Synthesis and characterization of soluble poly(arylene ether ketone)s with high glass transition temperature based on 3,6‐bi(4‐fluorobenzoyl)‐N‐alkylcarbazole

3,6‐bi(4‐fluorobenzoyl)‐N‐methylcarbazole and 3,6‐bi(4‐fluorobenzoyl)‐N‐ethylcarbazole were synthesized and used to prepare poly(arylene ether ketone)s (PAEKs) with high glass transition temperatures (T_g) and good solubility. High molecular weight amorphous PAEKs were prepared from these two difluoroketones with hydroquinone, phenolphthalein, 9,9‐bis(4‐hydroxyphenyl)fluorene and 4‐(4‐hydroxylphenyl)‐2,3‐phthalazin‐1‐one, respectively. All these polymers presented high thermal stability with glass transition temperatures being in the range 239–303 °C and a 5% thermal weight loss temperature above 460 °C. Compared with the T_g of phenolphthalein‐based PAEK (PEK‐C), fluorene‐based PAEK (BFEK) and phthalazinone‐based PAEK (DPEK) not containing a carbazole unit, these polymers presented a 30–50 °C increase in T_g. Meanwhile, PAEKs prepared from N‐ethylcarbazole difluoroketone showed good solubility in ordinary organic solvents, and all polymers exhibited excellent resistance to hydrochloric acid (36.5 wt%) and sodium hydroxide (50 wt%) solutions. In particular, phthalazinone‐based PAEK bearing N‐ethylcarbazole afforded simultaneously a T_g of 301 °C with good solubility. Tensile tests of films showed that these polymers have desirable mechanical properties. The carbazole‐based difluoroketones play an important role in preparing soluble PAEKs with high T_g by coordinating the relationship between chain rigidity resulting from the carbazole unit and chain distance from the side alkyl. © 2014 Society of Chemical Industry     

Synthesis and properties of novel phosphorus‐containing poly(ether ether ketone ketone)s

A novel monomer, bis[4‐(4‐fluorobenzoyl)phenyl]phenylphosphine oxide, was synthesized through the reaction of bis(4‐chloroformylphenyl) phenyl phosphine oxide with fluorobenzene. Three poly(ether ether ketone ketone)s derived from bis[4‐(4‐fluorobenzoyl)phenyl]phenylphosphine oxide and different aromatic bisphenols were prepared by aromatic nucleophilic substitution reactions. The resulting polymers had inherent viscosities in the range of 0.55–0.73 dL/g. The structures of the poly(ether ether ketone ketone)s were characterized with Fourier transform infrared and ¹H‐NMR. Thermal analysis indicated that the glass‐transition temperatures of the poly(ether ether ketone ketone)s were higher than 200°C, and the 5% weight loss temperatures in nitrogen were higher than 463°C. All the polymers showed excellent solubility in polar solvents such as N‐methyl‐2‐pyrrolidone, dimethylformamide, and dimethylacetamide and could also be dissolved in chlorinated methane. The polymers afforded transparent and flexible films by solvent casting. Organic phosphorous moieties also imparted good flame‐retardancy to the polymers. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Synthesis and properties of poly(aryl ether sulfone)s containing the phthalazinone moiety

Three series of poly(aryl ether sulfone)s (PAESs) containing the phthalazinone moiety in the polymer backbone were synthesized by solution polycondensation of bis(4-chlorophenyl) sulfone with three commercial bisphenols and 4-(4-hydroxyphenyl)-2,3-phthalazin-1-one. Bisphenol-A, hydroquinone, and bis(4-hydroxyphenyl) sulfone, or bisphenol-S, were selected as the commercial bisphenols for copolymerization. The synthesized polymers exhibited very high glass transition temperatures and excellent thermooxidative properties. They also showed superior mechanical properties and fair rheological properties. The introduction of relatively flexible moieties, such as benzene rings, onto the poly(phthalazinone ether sulfone) (PPES) chain led to a decrease in glass transition temperature with respect to the phthalazinone homopolymer. However, the processability of PPES was improved dramatically by the addition of these commercial bisphenols. The properties of synthesized PAESs can be tailored by changing the molar ratios of bisphenols to phthalazinone monomer. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 68:137–143, 1998     

