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1.
Alternating poly(amide urethane)s from ε-caprolactam, amino alcohols H2N-(CH2)x-OH (x=2-6), and diphenyl carbonate were prepared by polycondensation of α-hydroxy-ω-O-phenylurethanes 4a-e. The degree of oligomerization was adjusted by the conversion. Oligomers with two or three O-phenylurethane end groups and predetermined molecular weight were prepared by polycondensation of the α-hydroxy-ω-O-phenylurethanes 4a-e in the presence of comonomers with O-phenylurethane end groups in a given concentration. In order to prepare oligomers with hydroxyl and carboxyl groups at both chain ends suitable for coupling reactions, chain analogous reactions were performed with amino acids and amino alcohols. The microstructure of the polymers and the nature of end groups was determined by means of 1H NMR spectroscopy and the molecular weights were determined by means of gel permeation chromatography. The poly(amide urethane)s 5a-e prepared are semicrystalline materials with melting points between 150 and 200 °C. 相似文献
2.
The synthesis of alternating poly(amide urethane)s 5a-d was performed in three steps using ε-caprolactone, diamines, and diphenyl carbonate as starting materials. The microstructure and nature of the end groups of the poly(amide urethane)s were determined by means of 1H NMR spectroscopy, which reveals an alternating sequence of amide and urethane linkages in a linear chain with hydroxy and phenyl urethane end groups. The molecular weight and polydispersity of the polymers obtained (, ) were determined by means of gel permeation chromatography. The thermal properties determined by means of DSC show that the poly(amide urethane)s 5a-d are semicrystalline materials having one or two endothermic transitions similar to the poly(amide urethane)s 10a-d prepared from ε-caprolactam, amino alcohols, and diphenyl carbonate. Thermogravimetric analysis of poly(amide urethane)s 5a-b shows a single step decomposition, while poly(amide urethane)s 10a-c decompose in two steps indicating that different degradation mechanisms are operating. 相似文献
3.
The molecular architecture effect on active structure of miscellaneous polynorbornenes (Scheme 1) was investigated with pendant α,β-unsaturated amide or ester groups via ring-opening metathesis polymerization (ROMP). Remarkable differences in the reactivity and polymerization behavior of active norbornenes depend on various molecular architectures. Polynorbornenes derived from active norbornenes with ethylene between urethane group and ester group such as 3a,b (Scheme 1) showed excellent solubility. Organo-insoluble precipitate was obtained after ROMP of 5c with the amide group. Random copolymerization technique of bicyclo[2.2.1]hept-2-ene (NB) and 5c with amide group was considered to be a strategy to overcome the formation of precipitates, which expected to decrease the hydrogen bonding between two amide groups. High performance polynorbornenes with active groups could be designed with high potential of application for photoresist, UV curing and elastomers. Functional poly(5b) was incorporated into poly(methyl methacylate) [poly(MMA)] to produce AB cross-linked materials. The AB cross-linked material [15 wt% poly(5b), Td10=355 °C in nitrogen] had higher thermal stability than pure poly(MMA) (Td10=250 °C in nitrogen). 相似文献
4.
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
5.
Januka Budhathoki-Uprety 《Polymer》2010,51(10):2140-5954
Optically active, polycarbodiimides 3(a, b & c) with pyridine pendant groups were synthesized using [(R) - 2,2′- binaphthoxy] (di-isopropoxy) titanium(IV) catalyst. The polymers were characterized by 1H and 13C NMR, and IR. Thermal stability of these polymers (up to 162 °C by TGA), allows thermally demanding chemical transformations on their side chains without decomposition. Advantages include fine-tunability of the other pendant group of the carbodiimide monomer. This allows one to optimize the properties of the polymer without undergoing copolymerization or further post-polymerization modifications. Borane (BH3) was coordinated to poly 3 (a & b) to prepare the functional polymers 4 (a & b) respectively. A strong IR signature peak at 2368 cm−1 supports BH3 coordination. Gravimetric analysis indicates 97-99% borane complexation of the pyridine units. In addition, the thermal stability increased to 194 °C in poly 4a is consistent with the incorporation of BH3 to the pendant pyridine of the helical polycarbodiimide 3a. Poly 4 (a & b) can be used as supported reagents and successfully reduced the carbonyl compounds (5 a-e) in moderate to excellent yields (60-100%) and are shown to be efficient, non-volatile, stable, and mild supported-reducing reagents. Upon completion of the reduction reaction, the polymer support was quantitatively recycled as required for a green solid catalyst support. 相似文献
6.
