Poly(amide‐ester)s derived from dicarboxylic acid and aminoalcohol

A series of alternating aliphatic poly(amide‐ester)s, derived from dicarboxylic acid and aminoalcohols, were obtained by polycondensation in melt. All poly(amide‐ester)s were characterized by FTIR and ¹H/¹³C‐NMR spectroscopies. The synthesized polymers showed an inherent viscosity ranging from 0.4 to 1.0 dL g^?1. Thermal analysis showed melting points within the range 100–115°C and glass transition within the range 30–60°C. Decomposition temperatures were more than 200°C higher than the corresponding melting temperatures. The polymers can thus be processed from the melt. The processed polymers were partially crystalline with good thermal stability. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 95: 362–368, 2005     

Fully bio‐based polyesters derived from 2,5‐furandicarboxylic acid (2,5‐FDCA) and dodecanedioic acid (DDCA): From semicrystalline thermoplastic to amorphous elastomer

A serials of fully bio‐based poly(ethylene dodecanedioate‐2,5‐furandicarboxylate) (PEDF) were synthesized from Dodecanedioic acid (DDCA), 2,5‐Furandicarboxylic acid (2,5‐FDCA), and ethylene glycol through a two‐step procedure consisted of transesterification and polycondensation. After their chemical structures were confirmed by Nuclear Magnetic Resonance and Fourier Transform Infrared Spectroscopy, their thermal, mechanical, and biodegradation properties were investigated in detail. Results showed that the chemical composition of PEDFs could be easily controlled by the feeding mole ratio of DDCA to FDCA and they possessed the characteristic of random copolyester with the intrinsic viscosity ranged from 0.82 to 1.2 dL/g. With the varied mole ratio of DDCA to FDCA, PEDFs could be changed from semicrystalline thermoplastic to the completely amorphous elastomer, indicated by the elongation at break ranged from 4 for poly(ethylene 2,5‐furandicarboxylate) to 1500% for amorphous PEDF‐40. The amorphous PEDF‐30 and PEDF‐40 showed satisfactory shape recovery after cyclic tensile test, which was the typical behavior for elastomer. Enzymatic degradation test indicated that all the PEDFs were biodegradable and the degradation rate was heavily affected by their chemical compositions. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46076.     

Novel soluble fluorine-containing polyamides derived from 2-(4-trifluoromethylphenoxy)terephthalic acid and trifluoromethyl-substituted aromatic bis(ether amine)s

A series of new fluorine-containing polyamides were prepared directly by polycondensation of 2-(4-trifluoromethylphenoxy)terephthalic acid with four trifluoromethyl-substituted aromatic bis(ether amine)s in N-methyl-2-pyrrolidone (NMP) solution containing dissolved calcium chloride using triphenyl phosphite and pyridine as condensing agents. All the polymers showed excellent solubility in solvents such as NMP, N,N-dimethylacetamide, N,N-dimethylformamide, dimethyl sulfoxide, pyridine, tetrahydrofuran, and acetone at room temperature. These polymers had inherent viscosities between 0.67 and 1.09 dL/g, and their weight-average molecular weights and number-average molecular weights were in the range of 48,200–68,000 and 29,500–39,400, respectively. The resulting polymers showed glass-transition temperatures between 189 and 214 °C and 10% weight loss temperatures ranging from 475 to 483 °C, and char yields at 800 °C higher than 50% in nitrogen. All polymers were amorphous and could be cast into transparent, flexible, and strong films from DMAc solutions with tensile strengths of 71–115 MPa, elongations at break of 6–9%, and tensile moduli of 2.7–3.2 GPa. These polymers had low dielectric constants of 3.14–3.31 (1 MHz), low moisture absorption in the range of 0.88–1.60%, and high transparency with an ultraviolet–visible absorption cut-off wavelength in the 320–340 nm range.     