Polycondensation of bis(cyanoacetate) and a,10bdihydrobenzofuro[2,3‐b]benzofuran‐2,9‐dicarbaldehyde via knoevenagel reaction: Synthesis of donor–acceptor polymers containing shoulder‐to‐shoulder main chains

Compound 5 a ,10 b ‐dihydrobenzofuro[2,3‐ b ]benzofuran‐2,9‐dicarbaldehyde ( II ) was prepared by two‐step reactions from p‐cresol and glyoxal. The bis(cyanoacetate) monomers ( III ) were prepared in a high yield by reacting ethyl cyanoacetate with the appropriate diol in the presence of tetra‐n‐butyl titanate. The polymers from II and III were synthesized by Knoevenagel polycondensation that was first carried out in anhydrous THF and followed by a solid‐state polycondensation, and main‐chain polymers with good glass transition temperatures in high yield were obtained. The polymerization of II and III afforded polymers IV , which exhibited good solubility in most organic solvents. The structure of all the monomers and polymers were characterized by conventional spectroscopic methods. The synthesized polymers contain acceptor groups (cyanide and carbonyl) and a donor group (benzodihydrofuran) in their main chain. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 81: 505–511, 2001     

Synthesis of soluble and thermally stable poly(N‐arylenebenzimidazole)s

Six new bis(benzimidazolyl) monomers containing ether, sulfonyl and ketone groups were synthesized efficiently. A series of poly(N‐arylenebenzimidazole)s were prepared using an aromatic nucleophilic displacement reaction that removed the N–H sites from the novel bis(benzimidazolyl) derivatives with activated aromatic difluorides in sulfolane. The reaction was carried out at 210 °C in the presence of anhydrous potassium carbonate. All resulting polymers showed essentially amorphous patterns. This was consistent with the calculated results. Differential scanning calorimetry and thermogravimetric measurements showed that the polymers had high glass transition temperatures (>240 °C), good thermostability and high decomposition temperatures (>400 °C). These novel polymers also showed easy solubility. © 2013 Society of Chemical Industry     

Soluble and crosslinkable poly(phthalazinone ether ketone)s with pendent terminal ethynyl groups: synthesis,characterization and click modification

New poly(phthalazinone ether ketone)s (PPEKs) with pendent terminal ethynyl groups were synthesized by the aromatic nucleophilic substitution (S_NAr) polycondensation reaction of a new bisphenol monomer, 2‐(3‐ethynylphenyl)hydroquinone, with 4‐(4′‐hydroxyphenyl)phthalazin‐1(2H)‐one and 4,4′‐bis(4‐fluorophenyl) ketone, followed by click modification reaction with 1‐azidopyrene. Fourier transform infrared and NMR spectral data of the model compound indicated that the terminal ethynyl groups were stable in S_NAr reaction conditions, thus allowing the synthesis of the desired polymers. The PPEKs obtained with glass transition temperature (T_g) in the range 152–245 °C were amorphous, characterized by wide‐angle X‐ray diffraction, and dissolved in organic solvent to cast into transparent and flexible films. Differential scanning calorimetry results indicated that the curing reaction of the terminal ethynyl groups of the copolymers took place upon heating to 250 °C. The T_g of cured PPEKs was increased to about 260 °C. They also exhibited excellent thermal stability with 5% weight loss temperatures ranging from 448 to 527 °C in various atmospheres. The PPEKs with pendent terminal ethynyl groups were subsequently functionalized with pyrene through click reaction. A dilute chloroform solution displayed a red‐shifted emission profile. © 2014 Society of Chemical Industry     

Synthesis of novel poly(phthalazinone ether sulfone ketone)s and improvement of their melt flow properties

