Synthesis and characterization of new soluble cardo polyamides containing the tricyclo[5.2.1.02,6]decane group

A new cardo dicarboxylic acid, 8,8‐bis[4‐(4‐carboxyphenoxy)phenyl]tricyclo[5.2.1.0^2,6]decane (BCPTD), was synthesized from 4,4′‐(octahydro‐4,7‐methano‐5H‐inden‐5‐ylidene)bisphenol and p‐fluorobenzonitrile via aromatic nucleophilic substitution followed by hydrolysis. A series of new cardo polyamides was prepared by the direct polycondensation of BCPTD and various aromatic diamines in N‐methyl‐2‐pyrrolidinone (NMP) with triphenyl phosphite and pyridine as the condensing agents. Polymers were produced with moderate to high inherent viscosities of 0.65 to 1.08 dL g⁻¹. The polymers, except for polymer PA1 , exhibited number‐average molecular weights and weight‐average molecular weights in the range of 38,400 to 86,300 and 57,800 to 148,000, respectively. Nearly all of the polymers were readily soluble in polar solvents such as NMP, N,N‐dimethylacetamide, N,N‐dimethylformamide, and dimethyl sulfoxide as well as in less polar solvents such as pyridine, γ‐butyrolactone, and tetrahydrofuran. All of the polymers were amorphous, and the polyamide films had a tensile‐strength range of 75 to 128 MPa and a tensile‐modulus range of 2.0 to 2.8 GPa. These polyamides had glass‐transition temperatures between 240 and 269°C and 10% weight‐loss temperatures in the range of 477 to 508°C and 471 to 518°C in nitrogen and air atmospheres, respectively. © 2000 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 38: 74–79, 2000     

Chemoselective polyesterification by direct polycondensation

A convenient method for the synthesis of polyester‐containing amino substitutes on the aromatic rings of the backbone has been developed. This polyester was prepared by chemoselective polyesterification of isophthalic acid with bisphenol having an amino group in the presence of the condensing agent diphenyl(2,3‐dihydro‐2‐thioxo‐3‐benzoxazolyl)phosphonate ( 1 ) and 1,5‐diazabicyclo[4,3,0]‐5‐nonene as a base. The model reactions were carried out in detail to elucidate appropriate conditions of chemoselective polyesterification. Direct polycondensation of isopthalic acid with 4,4′‐[1‐(4‐aminophenyl)ethylidene]bisphenol proceeded smoothly under mild conditions and produced the desired polyester with a number average molecular weight of 11,000 and M_w/M_n of 2.22. The polymer obtained was characterized by IR, ¹H, and ¹³C NMR spectroscopies. © 2000 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 39: 78–85, 2001     

Synthesis and characterization of new organosoluble polyamides derived from bis[4‐(4‐carboxyphenoxy) phenyl]diphenylmethane

A new dicarboxylic acid containing a diphenylmethylene linkage, bis[4‐(4‐carboxyphenoxy)phenyl]diphenylmethane (BCAPD), was prepared from bis(4‐hydroxphenyl)diphenylmethane and p‐fluorobenzonitrile via an aromatic nucleophilic substitution reaction followed by hydrolysis. A series of novel polyamides were prepared by the direct polycondensation of BCAPD and various aromatic diamines. The polymers were produced with moderate to high inherent viscosities of 0.80–0.85 dL g^?1. Nearly all the polymers were readily soluble in polar solvents such as N‐methyl‐2‐pyrrolidinone, N,N‐dimethylacetamide, N,N‐dimethylformamide, and dimethyl sulfoxide, in less polar solvents such as pyridine and cyclohexanone, and in tetrahydrofuran. All the polymers were amorphous, and the polyamide films had a tensile strength and a tensile modulus greater than 80 MPa and 2.0 GPa, respectively. These polyamides had glass‐transition temperatures between 249 and 274 °C, and their temperatures at a 10% weight loss were 477–538 and 483–540 °C in nitrogen and air atmospheres, respectively. © 2001 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 39: 1156–1161, 2001     

Soluble aromatic poly(ether amide)s containing aryl‐, alkyl‐, and chloro‐substituted phthalazinone segments

