Synthesis and characterization of siloxane copolyesters containing phenylindane linkages

A novel series of siloxane copolyesters containing 1,1,3‐trimethyl‐3‐(p‐hydroxyphenyl)‐5‐indanol (phenylindane bisphenol), diphenyl terephthalate (DPT), diphenyl isophthalate (DPI), and eugenol end‐capped siloxanes in varying ratios were prepared at a temperature range of 200–290°C under reduced pressure using dibutyl tin dilaurate catalyst by melt polycondensation. The siloxane‐containing copolyesters were characterized by infrared and ¹H NMR spectroscopy, elemental analysis, solution viscosity, thermogravimetric analysis, differential scanning calorimetry, and X‐ray diffraction. The effect of incorporation of siloxane moiety was studied on the properties of phenyl indane/DPT/DPI coplyester. The glass transition temperatures of copolyesters were decreased from 235 to 124°C by incorporation of 10% eugenol end‐capped siloxane without affecting the thermal properties. All copolyesters were found to be soluble in commonly used organic solvents and had film forming properties. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 2668–2674, 2006     

Synthesis and characterization of copolyarylates using tin octoate as a catalyst

A series of copolyarylates of bisphenol A (BPA) with varying ratios of diphenyl terephthalate (DPT) and diphenyl isophthalate (DPI) were prepared by melt polymerization at a temperature ranging from 200 to 290°C under reduced pressure in the presence of tin octoate catalyst. Tin octoate catalyst has been extensively used for the preparation of biodegradable polymers namely, poly(lactic acid), poly(glycolic acid), and poly(lactide‐glycolide) copolyesters. However, there are no reports on the preparation of copolyesters by melt polymerization using tin octoate catalyst. The effect of tin octoate catalyst was studied on the preparation of BPA/DPT/DPI copolyarylates. The copolyarylates were characterized by infrared and ¹H NMR spectroscopy, solution viscosity, thermogravimetric analysis, differential scanning calorimetry, and X‐ray diffraction. The solution viscosities of copolyarylates were varied from 0.43 to 0.56 dL/g and the glass transition temperature (T_g) of copolyarylates was varied from 155 to 222°C by varying the ratio of DPT and DPI. Most of the copolyarylates were found to be soluble in commonly used organic solvents and had film‐forming properties. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 70–77, 2006     

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 thermal characterization of random poly(butylene terephthalate‐co‐2‐methyl‐ethylene terephthalate) copolyesters

Poly(butylene terephthalate‐co‐2‐methyl‐ethylene terephthalate) (PBT/MET) was synthesized by incorporating 1,2‐propandiol(1,2‐PDO) into PBT chains. The molar composition and chemical structure of PBT/MET copolyesters were confirmed by means of FT‐IR and ¹H‐NMR. To investigate the effect of 1,2‐PDO on the thermal properties of PBT/MET copolyesters, the copolymerizations were carried out by varying various contents of MET units, and the prepared materials were evaluated by differential scanning calorimetry and thermogravimetric analysis. Results suggested that with the increase of the content of 1,2‐PDO, the amount of crystallinity and the melting temperature decline, while the glass transition temperature increases and the copolyesters become more transparent and brittle with respect to PBT homopolymer. In addition, the T_g‐composition and T_m‐composition data are well subjected to the Wood equation and Flory's equation, respectively. All these copolyesters are found to consist of the general trend displayed by copolymers reported elsewhere. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

New polymer syntheses VIII. Synthesis,characterization and morphology of new unsaturated copolyesters based on dibenzylidenecycloalkanones

A new interesting class of linear, unsaturated copolyesters based on dibenzylidenecycloalkanones has been synthesized by interfacial polycondensation of isophthaloyl chloride or sebacoyl chloride with 2,5-bis(p-hydroxybenzylidene) cyclopentanone I, 2,6-bis(p-hydroxybenzylidene) cyclohexanone II, 2,6-divanillylidenecyclohexanone III or 2,7-bis(p-hydroxybenzylidene)cycloheptanone IV at ambient temperature. The resulting copolyesters were characterized by elemental analyses, IR spectroscopy, and solubility. Additionally, inherent viscosities of copolyesters in the range 0·53–0·98dlg⁻¹ were determined. The thermal properties of the polymers were evaluated by TGA and DSC measurements and correlated with their structural units. The crystallinity of some copolyesters was examined by X-ray analysis. In addition, the electrical properties of the copolyesters were tested and the morphology of selected examples of the copolyesters was examined by scanning electron microscopy. © 1998 Society of Chemical Industry     

