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1.
Copolymers of aniline and toluidine were synthesized by oxidative chemical polymerization using different ratios of the monomers in the feed, and characterized by a number of techniques including UV–visible, IR, Raman, 1H NMR and EPR spectroscopies, as well as by thermogravimetric analysis and conductivity measurements. The properties of the copolymers are influenced by the amount of toluidine in the copolymer. Poly(o‐toluidine) and poly(m‐toluidine) are noticeably different in their solubility and conductivity. The copolymers show better solubilities than polyaniline but have lower conductivities. Differences in the properties of the salt and base forms of the copolymers are pointed out. Copyright © 2003 Society of Chemical Industry  相似文献   

2.
Copolymers (P(PDA/Ar)) of o‐phenylenediamine with aniline (Ar = ANi), 3,4‐ethylenedioxythiophene (Ar = EDOT) and 2,3,5,6‐tetrafluoroaniline (Ar = TFANi) were synthesized via polycondensation initiated by ammonium persulfate. The NH2 group content in the copolymers was determined by analyzing the 1H NMR spectra of the N‐acetylated copolymers. Copolymers crosslinked by viologen (1,1'‐disubstituted 4,4'‐bipyridinium dichloride) were obtained by reaction involving the reactive NH2 groups in the copolymers. The absorption wavelengths of solutions of the copolymers and the electrochemical oxidation and reduction potentials of cast films of the copolymers were affected by the electrical properties of the Ar unit. © 2016 Society of Chemical Industry  相似文献   

3.
Aromatic diamine monomers, including o‐phenylenediamine (oPD), 4‐methyl‐o‐phenylenediamine (4Me‐oPD), 4,5‐dimethyl‐o‐phenylenediamine (dMe‐oPD) and 4‐(tert‐butyl)‐o‐phenylenediamine (tBu‐oPD), were polymerized by chemical oxidation using ammonium persulfate as an oxidant. Aluminium triflate (Al(OTf)3) was also used for the first time as a co‐catalyst under various reaction conditions for the polymerization of oPD derivatives. The polymerization yield was improved when Al(OTf)3 was introduced to the polymerization reaction for most polymers. The solubility of poly(4‐methyl‐o‐phenylenediamine) (P(4Me‐oPD)), poly(4,5‐dimethyl‐o‐phenylenediamine) (P(dMe‐oPD)) and poly(4‐(tert‐butyl)‐o‐phenylenediamine) (P(tBu‐oPD)) polymers was improved compared with the poly(o‐phenylenediamine) (P(oPD)) polymers in most common solvents. The homopolymers obtained were characterized by Fourier transform IR spectroscopy, UV?visible spectroscopy, 1H and 13C NMR, wide‐angle X‐ray diffraction, DSC and TGA. The results showed that the yield, solubility and structure of the polymers are significantly dependent on the polymerization conditions. DSC measurements indicated that the polymers exhibited melting and crystallization transitions. The polymers also showed good thermal stability and decompose above 400 °C in nitrogen. © 2013 Society of Chemical Industry  相似文献   

4.
Cross‐linked hydroxy terminated polybutadiene (HTPB)‐based polyurethaneurea (PU), HTPB‐divinyl benzene (DVB)‐PU, was synthesized by a three‐step polymerization process. It was first used as membrane material to separate p‐/o‐xylene mixtures by pervaporation (PV). The effects of the content of cross‐linker DVB, feed concentration, and operating temperature on the PV performance of HTPB‐DVB‐PU membranes were investigated. The membranes demonstrated p‐xylene permselectivity as well as high total flux. The introduction of DVB significantly enhanced the temperature resistance ability of the HTPB‐DVB‐PU membranes. With increasing DVB content, the separation factor increased while the total flux decreased a little. The highest separation factor reaches 2.01 and the total flux is 33 g/m2h with feed concentration of 10 wt % p‐xylene at 30°C. These PV performances with increasing DVB content were explained in terms of the view point of chemical compositions and physical structures of the HTPB‐DVB‐PU membranes. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012  相似文献   

