亲电缩聚反应合成芳香环状低聚醚酮砜及其开环聚合

"假高稀"条件下,以邻苯二酰氯为酰基化试剂,Lewis碱NMP存在下,通过亲电缩聚反应高产率地合成了2种芳香环状聚醚酮砜低聚物,利用MALDI-TOF-MS,NMR,GPC,FTIR,DSC等手段对环状结构进行了精确的表征.在负离子引发剂联苯双酚钾存在下,环状低聚物3a进行熔融开环聚合,得到了高分子量的线型聚合物,Tg为221.8℃.利用流变仪监测了环状低聚物3a开环聚合过程中的流变行为,结果表明,开环聚合初期的引发阶段,熔融体的黏度低于10Pa.s,随着时间的延长,黏度快速增长,而且低黏度的引发阶段随着引发剂浓度的增加而变短.     

Poly(aryl ether amide)s

A general method for the preparation of poly(aryl ether amide)s has been developed where the generation of an aryl ether linkage is the polymer-forming reaction. The amide linkage was found to be sufficiently electron-withdrawing to activate halo-substituents towards nucleophilic aromatic substitution analogous to conventional activating groups (i.e., sulfone, ketone, etc.). Model reactions demonstrated that the amide-activated displacement occurred with high selectivity in near quantitative yield and was judged suitable as a polymer-forming reaction. Appropriately fluoro-substituted amides were prepared and subjected to displacement polymerization with bisphenoxides in a N-methyl-2-pyrrolidone (NMP)/N-cyclohexyl-2-pyrrolidone (CHP) solvent mixture. High molecular weight polymers with glass transition temperatures in the 200–225°C range were obtained. © 1993 John Wiley & Sons, Inc.     

Fully aromatic poly(ether ketone)s bearing macrocycle pendants: Synthesis and crosslinking

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     

Living/controlled cationic cyclopolymerization of divinyl ether with a cyclic acetal moiety: Synthesis of poly(vinyl ether)s with high glass transition temperature based on incorporation of cyclized main chain and cyclic side chains

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 (M_n) 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 (T_g) and thermal decomposition temperature (T_d) of poly( 1 ) (M_n = 7870, M_w/M_n = 1.57) were found to be 166 and 338 °C, respectively, indicating that poly( 1 ) had high T_g and high thermal stability. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 952–958, 2010     

氧化偶联聚合方法合成电活性聚芳醚酮

通过氧化偶联聚合方法成功地合成出电活性聚芳醚酮. 该反应条件温和, 操作简单, 室温下即可进行. 用红外光谱、核磁共振谱、高效凝胶渗透色谱、循环伏安、热失重、X射线衍射等技术对所合成的聚合物进行了表征, 并探讨了聚合物的性能.     

Isolation,spectra, structure,and ring-opening polymerization of strained macrocyclic aryl(ether ketone) dimer

Macrocyclic arylene ether ketone dimer was isolated from a mixture of cyclic oligomers obtained by the nucleophilic substitution reaction of bisphenol A and 4,4′-difluorobenzophenone and easily polymerized to high molecular weight linear poly-(ether ketone). The cyclic compound was characterized by FTIR, ¹H- and ¹³C-NMR, and single-crystal x-ray diffraction. Analysis of the spectral and crystal structure reveals extreme distortions of the phenyl rings attached to the isopropylidene center and of the turning points of the molecular polygons. The release of the ring strain on ring-opening combined with entropical difference between the linear polymer chain and the more rigid macrocycle at temperatures of polymerization may be the proposed motivating factors in the polymerization of this precursor to high molecular weight poly(ether ketone). © 1997 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 35 : 1753–1761, 1997     

Structural modifications in imide-aryl ether phenylquinoxaline random copolymers

A rigid rod polyimide derived from biphenyldianhydride (BPDA) and p-phenylenediamine (PDA) was modified by the incorporation of diamines containing performed phenylquinoxaline and aryl ether linkages, and the morphology and mechanical properties of the resulting imide-aryl ether phenylquinoxaline copolymers were investigated. These phenylquinoxaline containing diamines, 1, 4-bis[6-(3-aminophenoxy)-3-phenyl-2-quinoxalinyl] benzene and 1, 4-bis[6-(4-aminophenoxy)-3-phenyl-2-quinoxalinyl] benzene, were prepared by a novel nucleophilic aromatic substitution reaction of 1,4-(6-fluoro-3-phenyl-2-quinoxalinyl) benzene with either 1, 3- or 1, 4-aminophenol in the presence of K₂CO₃, respectively. The diamines were utilized as co-monomers with BPDA and PDA to synthesize poly(amicacids.) Films were cast and cured (350°C) to effect imidization, affording films which showed high elongations and moduli. The copolymers with high phenylquinoxaline compositions displayed T_g's in the 300°C range, and the thermal stability of the copolymers was comparable to that of the parent polyimide. The copolymers also showed improved auto- or self-adhesion, particularly those which showed a T_g, allowing sufficient molecular motion for interdiffusion.     

