Synthesis of poly(aryl ether ketone)s containing diphenyl moieties by electrophilic Friedel–Crafts solution polycondensation

A new monomer, 4,4′‐bis(4‐phenoxybenzoyl)diphenyl (BPOBDP), was prepared by Friedel–Crafts reaction of 4‐bromobenzoyl chloride and diphenyl, followed by condensation with potassium phenoxide. Novel poly(ether ketone ketone) (PEKK)/poly(ether ketone diphenyl ketone ether ketone ketone) (PEKDKEKK) copolymers were synthesized by electrophilic Friedel–Crafts solution copolycondensation of isophthaloyl chloride (IPC) with a mixture of diphenyl ether (DPE) and BPOBDP, in the presence of anhydrous aluminum chloride and N‐methyl‐pyrrolidone (NMP) in 1,2‐dichloroethane (DCE). The copolymers obtained were characterized by various analytical techniques such as FT‐IR, DSC, TGA, and wide‐angle X‐ray diffraction (WAXD). The results showed that the resulting copolymers exhibited excellent thermal stability due to the existence of diphenyl moieties in the main chain. The glass transition temperatures are above 152°C, the melting temperatures are above 276°C, and the temperatures at a 5% weight loss are above 548°C in nitrogen. The copolymers with 50–70 mol% BPOBDP had tensile strengths of 101.5–102.7 MPa, Young's moduli of 3.23–3.41 GPa, and elongations at break of 12–17%. All these copolymers were semicrystalline and insoluble in organic solvents. Copyright © 2008 John Wiley & Sons, Ltd.     

四臂星形嵌段共聚物s-PDLLA-b-PEG的合成

季戊四醇与D,L-丙交酯开环聚合制得末端为羟基的四臂星形聚乳酸(s-PDLLA);s-PDLLA与羧基封端的聚乙二醇单甲醚(CT-mPEG)完成酯化反应,合成了以季戊四醇为核,以聚乳酸为内部嵌段、聚乙二醇为外部嵌段的四臂星形聚(D,L-乳酸)-聚乙二醇嵌段共聚物(s-PDLLA-b-PEG),其结构经1H NMR,IR和GPC表征。     

Synthesis and characterization of novel biodegradable copolyesters by transreaction of poly(ethylene terephthalate) with copoly(succinic anhydride/ethylene oxide)

Poly(ethylene terephthalate)/copoly(succinic anhydride/ethylene oxide) copolymers, (PET/PES copolymers) were synthesized by the transreaction between PET and PES and characterized with GPC, ¹H NMR, and DSC. Most of the copolymers obtained were random copolymers. The films cast of these copolymers were transparent. The thermal, mechanical properties, and biodegradability of the copolymers obtained were studied with respect to the composition and lengths of aliphatic and aromatic units in the copolymers. In the copolymers having high PET content, the melting points, due to the PET segment, were observed by DSC measurement, although the fusion heats of the copolymers were small. The enzymatic hydrolyzability by a lipase from Rhizopus arrhizus and biodegradability by activated sludge of the copolymers decreased with an increase in PET content. When the length of succinic acid unit in the copolymer was below 2, the hydrolyzability of the copolymers decreased considerably. The tensile strengths of the cast films prepared from the copolymers synthesized by the transreaction increased with an increase in PET content, whereas, the elongations at break decreased. Their tensile strengths were half, and the elongations were double compared to those of PET homopolymer film. © 2000 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 38: 4478–4489, 2000     

Synthesis of copolymers of poly(ether sulfone ether ketone ketone) and poly(ether ketone diphenyl ketone ether ketone ketone) by electrophilic Friedel–Crafts solution polycondensation

A new monomer, 4,4′‐bis(4‐phenoxybenzoyl)diphenyl(BPOBDP), was synthesized via a two‐step synthetic procedure. A series of novel poly(ether sulfone ether ketone ketone)/poly(ether ketone diphenyl ketone ether ketone ketone) copolymers were prepared by electrophilic Friedel–Crafts solution copolycondensation of isophthaloyl chloride (IPC) with a mixture of 4,4′‐diphenoxydiphenylsulfone (DPODPS) and 4,4′‐bis(4‐phenoxybenzoyl)diphenyl (BPOBDP), in the presence of anhydrous aluminum chloride and N‐methylpyrrolidone (NMP) in 1,2‐dichloroethane (DCE). The copolymers with 10–50 mol% DPODPS are semicrystalline and have remarkably increased T_gs over commercially available PEEK and PEKK. The copolymers with 40–50 mol% DPODPS had not only high T_gs of 170–172°C, but also moderate T_ms of 326–333°C, which are extremely suitable for melt processing. These copolymers have tensile strengths of 96.5–108.1 MPa, Young's moduli of 1.98–3.05 GPa, and elongations at break of 13–26% and exhibit excellent thermal stability and good resistance to acidity, alkali, and common organic solvents. Copyright © 2009 John Wiley & Sons, Ltd.     

