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1.
Toru Katsumata 《Polymer》2008,49(12):2808-2816
The polymerization of diphenylacetylene derivatives possessing tert-amine moieties, such as triphenylamine, N-substituted carbazole and indole, was examined in the presence of TaCl5-n-Bu4Sn (1:2) catalyst. A polymer with high molecular weight (Mw = 570 × 103) was obtained in good yield by the polymerization of diphenylamine-containing monomer 1b, whereas the isopropylphenylamine derivative (1c) gave a polymer with relatively low molecular weight (Mw = 2.4 × 103). The polymerization of monomer 1d containing cyclohexylphenylamine group did not proceed; however, carbazolyl- and indolyl-containing monomers also produced polymers. Poly(1b), poly(2f) and poly(4b) could be fabricated into free-standing membranes by casting toluene solutions of these polymers. The gas permeability of poly(1b) was too low to be evaluated accurately whereas poly(4b) possessing two chlorine atoms in the repeating unit showed higher gas permeability than that of poly(1b); furthermore, poly(2f) having trimethylsilyl and 3-methylindolyl groups exhibited relatively high gas permeability (). In the cyclic voltammograms of diphenylamino group-containing polymers, poly(1b) and poly(2b), the intensities of oxidation and reduction peaks decreased more than those of carbazolyl-containing poly(2a). The molar absorptivity (?) of poly(1b) at ∼700 nm increased with increasing applied voltage in the UV-vis spectrum. 相似文献
2.
The low efficiency of p-toluenesulfonyl chloride (TsCl) initiator for the polymerization of methyl methacrylate (MMA), when used in conjunction with N,N,N′,N″,N″-pentamethyldiethylenetriamine (PMDETA) and CuBr under atom transfer radical polymerization (ATRP) conditions was investigated. A major by-product in the formation of poly(methyl methacrylate) was identified as N,N-dimethyl-p-toluenesulfonamide (5) and accounted for approximately half of the initiator. Compound 5 was shown to form by the direct reaction of PMDETA and TsCl. In a model experiment equimolar amounts of TsCl, PMDETA and CuBr reacted at 80°C in p-xylene resulted in the formation of 5 and two other unsaturated sulfones 2-methyl-3-[(4-methylphenyl)sulfonyl]-2-propenoic acid methyl ester (6) and 2-[[4-methylphenyl)sulfonyl]methyl]-2-propenoic acid methyl ester (7), formed by the dehydrohalogenation and subsequent isomerization of an intermediate chloro-adduct, 1-(4-methylbenzenesulfonyl)-2-chloro-2-(methyl)methyl propionate (2). Molecular modeling predicted the unsaturated sulfone 7 was thermodynamically more stable than the higher conjugated sulfone 6 and this was confirmed by the isomerization of 6 to 7 at room temperature under mild basic conditions. The absence of 6 and 7 in the polymerization of MMA under ATRP conditions showed that in the early stages of polymerization in the presence of excess MMA, the intermediate chloro-adduct 2 is not formed. 相似文献
3.
Catalytic behavior of tetrahydroborate complexes of rare earth metals, Ln(BH4)3(THF)x (1: Ln = La, x = 3; 2: Ln = Pr, x = 2; 3: Ln = Nd, x = 3; 4: Ln = Sm, x = 3; 5: Ln = Y, x = 2.5; 6: Ln = Yb, x = 3), for ring-opening polymerization (ROP) of six-membered cyclic esters, δ-valerolactone (VL) and d,l-lactide (d,l-LA), was studied. The controlled polymerization of VL with 1-6 proceeded in THF at 60 °C. The catalytic activities of these complexes for the ROP of VL were observed to be in order of the ionic radii of the metals: 1(La) ≥ 2(Pr) ≥ 3(Nd) > 4(Sm) > 5(Y) > 6(Yb). The obtained polymers were demonstrated to be hydroxy-telechelic by 1H NMR and MALDI-TOF MS spectroscopy. The controlled ROP of d,l-LA also proceeded by these complexes. The activities of these complexes for the d,l-LA ROP were also in order of the ionic radii of the metals. 相似文献
4.
