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1.
Ring-opening metathesis polymerization (ROMP) of exo-N-(1-adamantyl)-7-oxanorbornene-5,6-dicarboximide (AdONDI) (3a), exo-N-cyclohexyl-7-oxanorbornene-5,6-dicarboximide (ChONDI) (3b) and exo-N-phenyl-7-oxanorbornene-5,6-dicarboximide (PhONDI) (3c) using well-defined alkylidene ruthenium catalysts (PCy3)2(CI)2RuCHPh (I) and (1,3-dimesityl-4,5-dihydroimidazol-2-ylidene) (PCy3)CI2RuCHPh (II) was studied. The catalysts I and II gave polymers with around 70% and 50% trans vinylene content, respectively. The homopolymer of 3a had a Tg of 198 °C, while poly-3b showed a Tg of 122 °C. Copolymers of 3a, 3b and 3c with norbornene (NB) showed significant Tg increases over poly-NB.  相似文献   

2.
A diarylethene dimer linked by a phenyl group was synthesized and the photochromic behavior was examined. Upon irradiation with ultraviolet light (λ=313 nm), a hexane solution of the diarylethene dimer (1a) turned purple blue. Upon further prolonged irradiation the color changed to blue. The purple-blue and blue colors are due to the formation of a dimer having one open- and one closed-ring forms (1b) and a dimer having two closed-ring forms (1c), respectively. Both 1b and 1c returned to 1a by irradiation with visible light (λ>500 nm). The photochromic reactivity was evaluated by measuring quantum yields of the photocyclization and photocycloreversion reactions. The photocyclization quantum yield was 0.50. The cycloreversion quantum yield from 1c to 1b (0.0026) was lower than that from 1b to 1a (0.0094).  相似文献   

3.
2,4-Di-2-hydroxyethoxy)benzylidenemalononitrile (3) was prepared and condensed with 2,4-toluenediisocyanate and 3,3-dimethoxy-4,4-biphenylenediisocyanate to yield unprecedented novel Y-type polyurethanes (4-5) containing 2,4-dioxybenzylidenemalononitrile group as a nonlinear optical (NLO) chromophore, which constitutes a part of the polymer backbone. The resulting polyurethanes 4-5 were soluble in common organic solvents such as acetone and DMF. Polymers 4-5 showed a thermal stability up to 260 °C from thermogravimetric analysis (TGA) with differential scanning calorimetry (DSC) giving Tg values around 143-156 °C. The approximate lengths of aligned NLO-chromophores estimated from AFM images of poled polymer films were about 10 nm. The SHG coefficients (d33) of poled polymer films were around 7.4 × 10−9 esu. These Poled polymers exhibited a greater thermal stability of dipole alignment even at 10 °C higher than Tg, and no SHG decay was observed below 155 °C due to the partial main chain character of the polymer structure and extensive hydrogen bonds between urethane linkage, which is acceptable for NLO device applications.  相似文献   

4.
Homo/co-poly(decyloxymethacrylate)s containing thermally reversible nitro and cyano substituted azobenzenes and thermally irreversible fulgimide units in the pendant respectively were synthesized by free radical addition polymerization method and investigated their photochromic property. The dual-mode optical switching property of copolymers F-co-N and F-co-C was investigated and revealed C-form of fulgimide in F-co-N altered the electron withdrawing nature of nitro group in the terminal azobenzene. The UV exposed films of F-co-N and F-co-C were annealed around their Tg and found that thermally reversible cis-form of azobenzene isomerized to trans-form and thermally irreversible C-form of fulgimide unaltered. Both photochromic units in the resultant film were converted into planar configurations with good fluorescence property.  相似文献   