A series of novel aromatic diamines ( 2 – 4 ) containing the alkyl‐, aryl, or chloro‐substituted group of phthalazinone segments were synthesized via two synthetic steps starting from 4‐(3‐R‐4‐hydroxyphenyl)‐2,3‐phthalazinone‐1 (R = Ph, CH₃, Cl). Three series of aromatic polyamides containing phthalazinone moieties were prepared through diamines 2 – 4 reacting with different aromatic dicarboxylic acids via a direct Yamazaki–Higashi phosphorylation polycondensation reaction. The resulting aromatic polyamides had inherent viscosities in the range of 0.40–0.76 dL/g. The thermal property of the polyamides was examined with DSC and thermogravimetric analysis. The glass‐transition temperatures of these polyamides ranged from 298 to 340 °C. The 10% mass‐loss temperature was above 405 °C under nitrogen. Structures of monomers 2 – 4 and the polymers were confirmed by Fourier transform infrared spectroscopy, ¹H NMR, and mass spectrometry. Good solubility of these polymers in polar solvents such as N‐methylpyrrolidone, dimethylformamide, dimethylacetamide (DMAc), and m‐cresol was observed, and tough, flexible films were obtained from the polymer's DMAc solutions. The effect of the substituted group on the physical property of polymers was also investigated. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 2026–2030, 2004     

Polyterephthalamides with naphthoxy‐pendent groups

A series of new aromatic polyamides having pendent naphthoxy groups were synthesized by the triphenyl phosphite‐activated polycondensation of (2‐naphthoxy)terephthalic acid (NOTPA) with various aromatic diamines in a medium consisting of N‐methyl‐2‐pyrrolidone (NMP), pyridine, and calcium chloride. The diacid monomer NOTPA was prepared from the nitro displacement of dimethyl 2‐nitroterephthalate with the potassium naphthoxide of β‐naphthol, followed by base‐induced ester hydrolysis. All the resulting polymers were noncrystalline and readily soluble in aprotic polar solvents such as NMP and N,N‐dimethylacetamide. Almost all the polymers could be solution‐cast to tough, creasable amorphous films with good mechanical properties, the values of tensile strengths ranging from 90 to 124 MPa with initial moduli ranging from 1.72 to 2.51 GPa. Except for two examples, all the other polyamides displayed discernible glass transitions between 189 and 248 °C in the differential scanning calorimetric traces. These polyamides showed insignificant decomposition below 400 °C in nitrogen or air. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 1781–1789, 2002     

Synthesis and micellization of star‐like hyperbranched polymer with poly(ethylene oxide) and poly(ε‐caprolactone) arms

Novel star‐like hyperbranched polymers with amphiphilic arms were synthesized via three steps. Hyperbranched poly(amido amine)s containing secondary amine and hydroxyl groups were successfully synthesized via Michael addition polymerization of triacrylamide (TT) and 3‐amino‐1,2‐propanediol (APD) with feed molar ratio of 1:2. ¹H, ¹³C, and HSQC NMR techniques were used to clarify polymerization mechanism and the structures of the resultant hyperbranched polymers. Methoxyl poly(ethylene oxide) acrylate (A‐MPEO) and carboxylic acid‐terminated poly(ε‐caprolactone) (PCL) were sequentially reacted with secondary amine and hydroxyl group, and the core–shell structures with poly(1TT‐2APD) as core and two distinguishing polymer chains, PEO and PCL, as shell were constructed. The star‐like hyperbranched polymers have different sizes in dimethyl sulfonate, chloroform, and deionized water, which were characterized by DLS and ¹H NMR. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 1388–1401, 2008     

Synthesis and characterization of new soluble polyamides from 1,1‐bis[4‐(4‐carboxyphenoxy)phenyl]‐4‐tert‐butylcyclohexane and various diamines

