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1.
Several novel side‐chain liquid crystalline (LC) polysiloxanes bearing cholesteryl cinnamate mesogens and trifluoromethyl‐substituted mesogens were synthesized by a one‐step hydrosilylation reaction with poly(methylhydrogeno)siloxane, a cholesteric LC monomer cholesteryl 3‐(4‐allyloxy‐phenyl)‐acryloate and a fluoro‐containing LC monomer 4‐[2‐(3‐trifluoromethyl‐phenoxy)‐acetoxy]‐phenyl 4‐allyloxy‐benzoate. The chemical structures and LC properties of the monomers and polymers were characterized by use of various experimental techniques, such as FTIR, 1H‐NMR, 13C‐NMR, TGA, DSC, POM, and XRD. The temperatures at which 5% weight loss occurred were greater than 300°C for all the polymers, and the residue weight near 600°C increased slightly with increase of the trifluoromethyl‐substituted mesogens in the fluorinated polymer systems. The samples containing mainly cholesteryl cinnamate mesogens showed chiral nematic phase when they were heated and cooled, but the samples containing more trifluoromethyl‐substituted mesogens exhibited chiral smectic A mesophase. The glass transition temperature of the series of polymers increased slightly with increase of trifluoromethyl‐substituted mesogens in the polymer systems, but mesophase–isotropic phase transition temperature did not change greatly. In XRD curves, the intensity of sharp reflections at low angle increased with increase of trifluoromethyl‐substituted mesogens in the fluorinated polymers systems, indicating that the smectic order derived from trifluoromethyl‐substituted mesogens should be strengthened. These results should be due to the fluorophobic effect between trifluoromethyl‐substituted mesogens and the polymer matrix. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010  相似文献   

2.
The synthesis of new chiral smectic A (SA) side‐chain liquid crystalline polysiloxanes (LCPs) and ionomers (LCIs) containing 4‐allyloxy‐benzoyl‐4‐(S‐2‐ethylhexanoyl) p‐benzenediol bisate (ABB) as mesogenic units and 4‐[[4‐(2‐propenyloxy)phenyl]azo]benzenesulfonic acid (AABS) as nonmesogenic units is presented. The chemical structures of the monomers and polymers are confirmed by FTIR spectroscopy or 1H–NMR. Differential scanning calorimetry (DSC), optical polarizing microscopy, and X‐ray diffraction measurements reveal that all the polymers PI–PIV and ionomers PV–PVI exhibit SA texture. The results seem to demonstrate that the tendency toward the SA‐phase region increases with increasing sulfonic acid concentration, and the thermal stability of the SA phase is determined by the flexibility of the polymer backbones and the interactions of sulfonic acid groups. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 80: 2335–2340, 2001  相似文献   

3.
The synthesis of chiral side‐chain liquid‐crystalline polysiloxanes containing both cholesteryl undecylenate (MI) and 4‐allyloxy‐benzoyl‐4‐(S‐2‐ethylhexanoyl) p‐benzenediol bisate (MII) mesogenic side groups was examined. The chemical structures of the obtained monomers and polymers were confirmed with Fourier transform infrared spectroscopy or 1H‐NMR techniques. The mesomorphic properties and phase behavior of the synthesized monomers and polymers were investigated with polarizing optical microscopy, differential scanning calorimetry, and thermogravimetric analysis (TGA). Copolymers IIP–IVP revealed a smectic‐A phase, and VP and VIP revealed a smectic‐A phase and a cholesteric phase. The experimental results demonstrated that the glass‐transition temperature, the clearing‐point temperature, and the mesomorphic temperature range of IIP–VIP increased with an increase in the concentration of mesogenic MI units. TGA showed that the temperatures at which 5% mass losses occurred were greater than 300°C for all the polymers. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 2670–2676, 2002  相似文献   