5.
Two 1-thiazolyl-2-thienylcyclopentene derivatives, 1a and 2a, and a 1-thiazolyl-2-vinylcyclopentene derivative 3a have been synthesized in an attempt to obtain photochromic compounds which change the color from colorless to yellow, and have low photocycloreversion quantum yields and high absorption coefficients of the colored isomers. All of these compounds underwent reversible photochromic reactions. Compounds 1a and 2a in toluene solutions changed the color upon 313 nm light irradiation from colorless to orange and pink, in which absorption maxima were observed at 494 nm (ε=10,000 M−1 cm−1) and 525 nm (ε=8500 M−1 cm−1), respectively. On the other hand, the colorless toluene solution of 3a turned yellow upon irradiation with 313 nm light, in which the absorption maximum was observed at 416 nm (ε=17,100 M−1 cm−1). The photocyclization/cycloreversion quantum yields of 3 were 0.19 and 0.0014, respectively. The conversion from the open- to the closed-ring isomer of 3 in the photostationary state under irradiation with 313 nm light was close to 100%.  相似文献   

6.
This paper describes the preparation and characterization of homopolymers of 3-oligo(dimethylsiloxane)thiophene macromonomers, V-VIII, and copolymers with 3-methylthiophene. The thiophene macromonomers were prepared by hydrosilylation reaction between ω-(Si-H)-oligo(dimethylsiloxane), I-IV, and 3-propenylthiophene using a platinum-divinyltetramethyldisiloxane complex as the catalyst. The products were characterized by 1H, 13C, 29Si NMR and IR spectroscopy; DSC (differential scanning calorimetry) and GPC studies. Two distinct glass transition temperatures are observed for poly[VIII], a Tg at −79 °C corresponds to the soft oligo(dimethylsiloxane) phase and the Tg at 190 °C corresponds to the hard thiophene backbone. Homopolymers of V and VI, and copolymers may be doped with I2 to generate electronic conductive material, a copolymer of poly[V]-co-poly[3-methylthiophene] (50/50, w/w) has an electronic conductivity value of 5 × 10−5 S/cm at 25 °C. The polymers are tractable and may be molded into thin films; a number of the polymers are soluble in organic solvents. Polythiophene modified with oligosilioxanes are biocompatibile; the polymers minimally interfere with the growth of HeLa cells.  相似文献   

7.
Two novel amphiphilic BAB-type block copolymers, ADN-PEG3400-ADN and Py-PEG3400-Py containing deep blue and bluish-green fluorescent moieties were prepared using atom transfer radical polymerization (ATRP) (where, ADN = poly(9,10-di(1-naphthalenyl)-2-vinylanthracene), Py = poly(1-vinyl pyrene) and PEG3400 = poly(ethylene glycol) with Mn = 3400 g/mol). The GPC number averaged molecular weights (MW) of the block copolymers were Mn = 9600 and 13,800 g/mol, respectively, based on polystyrene MW standards. The PEG3400 segment has a melting temperature (Tm peak) at 64–65 °C, whereas the glass transition temperatures (Tg midpoint) of the ADN and Py segments were found to be 230 °C and 193 °C, respectively, and are similar to their respective homopolymers indicating complete microphase segregration. The photoluminescence (PL) emission of the copolymers ADN-PEG3400-ADN exhibited two maxima at 423.5 nm and 441.5 nm while Py-PEG3400-Py has a maximum at 488.5 nm. Both copolymers form individual spherical micelles with diameter from 30 to 90 nm for Py-PEG3400-Py and 40–160 nm for ADN-PEG3400-ADN. The micelles, however, transform into cross-linked pearl-necklace-like aggregates at polymer concentrations above 1000 ppm, which may be attributed to the physical cross-linking between adjacent spherical micelles caused by the PEG3400 segments.  相似文献   