White‐light‐emitting hybrid film from fluorescent hyperbranched poly(amido amine)

The flexible, strong, and tough white‐light‐emitting (WLE) hybrid films are highly demanded in large‐scale displays, including TV sets, monitors, and electronic interactive devices. In this work, a kind of WLE hybrid film was fabricated from hyperbranched poly(amido amine) (HPAMAM) and nanoclay with the incorporation of riboflavin (VB₂) and rhodamine B (RhB). The fluorescence emission of HPAMAM was partially absorbed and effectively transferred into green and red color, which combined into a bright white light with the residue blue fluorescence. Due to the alignment of nanoclay inside the HPAMAM matrix, in addition to the strong interaction among the HPAMAM molecules and that between HPAMAM and nanoclay, this hybrid film shows to be strong and tough. The mechanical strength is about 20 MPa and the elongation is about 30%. It is convinced that this hybrid film is promising in flexible large‐scale displays. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46015.     

A novel compound, 7,10-dihydroxy-8(E)-octadecenoic acid from oleic acid by bioconversion

Sixty-two cultures from the Agricultural Research Service (ARS) Culture Collection and 10 cultures isolated from soil and water samples in Illinois were screened for their ability to convert agricultural oils to value-added industrial chemicals. A new compound, 7,10-dihydroxy-8(E)-octadecenoic acid (DOD), was produced from oleic acid at a yield of greater than 60% by bacterial strain PR3 which was isolated from a water sample in Morton, IL. To our knowledge, DOD has not been previously reported. The optimum time, pH and temperature for the production of DOD were 2 days, 7.0, and 30°C, respectively. The production of DOD is unique in that it involves hydroxylation at two positions and rearrangement of the double bond of the substrate molecule.     

Crosslinkable poly(lactic acid)‐based materials: Biomass‐derived solution for barrier coatings

The demand for biobased barrier packaging alternatives is constantly growing. Poly(lactic acid) (PLA)‐based polymers are one of the most extensively studied biomass‐derived synthetic polymers; however, they typically lack water‐barrier properties. We synthesized a copolymer of d ,l ‐lactic acid, 1,4‐butanediol, and itaconic acid [poly(d ,l ‐lactic acid–1,4‐butanediol–itaconic acid) (PLABDIA)] via bulk polycondensation. The radical crosslinking reactions of the synthesized polymer were investigated with bulk crosslinking trials to find a formulation that was suitable for a rapidly crosslinkable barrier coating. The crosslinking efficiency was tested with methacrylate and acrylate crosslinkers together with peroxide radical initiators. Poly(ethylene glycol) diacrylate (number‐average molecular weight = 250 g/mol) together with dilauroyl peroxide proved to be the best crosslinker–initiator combination. An aqueous dispersion of PLABDIA was prepared with a thermomechanical method and applied to commercial boxboard on a pilot‐scale line coater. With a coating weight of 10 g/m², a water vapor transmission rate of 22.8 g/m²d was achieved, and this coating outperformed commercial extruded PLA coatings. The samples also showed very good grease resistance and would, therefore, be a good solution for the packaging of dry and fatty goods. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 44326.     

Fluorinated poly(aryl thioether)s and poly(aryl sulfone)s derived from 2,3,4,5,6‐pentafluorobenzoic acid

Poly(aryl thioether)s (F‐PTEs) containing 2,3,5,6‐tetrafluoro‐1,4‐phenylene moiety and polar moiety, such as 1,3,4‐ozadiazole, ether ketone, and amide groups, were synthesized by nucleophilic aromatic substitution reaction of aryl fluorides and 4,4′‐thiobisbenzenthiol. F‐PTEs were amorphous with good thermal properties including high glass transition temperature (T_g) and thermal stability, solubility, and hydrophobicity. F‐PTEs were transformed into poly(aryl sulfone)s (F‐PSs) by the oxidation reaction with hydrogen peroxide in acetic acid. Because of the sulfone group, the T_gs of the F‐PSs were 30–40°C higher than those of the corresponding F‐PTEs. F‐PSs maintained solubility in polar aprotic solvents and exhibited hydrophobicity in spite of the content of polar sulfone groups due to the highly substituted fluorine atoms. These F‐PTEs and F‐PSs were a new class of high‐performance polymers. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Synthesis,characterization, and soil biodegradation study of polyamides derived from the novel bioactive diacid monomer 5‐(2‐phthalimidoethanesulfonamido) isophthalic acid

