Crosslinkable polyesters containing styrylpyridine segments

Polyesters containing styrylpyridine segments were synthesized with the bisphenols 2,6-di[2-(2-hydroxy-1-naphthyl)vinyl]pyridine, 2-[2-(2-hydroxy-1-naphthyl)vinyl]-8-hydroxyquinoline, and 2-(4-hydroxystyryl)-8-hydroxyquinoline as starting materials. The polyesters were characterized by inherent viscosity measurements, Fourier transform infra-red, ¹H nuclear magnetic resonance, X-ray, differential thermal analysis, thermomechanical analysis, thermogravimetric analysis, and isothermal gravimetric analysis. The polymers were amorphous or microcrystalline and were soluble in hot, polar, aprotic solvents containing 5 wt % LiCl. They showed T_g at 112–175°C and T_m at 165–295°C. After heat curing, the polyesters yielded resins which were stable up to 367–335°C in N₂ and 347–329°C in air and afforded anaerobic char yields of 72–64% at 800°C. © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 64: 1135–1141, 1997     

Characterization of commercial aliphatic hyperbranched polyesters

Commercially available Boltorn Hx (x=20, 30) hyperbranched (HB) polyesters of different theoretical core/monomer ratio (1/12 for H20 and 1/28 for H30) were characterized with respect to molar mass, composition, and structure. The results were compared to those obtained for the Boltorn H40 with a core/monomer ratio of 1/60 [?agar E, ?igon M. Macromolecules 2002;35:9913 [11]]. The main side reaction in the pseudo one-pot synthesis of Boltorn polymers is a self-condensation of bis-MPA leading to the formation of HB structures without a core molecule. These are actually branches containing an unreacted carboxyl group. The fraction of HB structures without a core molecule increases with decreasing core/monomer ratio due to the decreasing fraction of HB structures with a core molecule. Since HB structures without a core molecule are of lower molar masses than HB structures with a core molecule, they particularly decrease the number average molar masses of the samples compared to the theoretically calculated ones. The polydispersity of Boltorn Hx increases with decreasing core/monomer ratio. Some of the hydroxyl groups were found to react intramoleculary forming ether bonds. Boltorn Hx polyesters have low degrees of branching due to the limited carboxyl group conversions, low DP_n values, the presence of the core unit, and lower reactivity of hydroxyl groups in linear repeat units compared to those in terminal ones. The degree of branching according to Frey increases with decreasing core/monomer ratio.     

Thermostable polyesters containing imide and phenylquinoxaline units

Thermostable, heterocyclic polyesters containing imide and phenylquinoxaline units have been synthesized by solution polycondensation of bis(hydroxyphenylquinoxaline) derivatives with diacid dichlorides containing preformed imide rings or by the reaction of bis(aminophenylquinoxaline) derivatives with dianhydrides containing ester groups. The thermal stability of these compounds is discussed and compared with related heterocyclic polymers. Electrical properties of the polycondensates were also studied.     

含萘高性能聚酯及中间体的研究

本文介绍了含萘高性能聚酯发展、合成及应用情况,并以聚萘二甲酸醇酯、TLCP及其关键中间体2,6-萘二甲酸、2-羟基-6-萘甲酸为例,指出了国内发展的瓶颈。     

Liquid crystalline aromatic polyesters containing para-linked dimethylbiphenylene moieties

A series of liquid crystalline aromatic polyesters containing 3,3′-dimethylbiphenyl-4,4′-dicarboxylic acid and 3,4′-dimethyl-biphenyl-4,3′-dicarboxylic acid was prepared by a melt polycondensation procedure and characterized by elemental analysis, DSC and TMA measurements, and optical polarizing microscopy. An optimal composition of the copolymer having a melting temperature around 300°C is proposed and the rheological behavior is discussed. Most of the mechanical properties of this copolymer were found to be close to those of Vectra A950® used as a reference sample. © 1996 John Wiley & Sons, Inc.     