8.
Radical polymerizations of α-allyloxymethylstyrene (1) and copolymerizations of α-(2-phenylallyloxy)methylstyrene (2) were undertaken to acquire comprehensive understanding on polymerization behavior of these dienes and to get polymers with high thermal stability and high glass transition temperature (Tg). One of the monofunctional counterparts of 1 is a derivative of α-methylstyrene, the ceiling temperature of which is low, and the other is an allyl compound that is well-known for the low homopolymerization tendency. This means that the intermolecular propagation reactions leading to pendant uncyclized units are suppressed during the polymerization of 1 to yield highly cyclized polymers. In fact, the degree of cyclization of poly(1) obtained at 140 °C attained the value 92%. Structural studies revealed that repeat cyclic units of poly(1) consist exclusively of five-membered rings. Poly(1) was found to be stable up to 300 °C, but its Tg values were detected at around 100 °C. They are considerably lower than the targeted values which should lie between 180 and 220 °C. An additional drawback of poly(1) is its low molecular weight probably due to a degradative chain transfer. For this reason, copolymerizations of 2 with 1 and with styrene were also carried out to seek for the possibility to control the thermal properties precisely. Monomer 2 was chosen, since it has been reported in our previous work that it yields polymers with thermal stability up to 300 °C and Tg higher than 250 °C. Copolymerization of 2 with styrene afforded polymers with desired thermal properties and high molecular weight.  相似文献   

9.
Matrix-assisted laser desorption/ionization (MALDI) mass spectrometry and NMR spectroscopy have been applied for characterization of novel poly-(ether-urethane)s (PolyEU) based on various diols derived from starch and two diisocyanates. First, numerous polyurethanes soft and hard blocks were prepared by polyaddition of isosorbide (3), isomannide (4) or isoidide (5) with 4,4′-diphenylmethane diisocyanate (MDI) (7) or hexane-1,6-diisocyanate (HDI) (8). The polyaddition of isoidide and MDI yields 85% of polyurethane hard block with high inherent viscosity (ηinh = 0.35 dL/g) with linear chains as the main products. In the case of polyurethane based on isosorbide and MDI a large amount of cyclic compounds was formed with relatively high viscosity (ηinh = 0.29 dL/g) and good yield (77%). This polyurethane hard block presents a high glass transition temperature (Tg = 183 °C) and an excellent thermal stability until 250 °C (Tg = 77 °C of the polyurethane soft block based on isosorbide and HDI). Second, polyaddition of an aliphatic diol (6a) based on isosorbide and MDI yielded new poly-(ether-urethane) soft-hard blocks with quantitative yield (>95%). This polymer is soluble in common organic solvents and has a number-average molecular weight of 7950 Da with a polydispersity index of 1.43. The MALDI-TOF spectrum of this poly-(ether-urethane) indicated the formation of high molar fraction of cycles (Ca and Cb). The pure cyclic poly-(ether-urethane) soft-hard block presents a Tg of 141 °C.  相似文献   

10.
A number of difluorophenyl benzoxazole (DB) monomers and 4,4′-difluorobenzophenone (DFB) were subjected to fluoro-displacement with two different phenoxides in a polar aprotic solvent. A series of novel poly(ether-ketone benzoxazole) copolymers (PAEKBOs) were more readily prepared, in which the generation of aryl-ether linkages was the copolymer forming reaction. The effects of monomer structure and polymerization conditions on the polymerization results and polymer solubility were analyzed. Copolymers 1, 2-X, 4 and 6 were obtained with high molecular weight. Copolymers 2-X and 4 showed organic solubility, especially the copolymers 2-X could dissolve in many usual organic solvents at the solid concentration of up to 20 wt%. TGA and DSC measurements confirmed that the copolymers 2-X, 4 and 6 were thermally stable up to 500 °C, and showed single enhanced Tgs and an amorphous morphology. The copolymers behaved in many respects as engineering thermoplastics. The properties and the processability of several members of the PAEKBOs offer the prospect of being candidates to substitute poly(ether-ether-ketone) (PEEK) using in a wider usage temperature range and being high performance materials for many applications as films, coatings for optical and electronic devices and gas separation membranes.  相似文献   