5.
Copolymers of sodium o‐methacryloylaminophenylarsonate (o‐MAPHA‐Na) 1 and p‐methacrylolylaminophenylarsonate (p‐MAPHA‐Na) 2 with sodium acrylate (AA‐Na) 3 , sodium methacrylate (AM‐Na) 4 and acrylamide (AAD) 5 were prepared by free radical polymerization in aqueous media at 70°C using potassium persulfate (K2S2O8) as the initiator. The total monomer concentration was carried out at 0.5M and the feed ratio ( M1 : M2 ) was varied from 10 : 90 to 90 : 10 mol%. The kinetic study was carried out by dilatometric method. The copolymer compositions were calculated by arsenic content in the copolymers. The As content (ppm) was determined by atomic absorption spectrometry (AAS). The reactivity ratios (r1, r2) were estimated by the Kelen‐Tüdös linearization method as well as error‐in‐variables method using the computer program RREVM®. In all cases, r1 < 1 and r2 > 1, indicating a tendency to form random copolymers. The values suggest that the copolymers contain a larger proportion of comonomer (i.e., AA‐Na, AM‐Na, or AAD). Weight‐average molar masses (M w) of copolymers were determined by multi‐angle light scattering. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010  相似文献   

6.
Poly(aniline‐coo‐chloroaniline) salts were synthesized by chemical copolymerization of aniline with o‐chloroaniline using three different acids. The polymer salt samples were heat treated at four different temperatures (150, 200, 275 and 375 °C) and the thermal stability of the polymer salts were studied by conductivity, electron paramagnetic resonance (EPR), infrared (IR) and electronic absorption spectral measurements. The conductivity of the copolymers could be controlled in a broad range from 10 S cm−1 for homopolymer of aniline to 10−4 S cm−1 for those of o‐chloroaniline. No structural changes took place up to 200 °C and this was confirmed from EPR, IR and electronic absorption spectra. No definite correlation exists between conductivity and spin concentration. © 2000 Society of Chemical Industry  相似文献   

7.
High‐conversion (HC) copolymers of aniline and o‐methoxyaniline (o‐anizidine) were synthesized for the first time by chemical oxidative copolymerization using various polymerization techniques (simultaneous or consecutive introduction of comonomers into the polymerizing system). Low‐conversion (LC) copolymers have also been synthesized for comparison. The polymers obtained were characterized using 1H‐NMR, infrared, and electronic absorption spectroscopy, differential scanning calorimetry, and electrical conductivity measurements. Solubility characteristics and composition of different fractions of the copolymers were also determined. It was shown that in contrast to the LC copolymers, HC copolymers reveal relatively poor solubility. Electrical conductivity of copolymers and also of o‐methoxyaniline homopolymer is lower compared to polyaniline, which correlates with notable hypsochromic (blue) shift of the bands in electronic absorption spectra. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 99: 75–81, 2006  相似文献   

8.
In this study, poly(o‐anisidine) [POA], poly(o‐anisidine‐co‐aniline) [POA‐co‐A], and polyaniline [PANi] were chemically synthesized using a single polymerization process with aniline and o‐anisidine as the respective monomers. During the polymerization process, p‐toluene sulfonic acid monohydrate was used as a dopant while ammonium persulfate was used as an oxidant. N‐methyl‐pyrolidone (NMP) was used as a solvent. We observed that the ATR spectra of POA‐co‐A showed features similar to those of PANi and POA as well as additional ones. POA‐co‐A also achieved broader and more extended UV–vis absorption than POA but less than PANi. The chemical and electronic structure of the product of polymerization was studied using Attenuated Total Reflectance spectroscopy (ATR) and UV–visible spectroscopy (UV–vis). The transition temperature of the homopolymers and copolymers was studied using differential scanning calorimetry and the viscosity average molecular weight was studied by using dilute solution viscometry. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010  相似文献   