Toru Katsumata 《Polymer》2009,50(6):1389-6640
The ring-opening metathesis polymerization (ROMP) of norbornene derivatives 1-5 bearing oligomeric siloxane pendant groups was carried out with Grubbs 1st and 2nd generation, and Grubbs-Hoveyda ruthenium (Ru) catalysts. Monomer 1 gave high-molecular-weight polymers (Mn ca. 27?000-180?000) in high yields (80-100%). Monomers 2-5 also polymerized with Ru carbene catalysts to give high-molecular-weight polymers (Mn ca. 34?000-240?000) in high yields (66-100%). The onset temperatures of weight loss (T0) of the polymers were 180-250 °C. The glass transition temperatures (Tgs) of poly(1) and poly(2) bearing branched siloxane linkages were near or higher than room temperature (27 and 101 °C). Meanwhile, the Tgs of poly(3)-poly(5) bearing linear siloxane linkages were much lower (−115 to −23 °C), and decreased with increasing length of the siloxane linkages. Poly(1) and poly(2) were hydrogenated completely, which was confirmed by 1H NMR spectroscopy. The free-standing membranes of poly(1) and poly(2) showed high gas permeability; especially poly(2) is the most permeable to various gases among ROMP-polynorbornene derivatives reported so far. 相似文献
7.
Novel chiral acetylene monomers bearing carbazole and triphenylamine groups, namely, (S)-3-butyn-2-yl 2-(9-carbazolyl)ethyl carbonate (1) and (S)-3-butyn-2-yl 4-(diphenylamino)benzoate (2) were synthesized, and polymerized with Rh+(nbd)[η6-C6H5B−(C6H5)3] catalyst to give the corresponding polymers with moderate molecular weights (Mn 13.0 × 103 and 15.5 × 103) in good yields (86% and 88%). CD spectroscopic studies revealed that poly(1) and poly(2) took predominantly one-handed helical structure in CHCl3. The helical structures of poly(1) and poly(2) were very stable against heating and addition of MeOH. The solution of poly(1) and poly(2) emitted fluorescence in 0.52% and 7.2% quantum yields, which were lower than those of the corresponding monomers 1 and 2 (22.5% and 76.5%). The cyclic voltammograms of the polymers indicated that the oxidation potentials of the polymers were lower than those of the monomers. The polymers showed electrochromism and changed the color from pale yellow to pale blue by application of voltage, presumably caused by the formation of polaron at the carbazole and triphenylamine moieties. The onset temperatures of weight loss of poly(1) and poly(2) were 225 and 270 °C under air. 相似文献
8.
Novel acetylene monomers containing carbazole with chiral menthyl and bornyl groups, 9-(1R,2S,5R)-menthyloxycarbonyl-2-ethynylcarbazole (1), 9-(1S,2R,5S)-menthyloxycarbonyl-2-ethynylcarbazole (2), 9-(1R,2S,5R)-menthyloxycarbonyl-3-ethynylcarbazole (3) and 9-(1S)-bornyloxycarbonyl-2-ethynylcarbazole (4) were synthesized and polymerized with a Rh catalyst to give the corresponding polymers [poly(1)-poly(4)] with moderate Mn value of (11.5-92.2) × 103 in good yields (77-89%). CD spectroscopic studies revealed that poly(1), poly(2) and poly(4) took predominantly one-handed helical structure in CHCl3, THF, toluene, and CH2Cl2, while poly(3) did not. Addition of methanol to CHCl3 solutions of poly(1) and poly(2) resulted in the formation of aggregates showing smaller CD signals at 275 and 320 nm. The helical structure of poly(1) and poly(2) was very stable against heating. The polymers emitted fluorescence in 0.40-2.90% quantum yields. Poly(4) exhibited an obvious oxidation peak at 1.10 V. The polymers were thermally stable below 300 °C. 相似文献
9.