4.
A new atom transfer radical polymerization (ATRP) initiator, namely 2‐(1,1‐bis(4‐(allyloxy)phenyl)‐3‐oxoisoindolin‐2‐yl)ethyl 2‐bromo‐2‐methylpropanoate, was synthesized starting from phenolphthalein, a commercially available and an inexpensive chemical. Well‐ defined bis‐allyloxy functionalized polystyrene macromonomers (Mn,GPC 4800–11 700 g mol?1) with controlled molecular weight and narrow molecular weight distribution (1.05–1.09) were synthesized using ATRP by varying the monomer to initiator feed ratio. The presence of allyloxy functionality on polystyrene was confirmed by Fourier transform infrared and 1H NMR spectroscopy. A kinetic study of polymerization revealed pseudo‐first‐order kinetics with respect to monomer consumption. Initiator efficiency was found to be in the range 0.80–0.95. Matrix‐assisted laser desorption ionization time of flight spectra showed a narrow molecular weight distribution with control over the molecular weight. The reactivity of the allyloxy groups on polystyrene was successfully demonstrated by quantitative photochemical thiol‐ene click reaction with benzyl mercaptan as the model thiol reagent. Furthermore, the thiol‐ene click reaction was exploited to introduce other reactive functional groups such as hydroxyl and carboxyl by reaction of α,α′‐bis‐allyloxy functionalized polystyrene with 2‐mercaptoethanol and 3‐mercaptopropionic acid, respectively. © 2014 Society of Chemical Industry  相似文献   

5.
Catalytic thermal cleavage of thiocarbonylthio end‐groups for RAFT synthesized polymers is usually accompanied by other side reactions such as chain‐scission and crosslinking. Occurrence of these side reactions depends on polymers, end‐groups, and oxidation–reduction property of reaction media in a liquid phase. Herein, well‐defined hydrophilic poly(4‐vinylpridine) (P4VP) and hydrophobic polystyrene (PS) are synthesized via a controlled RAFT polymerization in the presence of S‐1‐Dodecyl‐S′‐(R,R′‐dimethyl‐R″‐acetic acid) trithiocarbonates (DDMAT). Then their thiocarbonylthio end‐groups are cleaved through catalytic thermolysis in a liquid phase. Under the catalysis of Cu(0), all S‐containing groups can be removed at 165 °C in 3 h. To study the effect of solvent on thermolysis and microstructure of polymer, nitrobenzene of oxidation property and diethylene glycol of reduction property are chosen as solvents. Because of oxidizing property of nitrobenzene, Z groups of RAFT agent are eliminated at the same time that thiocarbonylthio end‐groups are removed. Therefore crosslinking among multipolymer chains occurs. While diethylene glycol is used as a solvent, no crosslinking occurs. Diethylene glycol is superior to nitrobenzene for synthesis of well‐defined polymer without S‐containing groups. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43992.  相似文献   

6.
GY Han  GQ Shi  LT Qu  JY Yuan  FE Chen  PY Wu 《Polymer International》2004,53(10):1554-1560
N‐Substituted pyrrole derivatives with chiral side groups have been synthesized and electrochemically polymerized in acetonitrile containing tetrabutylammonium perchlorate (TBAClO4) and (S)‐(+)‐camphor‐10‐sulfonic acid ((S)‐(+)‐CSA) or (R)‐(?)‐camphor‐10‐sulfonic acid ((R)‐(?)‐CSA). The resulting N‐substituted polypyrrole films were characterized by cyclic voltammetry, infrared, Raman and X‐ray photoelectron (XPS) spectroscopies. XPS results demonstrated that the as‐grown polymer films are preferably doped by CSA anions when the monomer and the CSA anion have the same optical rotation dispersion (ORD). Furthermore, the conductivities of the polymers synthesized in the media containing CSA with the same ORD of the corresponding monomers were measured to be about 2–10 times higher than those of polymers obtained from electrolytes without CSA. Copyright © 2004 Society of Chemical Industry  相似文献   

