–109.8 MPa, Young's moduli of 2.53–2.69 GPa, and elongations at break of 9–11% and exhibited high thermal stability and good resistance to organic solvents. Copyright © 2009 John Wiley & Sons, Ltd. 相似文献
8.
Tamotsu Hashimoto Hiromi Takagi Yuko Hasegawa Haruki Matsui Michio Urushisaki Toshikazu Sakaguchi 《Journal of polymer science. Part A, Polymer chemistry》2010,48(4):952-958
Cationic cyclopolymerization of 2‐methyl‐5,5‐bis(vinyloxymethyl)‐1,3‐dioxane ( 1 ), a divinyl ether with a cyclic acetal group, was investigated with the HCl/ZnCl2 initiating system in toluene and methylene chloride at ?30 °C. The reaction proceeded quantitatively to give gel‐free, soluble polymers in organic solvents. The number‐average molecular weight (Mn) of the polymers increased in direct proportion to monomer conversion, and further increased on addition of a fresh monomer feed to the almost completely polymerized reaction mixture, indicating that the polymerization proceeded in living/controlled manner. The contents of the unreacted vinyl groups in the produced soluble polymers were less than ~3 mol %, and therefore, the degree of cyclization was determined to be ~97%. In contrast, the pendant cyclic acetal groups remained intact in the polymers under the present cationic polymerization conditions. These facts show that cyclopolymerization of 1 almost exclusively occurred and the poly(vinyl ether)s with the cyclized repeating units and cyclic pendant acetal rings were obtained. Glass transition temperature (Tg) and thermal decomposition temperature (Td) of poly( 1 ) (Mn = 7870, Mw/Mn = 1.57) were found to be 166 and 338 °C, respectively, indicating that poly( 1 ) had high Tg and high thermal stability. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 952–958, 2010 相似文献
9.
Binary melt‐blended mixtures of two aryl ether ketone polymers (i.e., a new poly(aryl ether ketone) (code name PK99) and poly(ether ether ketone) (PEEK), have been studied. Polymer miscibility in glassy amorphous (or melt) domains has been demonstrated for the binary blend comprising of two aryl‐ether‐ketone‐type semicrystalline polymers. Composition‐dependent, single Tg was observed within full composition range in the PK99/PEEK blends, and the narrow Tg breadth also suggests that the scale of mixing was fine and uniform. To better resolve any possible overlapping Tg's, physical aging was imposed on a comparison set of blend samples for the purpose of improving detectability of overlapped multiple transitions if existing. The result still showed one single Tg. The relative sharp Tg and lack of cloud point transition suggest that the scale of molecular intermixing is good. Phase homogeneity was further confirmed using optical and scanning electron microscopy. The X‐ray diffractograms suggest that isomorphism does not exist in the PK99/PEEK blends and that the crystal forms of the respective polymers remain distinct and unchanged by the miscibility in the amorphous region. © 1999 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 37: 1485–1494, 1999 相似文献
10.
Anjeza Beharaj Iriny Ekladious Mark W. Grinstaff 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2019,131(5):1421-1425
Insertion of CO2 into the polyacrylate backbone, forming poly(carbonate) analogues, provides an environmentally friendly and biocompatible alternative. The synthesis of five poly(carbonate) analogues of poly(methyl acrylate), poly(ethyl acrylate), and poly(butyl acrylate) is described. The polymers are prepared using the salen cobalt(III) complex catalyzed copolymerization of CO2 and a derivatized oxirane. All the carbonate analogues possess higher glass‐transition temperatures (Tg=32 to ?5 °C) than alkyl acrylates (Tg=10 to ?50 °C), however, the carbonate analogues (Td≈230 °C) undergo thermal decomposition at lower temperatures than their acrylate counterparts (Td≈380 °C). The poly(alkyl carbonates) exhibit compositional‐dependent adhesivity. The poly(carbonate) analogues degrade into glycerol, alcohol, and CO2 in a time‐ and pH‐dependent manner with the rate of degradation accelerated at higher pH conditions, in contrast to poly(acrylate)s. 相似文献
11.