11.
Two series of new polyamides containing flexible ether linkages and laterally attached side rods (3a-i and 4a-i) were synthesized from 2,5-bis(4-aminophenoxy)-[1,1;4,1]terphenyl (1a) and 2,5-bis(4-amino-2-trifluoromethylphenoxy)-[1,1;4,1]terphenyl (1b), respectively, with various aromatic dicarboxylic acids by the direct phosphorylation polycondensation. The polymers were produced with high yields and moderate to high inherent viscosities (0.41-0.97 dl/g) that corresponded to weight-average molecular weights (by size exclusion chromatography) of 47,000-65,000. Except for some polyamides that derived from rigid diacids, the obtained polyamides were readily soluble in aprotic polar solvents, such as N-methyl-2-pyrrolidone (NMP) and N,N-dimethylacetamide (DMAc), and could afford flexible and tough films via solvent casting. The polymer films cast from DMAc solutions possessed tensile strengths of 85-106 MPa and initial moduli of 1.82-2.96 GPa. These polyamides showed glass-transition temperatures (Tg) in the range of 206-263 °C (by DSC) and softening temperatures (Ts) in the range of 211-253 °C (by TMA). Decomposition temperatures (Td) for 10% weight loss all occurred above 400 °C (by TGA) in both nitrogen and air atmospheres. The polyamides 4a-i derived from trifluoromethyl-substituted diamine 1b generally showed a higher solubility, Tg and Ts but lower thermal stability as compared to the analogous polyamides 3a-i based on diamine 1a.  相似文献   

12.
Phase transitions in the elpasolite-type K3AlF6 complex fluoride were investigated using differential scanning calorimetry, electron diffraction and X-ray powder diffraction. Three phase transitions were identified with critical temperatures , and . The α-K3AlF6 phase is stable below T1 and crystallizes in a monoclinic unit cell with a=18.8588(2)Å, b=34.0278(2)Å, c=18.9231(1)Å, β=90.453(1)° (a=2accc, b=4bc, c=ac+2cc; ac, bc, cc—the basic lattice vectors of the face-centered cubic elpasolite structure) and space group I2/a or Ia. The intermediate β phase exists only in very narrow temperature interval between T1 and T2. The γ polymorph is stable in the T2<T<T3 temperature range and has an orthorhombic unit cell with a=36.1229(6)Å, b=17.1114(3)Å, c=12.0502(3)Å (a=3ac−3cc, b=2bc, c=ac+cc) at 250 °C and space group Fddd. Above T3 the cubic δ polymorph forms with ac=8.5786(4)Å at 400 °C and space group . The similarity between the K3AlF6 and K3MoO3F3 compounds is discussed.  相似文献   

13.
The reactions of the trimethylsiloxychlorosilanes (Me3SiO)RR′SiCl (1a-h: R′ = Ph, 1a: R = H, 1b: R = Me, 1c: R = Et, 1d: R = iPr, 1e: R = tBu, 1f: R = Ph, 1g: R = 2,4,6-Me3C6H2 (Mes), 1h: R = 2,4,6-(Me2CH)3C6H2 (Tip); 1i: R = R′ = Mes) with lithium metal in tetrahydrofuran (THF) at −78 °C and in a mixture of THF/diethyl ether/n-pentane in a volume ratio 4:1:1 at −110 °C lead to mixtures of numerous compounds. Dependent on the substituents silyllithium derivatives (Me3SiO)RR′SiLi (2b-i), Me3SiO(RR′Si)2Li (3a-g), Me3SiRR′SiLi (4a-h), (LiO)RR′SiLi (12e, 12g-i), trisiloxanes (Me3SiO)2SiRR′ (5a-i) and trimethylsiloxydisilanes (6f, 6h, 6i) are formed. All silyllithium compounds were trapped with Me3SiCl or HMe2SiCl resulting in the following products: (Me3SiO)RR′SiSiMe2R″ (6b-i: R″ = Me, 7c-i: R″ = H), Me3SiO(RR′Si)2SiMe2R″ (8a-g: R″ = Me, 9a-g: R″ = H), Me3SiRR′SiSiMe2R″ (10a-h: R″ = Me, 11a-h: R″ = H) and (HMe2SiO)RR′SiSiMe2H (13e, 13g-i). The stability of trimethylsiloxysilyllithiums 2 depends on the substituents and on the temperature. (Me3SiO)Mes2SiLi (2i) is the most stable compound due to the high steric shielding of the silicon centre. The trimethylsiloxysilyllithiums 2a-g undergo partially self-condensation to afford the corresponding trimethylsiloxydisilanyllithiums Me3SiO(RR′Si)2Li (3a-g). (Me3)Si-O bond cleavage was observed for 2e and 2g-i. The relatively stable trimethylsiloxysilyllithiums 2f, 2g and 2i react with n-butyllithium under nucleophilic butylation to give the n-butyl-substituted silyllithiums nBuRR′SiLi (15g, 15f, 15i), which were trapped with Me3SiCl. By reaction of 2g and 2i with 2,3-dimethylbuta-1,3-diene the corresponding 1,1-diarylsilacyclopentenes 17g and 17i are obtained.X-ray studies of 17g revealed a folded silacyclopentene ring with the silicon atom located 0.5 Å above the mean plane formed by the four carbon ring atoms.  相似文献   

