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1.
Miroslav Huski?  Majda ?igon 《Polymer》2003,44(20):6187-6193
Side-chain polyesters and polyester hydrochlorides were synthesized from α-(bis(2-hydroxyethyl)amino)-ω-(4′-methoxy biphenyl-4-oxy) alkanes with different spacer lengths (Cn-diol, n=6, 8, 10) and terephthaloyl chloride. Since N-substituted diethanolamine acts as a stronger acid acceptor than triethylamine or pyridine, polyester hydrochlorides are formed during polyesterification instead of polyesters. Polyesters can be prepared from a chloroform solution of polyester hydrochlorides by extraction of HCl. During the polyesterification, linear polymers as well as cyclic oligomers are formed. All polymers were analyzed by 1H NMR, size exclusion chromatography (SEC), differential scanning calorimetry (DSC), X-ray spectroscopy (XND) and polarizing optical microscopy (POM). Polyesters and polyester hydrochlorides differ greatly in solubility and thermal properties. Although no liquid crystalline phase transitions were detected for either kind of polymer, an ordered structure was observed in XRD experiments for both polymers and was ascribed to a crystal smectic E phase.  相似文献   

2.
Liquid crystalline polyesters based on hexanediol, dimethyl 4,4′‐biphenyldicarboxylate, and various levels of dimethyl 5‐sodiosulfoisophthalate (0–20 mol%) were prepared using a conventional melt polymerization process. The presence and quantification of the ionic functionality was surveyed using 1H NMR spectroscopy. Solution viscosities and corresponding molecular weights decreased when the ionic monomer concentration exceeded a critical value (higher than 3 mol%). Differential scanning calorimetry indicated a maximum in the isotropic transition temperature versus ionic modification at approximately 10 mol%. Dynamic mechanical analysis indicated that the glass transition temperature was suppressed due to ionic association at high concentrations (greater than 3 mol%) of ionic functionality. Polarized light microscopy and wide‐angle X‐ray diffraction were used to identify the smectic liquid crystalline and crystalline phases. © 2002 Society of Chemical Industry  相似文献   

3.
Side‐chain liquid‐crystalline copolymethacrylates (PMm's), containing para‐nitro azobenzene as the mesogenic group and 2‐hydroxylethyl methacrylate (HEMA) as a comonomer, were synthesized by radical polymerization, and their corresponding liquid‐crystalline elastomers (LCEm's) were prepared through chemical crosslinking. All of the polymers (PMm's) and the elastomers studied showed enantiotropic smectic A phases; the clearing temperature (Ti) of the PMm polymers decreased with increasing amount of HEMA, and the Ti of the corresponding LCEm's decreased compared to that of their precursors. Small‐angle X‐ray scattering studies on the copolymers quenched from their liquid‐crystalline phases indicated that the characteristic distance increased with increasing amorphous component content and thus, the amorphous components were in between the smectic layers. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 88: 2275–2279, 2003  相似文献   

4.
A series of side‐chain liquid‐crystalline methacrylic copolymers, having various amounts of 4′‐(4‐decyloxyphenyl)‐4‐(hexyloxy)‐azobenzene as the mesogenic group, were synthesized and characterized by differential scanning calorimetry, polarizing optical microscopy and X‐ray diffraction to determine their mesomorphic properties, and by UV?visible spectrometry to elucidate their optical absorption characteristics. Also, birefringence and surface relief gratings were photoinduced in the films using a laser beam of 413 nm. Copolymers with high mesogen contents display a polymorphic behavior of the smectic type. The smectic order tends to disappear as the content of mesogens in the copolymer decreases, going from extended lamellar domains of chromophores packed in a parallel position, typical for smectic liquid crystals, to small aggregates of chromophores dispersed in an amorphous matrix. Important hypsochromic shifts (Δλmax ≈ 20 nm), associated with π interactions between neighboring aromatic groups, confirm the aggregation of chromophores in lamellar structures. The light‐induced birefringence (0.005 ? 0.06) is not as high as expected but it corroborates that there exists a tight interplay between photoinduced orientation and intrinsic molecular order. Surface relief gratings were recorded in copolymers with low mesogen content (15 ? 30 mol%), showing by atomic force microscopy sinusoidal profiles with an average depth of around 150 nm. © 2013 Society of Chemical Industry  相似文献   

