Z-protected glutamic acid-based biodegradable thermoplastic and thermosetting polyesters: Synthesis and characterization

Biodegradable polymers were formed from N-benzyloxycarbonyl-l -glutamic acid with the comonomers ethylene glycol, diglycidyl ether of 1,4-butanediol, and diglycidyl ether of bisphenol A. The three polymers were a linear and a crosslinked heterochain polyester and a crosslinked polyester that contained aromatic units within its network chains. The thermoplastic resin and the soluble fractions for the thermosetting resins were characterized by gel permeation chromatography. Conversions for carboxylic acid were determined by titrations. A quality, 22,000 molecular weight thermoplastic resin was formed. The two thermosets were cured past their gel points. Gelation analysis revealed that the relative rate constants for the sequential oxirane/acid and alcohol/acid reactions were distinct. With diglycidyl ether of 1,4-butanediol, the ratio of the respective rate constants was 3; with diglycidyl ether of bisphenol A, the ratio approached 200. The resins hydrolyzed to monomers in the presence of lipase, but in the presence of a mixed microbial culture, only the first two resins decayed to biomass, respiratory gases, and water. The third resin was inert during the period of observation. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 73: 869–879, 1999     

Synthesis and adsorption properties for metal ions of crosslinked chitosan acetate crown ethers

Two novel chitosan derivatives—crosslinked chitosan dibenzo‐16‐c‐5 acetate crown ether (CCTS‐1) and crosslinked chitosan 3,5‐di‐tert‐butyl dibenzo‐14‐c‐4 diacetate crown ether (CCTS‐2)—were synthesized by the reaction of crosslinked chitosan with dibenzo‐16‐c‐5 chloracetate crown ether and 3,5‐di‐tert‐butyl dibenzo‐14‐c‐4 dichloracetate crown ether with the intent of forming polymers that could be used in hazardous waste remediation as toxic metal‐binding agents in aqueous environments. Their structures were confirmed with elemental analysis, infrared spectral analysis, and X‐ray diffraction analysis. In the infrared spectra of CCTS‐1 and CCTS‐2, the characteristic peaks of aromatic backbone vibration appeared at 1595 cm⁻¹ and 1500 cm⁻¹; the intensity of the N H and O H stretching vibration in the region of 3150–3200 cm⁻¹ decreased greatly. The X‐ray diffraction analysis showed that the peak at 2θ = 20° decreased greatly in CCTS‐1 and CCTS‐2. The adsorption and selectivity properties of CCTS‐1 and CCTS‐2 for Pb²⁺, Cu²⁺, Cr³⁺, and Ni²⁺ were studied. Experimental results showed that the two crosslinked chitosan derivatives had not only good adsorption capacities for Pb²⁺, Cu²⁺, but also high selectivity for Pb²⁺, Cu²⁺ in the coexistence of Ni²⁺. For aqueous systems containing Pb²⁺, Ni²⁺, or Cu²⁺, Ni²⁺, CCTS‐1 only adsorbed Pb²⁺ or Cu²⁺. For aqueous systems containing Pb²⁺, Cr²⁺ and Ni²⁺, CCTS‐2 had high adsorption and selectivity properties for Pb²⁺. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 71: 2069–2074, 1999     

Crosslinking of epoxidized natural oils with diepoxy reactive diluents

The different natural oils epoxidized with 3‐chloroperbenzoic acid were crosslinked with diepoxy reactive diluents, bisphenol A propoxylate diglycidyl ether, and 3,4‐epoxycyclohexylmethyl‐3,4‐epoxyclohexane‐carboxylate, using cationic initiator at 60°C and photoinitiators at the room temperature. The insoluble fraction of the polymeric products was 59–90%. The Young modulus of the crosslinked polymer films ranged from 2 to 861 MPa. The 10% weight loss temperatures of the crosslinked polymers estimated by thermogravimetric analysis were in the range from 250 to 420°C. The water vapor transmission rate of the crosslinked biopolymer films ranged from 6 to 49 g/m²/24 h. Biochemical oxygen demand and biodegradation in soil of the crosslinked polymers were studied. The crosslinked polymers showed higher biodegradation rate than cellulose, starch, and polyvinylalcohol. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Ultrasonic properties of some diamine cured aliphatic epoxy polymers

Longitudinal sound speed and absorption were measured from 0° to 100°C at a frequency of 2 MHz on an aliphatic epoxy resin (butanediol diglycidyl ether) crosslinked with four different curing agents—three aliphatics of differing chain lengths and one aromatic. The ultrasonic properties were found to be dominated by the glass transition in a manner qualitatively similar to linear polymers. In the aliphatic series, the ultrasonic properties all fell on the same master curves when plotted as functions of T ? T_g, but the aromatic curing agent was qualitatively different. For a single relaxation time model, the sound absorption peak for the aliphatic series would be 55 dB cm^?1. The measured peak of 28 dB cm^?1 shows that the glass transition involves a distribution of relaxation times.     