A new dicarboxylic acid monomer, 1,1‐bis[4‐(4‐carboxyphenoxy)phenyl]‐4‐tert‐butylcyclohexane, bearing a pendent tert‐butylcyclohexylidene group was prepared in three steps from 4‐tert‐butylcyclohexanone. The monomer was reacted with various diamines to produce a series of new polyamides with triphenyl phosphite and pyridine as condensing agents. These polyamides were produced with inherent viscosities of 0.74 to 1.02 dL g⁻¹. All the polymers were characterized by X‐ray diffraction that revealed this amorphous nature. These polymers exhibited excellent solubility in a variety of solvents. Almost all the polymers could be dissolved in N‐methyl‐2‐pyrrolidinone, N,N‐dimethylacetamide (DMAc), N,N‐dimethylformamide, dimethyl sulfoxide, pyridine, and even in tetrahydrofuran and cyclohexanone. These polymers showed glass‐transition temperatures between 223 and 256 °C and decomposition temperatures at 10% weight loss ranging from 468 to 491 °C and 469 to 498 °C in nitrogen and air atmospheres, respectively. Transparent, tough, and flexible films of these polymers were cast from the DMAc solutions. These polymer films had tensile strengths ranging from 76 to 99 MPa, elongations at break from 7 to 19%, and initial moduli from 2.1 to 2.7 GPa. © 2000 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 38: 797–803, 2000     

Synthesis and characterization of novel polyamide‐imides containing noncoplanar 2,2′‐dimethyl‐4,4′‐biphenylene unit

A new diimide‐dicarboxylic acid, 2,2′‐dimethyl‐4,4′‐bis(4‐trimellitimidophenoxy)biphenyl (DBTPB), containing a noncoplanar 2,2′‐dimethyl‐4,4′‐biphenylene unit was synthesized by the condensation reaction of 2,2′‐dimethyl‐4,4′‐bis(4‐minophenoxy)biphenyl (DBAPB) with trimellitic anhydride in glacial acetic acid. A series of new polyamide‐imides were prepared by direct polycondensation of DBAPB and various aromatic diamines in N‐methyl‐2‐pyrrolidinone (NMP), using triphenyl phosphite and pyridine as condensing agents. The polymers were produced with high yield and moderate to high inherent viscosities of 0.86–1.33 dL · g⁻¹. Wide‐angle X‐ray diffractograms revealed that the polymers were amorphous. Most of the polymers exhibited good solubility and could be readily dissolved in various solvents such as NMP, N,N‐dimethylacetamide (DMAc), N,N‐dimethylformamide (DMF), dimethyl sulfoxide, pyridine, cyclohexanone, and tetrahydrofuran. These polyamide‐imides had glass‐transition temperatures between 224–302 °C and 10% weight loss temperatures in the range of 501–563 °C in nitrogen atmosphere. The tough polymer films, obtained by casting from DMAc solution, had a tensile strength range of 93–115 MPa and a tensile modulus range of 2.0–2.3 GPa. © 2000 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 39: 63–70, 2001     

A highly rigid diamine monomer derived from naturally occurring myo‐inositol and its use for polyamide synthesis

A rigid diamine was synthesized from myo‐inositol, a naturally occurring cyclic hexaol, and used as a monomer to synthesize polyamides. myo‐Inositol was treated with 1,1‐dimethoxycyclohexane to yield a bisketal bearing two hydroxyl groups, and from this bisketal, the target diamine was synthesized in three steps: (1) derivation of the diol into the corresponding bistriflate, (2) nucleophilic substitution of the bistriflate with sodium azide yielding a diazide, and (3) reduction of the diazide to the target diamine. The target diamine readily underwent polycondensation with dicarboxylic acid chloride in solution. The resulting polyamides, whose main chain inherited the rigid 5‐6‐5 system from the diamine monomers, have high glass transition temperatures. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2016 , 54, 3436–3443     

Preparation and characterization of aromatic polyamides based on ether-sulfone-dicarboxylic acids