A new bioactive diacid monomer, 5‐(2‐phthalimidoethanesulfonamido) isophthalic acid ( 6 ), was synthesized in three steps. This monomer can be regarded as biologically active aromatic diacid and may be used in the design of biodegradable and biological materials. This monomer was polymerized with several aromatic diamines by step‐growth polymerization to give a series of biodegradable and highly thermally stable polyamides (PAs) with good yield (70–82%) and moderate inherent viscosity between 0.38–0.68 dL/g in a system of triphenylphosphite/pyridine/N‐methyl‐2‐pyrolidone/CaCl_2. The new aromatic diacid 6 and all of the PAs derived from this diacid and aromatic diamines were characterized by Fourier transform infrared, ¹H‐NMR, ¹³C‐NMR, and elemental analysis techniques. The thermal stability of the PAs was determined by thermogravimetric analysis and differential scanning calorimetry techniques under a nitrogen atmosphere, and we found that they were moderately stable. The soil biodegradability behavior of 6 and all of the PAs derived from this diacid and aromatic diamines were investigated in culture media, and we found that the synthesized diacid 6 and all of the PAs were biodegradable under a natural environmental. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Polyelectrolyte multilayers of poly(vinylamine hydrochloride‐co‐N‐vinylformamide) with variable primary amine content and a weak polyacid poly(acrylic acid)

Poly(vinylamine hydrochloride‐co‐N‐vinylformamide) [poly(VAm‐co‐NVF)] with variable VAm content, and a weak polyacid poly(acrylic acid) were assembled on a quartz crystal microbalance (QCM) substrate from their aqueous solutions, thus forming polyelectrolyte multilayers. The effects of varying the VAm content on assembly profiles and film structures were analyzed by quantitative QCM analysis, attenuated total reflection spectra techniques, and atomic force microscopic observation. At a VAm content of less than 40% of the total number of poly(VAm‐co‐NVF) units, the layer‐by‐layer assembly did not proceed, and the frequency shift of the QCM zigzagged with the step number. Above 40% VAm content, the frequency increased continuously with an increasing number of steps. The assembly amount was also maximal at 40% VAm content. The films obtained swelled with water molecules, and this swelling was followed by an increase in thickness in the aqueous phase. The results obtained were compared to those obtained from a combination of poly(VAm‐co‐NVF) and a strong polyacid, poly(sodium styrenesulfonate). © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 3927–3933, 2006     

Polyurethane dispersions derived from polycarbonatediols and m‐di(2‐isocyanatopropyl)benzene

Aqueous polyurethane dispersions derived from various polycarbonatediols, m‐di(2‐isocyanatopropyl)benzene(TMXDI), and various carboxylic diols including dimethylol propionic acid (DMPA), dimethylol butyric acid (DMBA), and a carboxylic polycaprolactonediol (Placcel 205BA) were prepared by a method in which the dispersing procedure was modified to enhance the molecular weight. The NH₂/NCO ratio during chain extension affected the molecular weight of the polyurethanes, significantly, and an optimum ratio of 0.67:1.0 was used. The molecular weight, particle size, tensile properties, and thermal properties of the polyurethane dispersions were investigated. The effect chemical structure of the polycarbonatediols on the properties shows no obvious trend, but the polyurethane dispersions derived from the carboxylic polycaprolactonediol exhibit smaller particle size and softer tensile properties when compared with those derived from DMPA and DMBA. POLYM. ENG. SCI., 2009. © 2009 Society of Plastics Engineers     

The preparation of hydroxystearic acids from red oil (Commercial oleic acid)

The hydroacetoxylation of red oil (commercial oleic acid) in acetic acid solution has been studied. The optimum hydroacetoxylation conditions were obtained under anhydrous conditions using sulphuric acid as a catalyst at:

1. 1.
   a concentration of 1% (based on the wt of red oil).     
   