Synthesis and characterization of biodegradable poly(?-caprolactone-co-β-butyrolactone)-based polyurethane

Poly(?-caprolactone-co-β-butyrolactone) (PCLBL)-based polyurethane (PCLBL-PU) was synthesized and its tensile properties and hydrolytic degradability were investigated in an attempt to improve the degradability of poly(?-caprolactone)-based polyurethane (PCL-PU). PCLBL was synthesized by the ring-opening polymerization of ?-caprolactone (CL) and β-butyrolactone (BL) with stannous octoate as a catalyst. The introduction of a small amount of BL units significantly decreased the crystallinity of PCLBL. The crystallinity of the soft segment of PCLBL-PU also decreased with increasing BL content, and thus its hydrolytic degradation rate was dramatically increased. PCLBL-PU polymerized with PCLBL containing 5.7 mol% of BL units showed very similar tensile properties to PCL-PU, but its hydrolytic degradation rate increased by 100% at 45 °C.     

三臂PPO-PDLA-PLLA 嵌段共聚物的制备与结构及其立构复合体的结晶行为

以环氧丙烷聚醚三元醇(PPO)为起始剂, 开环聚合D 型丙交酯(DLA), 合成三臂环氧丙烷聚醚三元醇-聚右旋乳酸(PPO-PDLA)嵌段预聚体. 采用端基活化技术对预聚体进行端羟基活化, 再与L 型丙交酯(LLA)进行逐步开环聚合,合成了不同分子量的三臂环氧丙烷聚醚三元醇-聚右旋乳酸-聚左旋乳酸(PPO-PDLA-PLLA)嵌段共聚物. 采用红外(FTIR)、核磁(NMR)和凝胶渗透色谱(GPC)等对三臂PPO-PDLA-PLLA 嵌段共聚物的测试表明, 合成的嵌段共聚物分子链具有很高的立构规整度; 通过调节LLA 单体与PPO-PDLA 预聚体的投料比, 不仅可控制产物的分子序列结构, 而且样品的数均分子量可大于100 kDa. 差示扫描量热仪(DSC)和广角X 射线衍射(WAXD)结果显示, 三臂PPO-PDLAPLLA嵌段共聚物的异构体链段分子间生成立构复合晶体, 其熔点约为200 ℃, 且没有PLLA 均聚物链段结晶现象. 实验结果表明, 这是一类具有实际应用价值的新型耐热聚乳酸(PLA)材料.     

Melt block copolymerization of ϵ-caprolactone and L-lactide

AB block copolymers of ϵ-caprolactone and (L )-lactide could be prepared by ring-opening polymerization in the melt at 110°C using stannous octoate as a catalyst and ethanol as an initiator provided ϵ-caprolactone was polymerized first. Ethanol initiated the polymerization of ϵ-caprolactone producing a polymer with ϵ-caprolactone derived hydroxyl end groups which after addition of L -lactide in the second step of the polymerization initiated the ring-opening copolymerization of L -lactide. The number-average molecular weights of the poly(ϵ-caprolactone) blocks varied from 1.5 to 5.2 × 10³, while those of the poly(L -lactide) blocks ranged from 17.4 to 49.7 × 10³. The polydispersities of the block copolymers varied from 1.16 to 1.27. The number-average molecular weights of the polymers were controlled by the monomer/hydroxyl group ratio, and were independent on the monomer/stannous octoate ratio within the range of experimental conditions studied. When L -lactide was polymerized first, followed by copolymerization of ϵ-caprolactone, random copolymers were obtained. The formation of random copolymers was attributed to the occurrence of transesterification reactions. These side reactions were caused by the ϵ-caprolactone derived hydroxyl end groups generated during the copolymerization of ϵ-caprolactone with pre-polymers of L -lactide. The polymerization proceeds through an ester alcoholysis reaction mechanism, in which the stannous octoate activated ester groups of the monomers react with hydroxyl groups. © 1997 John Wiley & Sons, Inc.     