Yue’e Peng Zhihua YangYanxin Wang Zhenyu LiuJianguo Bao Yan Hong 《Chemical Engineering Research and Design》2011,89(12):2620-2625
Diosgenin is an important starting material for the synthesis of steroidal hormone drugs in pharmaceutical industry. Acid hydrolysis of Dioscorea zingiberensis C. H. Wright (DZW) was the key step in the conversion of steroidal saponins to diosgenin in its manufacture factories. The pathways for the conversion of steroidal saponins to diosgenin during acid hydrolysis of DZW were studied experimentally. Three intermediate products and one byproduct were identified. The conversion pathways were from raw steroidal saponins zingiberensis newsaponin (1), deltonin (2), prosapogenin A of dioscin (3) to three intermediate products diosgenin-triglucoside (4), diosgenin-diglucoside (5) and trillin (6), and then to the product diosgenin (7) and byproduct 25-spirosta-3, 5-dienes (8). A maximum diosgenin yield of 2.5% was achieved when reacting in 0.8 M sulfuric acid for 6 h at 120 °C, while the intermediate products were just exhausted. After 6 h, the diosgenin yield decreased, due to the conversion of diosgenin to 25-spirosta-3, 5-dienes (8). The knowledge of the pathways for the conversion of steroidal saponins to diosgenin provide a scientific basis for assessing the performance of acid hydrolysis reaction in diosgenin manufacture factories by monitoring the content of three intermediate products (4-6). It also gives an alternative method for the synthesis of diosgenyl saponins (4-6) from plant material. 相似文献
5.
Atsushi Narumi Takeshi MatsudaHarumi Kaga Toshifumi SatohToyoji Kakuchi 《Polymer》2002,43(17):4835-4840
4-Vinylbenzyl glucoside peracetate 1 was polymerized with α,α′-bis(2′,2′,6′,6′-tetramethyl-1′-piperidinyloxy)-1,4-diethylbenzene 2 in chlorobenzene using (1S)-(+)-10-camphorsulfonic acid anhydrous (CSA) as an accelerator ([1]=0.4 M,[1]/[2]/[CSA]=75/1/1.3) at 125 °C for 5 h. The polymerization afforded poly(4-vinylbenzyl glucoside peracetate) having TEMPO moieties on both sides of the chain ends, 3, with a molecular weight (Mw,SLS) of 8500, a polydispersity index (Mw/Mn) of 1.09, and an average degree of polymerization of the 1 unit (x) of 17. Styrene (St) was polymerized with 3 in chlorobenzene at 125 °C (St/chlorobenzene=1/2, w/w). The polymerization successfully afforded polystyrene-poly(4-vinyl glucoside peracetate)-polystyrene, 4, when the polymerization time was below about 2 h. Polymer 4 with the Mw,SLS of 12,500, 17,900, and 29,400, the compositions (y-x-y) of 20-17-20, 45-17-45, and 100-17-100, and the Mw/Mn of 1.12, 1.14 and 1.17 were modified by deacetylation using sodium methoxide in dry-THF into polystyrene-poly(4-vinyl glucoside peracetate)-polystyrene, 5. The solubility of polymer 5 was examined using a good solvent for polystyrene such as toluene and for the saccharide such as H2O. 相似文献
6.