Effect of thermal crosslinking on the properties of sulfonated poly(phenylene sulfone)s as proton conductive membranes

The synthesis and characterization of crosslinked aromatic polymer membranes with high ion exchange capacity (IEC) values are reported. Through aromatic nucleophilic substitution polycondensation and the subsequent sulfonation reaction, the highly sulfonated polymers SPPSU‐2S and SPPSU‐4S with high molecular weight (M_n = 138–145 kDa, M_w = 200–279 kDa) and well‐defined structures were synthesized. By solution casting and thermal annealing treatment, flexible crosslinked membranes with high solvent insolubility were obtained. The membranes exhibited mechanical and chemical stability as confirmed by dynamic mechanical analysis (DMA) and conductivity measurement. The crosslinked SPPSU‐4S membrane with IEC = 3.20 meq/g showed the highest proton conductivity of 0.163 S/cm at 120 °C, 90% RH, and improved thermal stability compared with its precursor (uncrosslinked) membrane. The results show that simple annealing method could improve significantly membranes properties of highly sulfonated aromatic polymers. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 44218.     

A Newly Designed Dual‐Functional Epoxy Monomer for Preparation of Fishbone‐Shaped Heterochain Polymer with a High Damping Property at Low Temperature

A novel high purity dual‐functional epoxy monomer, diglycidyl ether of 4,4′‐diallyl‐bisphenol‐A, is deliberately designed for the construction of a fishbone‐shaped heterochain polymer by polymerizing it with the methyl phenyl polysiloxane. Their curing reactions with Jeffamine D230 are investigated. The cured fishbone‐shaped heterochain polymer presents a wide transition range spanning over 120 °C with a peak half‐width of 62 °C. In contrast to the traditional epoxy/polysiloxane materials, the cured fishbone‐shaped heterochain polymer takes full advantage of the cooperative effect of epoxy and polysiloxane exhibiting excellent damping properties (tan δ > 0.3) at temperatures near the T _g of the polysiloxane. This outstanding low‐temperature damping performance can be ascribed to the fishbone‐shaped structure of the heterochain polymer. These results provide new approach to explore high damping materials used at extremely low temperature (−125 °C).

     

In situ crosslinkable sulfonated polyaromatic ionomers for the polyelectrolyte used in proton exchange membrane fuel cell

Two series of sulfonated poly(arylene ether nitrile ketone) ionomers containing potential crosslinkable nitrile groups were synthesized in high yield by direct aromatic nucleophilic polycondensation of 1,4‐bis‐(4‐hydroxyphenyl)‐2,3‐dicyano ‐naphthalene ( 3 ) with different molar ratio of disodium 5,5′‐carbonyl‐bis‐(2‐fluorobenzene‐sulfonate) ( 4 ) to 5,5′‐carbonyl‐bis‐(2‐fluorobenzene) ( 5 ) or 4,4‐biphenol ( 7 ). Subsequently, the sulfonated polymeric ionomers were in situ crosslinked when cast into membranes from solution at 180°C under nitrogen protection. The structure of the synthesized polymers was characterized by ¹H‐nuclear magnetic resonance (NMR), Fourier‐transform infrared spectra, and elemental analysis. Comparing with the original polymeric membranes, the crosslinked membranes showed much better thermal and hydrolytic stabilities and superior mechanical properties as well as much lower swelling behavior, which were even better than Nafion 117 membrane. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Synthesis and characterization of novel aromatic polyamides derived from 2,2′‐bis(p‐phenoxyphenyl)‐4, 4′‐diaminodiphenyl ether