Thermotropic liquid crystalline polyesters containing naphthalenic mesogenic groups

Summary Recently, the use of naphthalene in liquid crystalline compounds has become more commonplace primarily in the industrial research into LC polymers with wholly aromatic structures. A large number of compositions have appeared in the patent literature, and have been well summarized in several recent articles. Even though a large number of LC naphthalene-containing copolyesters have been prepared and reported, much of this work deals with wholly aromatic systems which include no flexible spacers. In order to investigate the effects that the naphthalene structure has on liquid crystalline behaviour, a series of low molecular weight model compounds and polymers with flexible spacers were synthesized and characterized.     

Studies of novel water-soluble colored polyesters containing azo moiety

A series of water-soluble colored polyesters (polymeric dyes) were synthesized by interfacial polycondensation reaction of terephthaloyl chloride and various bisazodiols (monomeric dyes) that were derived from diarylidene cyclopentanone and diarylidene cyclohexanone by coupling with various diazonium salts of anthraquinone dyes containing the sodium salts of the sulfonic acid group. All the colored polyesters were characterized by their elemental analysis, IR and UV-visible spectroscopy, viscometry, solubility, and TGA. Color and dyeability of the polymeric dyes are discussed by comparing them with those of the corresponding monomeric dyes. The color fastness of the polymeric dyes show fair to very good fastness to light and very good to excellent fastness to washing, rubbing, perspiration, and sublimation. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 68: 2041–2048, 1998     

Synthesis and properties of aliphatic spirodilactam diphenol containing polyesters

A series of aromatic polyesters containing 1,6-diazaspiro[4,4]-nonane-2,7-dione were synthesized under phase-transfer conditions. The copolymers were obtained in essentially quantitative yield, theses were soluble in common organic solvents, and would readily form clear, colorless films from solution. The optimum conditions of polymerization, was obtained via polycondensation at room temperature and reaction time of 4 h in chloroform. All polymers were characterized by FTIR, GPC, viscosity, water contact angle, water absorption, TGA, DSC and TMA. The prepared polyesters showed excellent thermal stability, as measured by TGA (10 wt% loss), are only moderate due to the alicyclic component and range from 365 to 401 °C in air; however, glass transition temperatures are quite high (245-309 °C). The inherent viscosities of these solutions ranged from 0.77 to 1.40 dl g⁻¹, depending on the polyester structure. The structures of the polyesters were confirmed by FTIR spectroscopy.     

Synthesis and characterization of polyesters containing fluorescein dye units

Low molecular weight polyesters containing fluorescein units in their backbones were successfully synthesized. These fluorescent polymers showed a high solubility in most of the common organic solvents. The onset degradation temperatures of the polymers were greater than that of fluorescein. The glass transition temperatures were in the range 126-194 °C. The bathochromic fluorescence emissions in organic solutions at high concentrations, which resulted from the aggregation of fluorescein moieties, were prohibited by protecting the OH end groups with benzoyl groups. The polymer powders exhibited a maximum photoluminescence intensity at about 580 nm.     

Thermal degradation kinetics of polyesters containing mesogenic aromatic diols

A series of polyesters were synthesized by reacting structurally differing aromatic diols with either saturated (flexible) or unsaturated (rigid) dicarboxylic acid halide by a stirred interfacial polycondensation technique. Thermal degradation kinetics of these polyesters were investigated by applying Coats–Redfern and Horowitz–Metzger nonisothermal procedures. The dynamic thermogravimetry experiments were conducted in nitrogen to obtain differential thermogravimetric plots. Thermal stability of these polyesters was discussed on the basis of semiquantitative methods such as differential procedural decomposition temperature, integral procedural decomposition temperature, and fraction decomposition temperature (e.g., 10% DT). Degradation proceeded in multiple stages. The thermal degradation patterns and activation energies in these stages were discussed in relation to central bridging moieties of aromatic diol. The activation energies of these polyesters were found to be in the range of 100 to 200 kJ/mol. The effect of spacer type on activation energy was also reported. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 97: 784–792, 2005     

