Preparation and properties of biobased polyamides based on 1,9-azelaic acid and different chain length diamines

Polymer Bulletin - A series of environmentally friendly polyamides (PA69, PA109 and PA129) have been synthesized by carrying out step-melting polycondensation reactions of bioderived monomers:...     

Hydrolytic degradation of polyglycolic acid: Tensile strength and crystallinity study

The hydrolytic degradation of polyglycolic acid (PGA) was studied by examining the changes of tensile strength and the level of crystallinity of the suture material. It was found that the breaking stress decreased from 6.369 × 10^?1 at 0 day to 3.97 × 10^?3 Newton/Tex at 49 days. The sigmodial shape of the stress–strain curves gradually disappeared with increase in the duration of in vitra degradation. The endpoint titration method used to assess the degree of degradation beyond the period of measurable tensile strength showed that the percent of PGA degraded were 42, 56, and 70% at 49, 60, and 90 days, respectively. The level of crystallinity of PGA at various durations of degradation exhibited an initial increase in the degree of crystallinity from 40% at 0 day to an upper limit of 52% at 21 days, then gradual decrease to 23% at 90 days. This observation is essentially parallel to hydrolysis of cellulose and polyethylene terephthalate. The concept of microfibrillar structure of fibers provides the basis for the proposed degradation mechanism of PGA in vitro. It is believed that degradation proceeds through two main stages which are different in rate of degradation.     

A review on degradation mechanisms of polylactic acid: Hydrolytic,photodegradative, microbial,and enzymatic degradation

Recently, thoughtful disagreements between scientists concerning environmental issues including the use of renewable materials have enhanced universal awareness of the use of biodegradable materials. Polylactic acid (PLA) is one of the most promising biodegradable materials for commercially replacing nondegradable materials such as polyethylene terephthalate and polystyrene. The main advantages of PLA production over the conventional plastic materials is PLA can be produced from renewable resources such as corn or other carbohydrate sources. Besides, PLA provides adequate energy saving by consuming CO₂ during production. Thus, we aim to highlight recent research involving the investigation of properties of PLA, its applications and the four types of potential PLA degradation mechanisms. In the first part of the article, a brief discussion of the problems surrounding use of conventional plastic is provided and examples of biodegradable polymers currently used are provided. Next, properties of PLA, and (Poly[L-lactide]), (Poly[D-lactide]) (PDLA) and (Poly[DL-lactide]) and application of PLA in various industries such as in packaging, transportation, agriculture and the biomedical, textile and electronic industry are described. Behaviors of PLA subjected to hydrolytic, photodegradative, microbial and enzymatic degradation mechanisms are discussed in detail in the latter portion of the article.     

Synthesis and characterization of polyamides based on cubane-1,4-dicarboxylic acid

The direct polycondensations of cubane-1,4-dicarboxylic acid with 1,4-phenylenediamine (2 a), 4,4′-oxydianiline (2 b), 4,4′-sulfonyldianiline (2 c), and 9,9′-bis(4-aminophenyl)florene (2 d) were carried out in N-methyl-2-pyrrolidone/pyridine containing triphenylphosphite and lithium chloride at 110 °C for 9 h. Polyamide 3 a obtained from 2 a was scarcely soluble in organic solvent even during heating, and was soluble only in conc-H₂SO₄, whereas 3 c and 3 d derived from 2 c and 2 d, respectively, were readily soluble in N-methyl-2-pyrrolidone, N,N-dimethylacetamide, N,N-dimethylformamide, and dimethylsulfoxide. After treating polyamide 3 d with the rhodium complex catalyst in NMP, cubane units were quantitatively converted into cyclooctatetraenes. Received: 3 March 1997/Accepted: 1 April 1997     

Synthesis and properties of polyamides and copolyamides based on 2,6-naphthalene dicarboxylic acid