BACKGROUND: Wholly aromatic polyamides (aramids) are high‐performance polymeric materials with outstanding heat resistance and excellent chemical stabilities due to chain stiffness and intermolecular hydrogen bonding of amide groups. Synthesis of structurally well‐designed monomers is an effective strategy to prepare modified forms of these aramids to overcome lack of organo‐solubility and processability limitations. RESULTS: A novel class of wholly aromatic polyamides was prepared from a new diamine, namely 2,2′‐bis(p‐phenoxyphenyl)‐4,4′‐diaminodiphenyl ether (PPAPE), and two simple aromatic dicarboxylic acids. Two reference polyamides were also prepared by reacting 4,4′‐diaminodiphenyl ether with the same comonomers under similar conditions. M?_w and M?_n of the resultant polymers were 8.0 × 10⁴ and 5.5 × 10⁴ g mol^?1, respectively. Polymers resulting from PPAPE exhibited a nearly amorphous nature. These polyamides exhibited excellent organo‐solubility in a variety of polar solvents and possessed glass transition temperatures up to 200 °C. The 10% weight loss temperatures of these polymers were found to be up to 500 °C under a nitrogen atmosphere. The polymers obtained from PPAPE could be cast into transparent and flexible films from N,N‐dimethylacetamide solution. CONCLUSION: The results obtained show that the new PPAPE diamine can be considered as a good monomer to enhance the processability of its resultant aromatic polyamides while maintaining their high thermal stability. The observed characteristics of the polyamides obtained make them promising high‐performance polymeric materials. Copyright © 2009 Society of Chemical Industry     

Polyhydroxyesterimides from Renewable Resources: Synthesis,Characterization, Properties

Novel polyhydroxyesterimides were prepared by the reaction between diglycidyl monomers and diimidodiacids at the molar ratio 1/1 in the presence of triethylbenzylamonim chloride as catalyst. Diimidodiacids (DIMDA) were obtained from Diels-Alder adduct of resin acids with maleic anhydride and two aromatic diamines, at the molar ratio 1:2. The chemical reactions between the diglycidyl monomers (diglycidylether of bisphenol A -DGEBA and diglycidyl ether of hydroquinone–DGEHQ) and diimidodiacids were monitored by using differential scanning calorimetry (DSC). The chemical structures of the obtained monomers and polymers were established by means of elemental analysis, FT-IR, ¹H-NMR, and ¹³C-NMR methods. Thermal stability of the obtained polymers was also investigated and showed that they are reasonably thermostable.     

Synthesis,characterization, and cure reaction of methacrylate‐based multifunctional monomers for dental composites

The synthesis of 2,2‐bis[(4‐(2‐hydroxy‐3‐methacryloxyethoxy)phenyl]propane (BHEP) and (1‐methacryloxy‐3‐ethoxymethacryloxy‐2‐hydroxy)propane (MEHP) for use as the monomer phase in dental composites are reported. The monomers were prepared by the reaction of 2‐hydroxyethyl methacrylate (HEMA) with diglycidyl‐ether of bisphenol A (DGEBA) and with glycidyl methacrylate (GMA), respectively. The progress of the reaction was followed by measuring the disappearance of the epoxide group peak using FTIR and the structure of the monomers was characterized by ¹H‐NMR. BHEP and MEHP have lower viscosity because of the presence of long aliphatic spacer on both sides of the aromatic ring in BHEP and the absence of aromatic rings and the presence of only one hydroxyl group in each molecule of MEHP. Thermal curing of the monomers was conducted in a DSC using benzoyl peroxide as an initiator. Photopolymerization of the monomers was also conducted with the visible light using camphorquinone and N,N‐dimethylaminoethyl methacrylate as the photoinitiating system. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2007     

Thiol–ene networks and reactive surfaces via photoinduced polymerization of allyl ether functional hyperbranched polymers

A series of allyl ether functionalized hyperbranched (HB) polyester of three generations was synthesized from commercially available Boltorn^®. These modified HB polymers were homopolymerized to form films with a large number of residual allyl ether groups available for post film formation reactions. Additionally, the polyester multifunctional molecules were cured with a di and tetrathiol monomer in a one to one molar ratio to determine the effect of conversion on the resulting network thermal and physical properties. The same UV-cure chemistries were carried out with a similar second generation polyester dendrimer for comparison. This was in an effort to determine if there is any significant difference in the film chemical conversion and properties with dendrimers in comparison to HB molecules. The highly crosslinked films were obtained and characterized with respect to physical (DMTA) and thermal (DSC and TGA) properties.     

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     

Thermal and Mechanical Properties of Poly(arylene ether ketone)s Based on 5‐tert‐Butyl‐1,3‐bis(4‐fluorobenzoyl)benzene

An aromatic bishalide, 5‐tert‐butyl‐1,3‐bis(4‐fluorobenzoyl)benzene ( 2 ) was synthesized in high yield and purity by the reaction of 5‐tert‐butylisophthaloyl chloride ( 1 ) and fluorobenzene and polymerized by nucleophilic substitution reaction with commercially available aromatic bisphenols to prepare a series of high molecular weight poly(arylene ether ketone)s containing pendant tertiary butyl groups. The effect of molecular structure on the physical, thermal, mechanical and adhesion properties of the polymers was investigated.     