A series of novel poly(phthalazinone ether sulfone ketone)s was synthesized from bis(4-fluorophenyl) ketone, bis(4-chlorophenyl)sulfone, and 4-(4-hydroxybenzyl)-2,3-phthalazin-1-one through nucleophilic substitution polycondensation. The synthesized polymers exhibited surprisingly high glass transition temperatures and had excellent thermooxidative properties. The melt viscosities of these synthesized polymers are generally too high to be processed by common processing methods because of their very high glass transition temperatures and amorphous microstructure. An attempt was made to reduce their melt viscosities by solution blending the synthesized polymer with two kinds of oligomers: low molecular weight poly(phthalazinone ether sulfone ketone) and commercial poly(ether sulfone). The results proved that the addition of the oligomers to the polymers led to a marked decrease in melt viscosities. Furthermore, no obvious changes were observed in the thermal and mechanical properties of these blends after oligomer additions. © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 66: 1425–1432, 1997     

Synthesis and characterization of new polyamides derived from 1,3‐(4‐carboxy phenoxy) propane and aromatic diamines

Six new polyamides 5a‐f containing flexible trimethylene segments in the main chain were synthesized through the direct polycondensation reaction of 1,3‐(4‐carboxy phenoxy) propane 3 with six derivatives of aromatic diamines 4a‐f in a medium consisting of N‐methyl‐2‐pyrrolidone, triphenyl phosphite, calcium chloride, and pyridine. The polycondensation reaction produced a series of novel polyamides containing flexible trimethylene segments in the main chain in high yield with inherent viscosities between 0.32 and 0.68 dL/g. The resulted polymers were fully characterized by means of FTIR spectroscopy, elemental analyses, inherent viscosity, and solubility tests. Thermal properties of these polymers were investigated by using thermal gravimetric analysis (TGA) and differential thermal gravimetric (DTG). The glass‐transition temperatures of these polyamides were recorded between 165 and 190°C by differential scanning calorimetry, and the 10% weight loss temperatures were ranging from 360 to 430°C under nitrogen. 1,3‐(4‐Carboxy phenoxy) propane 3 was prepared from the reaction of 4‐hydroxy benzoic acid 1 with 1,3‐dibromo propane 2 in the presence of NaOH solution. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Synthesis and characterization of novel photo‐crosslinkable fluorinated poly(phthalazinone ether)s for optical waveguides

A series of novel photo‐crosslinkable fluorinated poly(phthalazinone ether)s containing 1,1‐diphenylethylene segments in the polymer main chain, used for optical waveguide materials, were synthesized by polycondensation reaction of decafluorobiphenyl with a mixture of 4‐(4‐hydroxylphenyl)(2H)‐phthalazin‐1‐one (DHPZ), 4,4‐(hexafluoroisopropylidene)diphenol and 1,1‐bis(4‐hydroxyphenyl)ethylene (BHPE) as co‐reactant. The feed ratio of DHPZ to total bisphenols varied from 0 to 80 mol%, while that of BHPE remained at 20 mol% for all polymers. The obtained copolymers show good solubility in some common polar organic solvents. The resulting polymers were photo‐crosslinked after UV irradiation for 10 min in the presence of a photoinitiator. The cured polymers show good chemical resistance, high thermal stability (temperatures of 1% mass loss after curing of 472–496 °C under nitrogen) and high glass transition temperatures (160–249 °C) which could be further increased by about 10 °C after photochemical crosslinking. By adjusting the copolymerizing bisphenol content, the refractive indices of transverse electric and transverse magnetic modes (at 1550 nm) of films of the polymers were exactly tuned in the range 1.5029–1.5661 and 1.4950–1.5502, respectively. The propagation losses of the cured films were measured and found to be less than 0.3 dB cm^?1 at 1550 nm, indicating the promise of these materials for passive optical waveguide devices. Copyright © 2011 Society of Chemical Industry     

Synthesis and characterization of phthalonitrile resins from ortho‐linked aromatic and heterocyclic monomers