Synthesis and characterization of biodegradable block copolymers of ϵ-caprolactone and D,L-lactide initiated by potassium poly(ethylene glycol)ate

Poly(D ,L -lactide)–poly(ϵ-caprolactone)–poly(ethylene glycol)–poly(ϵ-caprolactone)–poly(D ,L -lactide) block copolymer (PLA–PCL–PEG–PCL–PLA) was prepared by copolymerization of ϵ-caprolactone (ϵ-CL) and D ,L -lactide (D ,L -LA) initiated by potassium poly(ethylene glycol)ate in THF at 25°C. The copolymers with different composition were synthesized by adjusting the mole ratio of reaction mixture. The resulted copolymers were characterized by ¹H-NMR, ¹³C-NMR, IR, DSC, and GPC. Efforts to prepare copolymers with the corresponding structure of PCL–PLA–PEG–PLA–PCL and D ,L -lactide/ϵ-caprolactone random copolymers were not successful. © 1997 John Wiley & Sons, Inc.     

Synthesis and Characterization of Biodegradable Poly(ϵ-caprolactone)-b-Poly(L-lactide) and Study on Their Electrospun Scaffolds

A series of multi-block copolymers, poly(L-lactide)-b-poly (?-caprolactone) (PLLA-b-PCL) were synthesized. The first step of the synthesis consisted of the transesterification between the PLLA and 1,4-Butanediol, followed by the copolymerization of PLLA-diols and PCL, using isophorone diisocyanate (IPDI) as a coupling agent. The synthesized polymers were characterized by Fourier transform infrared (FTIR) spectra, differential scanning calorimetry (DSC) and wide angle X-ray diffraction (WAXD). PLLA/PCL block copolymers were electrospun into ultrafine fibers. The morphology of the electrospun fibrous scaffolds were investigated by Scanning Electron Microscopy (SEM). Results showed that the morphology and diameter of the fibers were affected by the electrospinning solution concentrationan and different weight ratio of PLLA/PCL. These electrospun PLLA-b-PCL fibrous membranes exhibited good flexibility and deformability. In comparison with the electrospun PLLA membrane, the electrospun fibrous membranes of PLLA-b-PCL demonstrated an enhanced elongation with still high tensile strength and Young's modulus to be beneficial for tissue engineering scaffolds.     

A novel class of organosoluble poly(arylene ether nitrile) copolymers containing methyl substituent and cardo xanthene moiety

9,9‐Bis(3‐methyl‐4‐hydroxyphenyl)xanthene (BMHPX) was synthesized in 72% yield by a HCl/ZnCl₂‐catalyzed condensation reaction of xanthenone with excess o‐cresol. Based on this new bisphenol monomer, a series of poly(arylene ether nitrile) (PAEN) and PAEN copolymers containing methyl substituent and cardo xanthene moiety were prepared by the nucleophilic substitution reaction of 2,6‐difluorobenzonitrile (DFBN) with BMHPX and with varying mole proportions of BMHPX to hydroquinone (HQ) (100/0–40/60) using N‐methyl‐2‐pyrrolidone (NMP) as solvent in the presence of anhydrous potassium carbonate. These polymers had inherent viscosities between 0.54 and 0.72 dl/g, and their weight‐average molecular weights and number‐average molecular weights were in the range of 32,600–36,400 and 17,300–18,300, respectively. All PAENs were amorphous and were soluble in dipolar aprotic solvents such as NMP and N,N‐dimethylacetamide (DMAc), and even in THF and chloroform at room temperature. The resulting polymers showed glass transition temperatures (T_g's) between 213–226°C, and the T_g values of the copolymers were found to increase with increase of the BMHPX units content in the polymer. Thermogravimetric studies showed that all the polymers were stable up to 404°C, with 10% weight loss temperatures ranging from 444 to 455°C, and char yields of 52–58% at 700°C in nitrogen. All new PAENs could be cast into transparent, strong, and flexible films with tensile strengths of 102–120 MPa, elongations at break of 14–18%, and tensile moduli of 3.3–3.7 GPa. Copyright © 2011 John Wiley & Sons, Ltd.     