A number of polyamides based on 2,6-naphthalene dicarboxylic acid (NDA) and various aromatic diamines were synthesized in N-methyl pyrrolidone (NMP) containing lithium chloride (LiCl) or calcium chloride (CaCl₂) by direct polycondensation using triphenyl phosphite and pyridine. The best reaction conditions for polycondensation were determined in terms of factors such as the amount of the solvency-promoting reagent such as LiCl or CaCl₂ and the initial reactant concentration. Thus, almost all polyamides were obtained with inherent viscosities above 1.0 and up to 3.28 dL/g. Similarly, high molecular weight copolyamides with inherent viscosities of 1.76–3.61 dL/g were prepared from 4,4′-oxydianiline (ODA) and mixed dicarboxylic acids of NDA/terephthalic acid (TPA) or NDA/isophthalic acid (IPA). The solubility of NDA homopolyamides depended on the diamine components. The polyamides derived from meta-, sulfone-, or alkylene-linked diamine showed increased solubility. Copolymerization of ODA with NDA/IPA led to a significant increase in solubility, whereas with NDA/TPA, it gave a limited improvement. All the homopolyamides and copolyamides showed an amorphous X-ray diffraction pattern. Almost all the polymers soluble in aprotic solvents can be solution-cast into strong and tough films. Glass transition shifts of some NDA polyamides can be observed in the differential scanning calorimetry (DSC) curves ranging from 243 to 345°C. Most NDA/IPA–ODA copolyamides also showed clear transitions in the range of 255–268°C. In nitrogen, all the polymers showed no significant weight loss up to 400°C, and their 10% weight loss temperatures were recorded in the range of 434–541°C. © 1994 John Wiley & Sons, Inc.     

Hydrolytic degradation and diffusion studies on a polyphosphate ester

A polyphosphate ester was synthesized by interfacial polycondensation of bisphenol‐A and phenylphosphorodichloridate. Accelerated hydrolytic degradation studies were conducted under alkaline conditions. The effect of concentration of alkali and temperature were monitored. The rate of degradation reached a maximum value at 6 molar sodium hydroxide solution and then reduced. The activation energy for hydrolytic degradation was found to be 45 kcal/mol. Diffusion of alkali into the polymer pellet was studied at various concentrations of alkali and at various temperatures. The rate of diffusion also attained a maximum at 6M NaOH and the activation energy for diffusion process was found to be 12 kcal/mol. © 2002 John Wiley & Sons, Inc. J Appl Polym Sci 84: 701–708, 2002; DOI 10.1002/app.10008     

Hydrolytic degradation of oligo(lactic acid): a kinetic and mechanistic study

This study shows that the degradation mechanism and kinetics of monodisperse oligo(lactic acid)s esterified with N-(2-hydroxypropyl)methacrylamide (HPMAm) are strongly influenced by the nature of the chain end. Oligomers with free hydroxyl chain ends degraded predominantly by chain end scission via a backbiting mechanism with a pseudo first-order rate constant k_bb=2.7 h⁻¹ in aqueous buffer (37 °C, pH 7.2). Once the hydroxyl groups were protected by acetylation, random chain scission became the rate limiting step with k_r=0.022 h⁻¹ under the same conditions. Using these rate constants, the theoretical time-resolved degradation profile was calculated for every (intermediate) degradation product and corresponded very well with the experimental results. The rate of formation of HPMAm was independent of the chain length for the acetylated oligomers, while the hydroxyl terminated oligomers with an even number of lactic acid units formed HPMAm more rapidly than oligomers with an odd number of units. The possibility to fine-tune the degradation rate is relevant when applied as e.g. hydrogels for controlled release or tissue engineering materials.     