   

Characterization of a novel bioactive poly[(lactic acid)‐co‐(glycolic acid)] and collagen hybrid matrix for dermal regeneration

Different strategies have been explored for the purpose of autologous or allogeneic dermal regeneration. We have developed a hybrid matrix by lyophilizing collagen within a poly[(lactic acid)‐co‐(glycolic acid)] (10:90, molar composition) knitted mesh, in order to assimilate the advantages of natural and synthetic materials. The porosity of the mesh was found to be almost 95 %, using Micro‐Computed Tomography Analysis, while the mechanical properties were comparable to native skin. In vitro biocompatibility was analyzed by culturing rat dermal fibroblasts in the matrices over 10 days. The cells were able to attach, proliferate and remain viable within the hybrid matrices. Subsequently, in vivo biocompatibility was analyzed by implanting the matrices subcutaneously in immunocompetent rats, for 2 weeks. Histological analysis showed that the poly[(lactic acid)‐co‐(glycolic acid)]–collagen hybrid matrices evoked minimal host tissue response in vivo. This study forms the basis of using poly[(lactic acid)‐co‐(glycolic acid)]–collagen hybrid matrices for our future work to develop a bioactive matrix for dermal regeneration. Copyright © 2005 Society of Chemical Industry     

A coordination polymer derived from the copper(II) complex of a bis-(salicylhydrazone) derived from iminodiacetic acid diethyl ester

A coordination polymer bearing alternate mononuclear and phenoxy-bridged dinuclear copper(II) motifs has been synthesised from a bis-(salicylhydrazone) derived from the diethyl ester of iminodiacetic acid. The structure of the polymer has been established by X-ray crystallography.     

Hydroformylation with recycled rhodium catalyst and one-step esterification-acetalation: A process for methyl 9(10)-methoxymethylenestearate from oleic acid

Previous studies on hydroformylation of methyl oleate with rhodium and triphenylphosphine or triphenylphosphite have led to a laboratory process for recycling the precious metal catalyst. Another catalyst recycling process has now been studied as the basis for converting commercially available oleic acid into the enol ether of methyl formylstearate. The process involves one-step esterification-acetalation of formylstearic acid made by hydroformylating oleic acid with rhodium and triphenylphosphine. Esterification-acetalation is done in a recycling system with methanol, an acid-exchange resin for catalysis, and molecular sieves to remove water from the reaction mixture. The dimethyl acetal methyl ester formed from formylstearic acid is thermally cracked and distilled in one pot to produce the enol ether, methyl methoxymethylenestearate. The soluble rhodium catalyst in the distillation residue is combined with the insoluble catalyst from filtration and recycled for hydroformylation. The product methoxymethylenestearate is a versatile and stable derivative for various potential industrial applications. Presented at the AOCS meeting, Cincinnati, September 1975.     

Synthesis and surface-active properties of trimeric-type anionic surfactants derived from tris(2-aminoethyl)amine

Trimeric-type anionic surfactants (3C_ntaAm, where n is a hydrocarbon chain length of 8, 10, or 12) with three hydrocarbon chains and three carboxylate headgroups were synthesized from tris(2-aminoethyl)amine, and their properties were investigated by surface tension, electrical conductivity, dynamic and static light-scattering, fluorescence of pyrene, and emulsification power techniques. The critical micelle concentrations (CMC) of 3C_ntaAm were 0.00092–0.00834 mmol dm⁻³, and the surface tensions at the CMC were 33.3–39.9 mN m⁻¹. The areas per molecule occupied by 3C₁₀taAm and 3C₁₂taAm were extremely small, showing they were highly compact at the air/water interface. In addition, adsorption or micellization behavior of 3C_ntaAm was estimated by parameters such as pC ₂₀ (the efficiency of surface adsorption), CMC/C ₂₀ (the ease of adsorption relative to the ease of micellization), and ΔG _M ^o (Gibbs energy of micellization). Dynamic and static light-scattering mesurements of 3C_ntaAm showed a hydrodynamic radius of 45–61 nm above the CMC and aggregation numbers of 10–82 at the CMC, respectively. The fluorescence intensity ratio of the first to the third band in the emission spectra of pyrene started to lower from far above the CMC for 3C₈taAm and 3C₁₀taAm, and below the CMC for 3C₁₂taAm. This suggests that loose micelles or premicellar aggregates are formed in solutions. Mixtures of aqueous solutions of 3C_ntaAm and toluene formed oil-in-water-type emulsions, and the stabilizing abilities were in the order of 3C₈taAm>3C₁₀taAm>3C₁₂taAm. The degree of emulsification of 3C₈taAm remained at 69% after 24 h of standing. Thus, 3C_ntaAm exhibited unique properties superior to monomeric or dimeric surfactants that were significantly influenced by their hydrocarbon chain lengths.