Effects of internal linkage groups of fluorinated diamine on the optical and dielectric properties of polyimide thin films 总被引:2,自引:0,他引:2
To investigate the difference of the trifluoromethyl (CF3) group and ether group affecting the optical property of fluorinated polyimides (PIs), we prepared 4,4′-bis(4-amino-2-trifluoromethylphenoxy)diphenyl ether (4) with three ether groups and 2,2-bis[4-(4-amino-2-trifluoromethylphenoxy)phenyl]hexafluoropropane (5) with four CF3 groups with 2-chloro-5-nitrobenzotrifluoride and 4,4′-dihydroxydiphenyl ether or 2,2-bis(4-hydroxyphenol)hexafluoropropane. Two series of organosoluble and light-colored PIs (4a-4c, 5a-5c) were synthesized from 4 and 5 with various aromatic dianhydrides: 3,3,4,4-benzophenonetetracarboxylic dianhydride (BTDA) (a), 4,4-oxydiphthalic anhydride (ODPA) (b), and 4,4-hexafluoroisopropylidenediphthalic anhydride (6FDA) (c), prepared through a typical two-step polymerization method. These PIs were soluble in amide polar solvents and even in less polar solvents. The glass-transition temperatures (Tg) of 4a-5c were 221-249 °C and the 10% weight-loss temperatures were above 530 °C. Their films had cutoff wavelengths between 339 and 399 nm and yellowness index ranges from 1.95 to 42.60. The dielectric constants estimated from the average refractive indices are 2.59-2.93 (1 MHz). In a comparison of the PI series based on 4, 5, and 4,4′-bis(4-amino-2-trifluoromethylphenoxy)biphenyl (6), we found that the CF3 group and ether group on the diamine had almost same effect in lowering the color, but the ether group had better thermal stability. The color intensity of the three PI series was lowered in the following order: 6 > 4 > 5. The PI 5c, synthesized from diamine 5 and dianhydride c, had six CF3 groups in a repeated segment and ether group at the same time, so it exhibited the lightest color among the three series. 相似文献
7.
A series of phosphoryl (PO) contained compounds: triethylphosphate (a), diethylphenylphosphate (b), ethyldiphenylphosphate (c) triarylphosphates (d and h-m), triphenylphosphine oxide (e), phenyl diphenylphosphinate (f) and diphenyl phenylphosphonate (g) have been prepared. Iron catalysts, which are generated in situ by mixing the compounds with Fe(2-EHA)3 and AliBu3 in hexane, are tested for butadiene polymerization at 50 °C. Phosphates donated catalysts have been, unprecedently, found to conduct extremely high syndiotactically (pentad, rrrr = 46.1-94.5%) enriched 1,2-selective (1,2-structure content = 56.2-94.3%) polymerization of butadiene. Introduction of electron withdrawing substituents on phenyl rings oftriphenylphosphate (k-m) remarkably promotes catalytic activity, while bulky substituent isopropyl at 2-position (h) has beneficial influence on regioselectivity. Employment of e, f or g as donor, results in a suppressed monomer conversion, accompanied by deteriorated 1,2-regioselectivity. The effects of polymerization conditions such as reaction temperature, types of cocatalysts and polymerization medium are also investigated by using catalyst system with tri(2,4-difluorophenyl)phosphate (m) as donor. Highly tolerance to polymerization temperature up to 80 °C is observed for the first time in the iron-based catalyst. 相似文献
8.
A new synthetic method for the preparation of poly(benzoxazole) (PBO) precursor, poly(o-hydroxyamide) (7) from bis(o-aminophenol) (5) and diphenyl isophthalate (6) has been developed. Polymer 7 was prepared by the polycondensation of 5 and 6 in 1-methyl-2-pyrrolidinone (NMP) at 185-205 °C. Model reactions were carried out in detail to elucidate appropriate conditions for the formation of 2-hydroxybenzanilide (3) from o-aminophenol (1) and phenyl benzoate (2). The photosensitive (PBO) precursor based on polymer 7 containing a 22% of benzoxazole unit and 30 wt% 1-{1,1-bis[4-(2-diazo-1-(2H)naphthalenone-5-sulfonyloxy)phenyl]ethyl}-4-{1-[4-(2-diazo-1(2H)naphthalenone-5-sulfonyloxy)phenyl]methylethyl}benzene (S-DNQ) showed a sensitivity of 110 mJ cm−2 and a contrast of 5.0 when it was exposed to 436 nm light followed by developing with a 2.38 wt% aqueous tetramethylammonium hydroxide solution at room temperature. A fine positive image featuring 8 μm line and space patterns was observed on the film of the photoresist exposed to 200 mJ cm−2 of UV-light at 436 nm by the contact mode. 相似文献
9.