This article describes the synthesis and properties of phthalonitrile polymers prepared from three different ortho‐linked monomers, namely 2,2′‐bis(3,4‐dicyanophenoxy)biphenyl, 1,2‐bis(3,4‐dicyanophenoxy)benzene and 2,2′‐bis(3,4‐dicyanophenoxy)‐1,3,4‐oxadiazole. The resins exhibited a low complex viscosity, with a varying range of processing temperatures for all three systems. Thermogravimetric analysis showed that the synthesized polymers exhibited high thermal and thermo‐oxidative stability. The high char yields, which ranged from 64 to 69% at 900 °C under nitrogen atmosphere, and the high glass transition temperatures of the polymers indicated a high crosslinking density in the network structure. Dynamic mechanical measurements demonstrated that the fully cured monomer 2,2′‐bis(3,4‐dicyanophenoxy)‐1,3,4‐oxadiazole exhibited no change in glass transition temperature or in storage modulus up to 500 °C. © 2013 Society of Chemical Industry     

Synthesis and characterization of new thermally stable poly(ester‐imide)s derived from 2,2′‐bis(4‐trimellitimidophenoxy)biphenyl and 2,2′‐bis(4‐trimellitimidophenoxy)‐1,1′‐binaphthyl and various aromatic dihydroxy compounds

A series of new alternating aromatic poly(ester‐imide)s were prepared by the polycondensation of the preformed imide ring‐containing diacids, 2,2′‐bis(4‐trimellitimidophenoxy)biphenyl (2a) and 2,2′‐bis(4‐trimellitimidophenoxy)‐1,1′‐binaphthyl (2b) with various aromatic dihydroxy compounds in the presence of pyridine and lithium chloride. A model compound (3) was also prepared by the reaction of 2b with phenol, its synthesis permitting an optimization of polymerization conditions. Poly(ester‐imides) were fully characterized by FTIR, UV‐vis and NMR spectroscopy. Both biphenylene‐ and binaphthylene‐based poly(ester‐imide)s exhibited excellent solubility in common organic solvents such as tetrahydrofuran, m‐cresol, pyridine and dichloromethane. However, binaphthylene‐based poly(ester‐imide)s were more soluble than those of biphenylene‐based polymers in highly polar organic solvents, including N‐methyl‐2‐pyrrolidone, N,N‐dimethylacetamide, N,N‐dimethylformamide and dimethyl sulfoxide. From differential scanning calorimetry thermograms, the polymers showed glass‐transition temperatures between 261 and 315 °C. Thermal behaviour of the polymers obtained was characterized by thermogravimetric analysis, and the 10 % weight loss temperatures of the poly(ester‐imide)s was in the range 449–491 °C in nitrogen. Furthermore, crystallinity of the polymers was estimated by means of wide‐angle X‐ray diffraction. The resultant poly(ester‐imide)s exhibited nearly an amorphous nature, except poly(ester‐imide)s derived from hydroquinone and 4,4′‐dihydroxybiphenyl. In general, polymers containing binaphthyl units showed higher thermal stability but lower crystallinity than polymers containing biphenyl units. Copyright © 2005 Society of Chemical Industry     

Synthesis and characterization of poly(arylene ether s‐triazine)s containing alkyl‐, aryl‐ and chloro‐substituted phthalazinone moieties in the main chain

Soluble and heat‐resistant polymers have great potential for use as processable, high‐temperature polymeric materials. In this study, four types of new poly(arylene ether s‐triazine)s containing alkyl‐, aryl‐ and chloro‐substituted phthalazinone moieties in the main chain were prepared through direct solution polycondensation of 2,4‐bis(4‐fluorophenyl)‐6‐phenyl‐s‐triazine with each of methyl‐, phenyl‐ and chloro‐substituted phthalazinones. A key feature of these polymers is the incorporation of phthalazinone and side groups into the poly(arylene ether s‐triazine) backbone to endow them with good solubility while maintaining other attractive properties. The polymers were obtained in high yields, and had inherent viscosities ranging from 0.38 to 0.55 dL g^?1. Their structure was characterized using Fourier transform infrared and NMR spectra and elemental analysis. The polymers were almost amorphous, and soluble in N‐methyl‐2‐pyrrolidone, pyridine, N,N‐dimethylacetamide, hot N,N‐dimethylformamide and sulfolane. Tough and nearly transparent films obtained by direct solution casting exhibited good mechanical properties. The resulting polymers displayed glass transition temperatures ranging from 255 to 265 °C and thermal decomposition temperatures for 10% mass loss ranging from 476 to 599 °C, according to differential scanning calorimetry and thermogravimetric analysis, respectively. The reactivity of substituted phthalazinones in nucleophilic displacement reactions and the effect of the side groups on the physical properties of the polymers were also investigated. The results obtained revealed that such s‐triazine‐containing polymers possessed good solubility while maintaining acceptable thermal stability and high mechanical strength with the incorporation of alkyl‐, aryl‐ and chloro‐substituted phthalazinone moieties into their backbones, which makes them an attractive series of high‐performance structural materials. Copyright © 2010 Society of Chemical Industry     