Highly fluorinated poly(ether‐imide)s derived from 2,2′‐bis(3,4,5‐trifluorophenyl)‐4,4′‐diaminodiphenyl ether and aromatic dianhydrides

A new diamine, 2,2′‐bis(3,4,5‐trifluorophenyl)‐4,4′‐diaminodiphenyl ether (FPAPE) was synthesized through the Suzuki coupling reaction of 2,2′‐diiodo‐4,4′‐dinitrodiphenyl ether with 3,4,5‐trifluorophenylboronic acid to produce 2,2′‐bis(3,4,5‐trifluorophenyl)‐4,4′‐dinitrodiphenyl ether (FPNPE), followed by palladium‐catalyzed hydrazine reduction of FPNPE. FPAPE was then utilized to prepare a novel class of highly fluorinated all‐aromatic poly(ether‐imide)s. The chemical structure of the resulting polymers is well confirmed by infrared and nuclear magnetic resonance spectroscopic methods. Limiting viscosity numbers of the polymer solutions at 25 °C were measured through the extrapolation of the concentrations used to zero. M_n and M_w of these polymers were about 10 000 and 25 000 g mol^?1, respectively. The polymers showed a good film‐forming ability, and some characteristics of their thin films including color and flexibility were investigated qualitatively. An excellent solubility in polar organic solvents was observed. X‐ray diffraction measurements showed that the fluoro‐containing polymers have a nearly amorphous nature. The resulting polymers had T_g values higher than 340 °C and were thermally stable, with 10% weight loss temperatures being recorded above 550 °C. Based on the results obtained, FPAPE can be considered as a promising design to prepare the related high performance polymeric materials. Copyright © 2011 Society of Chemical Industry     

Synthesis and characterization of poly(ester‐ether‐imide)s derived from 5‐(4‐trimellitimidophenoxy)‐1‐trimellitimido naphthalene

A series of novel aromatic poly(ester‐ether‐imide)s with inherent viscosity values of 0.44–0.74 dL g^?1 were prepared by the diphenylchlorophosphate‐activated direct polycondensation of an imide ring‐containing diacid namely 5‐(4‐trimellitimidophenoxy)‐1‐trimellitimido naphthalene ( 1 ) with various aromatic dihydroxy compounds in the presence of pyridine and lithium chloride. Owing to comparison of the characterization data, an ester‐containing model compound ( 2 ) was also synthesized by the reaction of 1 with phenol. The model compound 2 and the resulted polymers were fully characterized by FT‐IR and NMR spectroscopy. The ultraviolet λ_max values of the poly(ester‐ether‐imide)s were also determined. The resulting polymers exhibited an excellent organosolubility in a variety of high polar solvents such as N,N‐dimethylacetamide, N,N‐dimethylformamide, dimethyl sulfoxide, and N‐methyl‐2‐pyrrolidone. They were soluble even in common less polar organic solvents such as pyridine, m‐cresol, and tetrahydrofuran on heating. Crystallinity of the polymers was estimated by means of wide‐angle X‐ray diffraction. The resulted polymers exhibited nearly an amorphous nature. From differential scanning calorimetry thermograms, the polymers showed glass‐transition temperatures between 221 and 245°C. Thermal behaviors of the obtained polymers were characterized by thermogravimetric analysis, and the 10% weight loss temperatures of the poly(ester‐ether‐imide)s were found to be over 410°C in nitrogen. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Synthesis and characterization of new poly(amide‐imide)s based on 1,4‐bis(trimellitimido)‐2,5‐dichlorobenzene

A series of new aromatic poly(amide‐imide)s were synthesized by the triphenyl phosphite‐activated polycondensation of the diimide‐diacid, 1,4‐bis(trimellitimido)‐2,5‐dichlorobenzene (I), with various aromatic diamines in a medium consisting of N‐methyl‐2‐pyrrolidone (NMP), pyridine, and calcium chloride. The poly(amide‐imide)s had inherent viscosities of 0.88–1.27 dL g⁻¹. The diimide‐diacid monomer (I) was prepared from 2,5‐dichloro‐p‐phenylenediamine with trimellitic anhydride. All the resulting polymers were amorphous and were readily soluble in a variety of organic solvents, including NMP and N,N‐dimethylacetamide. Transparent, flexible, and tough films of these polymers could be cast from N,N‐dimethylacetamide or NMP solutions. Cast films had tensile strengths ranging from 92 to 127 MPa, elongations at break from 4 to 24%, and initial moduli from 2.59 to 3.65 GPa. The glass transition temperatures of these polymers were in the range of 256°–317°C, and the 10% weight loss temperatures were above 430°C in nitrogen. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 73: 271–278, 1999     