5.
A series of novel fluorinated aromatic polyesters containing trifluoromethylphenoxy pendant groups was synthesized by interfacial polycondensation of 2‐(4‐trifluoromethylphenoxy)terephthalyl chloride with various bisphenols in dichloromethane. The polyesters obtained in good yields had weight‐average molecular weights of 70,600–29,800 g/mol, polydispersities of 1.81–2.08, and were all amorphous. All polyesters were easily soluble in organic solvents such as N,N‐dimethylformamide, tetrahydrofuran, o‐chlorophenol, pyridine, and dichloromethane. These fluorinated polyesters showed glass transition temperature of 133–210°C, and good thermal stability with almost no weight loss up to 378°C, the 10% weight loss temperature of 472–523°C as well as char yield of 32–63% at 600°C in nitrogen. These polyester films cast from chloroform solutions exhibited tensile strengths ranging from 102 to 126 MPa, elongation at break from 6.3% to 11.7%, and tensile moduli from 2.1 to 3.3 GPa. The resulting polyester films also displayed low dielectric constants between 2.18 and 2.49 (1 MHz), high transparency with an ultraviolet‐visible absorption cut‐off wavelengths in the 332–355 nm range, and excellent electric strengths (50.4–65.6 kV/mm) and volume resistivity (2.51–6.03 × 1016 Ω cm). © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011  相似文献   

6.
The transport properties of polyelectrolytes with N‐alkyl‐N,N‐dimethyl‐N‐(2‐hydroxypropyl)ammonium chloride pendent groups (alkyl = octyl, dodecyl, or cetyl) randomly distributed along a polysaccharide backbone (dextran) in solutions were studied with viscometry and conductometry. This investigation mainly considered the influence of the side‐chain length and the solvent polarity on the polyelectrolyte behavior in salt‐free aqueous solutions. The viscometric data indicated that all the copolymers exhibited polyelectrolyte behavior, and they were plotted in terms of the Rao equation. The viscosity of the polycation with dodecyl as alkyl substituent was also measured in solvent mixtures of water and methanol. The conductometric behavior of these cationic polysaccharides was found to be influenced by the alkyl side‐chain length and the solvent polarity. A nonlinear dependence of the equivalent conductivity on the dielectric constant of the solvent was observed. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2009  相似文献   

7.
Two bisphenols, viz., 4,4′‐[1‐(2‐naphthalenyl)ethylidene]bisphenol and 4,4′‐[1‐(2‐naphthalenyl) ethylidene]bis‐3‐methylphenol were prepared by condensation of commercially available 2‐acetonaphthanone with phenol and o‐cresol, respectively. A series of new aromatic polyesters containing pendent naphthyl units was synthesized by phase‐transfer‐catalyzed interfacial polycondensation of these bisphenols with isophthaloyl chloride, terephthaloyl chloride, and a mixture of isophthaloyl chloride/terephthaloyl chloride (50 : 50 mol %). Inherent viscosities of polyesters were in the range 0.83–1.76 dL g−1, while number average molecular weights (Mn) were in the range 61,000–235,000 g mol−1. Polyesters were readily soluble in organic solvents such as dichloromethane, chloroform, tetrahydrofuran, m‐cresol, pyridine, N,N‐dimethylformamide, N,N‐dimethylacetamide, and 1‐methyl‐2‐pyrrolidinone at room temperature. Tough, transparent, and flexible films were cast from a solution of polyesters in chloroform. X‐Ray diffraction measurements displayed a broad halo at 2θ ≅ 19° indicating the amorphous nature of polyesters. Glass transition temperatures of polyesters were in the range 209–259°C. The temperature at 10% weight loss (T10), determined by TGA in nitrogen atmosphere, of polyesters was in the range 435–500°C indicating their good thermal stability. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010  相似文献   