9.
Electrochemical copolymerization of o‐dihydroxybenzene (oDHB) and 3‐methylthiophene (3MeT) was successfully achieved in boron trifluoride diethyl etherate by direct anodic oxidation of the monomer mixtures, although the oxidation potentials of oDHB and 3MeT were quite different. The influence of the applied polymerization potential on the synthesis of the copolymers was investigated. The higher applied potential favored the incorporation of 3MeT units into the copolymers. The structure and properties of the copolymers were investigated with UV‐vis spectroscopy, fluorescence spectroscopy, FTIR spectroscopy, and thermal analysis. The novel copolymers had many advantages, including good redox activity, good thermal stability, and high electrical conductivity. Additionally, the copolymers fluorescence properties that were tunable through changes in the feed ratio of the monomer mixtures. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010  相似文献   

10.
Copolymers of 2‐(o‐chlorophenyl)‐4‐methylene‐1,3‐dioxolane with methyl methacrylate and styrene were synthesized in benzene at 85 °C in the presence of 2,2′‐azobisisobutyronitrile as initiator. The structure of the resulting copolymers was investigated and a polymerization mechanism was proposed. The intrinsic viscosity of the copolymers in dilute solutions of carbon tetrachloride was determined as a function of temperature and conformational transitions were investigated. Copyright © 2004 Society of Chemical Industry  相似文献   

11.
A poly(o‐trimethylsilylphenylacetylene) [poly(o‐TMSPA)] initiated by a tungsten carbene complex was investigated under various conditions. The molar mass of poly(o‐TMSPA) increases with increasing the polymerization temperature and decreasing the initiator concentration. The X‐ray diffraction measurements show that poly(o‐TMSPA) has an amorphous structure. The water molecules preferentially permeate through the poly(o‐TMSPA) membranes. The effects of feed compositions, degree of swelling, and the molecular size of alcohols on the pervaporation performances were investigated. The separation factor and the permeation rate increase with increasing ethanol concentration in the feed. The diffusivity contributes to a major part to selective transport. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 74: 647–654, 1999  相似文献   

12.
Poly(o‐amino benzyl amine), poly(m‐amino benzyl amine), and the copolymers with aniline were synthesized in 10?4M HCl by using ammonium persulfate as oxidizing agent. The copolymers were synthesized at various feed mole fractions of comonomer diamine and characterized by elemental analysis, FTIR, 1H‐NMR spectroscopy, and electrical conductivity. The polymerization yield depended on the substituent position in the aromatic ring. Copper ion was incorporated in the polymers and the amount depended on the side groups position in the aromatic ring. The thermal stability increased when copper ions and aniline units were incorporated in the polymers. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 31–36, 2004  相似文献   

13.
Directly starting from d ,l ‐lactic acid (LA) and pyrimidine‐2,4,5,6‐tetramine (PTA), the copolymer P(LA‐co‐PTA) as a novel potential solid compatible polymeric flame retardant is synthesized as designed via melt polycondensation. When the molar feed ratio LA/PTA is 60/1, the optimal synthetic conditions are discussed. After the prepolymerization at 140°C for 8 h, using 0.5 wt % stannous oxide as the catalyst, the melt copolymerization at 160°C for 4 h gives the copolymer with the biggest intrinsic viscosity 0.88 dL g?1. The structures and properties of P(LA‐co‐PTA)s at different molar feed ratios are characterized by FT‐IR, 1H‐NMR, 13C‐NMR, GPC, XRD, DSC, and TGA. The decomposition temperatures of P(LA‐co‐PTA)s are higher than these of homopolymer poly(d,l ‐lactic acid) (PDLLA). All copolymers have higher char yield than PDLLA, and the more PTA in the feed content, the higher char yield. What's more, there are some residues at 700–800°C, indicating that P(LA‐co‐PTA)s have good charring ability. When the monomer PTA is introduced into polylactic acid by chemical bonding as purine (PU) unit formed during the condensation, both the PTA's relatively higher nitrogen content and the PU's similar structure with flame retardant benzimidazole are beneficial to improve the thermal stability and charring ability, especially the latter. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40275.  相似文献   