7.
《Reactive Polymers》1990,12(3):297-303
In this study functionalized water-swellable polyurethane ureas which were prepared by copolymerization of 3-allyloxy-1,2-propanediol with polyethyleneglycol, 4,4′-diphenylmethanediisocyanate and ethylenediamine are described. The number of reactive allyloxy groups in the polymer was determined using 1H NMR. Polymers containing 0.9 mmole or less allyloxy groups per g polymer were capable of forming water-swellable and flexible gels with good mechanical properties. The water uptake of the gels decreased as the number of allyloxy groups increased. The structure of the polymer shifted to a higher degree of phase mixing when allyloxy groups were introduced.  相似文献   

8.
A series of sulfonated poly(arylene biphenylsulfone ether) polymers containing up to two pendant sulfonic acid groups per repeat unit were successfully synthesized from 4,4′‐bis[(4‐chlorophenyl)sulfonyl]‐1,1′‐biphenyl (BCPSBP), disodium 3,3′‐disulfonate‐4,4′‐dichlorodiphenylsulfone (SDCDPS) and bisphenol A via aromatic nucleophilic displacement polycondensation. The resulting polymers were characterized by means of Fourier transform infrared and 1H NMR spectroscopy, gel permeation chromatography, differential scanning calorimetry and thermogravimetric analysis (TGA). The number‐average molecular weight (Mn) of the synthesized polymers was in the range 15 300–22 900 g mol?1, and the polydispersity indices (Mw/Mn) varied from 2.5 to 4.4. Tough membranes with SDCDPS/BCPSBP mole ratio up to 50:50 were successfully cast using N‐methyl‐2‐pyrrolidone (NMP). An increase of sulfonic acid groups in the polymer backbone resulted in increased solubility in aprotic polar solvents and glass transition temperature. The TGA curves of all the copolymers in acid form exhibited two distinct weight‐loss profiles. The influential characteristics of the polymer electrolyte membranes, such as tensile strength, water uptake, ion‐exchange capacity and proton conductivity, were characterized with respect to the pendant sulfonic acid groups. Atomic force microscopy phase images of the acid‐form membranes clearly showed the hydrophilic domains, with sizes increasing as a function of the degree of sulfonation. Copyright © 2010 Society of Chemical Industry  相似文献   

9.
Two acrylate monomers containing both mesogenic biphenyl group and photoreactive cinnamoyl group as well as different length of flexible spacers (i.e., n‐[4′‐(n‐cinnamoyloxyalkoxy)biphenyl‐4‐yloxy]alkyl acrylate, n = 4 (A4OO4C) and 6 (A6OO6C)) were synthesized for the first time. Their corresponding polymers (i.e., PA4OO4C and PA6OO6C) were obtained by free radical polymerization using AIBN as an initiator. The monomer A4OO4C showed smectic liquid crystalline phase and a clear fan texture was observed under optical polarizing microscope. However, no liquid crystalline phase was found for A6OO6C. In contrast, PA4OO4C showed no liquid crystalline phase while PA6OO6C showed a clear nematic schlieren texture during the cooling process. The optical polarized microscope of E5 cast on the top of the polymer film also showed the alignment. Furthermore, the irradiation of the polymer films by LP‐UV light led to the cycloaddition of the cinnamoyl groups, resulting in the simultaneous alignment of the biphenyl groups. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 4565–4572, 2006  相似文献   

10.
The synthesis of hemiphasmidic monomers 4‐[(3,4,5‐triethoxy)benzoyloxy]‐4′‐[(p‐allyloxy)benzoyloxy]biphenyl (M1), 4‐[(3,5‐diethoxy)benzoyloxy]‐4′‐[(p‐allyloxy)‐benzoyloxy]biphenyl (M2), and of the corresponding side‐chain liquid‐crystalline polysiloxanes (P1, P2) was carried out. For comparison, rodlike monomer 4‐[(p‐ethoxy)‐benzoyloxy]‐4′‐[(p‐allyloxy)benzoyloxy]biphenyl (M3) and its polysiloxanes (P3) were also prepared. The chemical structures of the monomers and polymers obtained were confirmed by FTIR and 1H‐NMR spectra. Their mesomorphic properties and phase behavior were investigated by differential scanning calorimetry, polarizing optical microscopy, and X‐ray diffraction measurements. The relationship between structures and properties was discussed. It was observed that M1 and M3 were enantiotropic nematic phase, M2 was monotropic mesophase, and their poly(methylsiloxanes) (P1–P3) possessed a broad range enantiotropic nematic phases and high thermal stability. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 95: 946–952, 2005  相似文献   