Two ether-sulfone-dicarboxylic acids, 4,4′-[sulfonylbis(2,6-dimethyl-1,4-phenylene)dioxy]dibenzoic acid (Me- III ) and 4,4′-[sulfonylbis(1,4-phenylene)dioxy]-dibenzoic acid ( III ), were prepared by the fluorodisplacement of 4,4′-sulfonylbis(2,6-dimethylphenol) and 4,4′-sulfonyldiphenol with p-fluorobenzonitrile, and subsequent alkaline hydrolysis of intermediate dinitriles. Using triphenyl phosphite (TPP) and pyridine as condensing agents, aromatic polyamides containing ether and sulfone links were prepared by the direct polycondensation of the dicarboxylic acids with various aromatic diamines in the N-methyl-2-pyrrolidone (NMP) solution containing dissolved calcium chloride. The inherent viscosities of the resulting polymers were above 0.4 dL/g and up to 1.01 dL/g. Most of the polyamides were readily soluble in polar solvents such as NMP, N,N-dimethylacetamide (DMAc), N,N-dimethylformamide (DMF), and dimethyl sulfoxide (DMSO), and afforded tough and transparent films by solution-casting. Most of the polymers showed distinct glass transition on their differential scanning calorimetry (DSC) curves, and their glass transition temperatures (T_g) were recorded between 212–272°C. The methyl-substituted polyamides showed slightly higher T_gs than the corresponding unsubstituted ones. The results of the thermogravimetry analysis (TGA) revealed that all the polyamides showed no significant weight loss before 400°C, and the methyl-substituted polymers showed lower initial decomposition temperatures than the unsubstituted ones. © 1997 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 35 : 2421–2429, 1997     

Synthesis and characterization of norbornane-containing cardo polyamides

A new diamine, 2,2-bis[4-(4-aminophenoxy)phenyl]norbornane (BAPN), containing both ether and norbornane cardo groups, was synthesized in three steps started from norcamphor. A series of cardo polyamides were obtained by the direct polycondensation of BAPN and various aromatic dicarboxylic acids in N-methyl-2-pyrrolidinone (NMP) using triphenyl phosphite and pyridine as condensing agents. Polyamides had inherent viscosities in the range of 0.82–1.58 dL g⁻¹, and were readily soluble in polar aprotic solvents such as NMP, N,N-dimethylacetamide (DMAc) and N,N-dimethylformamide and dimethyl sulfoxide. These polymers were cast in DMAc solution into transparent, flexible, and tough films that were further characterized by X-ray and mechanical analysis. All the polymers were amorphous, and the polyamide films had a tensile strength range of 71–89 MPa, an elongation at break range of 5–9%, and a tensile modulus range of 2.0–2.3 GPa. Polyamides showed glass transition temperatures in the range of 256–296°C as measured by DSC and thermogravimetric analysis indicated no weight loss below 450°C in nitrogen and air atmosphere. © 1999 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 37: 2791–2794, 1999     

High‐molecular‐weight poly(1,2‐propylene succinate): A soft biobased polyester applicable as an effective modifier of poly(l‐Lactide)

Poly(1,2‐propylene succinate) (PPS) having high molecular weight can be synthesized by multi‐step melt‐polycondensation of succinic acid (SA) and 1,2‐propylene glycol (PG) with various catalysts. The first step is noncatalytic esterification/oligomerization of the two monomers, followed by the second step of catalytic melt‐polycondensation. In this step, co‐catalyst systems of Zn(AcO)₂/Ge(OBu)₄ and Zn(AcO)₂/Ti(BuO)₄ are effective for obtaining PPS having middle molecular weights (>10.0 kDa). This middle‐molecular‐weight PPS is chain‐elongated in the third‐step polycondensation with Zn(AcO)₂ as the catalyst to obtain a molecular weight reaching 120 kDa. As verified by ¹H‐ and ¹³C‐NMR spectra combined with two‐dimensional experiments, PPS has a ω‐bis‐hydroxy structure where the PG units leave the secondary hydroxyl terminals in larger ratio than the primary hydroxyl terminals. The PPS polymers are amorphous in nature, showing T_g around −4 °C. PPS can be solution‐ and melt‐blended with poly(l ‐lactide) (PLLA). By melt‐blending a high‐molecular‐weight PPS in an amount of 7.5–15 wt %, the modulus of the PLLA films decreases below 2000 MPa and the tear strength increases twice, supporting the effectiveness of PPS polymer in imparting flexible nature to PLLA. PPS polymers can therefore be applicable as elastomeric or flexible plastic modifiers having a 100 % biobased content. © 2018 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2018 , 56, 1795–1805     