Synthesis and structural analysis of polyester prodrugs of norfloxacin

Two-, three- and four-arm, star-shaped poly(epsilon-caprolactone) and poly(D,L-lactide) homopolymers, and copolymers of epsilon-caprolactone with D,L-lactide were synthesized via ring-opening polymerization of cyclic esters in the presence of glycerol, penthaerythritol and poly(ethylene glycol) as initiators and stannous octoate as a catalyst. Thus obtained oligomers were successfully used in the synthesis of novel macromolecular prodrugs of norfloxacin. The structures of the polymers and prodrugs were elucidated by means of MALDI-TOF MS, NMR and IR studies.     

9,9-二(4-羟基苯基)呫吨、1,4-二(4-氟苯甲酰基)苯和双酚A三元共聚物聚醚醚酮酮的合成与表征

通过亲核取代反应,将9,9-二(4-羟基苯基)呫吨(BHPX)、1,4-二(4-氟苯甲酰基)苯和双酚A(BPA)进行三元共缩聚反应,合成了几种主链含二甲基甲烷和呫吨结构的聚醚醚酮酮无规共聚物(PEEKK-X/PEEKK-A),并以FTIR、DSC、TG、WAXD等对其结构和性能进行了表征.结果表明,共聚物的玻璃化转变温度(Tg)为185～218℃,均为无定形结构,其数均分子量为39500～41600,多分散性指数为1.94～2.05.在氮气、空气气氛中,在430℃之前不分解,5%的热失重温度(Td5)分别为490～511℃、480～505℃,在氮气中700℃时的残炭率均在40%以上;在常温下易溶于非质子极性溶剂(如NMP和DMAc)以及极性较弱的溶剂(如THF和CHCl3)中.共聚物均可通过溶液浇铸成膜,所得到的薄膜韧性好,透明且耐折,其拉伸强度为58～75MPa,杨氏膜量为1.95～2.70GPa,断裂伸长率为8%～13%.当双酚单体BHPX和BPA摩尔比为60/40～50/50时,所得到的PEEKK-X/PEEKK-A共聚物更有潜在的应用前景.     

Microwave-Assisted Synthesis of Poly(ε-caprolactone)-block-poly(ethylene glycol) and Poly(lactide)-block-poly(ethylene glycol)

Summary: This study reported the preparation and characterization of PCL-b-mPEG (poly(ε-caprolactone)-block-poly(ethylene glycol)) and PLL-b-mPEG (poly(L-lactide)-block-poly(ethylene glycol)) diblock copolymers by microwave heating and comparison of resulted products the ones with prepared by conventional heating. Diblock copolymers were synthesized successfully by the microwave-assisted ROP in the presence of stannous octoate (SnOct₂) as catalyst under nitrogen atmosphere in different monomer ratios. Structural and functional characterization of copolymers were performed by FTIR, ¹H-NMR and DSC. Molecular weight values were determined by GPC and also calculated from ¹H-NMR. According to the results, microwave irradiation allowed to obtain polymers with very narrow size distribution in very short reaction time. Similar polymers prepared by conventional heating were also synthesized for comparison. Molecular weight and conversion of polymers were increased by irradiation time. This change was continued until a certain time point after which no more increase was observed. It was concluded that microwave irradiation is a succesful method to obtain these diblock copolymers in very short reaction time and with a similar conversion obtained by conventional method.     

Semi‐interpenetrating polymer networks composed of poly(N‐isopropyl acrylamide) and polyacrylamide hydrogels

Three series of semi‐interpenetrating polymer networks, based on crosslinked poly(N‐isopropyl acrylamide) (PNIPA) and 1 wt % nonionic or ionic (cationic and anionic) linear polyacrylamide (PAAm), were synthesized to improve the mechanical properties of PNIPA gels. The effect of the incorporation of linear polymers into responsive networks on the temperature‐induced transition, swelling behavior, and mechanical properties was studied. Polymer networks with four different crosslinking densities were prepared with various molar ratios (25:1 to 100:1) of the monomer (N‐isopropyl acrylamide) to the crosslinker (methylenebisacrylamide). The hydrogels were characterized by the determination of the equilibrium degree of swelling at 25 °C, the compression modulus, and the effective crosslinking density, as well as the ultimate hydrogel properties, such as the tensile strength and elongation at break. The introduction of cationic and anionic linear hydrophilic PAAm into PNIPA networks increased the rate of swelling, whereas the presence of nonionic PAAm diminished it. Transition temperatures were significantly affected by both the crosslinking density and the presence of linear PAAm in the hydrogel networks. Although anionic PAAm had the greatest influence on increasing the transition temperature, the presence of nonionic PAAm caused the highest dimensional change. Semi‐interpenetrating polymer networks reinforced with cationic and nonionic PAAm exhibited higher tensile strengths and elongations at break than PNIPA hydrogels, whereas the presence of anionic PAAm caused a reduction in the mechanical properties. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 3987–3999, 2004     