Synthesis and characterization of poly(ether carbonate)s by melt‐phase interchange reactions of dihydroxy compounds with alkylene and arylene diphenyl dicarbonates containing ether groups

A new method of synthesis of poly(ether carbonate)s based on interchange reactions of dihydroxy compounds with alkylene and arylene diphenyl dicarbonates containing ether group was presented. The diphenyl dicarbonate monomers were prepared from phenyl chloroformate and dihydroxy compounds containing ether group (e.g., diethylene glycol, bis(2‐hydroxyethyl ether) of bisphenol A, and 4,4′‐oxydiphenol). The process consisted of a precondensation step under a stream of dry argon followed by a melt polycondensation at 230 or at 250°C under vacuum. Four series of poly(ether carbonate)s were prepared using this approach. Using alkylene and arylene diphenyl dicarbonate‐containing ether groups as monomers, the polycondensation reaction with dihydroxy compounds led to the formation of poly(ether carbonate)s having inherent viscosity values up to 0.56 dL/g and high thermal stability. The glass transition temperature values of polycarbonates were in the range 7–122°C. The polymers were characterized by inherent viscosity and spectroscopic (Fourier transform infrared spectroscopy and ¹H‐NMR and ¹³C‐NMR) and thermal (differential scanning calorimeteric and thermogravimetric) methods. This approach may permit the use of diphenyl dicarbonates containing other organic functional groups for the synthesis of polycarbonates containing those groups. © 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Syntheses and characterization of poly(butylene terephthalate) copolyesters modified with p‐acetoxybenzoic acid

Poly(butylene terephthalate) (PBT) copolyesters modified with seven compositions of p‐acetoxybenzoic acid (PABA) ranging from 10 to 70 mol % were prepared. The X‐ray diffraction patterns, the polarizing microscopy behaviors, and thermal analysis showed that the modified PBT contained more PABA homopolymer units (PABA–PABA) than PBT–PABA units in the copolyesters. On increasing PABA mole percenage, PBT crystallinity decreased and thermal stability increased. It was found that although the PBT copolyesters did not exhibit a clear liquid crystalline texture like the copolyester of poly(ethylene terephthalate) modified with PABA did, the PBT copolyester containing 70 mol % of PABA exhibited the typical shear thinning behavior of a liquid crystalline polymer. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 80: 1085–1095, 2001     

Synthesis and characterization of aromatic polyamides containing an s‐triazine ring with thiophenoxy linkages

A series of aromatic polyamides containing an s‐triazine ring with thiophenoxy linkages was synthesized from two new diacids, namely 2,4‐bis‐(4‐carboxyphenoxy)‐6‐thiophenoxy‐s‐triazine and 2,4‐bis‐(3‐carboxyphenoxy)‐6‐thiophenoxy‐s‐triazine, and commercially available aromatic diamines by using Yamazaki's phosphorylation reaction. The polyamides were obtained in good yields and were characterized by solubility tests, viscosity measurements, FTIR, ¹H and ¹³C NMR spectroscopy, X‐ray diffraction studies and thermogravimetric analysis. The polyamides were found to have inherent viscosities in the range of 0.35 to 0.56 dl g^?1 in N,N‐dimethylacetamide (DMAc) at 30 ± 0.1 °C. All the polyamides were readily soluble in solvents such as DMAc, N‐methyl‐2‐pyrrolidone (NMP), N,N‐dimethylformamide (DMF) and m‐cresol. Thermogravimetric analysis of the polyamides indicated no weight loss below 345 °C under a nitrogen atmosphere. Copyright © 2004 Society of Chemical Industry     