11.
The photodegradation processes of high‐density polyethylene (HDPE) films containing either a phthalocyanine‐based pigment, or a rutil (TiO2)‐based pigment, as well as of the unpigmented films stabilised differently were investigated during photo‐ageing, applying mechanical, gel content and XPS measurements. The phthalocyanine pigment‐containing film showed degradation characteristics (abrupt decrease of elongation at break after short irradiation period, no gel formation, high concentration of oxygen‐containing functional groups on the surface) similar to those of the films containing a low amount of stabiliser. The behaviour of the TiO2‐containing film and that of the unpigmented films containing a higher amount of stabiliser were also similar (slow decrease of elongation at break, increase of gel content, lower amount of oxygen‐containing functional groups on the surface). The concentration of oxygen‐containing functional groups in samples pigmented with phthalocyanine increased remarkably with increasing processing temperature. The results suggest that the phthalocyanine pigment influences the photostability indirectly, through reduction of the thermal stability of polymer due to the adsorption of the thermal stabiliser by the phthalocyanine pigment. Coating the surface of phthalocyanine with reactive surfactant improved the photostability of the HDPE film.  相似文献   

12.
A new, asymmetrical zinc phthalocyanine (aZnPc)‐functional photocurable copolymer was prepared by the combination of atom transfer radical polymerization and copper (I)‐catalyzed azide‐alkyne cyclo‐addition (CuAAC) click reaction and used as polymer matrix of polymer dispersed liquid crystal (PDLC) film. For this purpose, aZnPc was prepared through statistical condensation of 4‐tert‐butylphthalonitrile and 4‐pent‐4‐ynyloxyphthalonitrile. Double CuAAC click reaction between azido‐functional poly(methyl methacrylate‐co‐2‐(2‐bromoisobutyryloxy)‐ethyl methacrylate), terminal alkynyl‐substituted aZnPc, and 4‐ethynyl‐N,N‐dimethyl aniline yielded photocurable aZnPc‐functional copolymer. Thereby, synthesized copolymer was crosslinked in the presence of liquid crystalline mesogen 4′‐(octyloxy)‐4‐biphenylcarbonitrile by ultraviolet irradiation using benzophenone as initiator and ethylene glycol dimethacrylate as difunctional crosslinker. Thermal and optical properties of PDLC film were investigated by using differential scanning calorimetry and polarized optical microscopy. Smectic A liquid crystal mesophases were observed in both PDLC film and its mesogenic component 4′‐(octyloxy)‐4‐biphenylcarbonitrile. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41574.  相似文献   

13.
A novel polymer bearing coumarin pendants of 4‐allyloxy‐2H‐chromen‐2‐one (ACO) was synthesized by atom transfer radical polymerization (ATRP) in toluene at 110°C using 2‐Bromoisobutyryl bromide (BIBB), Cu (I) Br, and 2,2′‐bipyridyl (bpy) as initiator, catalyst, and ligand, respectively. The most appropriate molar concentration ratio of [ACO] : [BIBB] : [Cu (I) Br] : [bpy] was found to be 40 : 1 : 1 : 2 for controlled polymerization. Successful chain extension polymerization of poly (4‐allyloxy‐2H‐chromen‐2‐one) (PACO) confirms the livingness of the process. The activation energy (Ea) (76.26 kJ mol?1) and enthalpy of activation (ΔH?) (73.07 kJ mol?1) were in good agreement to each other proving the feasibility of the reaction and negative value of entropy of activation (ΔS?) (?320 J mol?1 K?1) supported the highly restricted movement of reacting species in transition state during polymerization. Initial polymer decomposition temperature of PACO was found to be 130°C. SEM analysis revealed that polymer surface is not smooth with pointed rod like shapes. The polymer/Ag nanocomposite was synthesized and examined in view of antibacterial effect against Enterococcus faecalis, Staphylococcus aureus, Escherichia coli, Proteus mirabilis, and Klebsiella pneumonae. PACO and its Ag nanocomposite (PACON) have been found to be active selectively against bacterial pathogen E. fecalis with minimum inhibitory concentration of 50 and 32 μg mL?1, respectively. © 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012  相似文献   