Star‐shaped cyclopolymers: A new category of star polymer with rigid cyclized arms prepared by controlled cationic cyclopolymerization and subsequent microgel formation of divinyl ethers

The combination of living/controlled cationic cyclopolymerization and crosslinking polymerization of bifunctional vinyl ethers (divinyl ethers) was applied to the synthesis of core‐crosslinked star‐shaped polymers with rigid cyclized arms. Cyclopolymerization of 4,4‐bis(vinyloxymethyl)cyclohexene ( 1 ), a divinyl ether with a cyclohexene group, was investigated with the hydrogen chloride/zinc chloride (HCl/ZnCl₂) initiating system in toluene at 0 °C. The reaction proceeded quantitatively to give soluble poly( 1 )s in organic solvents. The content of the unreacted vinyl groups in the produced polymers was less than ～3 mol%, and therefore, the degree of cyclization of the polymers was determined to be ～97%. The number‐average molecular weight (M_n) 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 living cyclopolymerization of 1 occurred. The chain linking reactions among the formed living cyclopolymers with 1,4‐bis(vinyloxy)cyclohexane ( 3 ) as a crosslinker in toluene at 0 °C produced core‐crosslinked star‐shaped cyclopoly( 1 )s [star‐poly( 1 )s] in high yield (100%). Dihydroxylation of the cyclohexene double bonds of star‐poly( 1 ) gave hydrophilic water‐soluble star‐shaped polymers with rigid arm structure [star‐poly( 1 )‐OH] with thermo‐responsive function in water. T_gs of star‐poly( 1 ) and star‐poly( 1 )‐OH were 135 °C and 216 °C, respectively; these values are very high as vinyl ether‐based star‐shaped polymers. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2015 , 53, 1094–1102     

Imide-aryl ether ketone block copolymers

Imide-aryl ether ketone block copolymers were prepared and their morphology and thermal and mechanical properties investigated. Two aryl ether ketone blocks were incorporated; the first was an amorphous block derived from bisphenol–A and the second block was a semi-crystalline poly(aryl ether ether ketone) prepared from a soluble and amorphous ketimine precursor. Bis(amino) aryl ether ketone and aryl ether ketimine oligomers were prepared via a nucleophilic aromaic substitution reaction with molecular weights ranging from 6,000 to 12,000 g/mol. The oligomers were co-reacted with 4,4′-oxydianiline (ODA) and pyromellitic dianhydride (PMDA) diethyl ester diacyl chloride in N-methyl–2-pyrrolidone (NMP) in the presence of N-methylmorpholine. The copolymer compositions, determined by H-NMR, of the resulting amic ester based copolymers ranged from 8 to 50 wt % aryl ether ketone or ketimine content. Prior to imide formation, the ketimine moiety of the aryl ether ketimine block was hydrolyzed (p-toluene sulfonic acid) to the ketone form producing the aryl ether ether ketone block. Compositions of this block were maintained low to retain solubility. Solutions of the copolymers were cast and cured to effect imidization, producing clear films with high moduli (ca. 2200 MPa) and elongations (33–100%). The copolymers displayed good thermal stability with decomposition temperatures in excess of 450°C. Multiphase morphologies were observed irrespective of the co-block type, block length or composition. © 1992 John Wiley & Sons, Inc.     

Synthesis and characterization of the B3-monomer and hyperbranched poly(aryl ether ketone)s

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. __________ Translated from Acta Scientianum Naturalium Universitatis Jilinensis, 2005, 5 (in Chinese)     

Synthesis and Characterization of a Novel Poly(aryl ether) Containing 4-Chloro-2,5-diphenyloxazole

4-Chloro-2,5-bis(4-fluorophenyl)oxazole monomer has successfully been synthesized using cyclization reaction of 4-fluorobenzoyl cyanide with 4-fluorobenzaldehyde. This monomer was converted to poly(aryl ether)s by nucleophilic substitution of the fluorine atoms on the benzene rings of oxazole monomer with bisphenol A. The influence of the reaction time on the molecular weight had been investigated. The polymers were identified by FT-IR,¹H-NMR and TGA. The products exhibited weight-average molar masses up to 2.81 x 10⁴g mol⁻¹ in GPC. These poly(aryl ether)s showed very high thermal stability up to 363 °C for 5 % weight loss in TGA under N₂.     