Synthesis and characterization of organo‐soluble poly(ether ether ketone)s and poly(ether ether ketone ketone)s containing pendant pentadecyl chains

Poly(ether ether ketone)s and poly(ether ether ketone ketone)s containing pendant pentadecyl chains were synthesized by polycondensation of each of the two bisphenol monomers viz, 1,1,1‐[bis(4‐hydroxyphenyl)‐4′‐pentadecylphenyl]ethane and 1,1‐bis(4‐hydroxyphenyl)‐3‐pentadecyl cyclohexane with activated aromatic dihalides namely, 4,4′‐difluorobenzophenone, and 1,3‐bis(4‐fluorobenzoyl)benzene in a solvent mixture of N,N‐dimethylacetamide and toluene, in the presence of anhydrous potassium carbonate. Polymers were isolated as white fibrous materials with inherent viscosities and number average molecular weights in the range 0.70–1.27 dL g^?1 and 76,620–1,36,720, respectively. Poly(ether ether ketone)s and poly(ether ether ketone ketone)s were found to be soluble at room temperature in organic solvents such as chloroform, dichloromethane, tetrahydrofuran, and pyridine and could be cast into tough, transparent, and flexible films from their solutions in chloroform. Wide angle X‐ray diffraction patterns exhibited a broad halo at around 2θ = ～ 19° indicating that the polymers containing pentadecyl chains were amorphous in nature. In the small‐angle region, diffuse reflections of a typically layered structures resulting from the packing of pentadecyl side chains were observed. The temperature at 10% weight loss, obtained from TG curves, for poly(ether ether ketone)s and poly(ether ether ketone ketone)s were in the range 416–459°C, indicating their good thermal stability. A substantial drop in glass transition temperatures (68–78°C) was observed for poly(ether ether ketone)s and poly(ether ether ketone ketone)s due to “internal plasticization” effect of flexible pendant pentadecyl chains. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Synthesis and characterization of novel poly(aryl ether ketone ketone)s containing the o‐dibenzobene moiety

The synthesis of a novel chloro monomer containing the 1,2‐dibenzoylbenzene moiety was described. The chloro monomer was reacted with 4‐(4‐hydroxyphenyl)‐1(2H)‐phthalazinone compound in the presence of excess anhydrous potassium carbonate in an aprotic solvent (Sulfolane), and high molecular weight amorphous poly(aryl ether ketone ketone) was synthesized. The polymers with high glass transition temperature were soluble in solvents such as chloroform and nitrobenzene at room temperature and easily cast into flexible, colorless, and transparent films. The 5% weight loss of the polymers was >400 °C. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 81: 1487–1492, 2001     

Poly(amides) and poly(imides) containing silicon and germanium in the main chain: Synthesis,characterization and thermal studies