14.
Two oxetane‐derived monomers 3‐(2‐cyanoethoxy)methyl‐ and 3‐(methoxy(triethylenoxy)) methyl‐3′‐methyloxetane were prepared from the reaction of 3‐methyl‐3′‐hydroxymethyloxetane with acrylonitrile and triethylene glycol monomethyl ether, respectively. Their homo‐ and copolyethers were synthesized with BF3· Et2O/1,4‐butanediol and trifluoromethane sulfonic acid as initiator through cationic ring‐opening polymerization. The structure of the polymers was characterized by FTIR and1H NMR. The ratio of two repeating units incorporated into the copolymers is well consistent with the feed ratio. Regarding glass transition temperature (Tg), the DSC data imply that the resulting copolymers have a lower Tg than pure poly(ethylene oxide). Moreover, the TGA measurements reveal that they possess in general a high heat decomposition temperature. The ion conductivity of a sample (P‐AN 20) is 1.07 × 10?5 S cm?1 at room temperature and 2.79 × 10?4 S cm?1 at 80 °C, thus presenting the potential to meet the practical requirement of lithium ion batteries for polymer electrolytes. Copyright © 2005 Society of Chemical Industry  相似文献   

15.
Poly(o‐toluidine) (PoT) and poly(o‐toluidine co aniline) were prepared by using ammonium persulfate initiator, in the presence of 1M HCl. It was dried under different conditions: room temperature drying (48 h), oven drying (at 50°C for 12 h), or vacuum drying (under vacuum, at room temperature for 16 h). The dielectric properties, such as dielectric loss, conductivity, dielectric constant, dielectric heating coefficient, loss tangent, etc., were studied at microwave frequencies. A cavity perturbation technique was used for the study. The dielectric properties were found to be related to the frequency and drying conditions. Also, the copolymer showed better properties compared to PoT alone. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 592–598, 2004  相似文献   

16.
A series of conducting copolymers were synthesized by chemical oxidative polymerization of imidazole (Imi) and pyridine (Py) in acetonitrile medium at ambient temperature. The yield, solubility, and conductivity of the copolymers were measured by changing the Imi/Py molar ratio from 0/100 to 100/0. The as‐prepared Imi/Py conducting copolymers were characterized by UV‐Visible, FTIR, 1H‐NMR, DSC, TGA, and XRD. The results suggest that the resulting copolymers were more easily soluble in most of the organic solvents than in polyimidazole. The polymer obtained is a real copolymer containing imidazole and pyridine units, but the Imi content calculated on the basis of the proton NMR spectra is lower than feed Imi content. The thermostability of the Imi/Py copolymer increases with increasing Imi unit content. The copolymers show comparatively higher conductivity and higher thermal stability than the homopolymer polypyridine and are lower than those of polyimidazole. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012  相似文献   

17.
Thermal radical copolymerization of styrene (S) and maleimide (MI) at 125°C in diglyme in the presence of 2,2,6,6‐tetramethylpiperidin‐1‐yloxyl radical (TEMPO) was studied. Mole fractions of maleimide in the feed, FMI, varied in the range 0.1–0.9. A quasiliving reaction process proceeded yielding copolymers with a low polydispersity (Mw/Mn = 1.17–1.41). The found azeotropic composition, (FMI)A = 0.46, did not differ substantially from that (0.5) in the conventional radical S‐MI copolymerization. At a higher conversion or MI content in the feed, deactivation of the copolymer chains occurred. The obtained TEMPO‐terminated S‐MI copolymers readily initiated polymerization of styrene; chain extension of the macroinitiators took place, giving poly(S‐co‐MI)‐block‐poly(S) diblock copolymers. The synthesized copolymers containing S and MI units were characterized by elemental analysis, NMR spectroscopy, size‐exclusion chromatography, and differential scanning calorimetry. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 1863–1868, 2004  相似文献   