14.
A polymer comprising of 2‐acrylamido‐2‐methyl propane sulfonic acid, N, N‐dimethyl acrylamide, allyloxy‐2‐hydroxy propane sulfonic acid (AHPS), acrylic acid, and N, N‐methylene bisacrylamide was synthesized by aqueous free radical copolymerization and tested as high temperature performing fluid loss additive (FLA) in oil well cement. Successful incorporation of AHPS was confirmed and characteristic properties of the copolymer were determined using size exclusion chromatography. The FLA showed excellent water retention in cement at 200°C/70 bar. At this temperature, polymer structure changed from branched to linear and hydrodynamic size decreased by ~50%, thus indicating potential fragmentation, while performance remained unaffected by these alterations. The FLA copolymer does not viscosify cement slurries which is advantageous in high temperature well cementing. The working mechanism of the AHPS‐based copolymer was found to rely on reduction of filtercake permeability which is caused by a voluminous coprecipitate of the FLA with tartaric acid retarder, mediated by Ca2+ ions. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013  相似文献   

15.
As a part of research work to elaborate polymeric materials for metal corrosion protection, we have developed a new family of phosphonic acid‐containing polymers. The synthesis and the characterization of polysulfones bearing alkyl phosphonate ester side groups are first described. These polymers are synthesized by direct polycondensation of a phosphonate ester‐containing bisphenol by aromatic nucleophilic substitution. The physicochemical properties of the resulting polymers are described. Acidic hydrolysis of phosphonate esters results in the formation of phosphonic acid groups. A series of phosphonic acid‐containing polysulfones is therefore obtained and characterized. A preliminary evaluation of the anticorrosive properties of these polymers is described. In 0.25M Na2SO4 solution, the corrosion rate of a polymer‐coated mild steel sample is much lower than of the free metal substrate. These results suggest that phosphonic acid‐containing polysulfones might be interesting as anticorrosive coatings. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41890.  相似文献   

16.
A silicon‐containing water‐borne polyurethane (PU) polymer with hydroxyl side groups was synthesized that was stable in basic conditions and also capable of reacting with a reactive dye to form a covalently bonded dye molecule. The silicon‐containing anionic water‐borne PU prepolymer was synthesized from H12‐4,4′‐diphenylmethane diisocyanate (H12‐MDI), polytetramethylene glycol, polydimethylsiloxane (PDMS), 2,2′‐bis(hydroxymethyl), propionic acid (anionic centers), and triethyleneamine using the prepolymer mixing method. Water was then added to emulsify and disperse the resin to form an anionic water‐borne PU prepolymer. N‐(2‐Hydroxyethyl ethylene diamine) (HEDA) was used to extend the prepolymer to form a water‐borne PU polymer with a side chain of hydroxyl groups, which can further react with the reactive dye to form a dyed PU. The reactive dye of chlorosulfuric acid esters of sulfatoethyl sulfones can react with the water‐borne PU polymer. Behaviors of alkali resistance and dyeing properties were observed. In consideration of thermal properties, the dye‐grafted PU polymers exhibited lower glass‐transition temperatures for soft segments and hard segments than those without dye. Concerning mechanical properties, it was found that the modulus and the strength of the dyed PU polymers decreased with grafting of the dye molecule, but elongation at break was increased. The alkali resistance increased with PDMS content. For dye‐uptake properties, the percentage of dye grafting was over 90%. Also, the dye‐grafted PU exhibited a lower percentage of dye migration than that of polymers with ethylene diamine instead of HEDA as a chain extender, and showed greater colorfastness to light. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 2045–2052, 2003  相似文献   