Poly(amides) and poly(imides) containing the heteroatoms Si or Ge in the main chain and bonded to four carbon atoms were synthesized and characterized by IR and ¹H, ¹³C and ²⁹Si NMR. The acid dichlorides bis(4‐chloroformylphenyl)‐dimethylgermane, bis(4‐chloroformylphenyl)‐diphenylgermane, bis(4‐chloroformylphenyl)‐dimethylsilane, and bis(4‐chloroformylphenyl)‐diphenylsilane were synthesized from the ditolyl derivatives, which were oxidized to the respective diacids. The dianhydrides bis(3,4‐dicarboxyphenyl)‐dimethylgermane dianhydride, bis(3,4‐dicarboxyphenyl)‐diphenylgermane dianhydride, bis(3,4‐dicarboxyphenyl)‐dimethylsilane dianhydride, and bis(3,4‐dicarboxyphenyl)‐diphenylsilane dianhydride were synthesized from the dixylyl derivatives, which were oxidized to the tetraacids. Fully aromatic diamines also containing Si or Ge were synthesized from 4‐bromo‐N,N‐bis(trimethylsilyl)‐aniline and diphenyl‐dichlorosilane or germane. The ditolyl and dixylyl derivatives were synthesized from 4‐bromo‐toluene or 4‐bromo‐xylene and dimethyl‐ or diphenyl‐dichlorogermane, dimethyl‐ or diphenyl‐dichlorosilane. The glass transition temperatures and the thermal stability were determined showing in general that the polymers with Si atom in the main chain presented higher values of both parameters due to the higher ionic character of the C? Si bond compared with the C? Ge one, and due to the lower size of the Si atom that presents lower rotational barriers. © 2006 Wiley Periodicals, Inc. J Appl PolymSci 102: 2768–2776, 2006     

Thermal and electrical properties of copoly(1,3,4‐oxadiazole‐ethers) containing fluorene groups

A series of aromatic copolyethers containing 1,3,4‐oxadiazole rings and fluorene groups was prepared by nucleophilic substitution polymerization technique of 9,9‐bis(4‐hydroxyphenyl)fluorene, 1 , or of different amounts of 1 and an aromatic bisphenol, such as 4,4′‐isopropylidenediphenol or phenolphthalein, with 2,5‐bis(p‐fluorophenyl)‐1,3,4‐oxadiazole. The polymers were easily soluble in polar solvents like N‐methylpyrrolidone, N,N‐dimethylacetamide, N,N‐dimethylformamide, and chloroform and can be cast from solutions into thin flexible films. They showed high thermal stability, with decomposition temperature being above 425°C. The polymers exhibited a glass‐transition temperature in the range of 195–295°C, with a reasonable interval between glass‐transition and decomposition temperature. Electrical insulating properties of some polymer films were evaluated on the basis of dielectric constant and dielectric loss and their variation with frequency and temperature. The values of the dielectric constant at 10 kHz and 20°C were in the range of 3.16–3.25. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Copolymerization and blending of poly(phthalazinone ether ketone)s to improve their melt processability

The melt processability of phthalazinone‐containing poly(aryl ether)s (PAEs) was improved through copolymerization and blending. Poly(phthalazinone ether ketone) (PPEK) copolymers containing phthalazinone and bisphenol‐A (BPA) moieties were synthesized through nucleophilic substitution polycondensation. The PPEK copolymers exhibited high glass transition temperatures, excellent thermooxidative properties, good mechanical properties and improved solubility, all of which can be tailored by changing the molar ratio of phthalazinone to bisphenol monomers. The rheological investigation indicated that the incorporation of the flexible BPA moiety into the main chain lowered the melt viscosity of the copolymers. To improve the melt processability further, polymer blends of a PPEK copolymer/polycarbonate (PC) were prepared. The results suggested that blending is an effective approach for improving the melt processability of phthalazinone‐containing PAEs. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 2575–2580, 2007     

Silicon‐containing anionic water‐borne polyurethane with covalently bonded reactive dye