Highly phenylated poly(aryl ether phthalazine)s

Two series of novel amorphous poly(aryl ether phthalazine)s have been prepared via an intramolecular ring closure reaction of poly(aryl ether ketone)s (PAEKs) with hydrazine monohydrate. Fluorinated PAEKs, which display solubility in solvents incorporating a ketone functionality such as acetone or ethyl acetate, were converted to poly(aryl ether phthalazine)s to observe if these polymers would display similar solubility characteristics. The poly(aryl ether phthalazine)s have glass transition temperatures in the range of 278–320°C and show 5% weight loss points greater than 500°C in air and nitrogen atmospheres. The fluorinated poly(aryl ether phthalazine)s were not soluble in ketonic solvents. A series of poly(aryl ether phthalazine)s incorporating pendant 2-naphthalenyl moieties has been prepared in an attempt to produce amorphous, thermally stable polymers with high glass transition temperatures. The polymers have glass transition temperatures in the range of 287–334°C and show 5% weight loss points greater than 500°C in air and nitrogen atmospheres. Poly(aryl ether phthalazine)s undergo an exothermic reaction above the glass transition temperature. The major product of this reaction is a rearrangement of the phthalazine moieties to quiazoline moieties, however some crosslinking of the polymers occurs. Cured samples of the poly(aryl ether phthalazine)s show a small increase in the polymer T_g and are insoluble in all solvents tested. © 1996 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 34:1897–1905, 1996     

Synthesis and ring‐opening polymerization of macrocyclic aryl ketone oligomers

A series of macrocyclic aryl ketone oligomers were prepared by the reaction of phthaloyl dichloride or isophthaloyl dichloride with various bridge‐linking electron‐rich aromatic hydrocarbons 3a–d under pseudo‐high dilution conditions in the presence of Lewis base via Friedel–Crafts acylation reaction. Detailed structural characterization of these oligomers confirmed the cyclic nature by a combination of MALDI‐TOF‐MS, GPC, and ¹H NMR analyses. These cyclic ketone oligomers have high solubility in organic solvents and the cyclic oligomers derived from phthaloyl dichloride are amorphous. The cyclic ketone oligomers readily undergo anionic ring‐opening polymerization in the melt by using potassium 4,4′‐biphenoxide as the initiator, producing linear, high molecular weight poly(ether ketone)s. Moreover, the isothermal chemorheology of the ring‐opening polymerization of cyclic oligomers 4a and 4b was also investigated. The results show that the shear viscosity of the molten reactive mixture is lower than 10 Pa · S at a constant shear rate of 0.05 rad/sec and increases slowly in the initial stage of ring‐opening polymerization. Copyright © 2009 John Wiley & Sons, Ltd.     

Novel poly(aryl ether phthalazinium) ionomers and their properties

The synthesis of N-phenyl phthalazinium salts by condensation of a 1,2-diaroylbenzene with phenylhydrazine is described. This reaction was utilized to prepare novel poly(aryl ether phthalazinium) ionomers by the direct condensation of poly(aryl ether ketone)s with phenylhydrazine. The preparation of poly(aryl ether phthalazinium) ionomers by methylation of poly(aryl ether phthalazine)s is also described. Most of the ionomers are amorphous, thermally stable, and soluble in organic solvents. They can be cast into flexible and strong films. The glass transition temperature of the ionomers ranges from 297 to 363°C, an increase of 12 to 100°C over the corresponding neutral polymers. © 1996 John Wiley & Sons, Inc.     

氟取代聚芳醚酮低温合成及其结构研究

通过傅克酰基化反应合成4,4'-二(4-氟苯甲酰基)二苯醚、4,4'-二(五氟苯甲酰基)二苯醚、4,4'-二(4-氟苯甲酰基)二苯硫醚以及4,4'-二(五氟苯甲酰基)二苯醚4种长链双卤单体,并进一步制备了含二氮杂萘酮聚芳醚酮聚合物.通过多氟取代双卤单体在含二氮杂萘酮聚芳醚酮聚合物主链中引入氟原子.多氟取代双卤单体具有多...     

Living cationic polymerization of vinyl ethers with a naphthyl group: Decisive effect of the substituted position on naphthalene ring

Living cationic polymerization of a vinyl ether with a naphthyl group [2‐(2‐naphthoxy)ethyl vinyl ether, βNpOVE] was achieved using base‐assisting initiating systems with a Lewis acid. The Et_1.5AlCl_1.5/1,4‐dioxane or ethyl acetate system induced the living cationic polymerization of βNpOVE in toluene at 0 °C. The living nature of this reaction was confirmed by a monomer addition experiment, followed by ¹H NMR and matrix‐assisted laser desorption ionization time‐of‐flight mass spectrometry (MALDI‐TOF‐MS) analyses. In contrast, the polymerization of αNpOVE was not fully controlled; under similar conditions, it produced polymers with broad molecular weight distributions. The ¹H NMR and MALDI‐TOF‐MS spectra of the resultant poly(αNpOVE) revealed that the products had undesirable structures derived from Friedel–Crafts alkylation. The higher reactivity of αNpOVE in electrophilic substitution reactions, such as the Friedel–Crafts reaction, was attributable to the greater electron density of the naphthyl ring, which was calculated based on frontier orbital theory. The naphthyl groups significantly affected the properties of the resultant polymer. For example, the glass transition temperatures (T_g) of poly(NpOVE)s are higher by approximately 40 °C than that of poly(2‐phenoxyethyl vinyl ether). © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012     

