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 new organosoluble polyaspartimides containing phosphorus

Novel polyaspartimides were successfully synthesized via Michael addition reactions involving phosphorus-containing diamines and bismaleimides as monomers and using p-toluenesulfonic acid and N-N-dimethylacetamide as a catalyst and a solvent, respectively. The yields of the polymerization and the molecular weights and inherent viscosities of the polymers increased with the increasing monomers' concentrations, with an upper limit of 0.92 mol/l. All of the obtained polymers were soluble in organic solvents and showed high glass transition temperatures of 227-256 °C, good thermal stability of 360-427 °C, high char yields of 53-64% in nitrogen and 25-46% in air at 700 °C.     

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     

Synthesis and characterization of new unsaturated polyesters containing cyclopentapyrazoline moiety in the main chain

3‐p‐Hydroxyphenyl‐6‐p‐hydroxybenzylidene cyclopentapyrazoline (III) and 3‐vanillyl‐7‐vanillylidene cyclopentapyrazoline (IV) were used as new starting materials for preparing new unsaturated polyesters. The polyesters were prepared by reacting (III) or (IV) with adipoyl, sebacoyl, isophthaloyl, and terephthaloyl dichlorides utilizing the interfacial polycondensation technique. The polyester samples have been characterized by elemental and spectral analyses. The polyesters have inherent viscosities of 0.55–0.97 dL/g. All the polyesters are semicrystalline and most of them are partially soluble in most common organic solvents but freely soluble in concentrated sulfuric acid. Their glass transition temperatures (T_g) range from 103.34 to 208.81°C, and the temperatures of 10% weight loss as high as 190 to 260°C in air, indicating that these aromatic polyesters have high T_g and excellent thermal stability. Doping with iodine dramatically raised the conductivity and produced dark brown colored semiconductive polymers with a maximum conductivity in the order of 3.1 × 10^?7 Ω^?1 cm^?1. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Synthesis and characterization of new aliphatic polyesters containing methanodinaphtho[1,3]dioxocin part

A novel dinaphthodioxocin‐containing diol monomer, 8,16‐methano‐16H‐dinaphtho[2,1‐d:1′,2′‐g][1,3] dioxocin‐2,14‐diol (MDDD) was synthesized in high yield and purity through the condensation of 2,7‐dihydroxynaphthalene with malonaldehydetetramethyl acetal at room temperature. It is used as a new monomer for the synthesis of a series of novel dinaphthodioxocin‐containing aliphatic polyesters by interfacial polycondensation method. The new diol monomer was fully characterized by IR, NMR, mass spectroscopies, and elemental analysis. Optimal conditions for polyesterification were obtained via study of the model compounds. Polyesters derived from MDDD and four aliphatic diacid chlorides had inherent viscosities ranging from 0.26 to 0.38 dL/g. The chemical structure of the polymers was fully characterized by IR, NMR spectroscopies, and elemental analysis. The physical properties of the polymers were studied. All the new polymers show good thermal stability and very good solubility in most organic solvents. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

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.     

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 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.     

Synthesis and flame retardancy of phosphorus containing polycarbonate

Novel P-containing copolycarbonate was prepared via melt polycondensation of diphenyl carbonate (DPC), bisphenol-A (BPA) and 2-(6-oxid-6H-dibenz〈;c,e〉〈1,2〉oxa-phosphorin-6-yl)-1,4-benzenediol (ODOPB). The copolycarbonates were characterized by infra-red spectra, reduced viscosity, and differential scanning calorimetry. The copolycarbonates with reduced viscosities of 0.21∼0.25 dL/g were obtained in quantitative yields. These phosphorus containing copolycarbonates have excellent thermal and flame retardant properties. Owing to the incorporation of the rigid structure of ODOPB and the pendant P group, the resulting phosphorus containing copolycarbonates exhibited better flame retardancy, higher char yield, higher degradation temperature and thermal stability than homopolymers of polycarbonate (PC). High LOI value and UL 94-VO rating could be achieved with a phosphorus content of as low as 0.75% for PC, and no fumes or toxic gas emissions were observed.     

Synthesis and characterization of new aromatic polyesters and poly(ester-imide)s containing phosphorous cyclic bulky groups

New phosphorous-containing polyesters were prepared by polycondensation of 2-(6-oxido-6H-dibenz<c,e><1,2>oxaphosphorin-6-yl)-1,4-naphthalene diol, 1, with different aromatic dicarboxylic acids using a SOCl₂/pyridine condensing agent. Two poly(ester-imide)s were prepared by polycondensation in solution at high temperature of the same aromatic bisphenol 1, with diacid chlorides containing preformed imide rings. The most of the polymers were easily soluble in polar organic solvents such as N-methylpyrrolidone, N,N-dimethylformamide and chloroform. They showed high thermal stability, the decomposition temperature being in the range of 330-442 °C and glass transition in the temperature range of 193-226 °C. One of these polymers exhibited thermotropic liquid crystalline behavior. Due to the presence of phosphorus the polymers gave high char yield in termogravimetric analysis, hence good flame retardant properties.     

Synthesis of new polyesters with methacrylate pendant groups

Summary A catalytic process for synthesis of new polyesters with methacrylate pendant groups is presented. Thus, zinc succinate catalyzed reaction of succinic anhydride with glycidyl methacrylate (GMA) in dimethoxyethane gives linear oligoesters with low molecular weights (1380-2400 Da). The polyester formation takes place via simultaneous ring opening of the cyclic anhydride and oxirane units. GMA component can be partially replaced with cyclohexeneoxide to obtain polyesters with methacrylate pendant groups in various percentages. Nearly colorless waxy polymers are obtained in excellent yields (69–97%) within 48–60 h. at 90 °C. In the study structure of the polymers have been elucidated by conventional spectroscopic techniques and photo-crosslinking of ability of their thin films have been tested by monitoring intensity of methacrylate double bonds, using IR-spectrometry methodology.     