8.
Structural study of two grafted polyesters, which were different in mechanical properties, was investigated by DMA, TEM, and high‐resolution solid‐state 13C‐NMR. Using DMA and TEM, a separated phase larger than 100 nm was not found in the grafted polyesters. The main chain and the side chain seemed miscible. Analysis of T1ρHs and their distributions made the difference of microstructure in the grafted polyesters clear. P(EA‐AA)‐grafted polyester, which was very brittle, had a separated phase in the grafted polyester. The separated phase was estimated to be at a size of about 3 nm. On the other hand, P(St‐DEF‐MAnh)‐grafted polyester, which was very ductile, had a homogeneous microstructure. The difference in the microstructures of the grafted polyesters seemed to effect the mechanical properties of the grafted polyesters. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 78: 392–402, 2000  相似文献   

9.
BACKGROUND: Hyperbranched polymers have received increasing attention in the fields of medicine, homogeneous catalysis and materials science. Hydroxyl‐functional aliphatic polyesters are one of the most widely investigated families of hyperbranched polymers. The research reported here is based on the preparation of a novel hyperbranched polyester and the modification of its terminal hydroxyl groups by biphenyl mesogenic units. RESULTS: 2,2,6,6‐Tetramethylolcyclohexanol as a core and 8‐[4′‐propoxy(1,1‐biphenyl)yloxy]octanoic acid as a mesogenic unit were synthesized. A hyperbranched polyester (HPE) was synthesized in one step and subsequently substituted by reaction of its terminal hydroxyl groups with the biphenyl mesogenic units to yield a novel liquid crystalline hyperbranched polyester (HPE‐LC). The chemical structures of all compounds were confirmed using Fourier transform infrared, 1H NMR and 13C NMR spectroscopy. The thermal behavior and the mesogenic properties of the biphenyl mesogenic unit and HPE‐LC were investigated using differential scanning calorimetry, polarized optical microscopy and wide‐angle X‐ray diffraction. The results demonstrated that the degree of branching of the HPE is ca 0.63. Both HPE‐LC and the biphenyl mesogenic unit exhibit mesomorphic properties, but HPE‐LC has a lower isotropic transition temperature and a wider transition temperature range than the biphenyl mesogenic unit. CONCLUSION: A novel liquid crystalline hyperbranched polyester was successfully synthesized, which exhibits mesomorphic properties. This polymer has good solubility in highly polar solvents and good thermal stability. Copyright © 2009 Society of Chemical Industry  相似文献   

10.
Mechanical properties of semi‐interpenetrating polymer network (semi‐IPN) elastomers consisting of chemical networks and self‐associative/non‐associative guest chains are demonstrated. Amorphous low Tg polyesters with thiol side groups (PE‐SH) are first synthesized by melt polycondensation. PE‐SH are then converted to polyesters containing COOH side groups (PE‐COOH) and amide side groups (PE‐amide) through Michael addition reaction of thiol groups with acrylic acid and acrylamide, respectively. Homogeneous semi‐IPN elastomers are obtained by thermal cross‐linking for bulk mixtures of PE‐COOH and PE‐amide in the presence of diepoxy cross‐linkers, where COOH and epoxy groups are reacted to form chemical cross‐links while the amide units form self‐complementary hydrogen bonds. Another sample containing non‐associative chains is also prepared by using polyester with N,N‐dimethylamide units, instead of PE‐amide. Dynamic mechanical analysis reveals that guest chain incorporation systematically brings plateau modulus reduction and a unique relaxation with higher tan δ value depending on the fraction and nature of guest chains. Tensile properties are also affected by the fraction and nature of guest chains; the incorporation of hydrogen bonded chains are beneficial to enhance breaking elongation and toughness without the sacrifice of maximum stress. The knowledge found in this work will be thus beneficial for creating tough soft materials with damping applications.  相似文献   