Synthesis of new polyesters containing phosphorus heterocycles and halogen

Two series of polyesters containing phenoxaphosphine rings and several halogens were synthesized by low-temperature solution polycondensation in the presence of triethylamine. One series, containing halogens only in the bisphenol moiety, was obtained from 2,8-dichloroformyl-10-phenylphenoxaphosphine-10-oxide and chlorinated bisphenol. In the second series, halogens belonged both to bisphenol and diacid dichlorides. For the last series, 2,8-dichloroformyl-10-(4-bromophenyl)phenoxaphosphine-10-oxide was prepared as a new monomer. All resulting polyesters were characterized by elemental analysis, reduced viscosity, IR and ¹H NMR spectroscopy, and thermogravimetric analysis. These polymers began to lose weight at about 400°C in air being seen as self-extinguishing ones.     

Aromatic polyesters (polyarylates) containing arylene sulfone ether linkages

A series of soluble aromatic polyesters (polyarylates) containing arylene sulfone ether linkages and having inherent viscosities of 0.36–1.10 dl/g were prepared by the two-phase low temperature polycondensation of 4,4′-[sulfonyl-bis(p-phenyleneoxy)]dibenzoyl chloride and 3,3′-[sulfonylbis(p-phenyleneoxy)]-dibenzoyl chloride with various bisphenols in an organic solvent-aqueous alkaline solution system in the presence of a phase transfer catalyst. Bisphenols 4,4′-[sulfonylbis(p-phenyleneoxy)]diphenol and 3,3′-[sulfonylbis(p-phenyleneoxy)]-diphenol were synthesized in quantitative yields by an improved procedure. The aromatic polyesters prepared were characterized by infrared spectroscopy, elemental analysis, solution viscosity, thermogravimetric analysis, differential scanning calorimetry and X-ray diffraction. The polyesters prepared had glass transition temperatures in the range 150–230°C and initial decomposition temperatures of 397–491°C. They gave transparent, tough and flexible films by the solution casting technique.     

Synthesis and characterization of new aromatic polyesters containing pendent naphthyl units

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 (M_n) 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     

Synthesis and characterization of aromatic polyesters containing multiple n-alkyl side chains

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.     

The b-loss process in liquid crystal polyesters containing 2,6-naphthyl groups

Dielectric and mechanical loss processes have been measured on a group of three polyesters containing 2,6-naphthyl groups in which the bordering ester linkage is joined to the naphthalene group in different ways. Systematic absences of the dielectric β loss process at about 50°C indicate that the process is associated with the naphthyl groups and neighbouring carbonyl groups undergoing a coordinated rotation motion about the main polymer axis.     

Flammability behavior of unsaturated polyesters modified with novel phosphorous containing flame retardants

Two phosphorous containing reactive flame retardants namely Triallyl phosphate (TAP) and diethylene glycol modified tetra‐allyl phosphate (DTAP) are synthesized and incorporated successfully in commercial Unsaturated polyester (UPR) in various amounts (5, 10, and 15 phr) to yield flame retardant unsaturated polyester (FRUPR) composites. The structures of reactive flame retardant monomers are confirmed by FTIR, ¹H‐NMR, and³¹P‐NMR spectroscopy. Further, FRUPR composites are characterized for their mechanical, thermal, and flame retardant properties. It is observed that tensile strength and hardness of composites are enhanced with the addition of flame retardants; however, flexural strength and impact resistance are lowered. Differential Scanning Calorimetry (DSC) study reveals that there is a significant increase in glass transition temperature with the addition of flame retardants suggesting the formation of dense and crosslinked structure in FRUPR composites. Thermal stability and the flame retardant properties are also observed to be improved with the increase in concentration of flame retardant in UPR as evidenced from Thermo‐gravimetric analysis (TGA). Beyond 10 phr concentration of flame retardants, all composites show V‐0 rating on UL‐94 test. Also, increase in phosphorous content in composites leads to gradual improvement in limiting oxygen index values. POLYM. COMPOS., 38:1483–1491, 2017. © 2015 Society of Plastics Engineers     