Hyperbranched poly(ether–urea)s using AB2‐type blocked isocyanate monomer and azide monomer: Synthesis,characterization, reactive end functionalization,and copolymerization with AB monomer

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 (M_w) 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 T_g'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     

Synthesis and characterization of fluorinated poly(aryl ether ketone)s containing 1,4-naphthalene moieties

The new monomer 2,2-bis[4-(4-{4-fluorobenzoyl}-1-naphthoxy)phenyl]hexafluoropropane ( 2 ) was synthesized in a two-step reaction sequence. 2,2-his[4-(1-naphthoxy)phenyl]-hexafluoropropane ( 1 ) was prepared using the Ullmann ether synthesis reaction of 4,4-(hex-afluoroisopropylidiene)diphenol with 1-bromonaphthalene. Friedel-Crafts acylation of 1 with 4-fluorobenzoyl chloride in methylene chloride containing dimethylsulfone selectively afforded 2 in 82% yield. The polycondensation of 2 with various bisphenols in DMAc in the presence of an excess of potassium carbonate as a condensation reagent was carried out at 165°C to quantitatively afford the corresponding fluorinated poly(aryl ether ketone)s containing 1,4-naphthalene moieties. Thermal analysis of the polymers showed them to have T_gs ranging from 194 to 230°C and to be thermally stable in air up with initial weight losses at about 500°C. In addition, these novel polymers exhibited excellent solubility in organic solvents including NMP, DMAc, and chloroform. © 1997 John Wiley & Sons, Inc.     

Copolymerization of bis(2-oxazoline)s,anhydrides, and diols or diamines. Reaction mechanisms and polymer properties

The preparation of linear poly(ester-amide)s from monoanhydrides, bis(2-oxazoline)s (namely 2,2′-(1,4-phenylene)bis(2-oxazoline)) and a third comonomer is discussed. The polymerization reactions were carried out in bulk between 150 and 200°C. When the third monomer is a diol, poly(ester-ester-amide)s are obtained. Diols of different structure were used: α,ω-diols having up to 12 carbon atoms, ethylene glycol oligomers (two or three repeating units), cyclic diols, etc.; glutaric, 3,3-dimethylglutaric and maleic anhydrides were used as monoanhydrides. The polymers were studied from the point of view of thermal properties, finding a substantial agreement between the structure of the monomers and the glass transition temperature of the polymers. By using primary diamines as a third comonomer, the reaction does not lead to the formation of a polymeric product. The failure of the polymerization was attributed to a competitive reaction that prevents the polymerization. After the amine group has reacted with the anhydride, cyclization of the so-formed carboxyalkylamide occurs, giving an imide derivative, unable to react further. Therefore, only a mixture of low molecular weight compounds is obtained in this case. When the diamine is secondary, the imidization reaction is not possible, and linear poly(amide-ester-amide)s are obtained. © 1997 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 35: 3241–3248, 1997     

Effect of reaction conditions on the molecular weight and polydispersity of linear poly(arylene ether phosphine oxide)s prepared from an AB monomer

A thorough study of the polymerization behavior of 4‐fluoro‐4′‐hydroxytriphenyl‐phosphine oxide, 2 , under nucleophilic aromatic substitution reactions has been carried out. The synthesis of 2 was achieved in excellent yields by the reaction of bis(4‐fluorophenyl)phenylphosphine oxide, 1 , with one equivalent of potassium hydroxide in DMSO/water. The structure and purity of 2 were confirmed via ¹H, ¹³C, and ³¹P NMR spectroscopy along with elemental analysis. Polymerization reactions of 2 in NMP or DMSO at 180 °C provided the corresponding linear poly(arylene ether phosphine oxide)s, PAEPOs, with number average molecular weights, M_n, ranging from 11,700 to 36,500 Da. All of the polymer samples were completely soluble in chloroform, tetrahydrofuran, DMSO, NMP, and DMAc. The polymerization reactions were accompanied by a competing intramolecular process that resulted in the formation of cyclic oligomeric species that were removed via a final precipitation from methanol. Analysis using ³¹P NMR spectroscopy and size exclusion chromatography (SEC) confirmed that the majority of the lower molecular weight cyclic species were removed via this process. The polymer samples formed tough films when chloroform solutions were slowly evaporated on a glass slide. The PAEPO samples prepared in this study exhibited excellent thermal stability with T_d (5%) values between 503 and 542 in air while the glass transition temperatures ranged from 223 to 237 °C. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 2099–2106, 2006