11.
A series of wholly carborane‐containing polyesters with high thermostability were successfully synthesized by the catalytic polycondensation of carborane diol monomers with carborane diacid chlorides. They can be used for the preparation of materials of high temperature resistant coatings and adhesive. The influence of solvent, reaction temperature, and reaction time on the molecular weight and yield of the polymers were studied. In comparison with the carborane‐free polyester, the carborane‐containing polyesters showed higher degradation temperature and char yield and lower degradation rate. The thermal gravimetric analyzer (TGA) curves indicate that the carborane group could effectively reduce the degradation rate of carborane‐containing polyesters, which give a char yield of exceeding 64% under air (47% under N2) at 700 °C. Such data are superior to the carborane‐free polyester, which showed a low char yield of around 0.3% under air (5% under N2) at the same condition. Moreover, the thermal transition mechanism of carborane‐containing polyesters was also studied. The FTIR spectra and TG‐FTIR analysis indicate that the carborane cage could react with oxygen to form BOB and BC linkages at elevated temperatures, which postpones the thermal decomposition of polyester and accounts for the high char yield. The newly prepared kind of high temperature polyesters have enormous technical and economic value, especially in the high temperature fields. They can be widely used as raw materials to prepare the high temperature resistant coatings or adhesives for automotive engine, aircraft and other equipments worked in high‐temperature environments. Under high environmental temperature, the good thermal stability is capable of keeping polyesters stable and expanding their service lives. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 44202.  相似文献   

12.
A series of thermotropic side‐chain liquid‐crystalline ionomers (LCIs) containing 4‐(4‐alkoxybenzyloxy)‐4′‐allyloxybiphenyl (M) as mesogenic units and allyl triethylammonium bromide (ATAB) as nonmesogenic units were synthesized by graft copolymerization upon polymethylhydrosiloxane. The chemical structures of the polymers were confirmed by IR spectroscopy. DSC was used to measure the thermal properties of these polymers. The mesogenic properties were characterized by polarizing optical microscopy, DSC, and X‐ray diffraction. Homopolymers without ionic groups exhibit smectic and nematic mesophases. The nematic mesophases of the ionomers disappear and the mesomorphic temperature ranges decrease with increasing concentration of ionic units. The influence of the alkoxy chain length on clearing temperature (Tc) values of ionomers clearly shows an odd‐even effect, similar to that of other side‐chain liquid‐crystalline polymers. The mesomorphic temperature ranges increase with increasing alkoxy chain length when the number of alkoxy carbon is over 3. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 2879–2886, 2003  相似文献   

13.
The synthesis and investigation are reported for the phase behavior of a set of three liquid-crystalline side chain polyesters (SCLCPs), consisting of aromatic diacids and diols bearing cyano biphenyl moieties in the side chain. The materials contain a chiral center in the main chain and show a cholesteric phase indicative of a helical order with a preferred twist. In addition, they exhibit Tg's below room temperature and smectic bilayer phases. Depending on the substitution pattern of the aromatic core, Sc* or SA* phases are observed. These polymers were synthesized in a four-step synthesis, starting from available materials. The dielectric relaxation behavior and the pyroelectric responses of the three SCLCPs tend to conform to their respective structure.  相似文献   