18.
Well‐defined methyl methacrylate (MMA) and 2‐(trimethylsiloxy)ethyl methacrylate (Pro‐HEMA) copolymers were prepared by atom‐transfer radical polymerization(ATRP), using CuCl/2,2′‐bipyridine as catalytic system and p‐toluenesulfonyl chloride as initiator. ATRP process of MMA and Pro‐HEMA was monitored by 1H NMR, and the kinetic curves of the MMA/Pro‐HEMA copolymerization were plotted in terms of the 1H NMR data. At low content of Pro‐HEMA in the feed composition, the copolymerization can be well controlled with the molecular weight, polydispersity and the monomer distribution in the copolymer chain. With the increase of Pro‐HEMA content in the feed mixture, the composition of the final copolymer deviates from the composition of the feed mixture gradually, and gradient copolymers of MMA/Pro‐HEMA can be obtained. Through the hydrolysis process, well‐defined copolymers of MMA/HEMA were obtained from poly(MMA/Pro‐HEMA). Copyright © 2003 Society of Chemical Industry  相似文献   

19.
Copolymers of 1‐vinyl‐1,2,4‐triazole (VTAz) and acrylic acid (AA) having different mole ratios were synthesized using free radical‐initiated solution polymerization in dimethylformamide at 70 °C with α,α′‐azobisisobutyronitrile as initiator in nitrogen atmosphere. The compositions of the synthesized copolymers for a wide range of monomer feeds were determined using Fourier transform infrared (FTIR) spectroscopy through recorded absorption bands for VTAz (1510 cm?1, C?N (triazole ring) stretching mode) and AA (1710 cm?1, C?O stretching mode) units. The structures of the copolymers were characterized using FTIR and 1H NMR spectroscopy. The copolymer compositions were also determined from 1H NMR analysis following proton signals of carboxyl group at 11.8–12.5 ppm of AA and of triazole ring at 7.5–8.1 ppm of VTAz. Monomer reactivity ratios for the VTAz‐AA pair were estimated using linear methods, i.e. Fineman–Ross (FR) and Kelen–Tüdös (KT). From FTIR evaluation, monomer reactivity ratios were calculated as r1 = 0.404 and r2 = 1.496 using the FR method and r1 = 0.418 and r2 = 1.559 using the KT method. These values were found to be very close to those obtained from NMR evaluation. The two cases r1r2 < 1 and r1 < r2 indicated the random distribution of the monomers in the final copolymers and the presence of a greater amount of AA units in the copolymer than in the feed, respectively. The observed relatively high activity of complexed growing radical‐AA? … VTAz was explained by the effect of complex formation between carbonyl groups and triazole fragments in chain growth reactions. Thermal behaviours of copolymers with various compositions were investigated using thermogravimetric and differential scanning calorimetric analyses. It was observed that thermal stabilities and glass transition temperatures of the copolymers increased resulting from complex formation between acid and triazole units. © 2012 Society of Chemical Industry  相似文献   

20.
A new main‐chain benzoxazine oligomer with o‐norbornene functionality as end groups has been designed and synthesized. As compared to traditional main‐chain type benzoxazine polymers, this benzoxazine oligomer with o‐norbornene terminal functionality can undergo further crosslinking polymerization after general ring‐opening polymerization of oxazine rings. Another main‐chain benzoxazine oligomer has also been designed based on the reaction of bisphenol‐A, 4,4′‐diaminodiphenylmethane, paraformaldehyde, and phenol for comparison. The structure of the synthesized oligomers is confirmed by 1H nuclear magnetic resonance spectroscopy and Fourier transform infrared spectroscopy (FTIR). The molecular weight has been determined by using gel permeation chromatography (GPC). The benzoxazine oligomer containing o‐norbornene functionality can polymerize with multiple polymerization mechanisms rather than the single mechanism common to traditional 1,3‐benzoxazine resins. The polymerization mechanisms are monitored by in situ FTIR and differential scanning calorimetry (DSC). Moreover, the thermoset derived from the benzoxazine oligomer containing o‐norbornene functionality exhibits high thermal stability with the transition temperature of 360 °C and a high Td5 of 404 °C. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 45408.  相似文献   

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