17.
Poly(4‐acryloylmorpholine), poly(4‐acryloylmorpholine‐co‐2‐acrylamido‐2‐methyl‐1‐propane sulfonic acid), and poly(2‐acrylamido‐2‐methyl‐1‐propane sulfonic acid) were synthesized by radical polymerization. The water‐soluble polymers obtained, containing tertiary amino, amide, and sulfonic acid groups, were investigated, in view of their metal binding properties, as polychelatogens by using the liquid‐phase polymer‐based retention technique, under different experimental conditions. The metal ions investigated were Ag(I), Cu(II), Co(II), Ni(II), Cd(II), Pb(II), Zn(II), Cr(III), and Al(III). © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 180–185, 2006  相似文献   

18.
Thermotropic liquid‐crystalline polymers (TLCPs) have aroused considerable interest due to their attractive properties as high‐performance materials. Significant research attention has been devoted to investigating the relationship among monomer structures, syntheses and end‐use properties of TLCPs. The study reported here concerns the preparation, characterization and melt spinning of novel copolyesters containing two different flexible units together with two different aromatic units in the polymer chains. A range of copolyesters based on p‐hydroxybenzoic acid (p‐HBA), m‐hydroxybenzoic acid, p‐hydroxyphenylacetic acid and poly(ethylene terephthalate) were synthesized. The liquid crystallinity, thermal properties and degrees of crystallinity of these copolyesters were investigated using hot‐stage polarized light microscopy, differential scanning calorimetry, thermogravimetry and wide‐angle X‐ray diffraction. Copolyester fibres were characterized using scanning electron microscopy. The copolyesters were melt‐processable, thermally stable and could be processed above their melting temperatures without degradation. The degree of crystal structure was found to depend upon the content of p‐HBA. The fibres prepared showed that polymer chains had a well‐developed fibrillar structure. Novel TLCPs containing flexible units in the main chain were synthesized and characterized. Copolyesters containing p‐HBA units ranging from 55 to 70 mol% exhibited phase‐separated liquid‐crystalline morphology, appropriate melting temperatures and high thermal stability for melt processing. Copyright © 2010 Society of Chemical Industry  相似文献   

19.
The copolymers of p‐phenylene di{4‐[2‐(allyloxy) ethoxy]benzoate} (p‐PAEB) with n‐propyl methacrylate (PMA) were synthesized. The liquid crystalline behavior and thermal properties of copolymers were studied by polarizing optical microscopy (POM), differential scanning calorimetry (DSC), X‐ray diffractometer (XRD), and torsional braid analysis (TBA). The results of XRD, POM, and DSC demonstrate that the phase texture of copolymers is affected by the composition of liquid crystal units in copolymers. The POM and XRD reveal that liquid crystal monomer (p‐PAEB) and copolymers of p‐PAEB with PMA are all smectic phase texture. The dynamic mechanical properties of copolymers are investigated with TBA. The results indicate that the phase transition temperatures and dynamic mechanical loss peak temperature Tp of copolymers are affected by the composition of copolymers and liquid crystal cross networks. The maximal mechanical loss Tp is 114°C and is decreased with added PMA. The behaviors of phase transition are affected by the crosslinking density, and it is revisable for lightly crosslinking LC polymer networks, but it is nonreversible for the densely crosslinking of LC polymer networks. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008  相似文献   

20.
A series of new side-chain liquid crystalline (LC) polyacetylenes containing 4-(trans-n-alkylcyclohexanylcarbonyloxy)phenyl 4-alkynyloxybenzoate side groups were synthesized by using [Rh(nbd)Cl]2, WCl6 and MoCl5 as polymerization catalysts. The synthesized polymers were characterized by differential scanning calorimetry, optical microscopy and X-ray diffraction measurements. The monomers showed a nematic phase while all polymers revealed the nematic, smectic A and smectic C phases. X-ray diffraction measurements proved that all the polymers show an interdigitated bilayer structure. The optical properties of the polymers were investigated by UV-vis and photoluminescent spectroscopies. The polymer films emitted green-blue photoluminescence at about 500 nm.  相似文献   

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