14.
A series of novel fluorinated polynaphthalimides (PNIs) (2a-g) were synthesized from 1,4,5,8-naphthalenetetracarboxylic dianhydride (NTDA) and trifluoromethyl (CF3)-substituted aromatic bis(ether amine)s (1a-g) by high-temperature solution polycondensation in m-cresol using isoquinoline as catalyst. Almost all the PNIs were readily soluble in polar solvents such as N-methyl-2-pyrrolidone (NMP) and N,N-dimethylacetamide (DMAc) and could be solution-cast to transparent and tough films with high tensile strengths. The PNIs exhibited high thermal stability, with glass-transition temperatures of 262-383 °C, 10% weight loss temperatures above 528 °C in nitrogen or air, and char yields at 800 °C in nitrogen higher than 50%. In comparison with analogous PNIs without the -CF3 substituents, these fluorinated PNIs revealed an enhanced solubility and better film-forming capability.  相似文献   

15.
The photochromic diarylethene, 1,2-bis(2-methyl-5-(2,2′-dicyanovinyl)-thien-3-yl)perfluorocyclopentene (1a), was synthesized by a novel method. Two kinds of single crystals of the compound were obtained depending on the different recrystallization conditions and their structures were determined by X-ray crystallographic analysis. Allomorphism of the photochromic diarylethene was discovered. The compound underwent a photochromic reaction both in solution and in the single crystalline phase of the anti-parallel conformer.  相似文献   

16.
Perfluoro(5-methylene-2,2-dimethyl-1,3-dioxolane) (1) was synthesized by utilizing a direct fluorination reaction. Compound 1 was an entirely novel monomer with difluoromethylene at position 5 on the dioxolane ring as an unprecedented polymerization site. It successfully polymerized with tetrafluoroethylene to afford copolymers, which had Tg values in the range of 60-90 °C. The content of monomer 1 in the obtained polymers was less than 20 mol%, which seemed insufficient for giving various unique properties to polymers. However, each polymer was expected to be a superior material because of their advanced thermal stability. Comparison with copolymers of 2,2-bis(trifluoromethyl)-4,5-difluoro-1,3-dioxole and tetrafluoroethylene is also discussed.  相似文献   

17.
3,4-Di-(2′-hydroxyethoxy)-4′-nitrobenzylidene II was prepared by condensation reaction of 3,4-dihydroxy-4′-nitrobenzylidene I with 1-chloro-2-ethanol. Monomer II was reacted with p-phenylene diisocyanate to yield polyurethane containing the non-linear optical chromophore 3,4-di-(2′-hydroxyethoxy)-4′-nitrobenzylidene. Polymer III shows thermal stability up to 300 °C in TGA thermogram. Tg value of the polymer obtained from DSC thermogram was 110 °C. The resulting polyurethane III was soluble in common organic solvents such as acetone, DMF and DMSO. The values of electro optic coefficient d33 and d31 of the poled polymer film were 3.15 × 10 −7 and 1.5 × 10 −7 esu, respectively.  相似文献   