A silicon‐containing water‐borne polyurethane (PU) polymer with hydroxyl side groups was synthesized that was stable in basic conditions and also capable of reacting with a reactive dye to form a covalently bonded dye molecule. The silicon‐containing anionic water‐borne PU prepolymer was synthesized from H₁₂‐4,4′‐diphenylmethane diisocyanate (H₁₂‐MDI), polytetramethylene glycol, polydimethylsiloxane (PDMS), 2,2′‐bis(hydroxymethyl), propionic acid (anionic centers), and triethyleneamine using the prepolymer mixing method. Water was then added to emulsify and disperse the resin to form an anionic water‐borne PU prepolymer. N‐(2‐Hydroxyethyl ethylene diamine) (HEDA) was used to extend the prepolymer to form a water‐borne PU polymer with a side chain of hydroxyl groups, which can further react with the reactive dye to form a dyed PU. The reactive dye of chlorosulfuric acid esters of sulfatoethyl sulfones can react with the water‐borne PU polymer. Behaviors of alkali resistance and dyeing properties were observed. In consideration of thermal properties, the dye‐grafted PU polymers exhibited lower glass‐transition temperatures for soft segments and hard segments than those without dye. Concerning mechanical properties, it was found that the modulus and the strength of the dyed PU polymers decreased with grafting of the dye molecule, but elongation at break was increased. The alkali resistance increased with PDMS content. For dye‐uptake properties, the percentage of dye grafting was over 90%. Also, the dye‐grafted PU exhibited a lower percentage of dye migration than that of polymers with ethylene diamine instead of HEDA as a chain extender, and showed greater colorfastness to light. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 2045–2052, 2003     

Synthesis and characterization of novel polyesterimides

A series of soluble novel polyesterimides was synthesized from diamines [a mixture of 2,2‐bis(4‐(4‐aminophenoxy)phenyl)propane (BAPP) with amine‐terminated polysiloxane (ATPS) in various mole ratios] and the ester‐group‐containing dianhydrides. The ester group containing dianhydrides in turn was synthesized by the transesterification reaction of trimellitic anhydride (TMA) with diacetate ester of hydroquinone (HQ), 4,4′‐dihydrophenyl (BP), 1,6‐hexanediol, or ethylene glycol. The resulted polyesterimides were characterized by using Fourier‐transform infrared spectroscopy, inherent viscosity, solubility, differential scanning calorimetry (DSC), and thermogravimetric analysis (TGA). The polyesterimides of BP and HQ had relatively high glass transition temperatures in the range of 214.7–227.2 and 195.7–210.5°C, respectively. The glass transitions decreased rather slowly with the increase in polysiloxane content. Thermal stability and the weight‐loss behavior of polyesterimides were studied by TGA. All polyesterimides of BP and HQ (BPI and HQI) showed no significant weight loss below 500°C in a N₂ environment, and the decomposition temperatures (T_d5%) of BPI and HQI were >520°C. Most polyesterimides were soluble in polar aprotic solvents and m‐cresol. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 94: 730–738, 2004     

Synthesis,spectral, and thermal characterization of photosensitive poly(ether–ester)s containing α,β‐unsaturated ketone moieties in the main chain derived from 2,6‐bis[4‐(3‐hydroxypropyloxy)‐3‐methoxybenzylidene]cyclohexanone

A series of photosensitive poly(ether–ester)s containing α,β‐unsaturated ketone moieties in the main chain were synthesized from 2,6‐bis[4‐(3‐hydroxypropyloxy)‐3‐methoxybenzylidene]cyclohexanone (BHPMBCH) and aliphatic and aromatic diacid chlorides. The diol precursor, BHPMBCH, was synthesized from 2,6‐bis(4‐hydroxy‐3‐methoxybenzylidene)cyclohexanone and 3‐bromo‐1‐propanol. The solubility of the polymers was tested in various solvents. The intrinsic viscosity of the synthesized polymers, determined by an Oswald viscometer, was found to be 0.06–0.80 g/dL. The molecular structures of the monomer and polymers were confirmed by Fourier transform infrared, ultraviolet–visible, ¹H‐NMR, and ¹³C‐NMR spectral analyses. The thermal properties were studied with thermogravimetric analysis and differential scanning calorimetry. The thermogravimetric analysis data revealed that the polymers were stable up to 220°C and started degrading thereafter. The thermal stability initially increased with increasing spacer length and then decreased due to negative effects of the spacer. The self‐extinguishing properties of the synthesized polymers were studied by the determination of the limiting oxygen index values with Van Krevelen's equation. In addition, the photocrosslinking properties of the polymer chain were studied with UV spectroscopy, and we observed that the rate of photocrosslinking increased significantly with increasing methylene carbon chain length of the acid spacer. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011