Hydrogen bonding in blends of polyesters with dipeptide‐containing polyphosphazenes

New biomedically erodible polymer composites were investigated. Polyphosphazenes containing the dipeptide side groups alanyl–glycine ethyl ester, valinyl–glycine ethyl ester, and phenylalanyl–glycine ethyl ester were blended with poly(lactide‐co‐glycolide) (PLGA) with lactic to glycolic acid ratios of 50 : 50 [PLGA (50 : 50)] and 85 : 15 [PLGA (85 : 15)] with solution‐phase techniques. Each dipeptide ethyl ester side group contains two N? H protons that are capable of hydrogen bonding with the carbonyl functions of PLGA. Polyphosphazenes that contain only the dipeptide ethyl ester groups are insoluble in organic solvents and are thus unsuitable for solution‐phase composite formation. To ensure solubility during and after synthesis, cosubstituted polymers with both dipeptide ethyl ester and glycine or alanine ethyl ester side groups were used. Solution casting or electrospinning was used to fabricate polymer blend matrices with different ratios of polyphosphazene to polyester, and their miscibilities were estimated with differential scanning calorimetry and scanning electron microscopy techniques. Polyphosphazenes with alanyl–glycine ethyl ester side groups plus the second cosubstituent were completely miscible with PLGA (50 : 50) and PLGA (85 : 15) when processed via solution‐casting techniques. This suggests that the hydrogen‐bonding protons in alanyl–glycine ethyl ester have access to the oxygen atoms of the carbonyl units in PLGA. However, when the same pair of polymers was electrospun from solution, the polymers proved to be immiscible. Solution‐cast miscible polymer blends were obtained from PLGA (50 : 50) plus the polyphosphazene that was cosubstituted with valinyl–glycine ethyl ester and glycine ethyl ester side groups. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Synthesis and characterization of new fluorinated aromatic polyesters containing trifluoromethylphenoxy pendant groups

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     

Group IVB metallocene polyesters containing camphoric acid and preliminary cancer cell activity

Polyesters were formed from the reaction of the salt of camphoric acid and Group IVB metallocene dichlorides using the interfacial polycondenzation process. The polyesters were formed in good yields with moderate chain lengths. Fourier transform infrared spectroscopy shows bands characteristic of the presence of both reactants with new bands characteristic of the formation of the M?O and M–O(CO) linkage present. The polymers largely exist in a bridging geometry of the carbonyl groups about the metal atom. Nuclear magnetic resonance shows the presence of bands derived from both reactants. Matrix-assisted laser desorption/ionization mass spectroscopy shows ion fragments to three units for the polymers with isotopic abundance characteristic of the presence of metal atoms in the ion fragment clusters. All the polymers exhibit good ability to inhibit all the tested cancer cell lines but the zironocene and hafnocene polymers exhibit especially good inhibition of the tested cancer cell lines that included two pancreatic cancer cell lines. They represent a potential new group of anticancer drugs.     

Synthesis and properties of aromatic polyamides and polyesters containing spiroacetal and silphenylene units

Summary New polyamides and polyesters containing spiroacetal and silphenylene units were prepared by the low-temperature interfacial polycondensation reaction of 4,4-diaminodibenzalpentaerythritol (4-ABP) or 4,4-dihydroxydibenzalpentaerythritol (4-HBP) with bis(4-chlorocarbonylphenyl)dimethylsilane (DMS) or bis(4-chlorocarbonylphenyl)diphenylsilane(DPS). The resulting polymers have inherent viscosities in the range of 0.130.90 dL/g at 30°C in N,N-dimethylacetamide. These polymers were readily soluble in various polar solvents and were able to be cast into transparent and tough films. The glass transition temperatures of the polymers were detected in the range of 161253°C in their differential scanning calorimetry traces. No evidence of melting point was observed in all polymers. The solution-casted film of polyamide (PA-I) derived from 4-ABP and DMS showed ultimate strength of 73.4 MPa and initial modulus of 13.4 GPa.