Stephen J. Grunzinger Teruaki Hayakawa Masa‐Aki Kakimoto 《Journal of polymer science. Part A, Polymer chemistry》2008,46(14):4785-4793
Hyperbranched poly(ether sulfone) was prepared in the presence of an oligomeric linear poly(ether sulfone) to generate multiblock hyperbranched‐linear (LxHB) copolymers. The LxHB copolymers were prepared in a two‐step, one‐pot synthesis by first polymerizing AB monomer to generate a linear block of a desired molecular weight followed by addition of the AB2 monomer in a large excess (19:1, AB2:AB) to generate the hyperbranched block. NMR integration analysis indicates that AB2:AB ratio is independent of the reaction time. Because the molecular weight still increases with reaction time, these results suggest that polymer growth continues after consumption of monomer by condensation into a multiblock architecture. The LxHB poly(ether sulfone)s have better thermal stability (10% mass loss > 343 vs. 317 °C) and lower Tg (200 vs. > 250 °C) than the hyperbranched homopolymer, higher Tg than the linear homopolymer (<154 °C), while little difference in the solubility character was observed between the two polymers. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 4785–4793, 2008 相似文献
12.
Sheng‐Huei Hsiao Liang‐Ru Dai 《Journal of polymer science. Part A, Polymer chemistry》1999,37(5):665-675
Four bis(ether anhydride)s, 4,4′‐(1,4‐phenylenedioxy)diphthalic anhydride (IV), 4,4′‐(2,5‐tolylenedioxy)‐diphthalic anhydride (Me‐IV), 4,4′‐(2‐chloro‐1,4‐phenylenedioxy)diphthalic anhydride (Cl‐IV), and 4,4′‐(2,5‐biphenylenedioxy)diphthalic anhydride (Ph‐IV), were prepared in three steps starting from the nucleophilic nitrodisplacement reaction of 4‐nitrophthalonitrile with the potassium phenoxides of hydroquinone and various substituted hydroquinones such as methylhydroquinone, chlorohydroquinone, and phenylhydroquinone in N,N‐dimethylformamide, followed by alkaline hydrolysis and dehydration. Four series of poly(ether imide)s were prepared from bis(ether anhydride)s with various aromatic diamines by a classical two‐step procedure. The inherent viscosities of the intermediate poly(amic acid)s were in the range of 0.40–2.63 dL/g. Except for those derived from p‐phenylenediamine and benzidine, almost all the poly(amic acid)s could be solution‐cast and thermally converted into transparent, flexible, and tough polyimide films. Introduction of the chloro or phenyl substituent leads to a decreased crystallinity and an increased solubility of the polymers. The glass transition temperatures (Tg) of these polyimides were recorded in the range of 204–263°C. In general, the methyl‐ and chloro‐substituted polyimides exhibited relatively higher Tgs, whereas the phenyl‐substituted ones exhibited slightly lower Tgs compared to the corresponding nonsubstituted ones. Thermogravimetric analysis (TG) showed that 10% weight loss temperatures of all the polymers were above 500°C either in nitrogen or in air. © 1999 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 37: 665–675, 1999 相似文献
13.
Riting Su Yusheng Qin Lijun Qiao Ji Li Xiaojiang Zhao Pixin Wang Xianhong Wang Fosong Wang 《Journal of polymer science. Part A, Polymer chemistry》2011,49(6):1434-1442
2‐Furyloxirane (FO), a monomer usually obtained from a nonpetroleum route, was prepared from the epoxidation reaction of furfural and trimethylsulfonium chloride. About 200–300 g FO can be obtained in each preparation process. Although anionic polymerization of FO generally gives low‐ molecular‐weight polymers even after long periods of polymerization, the reaction was greatly improved when macrocyclic ether was used as a cocatalyst to potassium tert‐butoxide. When 18‐crown‐6 was used as a cocatalyst, poly(2‐furyloxirane) (PFO) with a number‐average molecular weight (Mn) of 41.5 kg/mol and a polydispersity index of 1.3 was obtained at 94% yield after polymerization at 40 °C for 72 h. The PFO obtained contained a 61.7% head‐to‐tail (H‐T) structure in the absence of the macrocyclic ether, and it reached 70.6% when cryptand[2,2,2] was used as a cocatalyst. PFO with higher regioregular structures showed improved thermal properties. For PFO with Mn of around 20.0 kg/mol, its glass transition temperature (Tg) increased from ?3 to 6 °C when the H‐T content was increased from 61.7 to 70.6%. Raising the Mn of PFO also raised Tg. For PFO with 68.9% H‐T structure, its Tg could reach 7 °C when Mn was increased to 40 kg/mol. This study shows two effective ways to improve the thermal and mechanical performances of the polymer. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011 相似文献
14.