The Sonogashira-Hagihara polymerization of 3′,5′-diiodo-N-α-tert-butoxycarbonyl-l-tyrosine methyl ester (1) and 3′,5′-diiodo-N-α-tert-butoxycarbonyl-O-methyl-l-tyrosine methyl ester (2) with para-diethynylbenzene (3) was carried out to obtain optically active poly(m-phenyleneethynylene-p-phenyleneethynylene)s [poly(1) and poly(2)] with Mn’s ranging from 9900 to 15,000 in 80-87% yields. Poly(1) exhibited intense CD signals in DMSO and THF, but did not in CH2Cl2, indicating that it took a predominantly one-handed helical conformation in the former two solvents. On the other hand, there was no evidence for poly(2) to take a helical structure in these solvents. Poly(1) turned the CD sign at 390 nm from plus to minus in DMSO/H2O = 9/1 (v/v) by the addition of NaOH. Alkaline hydrolysis of ester moieties of poly(1) and poly(2) gave the corresponding polymers having carboxy groups [poly(1a) and poly(2a)]. Poly(1a) and poly(2a) increased the CD intensity by the addition of NaOH. 相似文献
10.
Polymerizations of various ester substituted 2,5-dichlorobenzoates [substituent: linear alkyl groups (1a-f), branched alkyl groups (1g-l), cyclohexyl groups (1m-o), phenyl groups (1p-r), and oxyethylene units (1s-v)] were investigated with Ni-catalyzed/Zn-mediated system in 1-methyl-2-pyrrolidone (NMP) at 80 °C. Most of monomers bearing linear and branched alkyl groups successfully polymerized to give relatively high-molecular-weight polymers (Mn = 10,000-20,800). However, the molecular weight of the polymer having eicocyl groups was low because of steric hindrance of long alkyl chain. The polymerizations of cyclohexyl 2,5-dichlorobenzoate and phenyl 2,5-dichlorobenzoate produced low-molecular-weight polymers, while the polymerizations of monomers with alkyl cyclohexyl and alkyl phenyl groups proceeded to afford polymers with relatively high-molecular-weights. The polymers possessing oxyethylene units were obtained, but the molecular weights were low when the oxyethylene chains were long. The gas permeability of membranes of poly(p-phenylene)s with alkyl chains increased as increasing the length of alkyl chain. The membranes of poly(p-phenylene)s with phenyl groups and oxyethylene units exhibited high densities and relatively low gas permeability. However, the CO2/N2 separation factor of membrane of poly(p-phenylene) having oxyethylene units was as large as 73.6. 相似文献
11.
Pyrene-functionalized chiral methylpropargyl esters, (R)-3-butyn-2-yl-1-pyrenebutyrate [(R)-1], (S)-3-butyn-2-yl-1-pyrenebutyrate [(S)-1], (R)-3-butyn-2-yl-1-pyrenecarboxylate [(R)-2], and 3-butyn-2-yl-1-pyrenecarboxylate [(R,S)-2] were polymerized with (nbd)Rh+[η6-C6H5B−(C6H5)3] to obtain the corresponding polymers with moderate molecular weights (Mn: 10?500-66?500) in good yields (82-97%). All the polymers were soluble in CHCl3, CH2Cl2, and THF. The polarimetric and CD spectroscopic data indicated that poly[(R)-1], poly[(S)-1], and poly[(R)-2] existed in a helical structure with predominantly one-handed screw sense in these solvents. The helical structure of poly[(R)-1] and poly[(S)-1] was stable upon heating and addition of MeOH, while that of poly[(R)-2] changed upon MeOH addition. The copolymerization of (R)-1 with (S)-1 was also conducted to obtain the copolymers satisfactorily. Poly[(R)-1], poly[(S)-1], and poly[(R)-2] emitted fluorescence smaller than the corresponding racemic copolymers. The fluorescence intensity was tuned by the addition of MeOH to THF solutions of the polymers. 相似文献
12.
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
13.
Ornithine- and lysine-based novel N-propargylamides, N-α-tert-butoxycarbonyl-N-δ-fluorenylmethoxycarbonyl-l-ornithine-N′-propargylamide (1), N-α-tert-butoxycarbonyl-N-?-fluorenylmethoxycarbonyl-l-lysine-N′-propargylamide (2), N-α-fluorenylmethoxycarbonyl-N-δ-tert-butoxycarbonyl-l-ornithine-N′-propargylamide (3), and N-α-fluorenylmethoxycarbonyl-N-?-tert-butoxycarbonyl-l-lysine-N′-propargylamide (4) were synthesized and polymerized with a rhodium catalyst. Polymers with moderate molecular weights were obtained in good yields. Poly(1)-poly(4) showed strong Cotton effects in THF, whose sign and wavelength depended on the substituents. They were satisfactorily converted into the corresponding polymers [poly(1a)-poly(4a)] with free amino groups. Poly(1a) and poly(2a) also formed a helix, while poly(3a) and poly(4a) did not. Poly(1a) and poly(2a) decreased the CD intensity by the addition of m- and o-phthalic acids. 相似文献
14.