14.
The aliphatic polyesters with high molecular weight have been prepared according to two methods. First is the synthesis of the polyesters by polycondensation of dimethyl succinate (DMS) with 1,4‐butanediol (BD) using various metal alkoxides as a catalyst. Among the metal alkoxides used, titanium tetraisopropoxide [Ti(OiPr)4] gave the best results (highest molecular weight and yield). Thus, we have prepared aliphatic polyesters using a variety combinations of diesters [MeOOC—(CH2)x—COOMe, x = 2–8] with BD by the catalysis of Ti(OiPr)4. The polyesters with high number‐average molecular weight (Mn > 35,000), except dimethyl adipate (DMA, x = 4)/BD polyester (Mn = 26,900), were obtained in high yield. The melting temperatures (Tm) of polyesters were relatively low (43.4–66.8°C) except that (115.6°C) of the DMS/BD polyester. Second is the synthesis of high molecular weight polyesters by chain extension reaction of lower molecular weight (Mn = 15,900–26,000) polyesters using hexamethylene diisocyanate (HDI) as a chain extender. The Mn values of chain‐extended polyesters consequently increased more than two times (Mn = 34,700–56,000). The thermal properties of polyesters hardly changed before and after chain extension. Enzymatic degradations of the polyesters were performed using three different enzymes (cholesterol esterase, lipase B, and Rhizopus delemar lipase) before chain extension. The enzymatic degradability varied depending on both thermal properties of polyesters [melting temperature and heat of fusion (crystallinity)] and the substrate specificity of enzymes, but it was the following order: cholesterol esterase > lipase B > R. delemar lipase. The 1H‐NMR spectrum of water‐soluble degraded products of the polyester indicated that the polyester was degraded into a condensation product of diol with diester in a monomer form. The enzymatic degradation of chain extended polyesters was slightly smaller than that before chain extension, but proceeded steadily. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 80: 340–347, 2001  相似文献   

15.
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   

16.
Effect of ethyl and n‐octyl branches on the properties of poly(ethylene adipate) (PEA) and poly(butylene succinate) (PBS) were investigated. Glass transition and melting temperature, crystallinity, melt viscosity, and spherulite growth rate were decreased with an increase in the degree of the chain branches. Introduction of ethyl branches as well as n‐octyl branches into PEA did not improve the tensile strength and modulus, while it reduced elongation and tear strength significantly. The presence of glycerol units less than 0.05 mol/mol of diacid units in PEA as well as in PSB also brought about damaging effects on the properties. Additional amount of glycerol units in the polyesters resulted in the formation of gel. However, addition of n‐octyl branches improved elongation and tear strength of PBS considerably without a notable decrease of tensile strength and modulus. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 77: 547–555, 2000  相似文献   

17.
The absorption spectra of two hemicyanine fluorescent dyes, namely, trans‐4‐[p‐(N,N‐di(2‐hydroxyethyl))‐amino‐styryl]‐N‐ethyl pyridinium bromide (DHEASPBr‐C2) and trans‐4‐[p‐(N,N‐di(2‐hydroxyethyl))‐amino‐styryl]‐N‐octyl pyridinium bromide (DHEASPBr‐C8), were studied at various levels of pH and high temperatures, and were then employed to dye cationic dyeable polyester. Their dyeing properties, fluorescent reflectance and colorimetric properties were explored. The novel fluorescent dyes existed in two forms of monocation and dication in solutions at low pH and high temperature. Overall, the influence of pH on colour depth and the maximum reflectance of dyed cationic dyeable polyester was extremely small. The adsorption mechanism of DHEASPBr‐C2 and DHEASPBr‐C8 on cationic dyeable polyester fibres was in good accord with the Langmuir type. Compared with DHEASPBr‐C2, DHEASPBr‐C8 exhibited comparatively faster adsorption rate, higher affinity and dye uptake, while its fluorescence shown by cationic dyeable polyester was slightly weak.  相似文献   