Synthesis and characterization of biodegradable poly(ϵ‐caprolactone urethane)s. I. Effect of the polyol molecular weight,catalyst, and chain extender on the molecular and physical characteristics

Biodegradable polyurethanes with potential for applications in medical implants were synthesized in bulk with aliphatic hexamethylene diisocyanate, isophorone diisocyanate, poly(?‐caprolactone) diols of various molecular weights, 1,4‐butane diol, 2‐amino‐1‐butanol, thiodiethylene diol, and 2‐mercaptoethyl ether chain extenders. The catalysts used were stannous octoate, dibutyltin dilaurate, ferric acetyl acetonate, magnesium methoxide, zinc octoate, and manganese 2‐ethyl hexanoate. The synthesis reactions were second‐order. All the materials had narrow, unimodal molecular weight distributions and polydispersity indices of 1.5–1.9. The chemical structures of the polyurethanes, as assessed from ¹H NMR and ¹³C NMR spectra, were in good agreement with the monomer stoichiometric ratios. The glass‐transition temperatures of the materials ranged from ?38 to ?57 °C and were higher for polymers based on isophorone diisocyanate and with higher hard‐segment contents. For polyurethanes with the same hard‐segment content, there was no effect of the material molecular weight on the thermal properties. The tensile strengths of the materials were 12–63 MPa, and the tensile moduli were 8–107 MPa. These increased with an increasing hard‐segment content. The least effective catalyst was magnesium methoxide, and the most effective was ferric acetyl acetonate. Stannous octoate and manganese 2‐ethyl hexanoate were less effective than dibutyltin dilaurate and zinc octoate. © 2001 John Wiley & Sons, Inc. J Polym Sci Part A: Polym Chem 40: 156–170, 2002     

Synthesis and Characterization of Four-Arm Star Poly(ϵ-caprolactone)-Block-Poly(cyclic-carbonate methacrylate) Copolymers by Combining Ring-Opening Polymerization With Atom Transfer Radical Polymerization

Well-defined four-arm star poly(?-caprolactone)-block-poly(cyclic carbonate methacrylate) (PCL-b-PCCMA) copolymers were synthesized by combining ring-opening polymerization (ROP) with atom transfer radical polymerization (ATRP). First, a four-arm poly(?-caprolactone) (PCL) macroinitiator [(PCL-Br)₄] was prepared by the ROP of ?-CL catalyzed by stannous octoate at 110°C in the presence of pentaerythritol as the tetrafunctional initiator followed by esterification with 2-bromoisobutyryl bromide. The sequential ATRP of CCMA monomer was carried out by using the (PCL-Br)₄ tetrafunctional macroinitiator (MI) and in the presence of CuBr/2, 2′-bipyridyl system in DMF at 80°C with [(MI)]:[CuBr]:[bipyridyl] = 1:1:3 to yield block polymers with controlled molecular weights (M_n (NMR) = 10700 to 27300 g/mol) by varying block lengths and with moderately narrow polydispersities (M_w/M_n = 1.2–1.4). Block copolymers with different PCL: PCCMA copolymer composition such as 50:50, 70:30 and 74:26 were prepared with good yields (48-74%). All these block copolymers were well characterized by NMR, FTIR and GPC and tested their thermal properties by DSC and TGA.     

Synthesis and characterization of tercopolymers derived from ε‐caprolactone,trimethylene carbonate,and lactide

A series of tri‐components copolymers with different molar ratios were synthesized via bulk ring‐opening copolymerization of trimethylene carbonate (TMC), L ‐lactide (LLA), and ε‐caprolactone (ε‐CL), using stannous octoate as catalyst. The sequence structure of the tercopolymer chain was characterized by ¹H and ¹³C nuclear magnetic resonance (NMR), Fourier transform infrared (FTIR), and gel permeation chromatography (GPC). The results showed that although block sequence of the corresponding monomers still existed in the tercopolymer chain, the random tercopolymers were ultimately obtained due to the transesterification during polymerization. For the samples TP1 and TP2, longer sequence of LLA existed in the molecular chains. The thermal properties of tercopolymers were investigated by differential scanning calorimetry (DSC) and the mechanical properties of the resulting copolymers were studied by using a tensile tester. The results indicated that the properties of these copolymers could be adjusted by changing the compositions of the copolymers. The resulting tercopolymers are expected to have potential uses as nerve regeneration and other biomedicine materials. Copyright © 2007 John Wiley & Sons, Ltd.     