18.
The hydrolytic degradation of a series of aregic carbohydrate-based polyamides derived from l-arabinose and d-xylose is described. These polyamides are those that are fully sugar-based (PA-SuSu), those derived from aldaric acids and polyalkylene diamines (PA-mSu), and those derived from diamine sugars and polyalkylene dicarboxylic acids (PA-Sun). Their physical properties and crystal structures depend on their constitution and the configuration of the carbohydrate-based moiety. The feasibility of the hydrolysis of these polyamides was, in general, related with such structural properties. Thus, the fully sugar-based PA-SuSu were amorphous, water-soluble materials, and were hydrolysed in water at 70 °C. PA-mSu were crystalline and more resistant to hydrolysis — they were degraded at pH 2 and 70 °C [Tg(s) 60-90 °C]. PA-Sun were amorphous and highly hygroscopic materials — they were hydrolysed in water at 37 °C [Tg(s) 25-40 °C].  相似文献   

19.
A new dicarboxylic acid, N-[3,5-bis(N-trimellitoyl)phenyl]phthalimide (1a), bearing three preformed imide rings was synthesized from the condensation of N-(3,5-diaminophenyl)phthalimide and trimellitic anhydride in glacial acetic acid at 1:2 molar ratio. For study of structure-properties relationship 1,3-bis(N-trimellitoyl)benzene (1b, as a reference) was also synthesized in a similar manner. 1a and 1b were characterized by spectroscopic methods and elemental analyses.A series of wholly aromatic poly(amide-imide)s with inherent viscosities of 0.63-1.09 dl g−1 was prepared by triphenyl phosphite-activated polycondensation from the triimide-dicarboxylic acid 1a and the reference monomer 1b with various aromatic diamines. All of the polymers were fully characterized by FT-IR and 1H NMR spectroscopy. The effects of the phthalimide pendent group on the polymers properties such as solubility, crystallinity, and thermal stability were investigated by comparison of the polymers. The polymers obtained from triimide-dicarboxylic acid 1a exhibited excellent solubility in a variety of solvents such as N-methyl-2-pyrrolidone, N,N-dimethylacetamide, N,N-dimethylformamide, and dimethylsulfoxide. These poly(amide-imide)s possessed glass-transition temperatures from 334 to 403 °C and exhibited excellent thermal stabilities and had 10% weight losses from 541 to 568 °C under a nitrogen atmosphere. Poly(amide-imide)s containing phthalimide pendent groups showed higher solubility, higher Tg and Td10% values than those having no phthalimide pendent groups.  相似文献   

20.
A series of poly(ether-imide)s (III) characterized by colorless, highly solubility was synthesized from 2,2-bis[4-(3,4-dicarboxyphenoxy)phenyl]propane dianhydride(BPADA) and various fluorinated aromatic diamines (Ia-h) in DMAc via polycondensation to form poly(amic acid) (II), followed by chemical (C) and thermal (H) imidization. These polymers had inherent viscosities ranging from 0.60 to 1.3 dL/g. These polyimides were highly soluble in a variety of organic solvent such as amide-type, ether-type and chlorinated solvents. Moreover, these poly(ether-imide) films were almost colorless, with an ultraviolet-visible absorption cutoff wavelength below 390 nm and low b* value (a yellowness index) of 4.6-18.0. The III series showed strength tensile of 72-101 MPa, elongation at break of 11-25%, initial modulus of 1.5-2.0 GPa. The glass transition temperature (Tg) of IIIa-h were in the range of 202-267 °C, and the decomposition temperature above 493 °C and left 40-65% char yield at 800 °C in nitrogen. They had the lower dielectric constants of 3.39-3.72 (1 MHz) and moisture absorptions in the range of 0.11-0.40%.  相似文献   

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