Synthesis and properties of soluble and light‐colored poly(amide‐imide‐imide)s on the basis of tetraimide‐dicarboxylic acid condensed from 4,4′‐oxydiphthalic anhydride, 2,2‐bis[4‐(4‐aminophenoxy)phenyl]propane,and m‐aminobenzoic acid,and various aromatic diamines

A new type of tetraimide‐dicarboxylic acid ( I ) was synthesized starting from the ring‐opening addition of m‐aminobenzoic acid, 4,4′‐oxydiphthalic anhydride, and 2,2‐bis[4‐(4‐aminophenoxy)phenyl]propane at a 2:2:1 molar ratio in N‐methyl‐2‐pyrrolidone (NMP), followed by cyclodehydration to the diacid I . A series of soluble and light‐colored poly(amide‐imide‐imide)s ( III _a–j) was prepared by triphenyl phosphite‐activated polycondensation from I with various aromatic diamines ( II _a–j). All films cast from N,N‐dimethylacetamide (DMAc) had cutoff wavelengths shorter than 390 nm (374–390 nm) and b* values between 25.26 and 43.61; these polymers were much lighter in color than the alternating trimellitimide series. All of the polymers were readily soluble in a variety of organic solvents such as NMP, DMAc, N,N‐dimethylformamide, dimethyl sulfoxide, and even in less polar m‐cresol and pyridine. Polymers III _a–j afforded tough, transparent, and flexible films that had tensile strengths ranging from 96 to 118 MPa, elongations at break from 9 to 11%, and initial moduli from 2.0 to 2.5 GPa. The glass‐transition temperatures of the polymers were recorded at 240–268 °C. They had 10% weight loss at a temperature above 540 °C and left more than 55% residue even at 800 °C in nitrogen. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 707–718, 2002; DOI 10.1002/pola.10153     

s‐Triazine‐based hyperbranched polyethers: Synthesis,characterization, and properties

A series of s‐triazine‐based hyperbranched polyethers (HBPE) have been synthesized to obtain thermostability but flexible polymers by an interfacial polycondensation of different diols as A₂ and cyanuric chloride as B₃ monomers using A₂ + B₃ approach in the presence of a phase transfer catalyst. The polymerization reaction parameters are optimized, and the results indicate that the optimum conditions for the interfacial polycondensation are a 2:3 mole ratio of cyanuric chloride to diol using butanediol, benzyldimethylhexadecyl ammonium chloride as the catalyst, dichloromethane as the organic solvent, and a three‐step procedure with keeping the reaction mixture at different low temperatures for 2h/2h/5h. Other techniques such as high‐temperature solution, one‐step polycondensation, and transesterification were also carried out to synthesize the HBPE but proved to be not suitable due to large number of side reactions. The synthesized polymers were characterized by FTIR, ¹H NMR, and ¹³C NMR spectroscopy, hydroxyl number determination, solution viscosity measurements, and GPC analysis. The thermal behavior of the hyperbranched polymer was investigated by thermogravimetric analysis and differential scanning calorimetry. All the results were compared with those from an analogous linear polyether, obtained from 2‐methoxy‐4,6‐dichloro‐s‐triazine and butanediol by using the same polymerization technique. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 3994–4004, 2010     

Synthesis of sulfonated aromatic poly(ether amide)s and their application to proton exchange membrane fuel cells