4-Vinylbenzyl glucoside peracetate (1) was copolymerized with divinylbenzene (DVB) using 1-phenyl-1-(2′,2′,6′,6′-tetramethyl-1′-piperidinyloxy)ethane (2) as an initiator in m-xylene at 138 °C for 20 h ([DVB]/[2]=28; [DVB]=0.62 mol L−1). The copolymerizations were performed using the mole fraction of 1 in the total feed of 1 and DVB (F1: [1]/[1]+[DVB]) ranging from 0.11 to 0.38 that produced the polystyrene (PSt) microgel with acetyl glucose, 3, in 46-53% yields. Dynamic laser light scattering (DLS) measurements showed that 3 was stably suspended in toluene as particles with average diameters (d's) ranging from 12 to 22 nm. A static laser light scattering (SLS) measurement gave the average molar mass, Mw,SLS, of 3 that ranged from 9.69×104 to 6.96×105. The numbers of the 1, 2, and DVB units in 3 (N1, N2, and NDVB, respectively) were from 111 to 238, from 17 to 208, and from 350 to 4510, respectively. The deacetylation of 3 was achieved by treatment with sodium methoxide in dry 1,4-dioxane to produce the PSt microgel with glucose as the hydrophilic segment, 4. The solubilities of 4 in toluene, CHCl3, THF, 1,4-dioxane, pyridine, DMF, DMSO, and H2O, and the mixture of H2O and 1,4-dioxane were examined, indicating that a hydrophilic property had been effectively introduced into 4. 相似文献
10.
The polymerization of 1-β-naphthyl-2-[(p-trimethylsilyl)phenyl]acetylene (8a) with TaCl5-n-Bu4Sn in cyclohexane provided a high molecular weight polymer (9a) (Mw=3.4×106). The corresponding monomers having p-dimethyl-t-butylsilyl and p-dimethyl(10-pinanyl)silyl groups in place of p-trimethylsilyl group in 8a also polymerized in a similar way to give high molecular weight polymers (9b, 9c, respectively; Mw>1×106). All these polymers were soluble in many common solvents such as toluene and chloroform, and provided free-standing membranes by casting from toluene solution. The oxygen permeability coefficients (PO2) of 9a at 25 °C was as high as 3500 barrers. The membrane of poly(1-β-naphthyl-2-phenylacetylene) (10a) was prepared by desilylation of the membrane of 9a with trifluoroacetic acid. Polymer 10a was insoluble in any solvents, and showed high thermal stability (the onset temperature of weight loss in air ∼470 °C). The PO2 value of 10a reached 4300 barrers. Not only the membrane of 9c but also its desilylation product 10c exhibited large optical rotations ([α]D=+2924 and +9800°, respectively) and strong CD signals. This indicates that the membrane of 10c maintains the helical main chain conformation of 9c with a large excess one-handed helix sense. 相似文献
11.
The electrochemical study of N-tert-butoxy-2,4-diphenyl-6-tert-butylphenylaminyl (1a), N-tert-butoxy-2,4-bis(4-chlorophenyl)-6-tert-butylphenylaminyl (1b), N-[2-(methoxycarbonyl)-2-propyl]-2,4-diphenyl-6-tert-butylphenylaminyl (2), and N-tert-butoxy-2,4,6-tris(4-chlorophenyl)phenylaminyl radicals (3) was performed by cyclic voltammetry using acetonitrile as the solvent and Bu4NPF6 as the supporting electrolyte. On cathodic scan (100 mV/s), all the radicals gave chemically reversible cyclic voltammograms, and the were determined to be −1.405 V (1a), −1.310 V (2a), −1.282 V (2b), and −1.195 V (3) (versus Fc+/Fc), respectively. On anodic scan (100 mV/s), on the other hand, 1a, 1b and 2 showed chemically reversible cyclic voltammograms, but 3 exhibited a partially reversible couple even on a scan rate of 500 mV/s, indicating that the cation species of 3 was less stable. The determined for 1a, 1b, 2 and 3 were 0.220, 0.280, 0.318 and 0.294 V (versus Fc+/Fc), respectively. The electrochemical data were compared with those of thioaminyl radicals, the corresponding sulfur analogues of 1-3. 相似文献
12.