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.     

含杂环多长碳链表面活性剂的合成及性能

以对苯二酚为原料,经MANNICH反应制得含杂环中间体1、2,进一步与长链卤代烷反应制得3种含杂环的多链表面活性剂34、、5。表面活性分析显示3、4可作为润湿剂、分散剂和消泡剂等。     

光敏性含磷丙烯酸酯的合成和性能研究

将三氯氧磷分别与乙二醇及一缩乙二醇反应合成了2种双磷酸酯酰氯,将其再进一步与丙烯酸羟乙酯反应,制备了2种四官能度的UV固化含磷丙烯酸酯,通过1H-NMR和FT-IR对最终产物结构进行了表征。研究了中间反应物配比对产物收率的影响,2种含磷丙烯酸酯对UV固化体系中C==C双键转化率的影响,固化膜的热稳定性和UV固化体系的物理力学性能。结果表明:双磷酸酯酰氯与丙烯酸羟乙酯物质的量比为1:3.94～3.97时,产物收率98.9%。2种含磷丙烯酸酯25℃下黏度较低(280mPa.s),固化膜800℃残炭率较高(5.5%),附着力1级,硬度5H,剪切强度12.7MPa,是优良的紫外光固化促进剂。     

Synthesis of new versatile functionalized polyesters for biomedical applications

A new family of branched polymers was synthesized for different biomedical applications such as the preparation of targeted nanoparticulate drug carriers. They are new copolymers of hydroxy-acids and allyl glycidyl ether. The functional groups (allyl-, hydroxyl- and carboxyl-) to which various groups will be grafted are linked to the polymer backbone. The resulting polymers were characterized by ¹H NMR, ¹³C NMR, size exclusion chromatography (SEC), elemental analysis and differential scanning calorimetry (DSC). In vitro cytotoxicity assays were also conducted to ensure biocompatibility of the polymers. In order to obtain some structural evidences, different molecules have been grafted on the pendant groups. The method allows a rapid and easy synthesis of allyl-, hydroxyl- and carboxyl-branched degradable polymers for grafting various bioactive molecules.     

Synthesis and properties of phosphorus containing advanced epoxy resins

A series of advanced epoxy resins with various epoxy equivalent weights were synthesized from a reactive phosphorus‐containing diol, 2‐(6‐oxido‐6H‐dibenz[c,e][1,2]oxaphosphorin‐6‐yl)‐1,4‐dihydroxy phenylene and diglycidyl ether of bisphenol A and then cured with 4,4′‐diaminodiphenyl sulfone, phenol novolac, or dicyandiamide. The parameters of the polymerization reaction (such as reaction time, catalyst) are discussed in this article. Thermal properties of cured epoxy resins were studied using differential scanning calorimetry, dynamic mechanical analysis, and thermal gravimetric analysis. The flame retardancy of cured epoxy resins was tested by limiting oxygen index. The relations between thermal properties, flame retardancy, and epoxy equivalent weights were also studied. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 75: 429–436, 2000     

Characterization of metal-ion containing polyesters

Summary The glass transition behavior of poly(diethylene glycol-co-succinic acid) (DEGSA) and its complexes obtained in the reaction with MgO have been investigated. The number average molar mass ( ) of the DEG-SA samples prior to complexation was determined by titration of the terminal COOH groups. The glass transition temperature (T_g) was measured as a function of molar mass and Mg²⁺ ion content. The dependence of T_g on obeyed the Fox-Flory relationship. Addition of increasing amounts of MgO to DEG-SA led to a gradual increase in T_g, and a decrease in the heat capacity change (c_p). This behavior is associated with complex formation between COO^-and Mg²⁺. The decrease in c_p is a result of ion-ion and to a lesser extent ion-dipole interactions which lower chain mobility. The common limiting T_g value for the three DEG-SA samples at an Mg²⁺/COO^- ratio of ca. 0.5 approaches T_g,, which is the corresponding T_g of a polymer of infinite molar mass.     

Synthesis,characteristic, and application of new flame retardant containing phosphorus,nitrogen, and silicon

In this study, the novel halogen‐free flame retardants (PSiN, A and B), which contain phosphorus, nitrogen, and silicon, have been synthesized. The structure of PSiN‐A is characterized by fourier transform infrared spectroscopy and proton nuclear magnetic resonance, and its thermal property is studied through thermo gravimetric analysis (TGA). PSiN‐A and B were blended with polypropylene(PP) to obtain PP/PSiN composites. The flame‐retardant properties of PP/PSiN composites are estimated by Limiting Oxygen Index (LOI) values, and their degradation behaviors are investigated through TGA, under nitrogen from room temperature to 800°C. The fire performance of PP is improved by PSiN(A or B): the LOI value of PP/PSiN‐A reach 26.0 vol% and the char yield is at 27 wt% at 800°C. The phosphorus in PSiN provides possibility for the PP blends to form char, and the silicon improves the thermal stability of char. The active energies of PSiN and PP are calculated through the method of Horowitz–Metzger. POLYM. ENG. SCI. 46:344–350, 2006. © 2006 Society of Plastics Engineers