Hydrolytic thermal degradation of poly(naphthoyleneimide benzimidazole) in concentrated sulfuric acid

Translational diffusion in 96% H₂SO₄ and intrinsic viscosity of poly(naphthoyleneimide benzimidazole) (PNIB) have been investigated in different stages of its degradation in solution in the temperature range from 65 to 120°C. The degradation rate constant k has been determined from the change in molecular weight M of degraded products with time at the fixed temperature of solution. The activation energy of the process E was calculated from the temperature dependence of k. The difference in E values at low and high temperatures was found. At degradation temperatures above 90°C, the activation energy of hydrolysis was obtained as E = 133 kJ/mol, which coincides with that of aromatic polyamides in sulfuric acid. The data obtained are compared with the results of the investigations of optical properties of products of PNIB degradation in solution and PNIB stability in the solid state. An explanation of anomalies observed during PNIB degradation at low temperatures is suggested. © 1995 John Wiley & Sons, Inc.     

Synthesis and characterization of polyamides based on natural monomers: l-lysine and l-aspartic acid

Nonpeptidic diamine-diacid type polyamides were prepared from natural α-amino acids, l-lysine and l-aspartic acid, under mild conditions. l-lysine carboxylic group was protected as a benzyl ester; l-aspartic acid amino group was protected as benzyloxycarbonyl (Z) or t-butyloxycarbonyl (BOC) derivatives. The activated ester method provided polyamides with protected amino and carboxyl side groups. The deprotection of these side groups revealed to be perfectly selective when the amino groups were protected as t-butyloxycarbonyl derivatives. Received: 20 February 1997/Revised: 8 April 1997/Accepted: 14 April 1997     

Hydrolytic degradation of nanocomposites based on poly(l‐lactic acid) and layered double hydroxides modified with a model drug

Hydrolytic degradation of a nanocomposite of poly(L‐lactic acid), PLA, and a layered double hydroxide (LDH) modified with the drug 4‐biphenyl acetic acid (Bph) has been studied. PLA/LDH‐Bph nanocomposite was prepared by solvent casting with 5 wt % of drug modified LDH and the hydrolytic degradation was carried out in a PBS solution at pH 7.2 and 37 °C. Neat PLA with 5 wt % 4‐biphenyl acetic acid was studied as reference material (PLA/Bph). The materials were studied by WAXS, TEM, TGA, DSC, SEM, FTIR, SEC and contact angle measurements. For PLA/Bph, an acid catalytic effect, caused by the drug, accelerates PLA mass loss. However, for PLA/LDH‐Bph, the presence of LDH produces a barrier effect that initially reduces the diffusion of the oligomers produced during hydrolytic degradation. DSC results demonstrate that Bph induces faster PLA crystallization and this effect is reduced in PLA/LDH‐Bph nanocomposites because of their lower drug content. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43648.     

Hydrolytic degradation of ionically cross-linked polyphosphazene microspheres

The hydrolytic degradation of gel microspheres based on calcium cross-linked phosphazene polyelectrolytes, poly[di(carboxylatophenoxy)phosphazene] (PCPP) and poly[(carboxylatophenoxy) (glycinato)phosphazene] (PCGPP), was investigated. These microspheres are of importance as carriers in protein and cell encapsulation. Both PCPP and PCGPP ionotropic polyphosphazene hydrogels are degradable in an aqueous environment (pH 7.4, 37°C). The degradation rates can be increased by incorporation of hydrolysis sensitive glycinato groups as the pendant structures in the polymer (PCGPP). Hydrolysis of these polymer hydrogels led to low molecular weight (<1,000 Da) products. The erosion and molecular weight profiles varied also according to the molecular weight of the polyphosphazene constituting the gel beads. Another approach to affect the degradation rates consists of coating microspheres with poly-L -lysine. Ionotropic polyphosphazene hydrogels have potential as biodegradable devices for controlled drug delivery systems. © 1994 John Wiley & Sons, Inc.     