A series of polyimides IIIa-h characterized by colorlessness, high transparency, high solubility, and good mechanical property, was synthesized from the aromatic dianhydride, 2,5-bis(3,4-dicarboxyphenoxy)-t-butylbenzene dianhydride (I), and various aromatic diamines (IIa-h) with pendent trifluoromethyl group via polyaddition, chemical imidization, and direct cast films. The III series showed more colorless than the polyimides (V and VI series) of 2,2-bis(3,4-dicarboxyphenyl)hexafluoropropane dianhydride (6FDA) contained, the VI series was synthesized from the II with 6FDA. These films III had cut-off wavelengths between 371 and 376 nm, as well as b* value (a yellowness index) ranging from 3.0 to 4.7. In fact, it is so far the most colorless aromatic polyimide in our systematical researches. The III series had inherent viscosity ranging from 0.72 to 1.33 dL/g and showed excellent solubility in a variety of organic solvents. They were soluble in a concentration of 5-10% in the amide polar solvent, ether solvent, and chlorinated solvent. These films showed strength tensile of 97-123 MPa, dielectric constants of 2.78-3.28 (1 MHz), and moisture absorptions of 0.11-0.36 wt%. The glass transition temperature of the III series was recorded at 214-259 °C, the 10% weight loss temperature was over 468 °C, and the residue was more than 47% at 800 °C in nitrogen. 相似文献
13.
Md. Abdul Mannan 《Polymer》2007,48(3):743-749
A new cyclic nitroxide 1 and the corresponding alkoxyamines 9 and 10 were synthesized and the polymerization of styrene (St) initiated with 10 was investigated. The NO-C bond of 9 is very weak, cleaving at room temperature. On the other hand, alkoxyamine 10 is stable at room temperature and the Aact and Eact for the NO-C bond homolysis were determined to be 1.4 × 1015 s−1 and 124.5 kJ mol−1, respectively. When the polymerization of St was carried out at 70 °C, the resultant poly(St) showed narrow polydispersities below 1.25. In the polymerization at 90 °C, the resulting poly(St) showed narrow polydispersity until 60% conversion, but Mw/Mn was rapidly increased above 60% conversion. On the other hand, the polymerization at 120 °C gave poly(St) with broad polydispersities. The unusual polymerization behavior was discussed on the basis of the SEC and ESR results. 相似文献
14.
The guest release and solution behavior during shell disruption of a polymeric nanocapsule are described. Hyperbranched polyethylenimine (PEI, Mn = 10?000) is chemically functionalized with multiple DAD hydrogen-bonding motifs (D and A: hydrogen-bonding donor and acceptor), leading to PEI232-(DAD)x (3) (x = 93 (3a), x = 46 (3b), x = 23 (3c), x = 12 (3d)). Meanwhile, polyethylene oxide (Mn = 2 200) is end-capped with thymine moieties (PEO-ADA) (4). Mixing of the hydrogen-bonding complementary 3 and 4 (DAD/ADA = 1) leads to a physical micelle (3·4) in apolar media, and the resulting micelle can completely and irreversibly transfer the ionic and water-soluble Congo red (CR) into chloroform phase by encapsulation. Experiment proves that the micelle can exist as a pseudo-unimolecular micelle (p-UIM, meaning one PEI in one micelle) or as aggregate, depending on the shell density. As a result, 3b·4 generally exists as a p-UIM while 3d·4 can exist as p-UIM only in a very narrow range of concentrations. The critical aggregation concentration (CAC) is also dependent on the core structure of the micelle, thus when the residual amines in the core of 3b are transformed into amide, the resulting 5b·4 shows a very low CAC. Small chemicals bearing DAD hydrogen-bonding motif can compete to bind with the PEO-ADA shell and destruct the p-UIM, leading to aggregation and precipitation of the p-UIM along with the CRs. Experiment proves that the CR has strong acid-base interaction with the PEI core of the p-UIM, but when the basicity of the PEI core is reduced by amidation, partial CRs can be released into the water phase. 相似文献
15.