Lin Cheng Lei Ying Juan Feng Chen Yi Wang Jian Ling Li Zhen Xu 《Journal of polymer science. Part A, Polymer chemistry》2007,45(8):1525-1535
Based on green chemistry, a simple and efficient direct synthesis of 4‐(4′‐hydroxyaryl)(2H)phthalazin‐1‐ones ( 2a–2f ) was developed in a two‐step reaction, in which the Friedel–Crafts acylation reaction of six phenols with phthalic anhydride was initially carried out and then followed by cyclization with hydrazine hydrate in good to excellent yields with high regioselectivity. A number of novel heterocyclic poly(arylene ether ketone)s were prepared conveniently from several unsymmetrical, twist, and noncoplanar phthalazinone‐containing monomers ( 2a–2f ) and an activated difluoro monomer via a N? C coupling reaction. It was very interesting that the obtained monomers and polymers exhibited diverse properties with the variation of the number and location of the substituted methyl groups. All these polymers had a high molecular weight with Mn and ηinh in the range of 44,960–169,000 Da and 0.38–0.79 dL/g, respectively. Actually, the obtained polymers displayed excellent thermal properties with Tg's ranging from 222 to 248 °C and 5% weight loss temperatures in nitrogen higher than 430 °C. Moreover, these polymers were readily soluble in common organic solvents, such as N‐methyl‐2‐pyrrolidone, chloroform, pyridine, and m‐cresol, and could be cast into flexible and colorless or nearly colorless films by spin‐coating or casting processes. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 1525–1535, 2007 相似文献
15.
A fluorinated diamine monomer containing flexible ether linkage and bulky trifluoromethyl substituents, namely, bis(4‐amino‐2‐trifluoromethylphenyl) ether (a), is employed to react with nonfluorinated 1,4‐bis(3,4‐dicarboxyphenoxy) benzene dianhydride (3) and CF3‐free 2,2‐bis[4‐(3,4‐dicarboxyphenoxy)phenyl] propane dianhydride (4), respectively, to prepare 2 novel soluble and optically transparent semi‐fluorinated poly (ether imide)s (PEIs; 3a and 4a). Compared with the corresponding PEIs based on nonfluorinated 4,4′‐diaminodiphenyl ether (b) and CF3‐free pyromellitic dianhydride (5), the novel semifluorinated PEIs 3a and 4a not only display better solubility in some organic solvents and higher optical transparency with cutoff absorption wavelength (λ0) below 370 nm but also maintain outstanding mechanical properties and thermal stability. 3a and 4a have tensile strength beyond 80 MPa and possess glass‐transition temperatures (Tg) beyond 210°C, coupled with the temperatures of 5% weight loss (T5%) exceeding 500°C. It is also found that 3a and 4a exhibit contact angles against water beyond 110° and water absorptions below 0.8% together with dielectric constants less than 3.2. 相似文献
16.
New fluorinated aromatic poly (ether ketone amide)s containing cardo structures were prepared by a heterogeneous palladium‐catalyzed polycondensation of fluorinated aromatic diiodides with ether ketone units, aromatic diamines containing cardo groups, and CO. Polymerizations were conducted in N,N‐dimethylacetamide at 120°C using 6 mol% of magnetic nanoparticles‐supported bidentate phosphine palladium (II) complex [Fe3O4@SiO2‐2P‐PdCl2] as catalyst and 1,8‐diazabicyclo[5,4,0]‐7‐undecene as base and resulted in fluorinated cardo poly (ether ketone amide)s with inherent viscosities up to 0.75 dL/g. All the polymers were readily soluble in many organic solvents and could afford transparent, flexible, and strong films by solution casting. These polymers showed good thermal stability with the glass transition temperature of 237°C–258°C, the temperature at 5% weight loss of 462°C–477°C in nitrogen. These polymer films also exhibited good mechanical properties, excellent electrical and dielectric performance, and high optical transparency. The incorporation of bulky fluorinated groups and cardo structures into polymer backbone has played an important role in the improvement of solubility, dielectric performance, and optical properties. Importantly, the heterogeneous palladium catalyst can easily be recovered from the reaction mixture by simply applying an external magnet and recycled up to 7 times without significant loss of catalytic activity. 相似文献
17.
Anindita Ghosh Shyambo Chatterjee Susanta Banerjee Hartmut Komber Brigitte Voit 《高分子科学杂志,A辑:纯化学与应用化学》2013,50(7):509-517
A new trifluoromethyl-activated AB monomer has been successfully synthesized by Pd-initiated coupling of 4-bromo anisole with 4-fluoro-3-trifluoromethylphenylboronic acid followed by demethylation. The monomer leads to a semifluorinated poly(arylene ether) by nucleophilic displacement polymerization reaction. The AB monomer has been further copolymerized with a corresponding AB 2 monomer to form the corresponding semifluorinated hyperbranched (hb) poly(arylene ether). The resulting linear and hb poly(arylene ether)s exhibited weight average molecular weight of 75700 and 144100 g/mol, respectively. The hb copolymer exhibited better solubility in different organic solvents compared to the linear poly(arylene ether). The polymers showed excellent thermal stability up to 522°C at 10% wt loss in air and glass transition temperatures as high as 187°C. The mechanical properties of the linear poly(arylene ether) film 1a exhibited tensile strength at break of 89 MPa, elongation at break of up to 3% and a Young’s modulus value of 2.66 GPa. The films of the polymers were hydrophobic in nature and showed water contact angle as high as 93.6°. 相似文献
18.