Synthesis and characterization of poly(ester ether siloxane)s

A series of novel thermoplastic elastomers based on ABA‐type triblock prepolymers, poly[(propylene oxide)–(dimethylsiloxane)–(propylene oxide)] (PPO‐PDMS‐PPO), as the soft segments, and poly(butylene terephthalate) (PBT), as the hard segments, was synthesized by catalyzed two‐step melt transesterification of dimethyl terephthalate (DMT) with 1,4‐butanediol (BD) and α,ω‐dihydroxy‐(PPO‐PDMS‐PPO) (M?_n = 2930 g mol^?1). Several copolymers with a content of hard PBT segments between 40 and 60 mass% and a constant length of the soft PPO‐PDMS‐PPO segments were prepared. The siloxane‐containing triblock prepolymer with hydrophilic terminal PPO blocks was used to improve the compatibility between the polar comonomers, i.e. DMT and BD, and the non‐polar PDMS segments. The structure and composition of the copolymers were examined using ¹H NMR spectroscopy, while the effectiveness of the incorporation of α,ω‐dihydroxy‐(PPO‐PDMS‐PPO) prepolymer into the copolyester chains was controlled by chloroform extraction. The effect of the structure and composition of the copolymers on the transition temperatures (T_m and T_g) and the thermal and thermo‐oxidative degradation stability, as well as on the degree of crystallinity, and some rheological properties, were studied. Copyright © 2006 Society of Chemical Industry     

Synthesis and properties of poly(trimethylene terephthalate‐co‐2‐methyl‐ethylene terephthalate) random copolyesters

Poly(trimethylene terephthalate‐co‐2‐methyl‐ ethylene terephthalate) random copolymers of various compositions were synthesized via traditional two‐step polycondensation by incorporating of 1,2‐propanediol. The molar composition of trimethylene terephthalate and 2‐methyl‐ethylene terephthalate units and chemical structure were confirmed by means of ¹H‐NMR and Fourier transform infrared. The thermal properties of the copolyesters were evaluated by DSC and TGA. As far as the thermal properties is concerned, the main effect of incorporation of 1,2‐propanediol was a lowering in the melting temperature, and an increment of glass transition temperature compared to homopolymer PTT. Due to the effect of the lateral methyl groups in the polymeric chain, the thermal stability is slightly decreased as the amount of the MET units is increased. Furthermore, the crystals of PTT/MET copolyesters were observed by hot‐stage optical polarizing microscopy at the indicated crystallization temperatures. As expected, the incorporation of MET units in the polymer chain of PTT was found to decrease the dimension of the crystals. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Synthesis and characterization of aromatic polyesters and copolyesters from 4,4′‐(1‐hydroxyphenylidene)diphenol and 4,4′‐(9‐fluorenylidene)diphenol

Two isophthalic polyesters from 4,4′‐(1‐hydroxyphenylidene)diphenol (BAP/ISO) and 4,4′‐(9‐fluorenylidene)diphenol (BF/ISO), and three different copolyesters containing 75, 50, and 25 mol % of BAP/ISO were synthesized by interfacial polycondensation. This preparation method yielded polymers and copolymers that produced flexible and transparent films when they were cast from solution. Proton NMR spectrometry studies showed that the isophthalic copolyesters were obtained as random copolymers with differences in comonomer composition no larger than 2.5 mol % with respect to the expected compositions. Wide‐angle X‐ray diffraction measurements indicated that all the polyesters and copolyesters were amorphous. The copolyesters showed amorphous patterns with maxima that fell between those of the polyesters. It was also found that thermal properties such as glass‐transition temperature, onset of decomposition temperature, thermal stability, dynamic mechanical storage modulus, and maximum on the α‐transition of the damping factor tan δ of BF/ISO were higher than those of BAP/ISO. The values of these thermal properties in the copolyesters fell between those of the polyesters and were dependent on the amounts of BF/ISO and BAP/ISO present in the copolyester in a linear fashion. Therefore, the thermal properties of a given copolyester can be predicted directly from the comonomers' composition. Overall, it shows that the interfacial polycondensation method is suitable to obtain these copolyesters in a controlled manner and that their properties can be tailored to be between those of the homopolyesters. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 2515–2522, 2002     

含DOPO的双酚A-单苯并(口恶)嗪合成、表征及其固化特性

以双酚A、苯胺、多聚甲醛为原料,合成了双酚A-双苯并(口恶)嗪（DBOZ）,再用其与DOPO（9,10-二氢-9-氧杂-10-磷杂菲-10-氧化物）反应,合成了含DOPO的双酚A-单苯并(口恶)嗪（DBDO）。采用红外、核磁共振（氢谱核磁共振和碳谱核磁共振）等分析手段对DBOZ和DBDO的化学结构进行了表征;采用差示扫描量热仪对DBOZ和DBDO的固化特性进行研究,使用热重分析分析了所得聚苯并(口恶)嗪的热稳定性。结果表明：在N₂气氛中,DBOZ在205℃左右开环聚合,热分解温度为312℃,在373℃分解速度达到最快,在800℃时的残碳率为37.19%;在N₂气氛中,DBDO的热分解温度为353℃,在443℃分解速度达到最快,在800℃时的残碳率为39.60%。     