Fast degradable poly(L‐lactide‐co‐ε‐caprolactone) microspheres for tissue engineering: Synthesis,characterization, and degradation behavior

Polymeric scaffolds play a crucial role in engineering process of new tissues and effect the cell growth and viability. PLCL copolymers are found to be very useful during cell growth due to their elastic behavior and mechanical strength. Thus, low molecular weight PLCL copolymers of various ratios viz. PLCL(90/10), PLCL(75/25), PLCL(50/50) and PCL were synthesized by ring opening polymerization using stannous octoate as a catalyst. Synthesized polymers were characterized by GPC, ¹H‐NMR, FTIR and XRD. The thermal properties of the copolymers were studied using TGA and DSC. Microspheres of about 100 μm diameter were prepared for different copolymers and their in vitro degradation behaviors were studied up to 108 days. It was observed that degradation of PLA content in polymer backbone occurs faster than PCL component which is also indicated by corresponding change in ratios of PLA/PCL, as determined by ¹H‐NMR. SEM images of microspheres depicted the surface morphology during degradation and suggested the faster degradation for PLCL (50:50). Copolymers of different thermal, mechanical properties and different degradation behaviors can be prepared by adjusting the composition of copolymers. Various synthesized polymers from this work have been tested in our laboratory as polymeric scaffold for soft tissue engineering. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 2755–2764, 2007     

Preparation and characterization of colorless alternate poly(amide-imide)s based on trimellitic anhydride and 2,2-bis[4-(3-aminophenoxy)phenyl]sulfone

Alternate poly(amide-imide) [P(A-alt-I)] was synthesized from two aromatic diamines and trimellitic anhydride (TMA). When the diamine was 2,2-bis[4-(3-aminophenoxy)phenyl]sulfone (BAPS), the resulted P(A-alt-I) was found to be of light color. Specifically, when BAPS was located between two amide groups in the P(A-alt-I) chain, the P(A-alt-I) was almost colorless. A series of P(A-alt-I)s (Series III) containing BAPS was synthesized through direct polycondensation of an aromatic dicarboxylic acid prepared from various aromatic diamines and TMA, as well as BAPS. Polymers of Series III were much lighter in color than those of the isomeric series (BAPS was located between two imide group). The series of P(A-alt-I)s III had inherent viscosities ranging 0.69–1.35 dL/g and good solubility in various solvents. The tensile strengths, elongations to break, and initial moduli of the films were 72–107 MPa, 7–12% and 1.93–2.39 GPa, respectively, and most of the films had no yielding. Polymers of Series III had glass transition temperatures 210–272°C and 10% weight loss temperatures in nitrogen 518–545°C, indicating excellent thermal stability. © 1999 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 37: 2421–2428, 1999     

Synthesis and properties of organosoluble poly(amide imide imide)s based on tetraimide dicarboxylic acid condensed from 4,4′‐(hexafluoroisopropylidene)diphthalic anhydride, 4,4′‐oxydianiline,and trimellitic anhydride and various aromatic diamines

A novel tetraimide dicarboxylic acid was synthesized with the ring‐opening addition of 4,4′‐(hexafluoroisopropylidene)diphthalic anhydride, 4,4′‐oxydianiline, and trimellitic anhydride in a 1/2/2 molar ratio in N‐methyl‐2‐pyrrolidone followed by azeotropic condensation to tetraimide dicarboxylic acid. A series of poly(amide imide imide)s (PAIIs) with inherent viscosities of 0.8–1.1 dL/g were prepared from tetraimide dicarboxylic acid with various aromatic diamines by direct polycondensation. Most of the PAIIs were readily soluble in a variety of amide polar solvents and even in less polar m‐cresol and pyridine. Solvent‐cast films had tensile strengths ranging from 99 to 106 MPa, elongations at break ranging from 8 to 13%, and initial moduli ranging from 2.0 to 2.3 GPa. The glass‐transition temperatures of these PAIIs were recorded at 244–276 °C. They had 10% weight losses at temperatures above 520 °C in air or nitrogen atmospheres. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 1092–1102, 2002