《高分子科学杂志,A辑:纯化学与应用化学》2013,50(10):1123-1133
Abstract Several poly(aryl ether)s have been prepared by the condensation of 1,3‐bis(4‐hydroxy phenyl) benzene with different trifluoromethyl activated bis‐fluoro compounds. IR, 1H and 13C NMR, and elemental analyses have established the resulting polymer structures. The properties of the polymers have been evaluated by DSC, TGA, dynamic mechanical analysis (DMA) and stress–strain analysis. The polymers 1a and 1c showed semi‐crystalline behavior as evident by sharp crystalline melting peaks at 299°C and 330°C along with glass transitions at 202°C and 216°C, respectively. The polymers showed very good thermal stability in air, high modulus, and high tensile strength with low elongation at break. 相似文献
19.
J. Xu Y. Z. Meng S. J. Wang A. S. Hay 《Journal of polymer science. Part A, Polymer chemistry》2006,44(10):3328-3335
A series of novel soluble pyridazinone‐ or pyridazine‐containing poly(arylene ether)s were prepared by a polycondensation reaction. The pyridazinone monomer, 6‐(4‐hydroxyphenyl)pyridazin‐3(2H)‐one ( 1 ), was synthesized from the corresponding acetophenone and glyoxylic acid in a simple one‐pot reaction. The pyridazinone monomer was successfully copolymerized with bisphenol A (BPA) or 1,2‐dihydro‐4‐(4‐hydroxyphenyl)phthalazin‐1(2H)‐one (DHPZ) and bis(4‐fluorophenyl)sulfone to form high‐molecular‐weight polymers. The copolymers had inherent viscosities of 0.5–0.9 dL/g. The glass‐transition temperatures (Tg's) of the copolymers synthesized with BPA increased with increasing content of the pyridazinone monomer. The Tg's of the copolymers synthesized from DHPZ with different pyridazinone contents were similar to those of the two homopolymers. The homopolymers showed Tg's from 202 to 291 °C by differential scanning calorimetry. The 5% weight loss temperatures in nitrogen measured by thermogravimetric analysis were in the range of 411–500 °C. 4‐(6‐Chloropyridazin‐3‐yl)phenol ( 2 ) was synthesized from 1 via a simple one‐pot reaction. 2 was copolymerized with 4,4′‐isopropylidenediphenol and bis(4‐fluorophenyl)sulfone to form high‐Tg polymers. The copolymers with less than 80 mol % pyridazinone or chloropyridazine monomers were soluble in chlorinated solvents such as chloroform. The copolymers with higher pyridazinone contents and homopolymers were not soluble in chlorinated solvents but were still soluble in dipolar aprotic solvents such as N‐methylpyrrolidinone. The soluble polymers could be cast into flexible films from solution. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 3328–3335, 2006 相似文献
20.
A random copolymer (RCP) containing poly(ether ether ketone) (PEEK) and thermotropic liquid crystalline polymer (TLCP) segments was synthesized. Its chemical structure and liquid crystalline properties were characterized by FT‐IR, differential scanning calorimetry (DSC) and polar light microscopy (PLM) respectively. A single glass transition temperature (Tg) at 134.0°C, a melting temperature (Tm) at 282.0°C and a temperature of ignition (Ti) at 331.3°C can be observed. Blends of PEEK and TLCP with and without RCP as compatibilizer were prepared by extrusion and the effect of RCP on the thermal properties, dynamic mechanical properties, morphology and static tensile mechanical properties of blends was investigated by means of DSC, dynamic mechanical analysis (DMA), scanning electron microscopy (SEM), etc. Dynamic mechanical measurements indicated that there appeared to be only a single tan δ peak resulting from the glass transition of the PEEK‐rich phase and the Tg value shifted towards higher temperature due to the presence of compatibilizer, as suggested partial compatibility. Morphological investigations showed that the addition of RCP to binary blends reduced the dispersed phase size and improved the interfacial adhesion between the two phases. The ternary compatibilized blends showed enhanced tensile modulus compared to their binary blends without RCP. The strain at break decreased for the ternary blends due to embrittlement of the matrix by the incorporation of some RCP to the matrix phase. Copyright © 2007 John Wiley & Sons, Ltd. 相似文献