A series of wholly aromatic sulfonated poly(ether amide)s (SPEAs) containing a sulfonic acid group on the dicarbonyl aromatic ring were prepared via a polycondensation reaction of sulfonated terephthalic acid (STA), terephthalic acid (TA), and aromatic diamine monomers. The degree of sulfonation was readily controlled by adjusting the monomer feed ratio of STA and TA in the polymerization process, and randomly sulfonated polymers with an ion exchange capacity (IEC) of 1.0–1.8 mequiv/g were prepared using this protocol. The chemical structures of randomly sulfonated polymers were characterized using NMR and FT‐IR spectroscopies. Gel permeation chromatography analysis of SPEAs indicated the formation of high‐molecular‐weight sulfonated polymer. Tough and flexible SPEA membranes were obtained from solution of N,N‐dimethylacetamide, and thermogravimetric analysis of these membranes showed a high degree of thermal stability. Compared with previously reported sulfonated aromatic polyamides, these new SPEAs showed a significantly lower water uptake of 10–30%. In proton conductivity measurements, ODA‐SPEA‐70 (IEC = 1.80 mequiv/g), which was obtained from polycondensation of 4,4′‐oxydianiline and 70 mol % STA, showed a comparable proton conductivity (105 mS/cm) to that of Nafion 117 at 80 °C. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 485–496, 2009     

Synthesis and properties of new polyamides derived from 2,2‐bis[4‐[2‐(4‐aminophenoxy)ethoxy]phenyl]sulfone by direct polycondensation

A series of new polyamides containing both sulfone and oxyethylene moieties in the polymer chain was prepared by the direct polycondensation of the diamine monomer 2,2‐bis[4‐[2‐(4‐aminophenoxy)ethoxy]phenyl]sulfone (BAEPS) and various aromatic dicarboxylic acids in N‐methyl‐2‐pyrrolidinone (NMP) using triphenyl phosphite and pyridine as condensing agents. Polymers were produced with inherent viscosities of 0.30–0.60 dl/g and identified by elemental analysis, and infrared and nuclear magnetic resonance spectra. Most of the polymers were readily dissolved in polar solvents such as NMP, dimethylsulfoxide, N,N‐dimethylacetamide, N,N‐dimethylformamide and m‐cresol at room temperature. Polymers containing rigid and symmetric p‐phenylene, naphthalene and p‐biphenylene moieties revealed a crystalline nature and showed no solubility in organic solvents. These polyamides had 10% weight loss temperatures ranging between 423 and 465 °C in nitrogen atmosphere and glass transition temperatures between 170 and 305 °C. The polymers with crystallinity nature exhibited melting endotherms (T_m) below 386 °C in differential scanning calorimetry trace. Copyright © 1999 John Wiley & Sons, Ltd.     

Synthesis and characterization of new soluble cardo polyamide‐imides containing cyclododecyl groups

A new cardo diimide‐dicarboxylic acid, 1,1‐bis[4‐(4‐trimellitimidophenoxy)phenyl]cyclododecane (BTPCD), containing a pendant cyclododecyl group was synthesized by the condensation reaction of 1,1‐bis[4‐(4‐aminophenoxy)phenyl]cyclododecane with trimellitic anhydride in glacial acetic acid. A series of new cardo polyamide‐imides were prepared by the direct polycondensation of BTPCD and various aromatic diamines in N‐methyl‐2‐pyrrolidinone (NMP) with triphenyl phosphite and pyridine as condensing agents. The polymers were produced in high yields and with moderate‐to‐high inherent viscosities of 0.72–1.02 dL g⁻¹. The number‐average and weight‐average molecular weights of the polymers ranged from 21,000 to 49,000 and 58,000 to 92,000, respectively. All the polymers exhibited excellent solubility and could be readily dissolved in various solvents such as NMP, N,N‐dimethylacetamide, N,N‐dimethylformamide, dimethyl sulfoxide, pyridine, cyclohexanone, and tetrahydrofuran. These polyamide‐imides had glass‐transition temperatures between 241 and 262 °C and 10% weight‐loss temperatures ranging from 469 to 511 °C in nitrogen. The polymer films had a tensile strength range of 79–108 MPa, an elongation at break range of 7–14%, and a tensile modulus range of 2.0–2.4 GPa. © 2000 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 38: 2787–2793, 2000     

Synthesis and properties of new soluble aromatic polyamides and polyimides on the basis of N,N′‐bis(3‐aminobenzoyl)‐N,N′‐diphenyl‐1,4‐phenylenediamine