Synthesis of aromatic carboxyl functionalized polymers by atom transfer radical polymerization

The synthesis of aromatic carboxyl functionalized polymers by atom transfer radical polymerization is described. The α‐bromo‐p‐toluic acid ( 1 ) initiated polymerization of styrene in the presence of copper(I) bromide and 2,2′‐bipyridyl affords quantitative yields of the corresponding aromatic carboxyl functionalized polystyrene ( 2 ). Polymerization proceeded via a controlled free radical process to afford quantitative yields of the corresponding aromatic carboxyl functionalized polymers with predictable molecular weights (M_n = 1600–25 900 g mol⁻¹), narrow molecular weight distribution (M_w /M_n = 1.1–1.40) and an initiator efficiency above 0.87. The polymerization process was monitored by gas chromatographic analysis. The functionalized polymers were characterized by thin layer chromatography, size exclusion chromatography, spectroscopy, potentiometry and elemental analysis. © 2000 Society of Chemical Industry     

Oligomeric poly(ether‐imide)s bearing ortho trifluoromethyl groups: Solubility,thermal studies,and optical properties

In the development of processable high‐temperature materials, six new aromatic poly(imide)s based on diamines containing ortho trifluoromethyl groups, ether linkages and R,R‐methylenes moieties (R = Me or Ph) and previously reported dianhydrides have been synthesized vía polycondensation reactions. All polymers were obtained with good yields, were soluble in a variety of polar aprotic solvents, and exhibited inherent viscosity (η_inh) values between 0.15 and 0.20 dL g^?1, which is indicative of low molecular‐weight species. Preliminary studies of their physical properties were carried out. The new materials were transparent in the visible region and they exhibited thermal decomposition temperatures ranging from 475 to 545 °C and glass‐transition temperatures varying from 288 to 304 °C. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46613.     

Synthesis of soluble and thermally stable poly[arylene ether amide (N‐arylenebenzimidazole)]s

Poly(arylene ether)s containing N‐arylenebenzimidazole and amide groups were prepared using an aromatic nucleophilic displacement reaction that replaced the N‐H sites from four different bis(benzimidazolyl) derivatives with activated aromatic difluorides containing ether and amide groups in sulfolane. The reaction was carried out at 210 °C in the presence of anhydrous potassium carbonate. The structures of the polymers were characterized by means of Fourier transform infrared, ¹H NMR spectroscopy and elemental analysis, and the results were largely consistent with the proposed structure. All resulting polymers showed an essentially amorphous nature. This was consistent with the calculated results. Differential scanning calorimetry and thermogravimetric measurements showed that the polymers had high glass transition temperatures (>190 °C), good thermostability and high decomposition temperatures (>400 °C). These novel polymers also showed easy solubility. Copyright © 2012 Society of Chemical Industry     

New poly(amide‐imide) syntheses. 24. Synthesis and properties of fluorinated poly(amide‐imide)s based on 2,2‐bis[4‐(trimellitimidophenoxy)phenyl]hexafluoropropane and various aromatic diamines

An imide ring‐performed dicarboxylic acid bearing one hexafluoroisopropylidene and two ether linkages between aromatic rings, 2,2‐bis[4‐(4‐trimellitimidophenoxy)phenyl]hexafluoropropane (II), was prepared from the condensation of 2,2‐bis[4‐(4‐aminophenoxy)phenyl]hexafluoropropane and trimellitic anhydride. A novel series of poly(amide‐imide)s having inherent viscosities of 0.72 ∼ 1.86 dL g⁻¹ was prepared by the triphenyl phosphite‐activated polycondensation from the diimide‐diacid (II) with various aromatic diamines in a medium consisting of N‐methyl‐2‐pyrolidone, pyridine, and calcium chloride. Several of the resulting polymers were soluble in polar amide solvents, and their solutions could be cast into transparent, thin, flexible films having good tensile properties and high thermal stability. The 10% weight loss temperatures were all above 495°C in air or nitrogen atmosphere, and the glass transition temperatures were in the range of 237°–276°C. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 71: 823–831, 1999