Amides and polyamides of m-phenylenedioxydiacetic acid

The reaction between m-phenylenedioxydiacetic acid (m-PhDDA) and phenoxyacetic acid (PhA) with isocyanic esters was studied in order to establish the working conditions for the synthesis of some polyamides prepared from m-PhDDA and diisocyanic esters. The polymers were characterized with respect to some physical properties as melting point, viscosity and IR-spectra. In the latter the peak at 1668–1700 cm^?1 was assigned to the C?O amide function. The thermogravimetrical curves show better thermal properties for the polymers obtained in high boiling solvents as trichlorobenzene (TCB) and tetraline (THN).     

Hydrolytic degradation of poly(L-lactic acid): Combined effects of UV treatment and crystallization

Amorphous and crystallized poly(L -lactic acid) (PLLA) films were prepared and the hydrolytic degradation of the ultraviolet (UV)-treated and UV-nontreated films was investigated. This study reveals that the combination of UV and thermal treatments can produce the PLLA materials having different hydrolytic degradation profiles and that the UV-irradiation in the environment will affect the design of recycling process for PLLA articles. In an early stage, the degrees of hydrolytic degradation monitored by weight loss (W_loss), number-average molecular weight (M _n), and melting temperature (T _m) were higher for the UV-treated films than for the UV-nontreated films. In a late stage, the trend traced by W_loss was reversed, and the difference in the degrees of hydrolytic degradation between the UV-treated and UV-nontreated films monitored by M _n and T _m became smaller, with the exception of the degrees of hydrolytic degradation of the amorphous films traced by T _m. Also, in the early stage, the degrees of hydrolytic degradation monitored by W_loss and M _n were higher for the crystallized films than for the amorphous films. In the late stage, this trend was reversed, with the exception of the degrees of hydrolytic degradation of the UV-treated films monitored by M _n. The main factors that determined the W_loss and T _m were the molecular weight and initial crystallinty but not the molecular structures such as terminal CC double bonds and crosslinks. © 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Synthesis and degradation of nonpeptidic α-amino acid-containing polyamides

This paper describes the synthesis of new water-soluble nonpeptidic α-amino acid-containing polyamides. Preliminary results of hydrolytic and enzymatic degradations of l-lysine and l-cystine-based polyamides are also presented. Most of these polymers revealed to be stable towards hydrolytic degradation. Only poly(l-cystyl-l-cystine) PCC IV was rapidly degraded in Tris buffer pH 7.4. Insoluble poly(adipoyl-l-lysine benzyl ester) could be degraded by papain and pepsin. Polyamides from l-cystine were shown to be more susceptible to enzymatic degradation. Trypsin, papain and glutathione reductase degraded PCC IV much more rapidly than Tris buffer 7.4 alone. Received: 6 January 1997/Accepted: 23 January 1997     

Hydrolytic degradation and cytotoxicity of poly(lactic-co-glycolic acid)/multiwalled carbon nanotubes for bone regeneration

Biodegradable poly(l -lactide-co-glycolide) (PLGA)/multiwalled carbon nanotubes (MWCNTs) scaffolds produced by thermally induced phase separation (TIPS) are studied for bone regeneration. Their magnetic properties, cytotoxicity, and in vitro degradation are investigated. Certain properties are analyzed at 37 °C over 16 weeks in phosphate buffer saline (PBS) solution, as a function of degradation time: morphology, mass loss, pH value of PBS, and thermal behavior. The presence of small quantities of nanotubes in the scaffolds, ≤0.5 wt %, leads to a weak magnetic response although the PLGA was diamagnetic. The incorporation of MWCNTs in the scaffolds generated a morphology and a very different process of in vitro degradation than might be expected in a PLGA scaffold. The in vitro degradation process started on week 13 and rapidly advanced, although the structural integrity of the scaffolds was maintained and no collapse of the structure occurred. Cytotoxicity tests on the samples showed cytotoxicity behavior at concentrations of over 0.3 wt % MWCNTs. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2020 , 137, 48439.     