A new N‐phenylated amide (N‐phenylamide) unit containing aromatic diamine, N,N′‐bis(3‐aminobenzoyl)‐N,N′‐diphenyl‐1,4‐phenylenediamine, was prepared by the condensation of N,N′‐diphenyl‐1,4‐phenylenediamine with 3‐nitrobenzoyl chloride, followed by catalytic reduction. Two series of organosoluble aromatic poly(N‐phenylamide‐imide)s and poly(N‐phenylamide‐amide)s with inherent viscosities of 0.58–0.82 and 0.56–1.21 dL/g were prepared by a conventional two‐stage method and the direct phosphorylation polycondensation, respectively, from the diamine with various aromatic dianhydrides and aromatic dicarboxylic acids. All polyimides and polyamides are amorphous and readily soluble in many organic solvents such as N,N‐dimethylacetamide and N‐methyl‐2‐pyrrolidone. These polymers could be solution cast into transparent, tough, and flexible films with high tensile strengths. These polyimides and polyamides had glass‐transition temperatures in the ranges of 230–258 and 196–229 °C, respectively. Decomposition temperatures of the polyimides for 10% weight loss all occurred above 500 °C in both nitrogen and air atmospheres. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 2564–2574, 2002     

Synthesis and chemical structural analysis of nitroxyl‐radical‐incorporated poly(acrylic acid/lactide/ϵ‐caprolactone) copolymers

The goal of this research is to synthesize biodegradable polymers that would have nitroxyl radical biological functions. Linear aliphatic polyesters were chosen as the starting materials. The hydroxyl‐terminated polylactide/?‐caprolactones (PBLC‐OHs) were first synthesized by melt ring‐opening copolymerization in the presence of benzyl alcohol and stannous octoate. PBLC‐OHs were used as the precursor for the synthesis of double bond‐functionalized polylactide/?‐caprolactones (PBLC‐Mas) by reacting the hydroxyl end groups of PBLC‐OH with maleic anhydride in melt at 130 °C. Acrylic acid/lactide/?‐caprolactone graft copolymers (PBLCAs) were then successfully carried out by the radical copolymerization of acrylic acid and PBLC‐Ma initiated by azobisisobutyronitrile. Finally, nitroxyl radicals [4‐amino‐2,2,6,6‐tetramethylpiperidine‐1‐oxy (TAM)] were incorporated into the carboxylic acid sites of the acrylic acid/lactide/?‐caprolactone copolymer (TAM‐PBLCA) by reacting TAM with PBLCA in the presence of N,N′‐carbonyl diimidazole. A high content of TAM was incorporated into the PBLCA copolymer. The polymers synthesized were characterized by ¹H and ¹³C NMR, Fourier transform infrared spectroscopy, and electron paramagnetic resonance spectra. © 2001 John Wiley & Sons, Inc. J Polym Sci Part A: Polym Chem 39: 4214–4226, 2001     

Synthesis and characterization of new soluble polyesters derived from various cardo bisphenols by solution polycondensation

A series of new polyesters was prepared from terephthaloyl (or isophthaloyl) chloride acid with various cardo bisphenols on solution polycondensation in nitrobenzene using pyridine as hydrogen chloride quencher at 150 °C. These polyesters were produced with inherent viscosities of 0.32–0.49 dL · g⁻¹. Most of these polyesters exhibited excellent solubility in a variety of solvents such as N,N‐dimethylformamide, tetrahydrofuran, tetrachloroethane, dimethyl sulfoxide, N,N‐dimethylacetamide, N‐methyl‐2‐pyrrolidinone, m‐cresol, and o‐chlorophenol. The polyesters containing cardo groups including diphenylmethylene, tricyclo[5.2.1.0^2,6]decyl, tert‐butylcyclohexyl, phenylcyclohexyl, and cyclododecyl groups exhibited better solubility than bisphenol A–based polyesters. These polymers showed glass transition temperatures (T_g's) between 185 °C and 243 °C and decomposition temperatures at 10% weight loss ranging from 406 °C to 472 °C in nitrogen. These cardo polyesters exhibited higher T_g's and better solubility than bisphenol A‐based polyesters. © 2000 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 38: 4451–4456, 2000