Titanium bis(2-pyridinethiolate) complexes, Ti(6-R-SPy)2(NMe2)2 (6-R-SPy = 6-R-2-pyridinethiolate, 3a: R = H; 3b: R = Me; 3c: R = Ph; 3d: R = C6H4-4-Me; 3e: R = C6H4-4-t-Bu; 3f: R = C6H3-3,5-Me2), and the titanium bis(2-pyridinolate) complexes, Ti(6-Ph-OPy)2(NMe2)2 (6-Ph-OPy = 6-phenyl-2-pyridinolate, 8) were prepared by treating Ti(NMe2)4 with 2 equiv. of 6-R-2-pyridinethiol or 6-Ph-2-pyridinol. The cis-configuration of the diamido moieties in the pseudo octahedral geometry was elucidated by X-ray crystallography for 3a. Reaction of M(NMe2)4 (M = Ti, Zr) with 4 equiv. of 2-pyridinethiol cleanly gave tetrakis(pyridinethiolate) complexes, M(6-H-SPy)4·THF (6: M = Ti; 7: M = Zr). The triangular dodecahedral geometries of 6 and 7 were also revealed by X-ray crystallography. These complexes catalyzed ethylene polymerization upon activation with MAO (methylaluminoxane) or MMAO (modified MAO). The catalytic activities of titanium bis(6-aryl-pyridinethiolate) systems were found to be remarkably higher than that of titanium bis(6-methyl-pyridinethiolate) system. Among the complexes synthesized in this study, Ti[6-(C6H3-3,5-Me2)-SPy]2(NMe2)2 (3f)/MMAO showed the highest activity (1200 kg/Ti-mol h atm) for ethylene polymerization at 60 °C under atmospheric pressure. In contrast, the activity of the corresponding 6-aryl-pyridinolate system 8/MMAO was rather low (9.3 kg/Ti-mol h atm). Both the N-S chelating structure and the bulky aryl substituents are essential for the high activities of the 6-aryl-pyridinethiolate complexes. 相似文献
16.
A series of poly(ether ketone) copolymers were prepared by nucleophilic aromatic polymerization reactions of 4-fluoro-4′-hydroxybenzophenone, 2, in the presence of varying percentages of ABn monomers based on a triarylphosphine oxide platform, 1a (2F), 1b (4F), and 1c (6F), where A=OH and B=F. As expected, the crystallinity of the samples decreased with an increasing ABn content. However, the tetrahedral geometry of the phosphine oxide-based ABn monomers proved to be much more efficient at lowering the melt temperature of the copolymers than was the corresponding ketone-based ABn monomer, 3,5-bis(4-fluorophenylbenzoyl)phenol, 4, that possesses a structure more similar to that of 2. Polymerization of 2 in the presence of as little as 5 mol% of bis-(3,4,5-trifluorophenyl)-(4-hydroxyphenyl)phosphine oxide, 1c (6F), afforded a completely amorphous polymer with a glass transition temperature of 168 °C that was soluble in hot NMP and DMSO. The copolymers also exhibited excellent thermoxidative stability with a number of samples displaying 5% weight loss temperatures, in air, well in excess of 500 °C. 相似文献
17.