Synthesis and characterization of phenoxy resins prepared from diglycidyl ether of bisphenol a and various aromatic dihydroxyl monomers

This work describes the synthesis of various phenoxy resins by in situ fusion reaction of aromatic dihydroxyl and low molecular weight liquid diglycidyl ether of bisphenol A (DGEBA) with an aryl phosphonium salt catalyst. FTIR and ¹H-NMR spectra and GPC analyses were performed to characterize the resins. Analyses results indicated that resins have an adequate high molecular weight and physical properties when the reaction occurred after 5–10 min at 225–230°C. In addition, DSC and TGA analyses were performed to investigate the thermal properties of these phenoxy resins. According to these results, the lack of steric hindrance of the molecular structure in these phenoxy resins depressed the changes of T_g and weight loss. A series of phenoxy modified epoxy networks containing narrower polydisperity and higher M_n will exhibit the most significant effect on impact toughness. Moreover, the FTIR spectrum of the phenoxy resin as a function of temperature correlates well with the glass transition temperature. Furthermore, results presented herein demonstrate effective miscibility with thermoplastic polyurethane elastomer (TPU). © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 73: 2369–2376, 1999     

酯交换法合成聚碳酸酯催化剂性能考察

以双酚A和碳酸二苯酯为原料,采用非光气熔融酯交换法合成聚碳酸酯。考察了氢氧化钾、氢氧化钠、四丁基氢氧化铵、碳酸钠、吡啶以及复合催化剂对聚碳酸酯合成反应速率及聚碳酸酯分子量和色差的影响。研究表明,氢氧化钾作为催化剂较适合于聚碳酸酯合成工艺,使用复合催化剂可以得到分子量较高、色差较低的聚碳酸酯。     

Synthesis and characterization of copolyesters containing the phosphorus linking pendent groups

Poly(ethylene terephthalate)‐co‐poly(ethylene DDP)s [PET‐co‐poly(ethylene DDP)s], were synthesized by charging 9,10‐dihydro‐9‐oxa‐10‐phosphaphenanthrene‐10‐oxide (DOP), itaconic acid, terephthalic acid, and ethylene glycol in one reactor to conduct the microaddition reaction (using H₂PtCl₆ as catalyst), esterification reaction, and polycondensation reaction. H₂PtCl₆ has demonstrated to be a highly efficient microaddition catalyst to improve the DDP conversion. The microaddition reaction of the phosphorus compound (DOP) with the itaconic acid can be proceeded at a significantly lower temperature (110°C) and results in higher conversion (> 98%). The use of the H₂PtCl₆ catalyst makes it possible to charge all the reactants in one reactor to produce high molecular weight phosphorus‐containing copolyesters without requiring the presynthesis of the DDP. These resulting copolyesters are identified by Fourier transform infrared spectroscopy, ¹H‐NMR, and differential scanning calorimetric analysis. Thermal characteristics, thermal stability, intrinsic viscosity, acid value, and rheological and mechanical properties of these copolyesters were also characterized. The presence of the bulky pendent phosphorus side groups in the copolyester tends to decrease the structural regularity and retards its crystallization. The formation of a protected char layer for the phosphorus‐containing copolyester raises the decomposition temperature of the copolyester under an oxygen atmosphere higher than that of PET. The limiting oxygen index values of all phosphorus‐containing copolyesters are all higher than 33. Higher phosphorus content results in decreasing crystallinity, lower melting temperature, lower decomposition temperature, as well as lower tensile strength, but increasing residual char after thermal degradation and higher limiting oxygen index value. The rheological behaviors of copolyesters remain similar to that of PET. The glass temperatures of copolyesters are all ∼ 77°C (76.8°–77.2°C). Incorporation of phosphorus moieties into its molecular chain has a significant effect on thermal and flame retardancy behavior. However, the crystal lattice of all copolyesters do not change with incorporation of the pendent phosphorus side group in the backbone of the copolyester. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 72: 109–122, 1999     