Performance improvement of polybenzoxazine by alloying with polyimide: effect of preparation method on the properties 总被引:3,自引:0,他引:3
Polymer alloys of polyimide and polybenzoxazine were prepared from the combination of a bifunctional benzoxazine monomer, 6,6′-(1-methylethylidene)bis(3,4-dihydro-3-2H-1,3-benzoxazine) (B-a) and a soluble polyimide (PI) or its precursor, poly(amide acid) (PAA), that was synthesized from oxydianiline (ODA) and bisphenol A di(phthalic anhydride) ether (BPADA). It was observed from DSC that the onset temperature for the curing exotherm of B-a in the blend with PAA was remarkably lowered compared with that of pristine B-a, while the curing temperature of B-a in the blend with PI was almost the same as that of pristine B-a. The cast films of PI/B-a or PAA/B-a were thermally treated at 150, 200 and 240 °C for 2 h each, affording deep wine, transparent films. The PI component in the polymer alloy films from PI/B-a dissolved thoroughly. On the other hand, the polymer alloy films from PAA/B-a were not soluble at all in NMP. The polymer alloy films from both PI/B-a and PAA/B-a showed only one glass transition temperature (Tg) from their viscoelastic analyses. The Tg values remarkably increased as the content of PI increased. The thermal stabilities of both films from PI/B-a and PAA/B-a increased as the PI component increased in the similar manner. 相似文献
15.
Tumula Venkateshwar Rao Yuko Uchimaru Jun-ichi Sugiyama Kazuhiko Takeuchi 《Polymer》2005,46(23):9736-9741
Treatment of a dihydrosilane (methylphenylsilane, 1) with mixtures of a diyne (p- or m-diethynylbenzene, 2a or 2b) and a triyne (1,3,5-triethynylbenzene, 3a or B,B′,B″-triethynyl-N,N′,N″-trimethylborazine, 3b; 1:2:3=100:95:5, 100:90:10, 100:80:20) in the presence of Pd-PCy3 (Cy=cyclohexyl) catalyst gave new crosslinked silylenedivinylene polycarbosilanes. In TGA the resulting crosslinked polymers tended to show higher Td5 values and higher char yields than the corresponding linear polymers. On the other hand, UV/vis absorption spectra of the crosslinked polymers obtained in the reactions of 2a or 2b with 3a exhibited increased broad peaks around 390 nm for 2a or 360 nm for 2b. Coincidently, their fluorescence spectra showed significant increase of the emission peaks in 400-550 nm. The crosslinked polymer derived from 2a and 3b, however, showed decrease of the absorption peak around 390 nm and profound depression of fluorescence peaks in 400-550 nm. 相似文献
16.
Diarylacetylene monomers having trimethylsilyl groups and other substituents (substituted biphenyl, 1a and 1b; trimethylsilylmethylphenyl, 1c-e) were synthesized and polymerized with TaCl5-n-Bu4Sn catalyst to produce the corresponding poly(diarylacetylene)s (2a-d). Polymers 2a-c had high molecular weights and were soluble in common organic solvents. Free-standing membranes of 2a-c as well as previously reported 2f-h were prepared by the solution-casting method. Desilylation of these Si-containing polymer membranes was carried out with trifluoroacetic acid to afford 3a, 3b, and 3f-h. Upon desilylation, biphenyl-containing membranes became less permeable (3a, b), whereas fluorene-containing membranes became more permeable (3f-h). In particular, 3h exhibited extremely high gas permeability (PO2 = 9800 barrers), which is about the same as that of poly(1-trimethylsilyl-1-propyne). Desilylated membranes 3a and 3f-h showed different gas permeability from that of polymers 2i-k which have the identical chemical structures and obtained directly by the polymerization of the corresponding monomers. 相似文献
17.