18.
A series of 2,2′-disubstituted-4,4′-dihydroxybiphenyl monomers was prepared from 3,4,5-tris(n-alkoxy)benzyl chlorides (n = 5, 6, 8, 10, 12) and tetramethylammonium salt of 4,4′-dihydroxydiphenic acid, which was synthesized from two different 5-step routes. 2,2′-Bis(trifluoromethyl)-4,4′-biphenyldicarboxylic acid was synthesized via 5-step route. A series of aromatic polyesters containing multiple alkyl side chains was prepared from the 2,2′-disubstituted-4,4′-dihydroxybiphenyl monomers and 2,2′-bis(trifluoromethyl)-4,4′-biphenyldicarboxylic acid using diisopropylcarbodiimide as a dehydrating agent and 4-(dimethylamino)pyridinium 4-toluenesulfonate as a catalyst at room temperature. Their thermal and solution properties were measured and compared with the polyester without multiple alkyl side chains. The polyesters displayed better solubility in common solvents such as chlorinated solvents and THF but lower thermal stability than the polyester without multiple alkyl side chains. The intrinsic viscosities of the polyesters ranged from 0.68 to 2.53 dL/g and their number-average molecular weights ranged from 19,300 to 61,400. Polyesters containing C5–10 side chains were amorphous while the two polyesters containing C12 side chains crystallized at ?27 and ?31 °C, respectively. The thermal stability of the polyesters decreased as a result of alkyl side chains. The films of polyesters were opaque, indicating that the aromatic backbones and aliphatic side chains underwent phase separation.  相似文献   

19.
Three series of main‐chain liquid‐crystalline polymers (P1, P2, and P3) were synthesized by an interfacial condensation reaction of sebacoyl dichloride with various amount of brilliant yellow, isosorbide, and 4,4′‐biphenydiol. P1 series are polyesters prepared from sebacoyl chloride and various amount of 4,4′‐biphenyldiol and isosorbide. P2 series are polyesters prepared from sebacoyl chloride and various amount of 4,4′‐biphenyldiol, brilliant yellow, and isosorbide. P3 series are polyesters prepared from sebacoyl chloride and various amount of 4,4′‐biphenyldiol and brilliant yellow. P2 and P3 are main‐chain liquid‐crystalline ionomers. P12 and P3 series were prepared as model polymers for comparison with the liquid crystalline behavior of ionomers, P2 series. The structures of the polymers were characterized by IR and UV spectroscopy. Differential scanning calorimetry was used to measure the thermal properties of the polymers. The mesogenic properties were investigated by polarized optical microscope, differential scanning calorimetry, and X‐ray diffraction measurements. The results show that P2 series are chiral smectic C (SmC*) and chiral smectic B (SmB*) liquid crystalline ionomers exhibiting broken focal‐conic texture and schlieren, as is the polymer P12, which has the same amount of 4,4′‐biphenydiol and isosorbide. The introduction of ionic units in P2 series leads to an increase of clearing point, but has not affected the mesogenic type and texture, as compared with the corresponding polymer P12. The introduction of chiral units in P2 series leads to a change of mesophase, as compared with P3 series, which exhibit smectic C mesogetic phase. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 99: 1254–1263, 2006  相似文献   

20.
Abstract

The interfacial tension (IFT) of 1 M solutions of N,N‐dialkyl amide in n‐dodecane against water and nitric acid has been measured at 303 K. Ten amides, namely, dibutyl hexanamide (DBHA), diisobutyl hexanamide (DiBHA), dibutyl octanamide (DBOA), dihexyl hexanamide (DHHA), dibutyl dodecanamide (DBDA), di n‐octyl butanamide (DOBA), diisooctyl butanamide (DiOBA), di n‐octyl isobutanamide (DOiBA), di n‐hexyl octanamide (DHOA), and di n‐octyl hexanamide (DOHA) were synthesized and used. The effect of concentration of DOHA on IFT against 3 M nitric acid was also studied. It was observed that the introduction of branching in an amide on either the acyl or the nitrogen side increases the IFT over its straight chain analogue, as in the case of DiOBA, DOiBA, and DiBHA. Increasing the carbon chain length on the acyl side, keeping the total carbon number constant, was found to increase the IFT considerably. Increasing the concentration of the amide resulted in a decrease in the IFT values, due to the lowering of the concentration of hydrophobic diluent. An increase in the uranium loading of the organic phase in the case of 1 M DOHA, was found to increase the IFT.  相似文献   

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