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 poly(ε-caprolactone) and copolyesters by catalysis with molybdenum compounds: polymers with acid-functional asymmetric telechelic architecture

Eight different molybdenum compounds were tested in the catalysts of ring-opening polymerization (ROP) of ε-caprolactone (CL). All homopolymerizations were conducted in bulk at 150 °C using a CL/molybdenum compound molar ratio of 200. Ammonium decamolybdate (NH₄)₈[Mo₁₀O₃₄] comes to be the best catalyst for ROP, based on its selectivity, short reaction times (2 h) and high conversions (98%). Aliphatic copolyesters with acid-funtional asymetric telechelic architecture -hydroxyl-ω-(carboxylic acid) (HA) were synthesized from lactones -such as CL, δ-valerolactone (VL) and γ-butyrolactone (BL)- by ring-opening copolymerization. HA-copolyesters, namely HA-poly(ε-caprolactone-co-γ-butyrolactone) (HA-PCB), HA-poly(δ-valerolactone-co-γ-butyrolactone) (HA-PVB) and HA-poly(ε-caprolactone-co-δ-valerolactone) (HA-PCV), were obtained at 150 °C in 2 h using ammonium decamolybdate as catalyt and water as initiator. A control of the degree of polymerization (DP, measured by NMR) can be achieved in the range between 6 and 24 for HA-PCB and HA-PCV, based on the initial monomer/initiator ratio. DP shows a linear dependence with M/H₂O ratio (where M=CL+(BL or VL)) in this range. The nature of hydroxyl and carboxylic acid end groups of HA-copolyesters was determined by ¹H and ¹³C NMR. Finally, HA-poly(ε-caprolactone-block-δ-valerolactone) (HA-PCbV) was successfully prepared by sequential copolymerization of HA-poly(ε-caprolactone) with VL and characterized by ¹H and ¹³C NMR, GPC and MALDI-TOF.     

Preparation and characterization of metal‐containing aromatic polyimides

A series of novel metal‐containing aromatic polyimides were synthesized from divalent metal oxide/hydroxide (MO/M(OH)₂) (M = Ba, Sr, Ca, Mg, Zn, Cd, Co, Ni, Pb, Cu), p‐aniline sulfonic acid (ASA), and 3,3′‐4,4′‐benzophenonetetracarboxylic dianhydride (BTDA). The C, H, N, and S contents were determined by elemental analysis, their structures were characterized by proton nuclear magnetic resonance (¹H‐NMR) and Fourier transform infrared (FT‐IR) spectroscopy, and the thermal properties of the polymers were also studied by TG–DTA. It is found that metal‐containing polyimides have a higher thermal stability. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 77: 2363–2369, 2000     

Synthesis and characterization of poly(dimethyl siloxane) containing poly(vinyl pyrrolidinone) block copolymers

ABA‐type block copolymers containing segments of poly(dimethyl siloxane) and poly(vinyl pyrrolidinone) were synthesized. Dihydroxyl‐terminated poly(dimethyl siloxane) was reacted with isophorone diisocyanate and then with t‐butyl hydroperoxide to obtain macroinitiators having siloxane units. The peroxidic diradical macroinitiators were used to polymerize vinyl pyrrolidinone monomer to synthesize ABA‐type block copolymers. By use of physicochemical methods, the structure was confirmed, and its characterization was accomplished. Mechanical and thermal characterizations of copolymers were made by stress–strain tests and differential scanning calorimetric measurements. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 71: 1915–1922, 1999     

Synthesis and characterization of end‐capped polyimides and their gas permeability properties

Polyimides (PIs) based on 3,3′,4,4′‐oxydiphthalic anhydride (ODPA) and 4,4′‐oxydianiline (ODA) end capped with two new monoamines and other four different monoamines have been synthesized with a view to study the effect of different functional groups at the end of polymer chain on solubility, gas permeability, and thermal properties. The new monoamines have been synthesized from 3‐pentadecylphenol, obtained by hydrogenation of cardanol, a major constituent of cashew‐nut shell liquid. Introduction of different functional groups at the end of polyimide (PI) based on ODPA and ODA, by end capping with different monoamines, alters oxygen and nitrogen gas permeability, solubility, and thermal properties. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 77: 627–635, 2000