Akito Fukui 《Polymer》2009,50(17):4159-5967
Diarylacetylenes having fluorenyl groups and other substituents (trimethylsilyl, t-butyl, bromine, fluorine) (1a-1) were polymerized with TaCl5-n-Bu4Sn. Monomers 1a-l produced high molecular weight polymers 2a-l (Mw 5.1 × 105-1.3 × 106) in 12-59% yields. All of the polymers were soluble in common organic solvents, and gave tough free-standing membranes by the solution casting method. The onset temperatures of weight loss of polymers 2a-l in air were over 400 °C, indicating considerably high thermal stability. All the polymer membranes showed high gas permeability; e.g., the oxygen permeability coefficient (PO2) of 2a was as large as 4800 barrers. Membrane 2d possessing two fluorine atoms at meta and para positions of the phenyl ring showed the highest oxygen permeability (PO2 = 6600 barrers) among the present polymers. 相似文献
18.
A mono methylether Salen-type ligand, SalenMe-H (1) is prepared in a one flask reaction by condensation of trans-1,2-diaminocyclohexane with 2-methoxybenzenaldehyde and followed by the addition of 2,4-di-tert-butylsalicylaldehyde. Further reaction of 1 with Mg(OBn)2 in THF produces a magnesium alkoxide, [(SalenMe)Mg(OBn)]2 (2). Compound 1 reacts with ZnEt2 yields monomeric complex (SalenMe)ZnEt (3), which further reacts with 1 molar equiv of benzyl alcohol giving [(SalenMe)Zn(OBn)]2 (4). Experimental results show that complexes 2 and 4 efficiently initiate the ring-opening polymerization of l-lactide and rac-lactide in a controlled fashion, yielding polymers with very low polydispersity indexes. Kinetic studies show a second-order dependency on [LA] and a first-order on [2] with magnesium complex 2 as an initiator. While zinc complex 4 is used as an initiator, the polymerization rate has a first order dependency on both [LA] and [4]. 相似文献
19.
Kazuya Matsumoto 《Polymer》2006,47(9):3043-3048
A novel thermally stable and low dielectric poly(2-naphthol) containing an adamantyl unit (3) has been developed. Polymer 3 was easily prepared by oxidative coupling polymerization of (1,3-adamantyl)bis(2-naphthol) with CuCl(OH)TMEDA as a catalyst. The polymerization produced regiocontrolled polymer 3 with a number-average molecular weight of 10,500 Da and a molecular weight distribution of 4.1. The 5% weight loss temperature of polymer 3 was 480 °C and no glass transition temperature was observed. The dielectric constants (ε) of polymer 3 estimated from the refractive index and the capacitance were 2.92 and 2.96, respectively. 相似文献
20.
Chih-Cheng Lee 《Polymer》2008,49(19):4211-4217
A series of vinyl copolymers (P1-P6) containing pendant hole-transporting triphenylamine (11-88 mol%) and carbazole chromophores were synthesized by radical copolymerization to investigate the influence of triphenylamine groups upon optoelectronic properties. The copolymers were readily soluble in common organic solvents and their weight-average molecular weights (Mws) were between 1.41 × 104 and 2.24 × 104. They exhibited moderate thermal stability with Td = 402-432 °C at 5% weight loss. The emission spectra (both PL and EL) of the blends [P1-P6 with 4 wt% Ir(ppy)3] showed dominant green emission (517 nm) attributed to Ir(ppy)3 due to efficient energy transfer from P1-P6 to Ir(ppy)3. The HOMO levels of P1-P6, estimated from onset oxidation potentials in cyclic voltammeter, were −5.42 to −5.18 eV, which are much higher than −5.8 eV of conventional poly(9-vinylcarbazole) (PVK) host owing to high hole-affinity of the triphenylamine groups. The optoelectronic performances of phosphorescent EL devices, using P1-P6 as hosts and Ir(ppy)3 as dopant (ITO/PEDOT:PSS/P1-P6:Ir(ppy)3 (4 wt%):PBD (40 wt%)/BCP/Ca/Al), were greatly improved relative to that of PVK. The best performance was obtained with P4 device, in which the maximum luminance and luminance efficiency were 11?501 cd/m2 and 10.6 cd/A, respectively. 相似文献