Hydrolytic and thermal degradation of polyethylene glycol compatibilized poly(lactic acid)-nanocrystalline cellulose bionanocomposites

This study investigates the effect of nanocrystalline cellulose (NCC) and polyethylene glycol (PEG) on the hydrolytic degradation behavior of poly(lactic acid) (PLA) bio-nanocomposites compared with that of neat PLA, under specific environmental condition, namely at 37°C in a pH 7.4 phosphate buffer medium for a time period up to 60 days. The water absorption, mass loss, molecular weight, and the morphologies of nanocomposites before and after degradation were explored. Thermogravimetric analysis (TGA) was used to study the thermal decomposition of the PLA/NCC/PEG nanocomposites before and after degradation. The results showed that the presence of hydrophilic NCC and PEG significantly accelerated the hydrolytic degradation of PLA, which was related to the rapid dissolution of PEG causing easy access of water molecules to the composites and initiating fast hydrolytic chain scission of PLA. The thermal degradation temperatures of the nanocomposites slightly decreased due to the poor thermal stability of NCC in comparison with that of the neat PLA. After degradation, the thermal stability of the separated PLA from nanocomposites significantly decreased because the molecular decreased during the hydrolytic process. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 46933.     

Hydrolytic degradation of poly(ethylene terephthalate)

Molecular weight is an important factor in the processing of polymer materials, and it should be well controlled to obtain desired physical properties in final products for end‐use applications. Degradation processes of all kinds, including hydrolytic, thermal, and oxidative degradations, cause chain scission in macromolecules and a reduction in molecular weight. The main purpose of this research is to illustrate the importance of degradation in the drying of poly(ethylene terephthalate) (PET) before processing and the loss of weight and mechanical properties in textile materials during washing. Several techniques were used to investigate the hydrolytic degradation of PET and its effect on changes in molecular weight. Hydrolytic conditions were used to expose fiber‐grade PET chips in water at 85°C for different periods of time. Solution viscometry and end‐group analysis were used as the main methods for determining the extent of degradation. The experimental results show that PET is susceptible to hydrolysis. Also, we that as the time of retention in hydrolytic condition increased, the molecular weight decreases, but the rate of chain cleavage decreased to some extent, at which point there was no more sensible degradation. The obtained moisture content data confirmed the end‐group analysis and viscometry results. Predictive analytical relationships for the estimation of the extent of degradation based on solution viscosity and end‐group analysis are presented. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 2304–2309, 2007     

Hydrolytic degradation studies on poly(phosphate ester)s

Eight poly(phosphate ester)s comprising five homopolymers (polymers I–V), two copolymers (polymers VI and VII), and one terpolymer (polymer VIII) were synthesized by interfacial polycondensation of phenyl phosphorodichloridate with various bisphenols. The polymers were characterized by spectroscopic techniques. The copolymer and terpolymer ratios were determined by ¹H‐NMR spectroscopy. The molecular weights of the polymers were determined by end‐group analysis using ³¹P‐NMR spectroscopy. Accelerated hydrolytic degradation studies under alkali‐catalyzed conditions showed that the polymer from biphenol (polymer IV) is the most stable and the polymer from thiodiphenol (polymer V) is the least stable. The products of hydrolytic degradation were analyzed and a suitable mechanism for the degradation of the polymers proposed. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 87: 626–631, 2003     

Preparation of a flocculant based on polyamides

A flocculant based on waste oligomers from the polycaprolactam production was synthesized by alkaline reduction with Ni/Al alloy. Both the reduced oligoamide and the sodium aluminate are precipitated by methanol. An oligomer, absorbed by a mineral carrier, is isolated as final product. The modified oligoamide was characterized by elemental analysis, IR spectra, and was shown to contain hydroxyl groups. The prepared flocculant may be used for the clarification of natural dilute (1%) clay suspensions and wastewaters. It accelerates the precipitation 35 times, giving a compact precipitate, which favors the decanting of the clarified liquid. The optimal concentration of the flocculant is 1.8 g/liter (corresponding to 0.06 g/liter oligomer).