Novel acetylene monomers containing N-phenyl-substituted carbazole (Cz) and triphenylamine (TPA) groups, namely, 3-ethynyl-9-phenylcarbazole (1) and p-(N,N-diphenylamino)phenylacetylene (2) were synthesized, and polymerized with several Rh-, W-, and Mo-based catalysts. Poly(1) and poly(2) with high number-average molecular weights (15?500-974?000) were obtained in good yields (77-97%), when [(nbd)RhCl]2-Et3N (nbd = norbornadiene) was used as a catalyst. The polymers exhibited UV-vis absorption peaks derived from the Cz and TPA moieties at 250-350 nm and polyacetylene backbone above 350 nm. The UV-vis absorption band edge wavelengths of the polymers were longer than those of the corresponding monomers. Poly(2) exhibited a UV-vis absorption peak at a longer wavelength than poly(1) did, which indicates that poly(2) has main chain conjugation longer than that of poly(1). The molecular weights and photoluminescence quantum yields of the polymers obtained by the polymerization using [(nbd)RhCl]2-Et3N were larger than those of the Rh+(nbd)[η6-C6H5B−(C6H5)3]-based counterparts. The cyclic voltammograms of the polymers indicated that they had clear electrochemical properties; the onset oxidation voltage of poly(1) was higher than those of N-alkyl-substituted Cz derivatives. The polymers showed electrochromism and changed the color from pale yellow to blue by application of voltage, presumably caused by the formation of charged polaron at the Cz and TPA moieties. The temperatures for 5% weight loss of the polymers were around 350-420 °C under air, indicating the high thermal stability. 相似文献
18.
Chin-Ping Yang 《Polymer》2006,47(20):7021-7033
Two series of novel polyimides (5a-g and 6a-g) containing flexible ether linkages and pendent trifluoromethyl (CF3) groups were synthesized from 1,4-bis(3,4-dicarboxyphenoxy)benzene dianhydride (3a) and 1,3-bis(3,4-dicarboxyphenoxy)benzene dianhydride (3b) with various CF3-substituted aromatic bis(ether amine)s (4a-g) via ring-opening polyaddition to poly(amic acid)s, followed by thermal or chemical imidization. These polyimides were readily soluble in a variety of organic solvents and could be solution-cast into flexible and tough films. The cast films exhibited high optical transparency and almost no color, with a UV-vis absorption edge of 368-382 nm and a very low b∗ value (a yellowness index) of 6.2-15.5. They had good thermal stability with glass-transition temperatures of 186-288 °C, and most of them did not show significant decomposition before 500 °C. Moreover, these polyimide films also possessed low dielectric constants of 2.79-3.49 (at 1 MHz) and low water uptakes (<0.65 wt%). 相似文献
19.
Baolin Wang Jifu Bi Chunyu Zhang Quanquan Dai Chenxi Bai Xuequan Zhang Yanming Hu Liansheng Jiang 《Polymer》2013
A new family of iron (II) complexes (2a–h) bearing tridentate 2-pyrazolyl substituted 1,10-phenanthroline ligands were successfully prepared and characterized by IR spectroscopy, elemental analysis, and mass spectra. Complexes 2a–f and 2h were further confirmed by the X-ray crystallographic analysis. 2a, 2b, 2e, and 2f adopted distorted trigonal bipyramidal configuration. 2c displayed a distorted octahedron formed by six coordinated nitrogen atoms of the two ligands. Linked by two bridged chloride atoms, complex 2d was a centrosymmetric dimmer, and complex 2h adopted a six-coordinate distorted octahedral geometry due to the coordination of two solvent molecules. These complexes activated by alkylaluminum were examined in butadiene polymerization. In combination with AliBu3, complexes 2a–c exhibited high catalytic activity (73.5%–94.3%) at 20 °C, whereas other complexes exhibited much lower activity. Interestingly, the activity and selectivity of the complexes increased as increasing polymerization temperature. In particular, 2b and 2c displayed both high activity (99% and 80%, respectively) and trans-1,4 selectivity (95.6% and 96.2%, respectively) at 60 °C. The trans-1,4 selectivity of 2b varied as alkylaluminum used as a cocatalyst, in the following order: AliBu3 > AlOct3 > AlEt3 > AlMe3, whereas much lower trans-1,4 selectivity was observed in the cases of using MAO and MMAO. 相似文献
20.
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