Synthesis and evaluation of different adsorbents based on poly(methacrylic acid–trimethylolpropane trimethacrylate) and poly(vinylimidazole–trimethylolpropane trimethacrylate) for the adsorption of tebuthiuron from aqueous medium

In the present study a new cross-linked copolymer poly(methacrylic acid–trimethylolpropane trimethacrylate) (named PMA) and poly(vinylimidazole–trimethylolpropane trimethacrylate) (named PVI) was synthesized through precipitation polymerization and applied to the adsorption of tebuthiuron. Adsorbent materials were characterized by using FT-IR, SEM, TGA, textural data, and elemental analysis. Kinetic study showed that the tebuthiuron adsorption was very quick and the equilibrium time was achieved at 20 min for both polymers. Experimental kinetic data for both polymers were very well described by the second-order kinetic model, thus indicating that tebuthiuron adsorption involves chemical adsorption in different binding sites, which could control the reaction rate. Adsorption equilibrium data were better fitted to the dual-site Langmuir–Freundlich model, which recognizes the existence of two kinds of adsorption sites on the polymer surface ascribed to the presence of carboxyl and carbonyl groups from PMA and imidazole ring and carbonyl group from PVI. The maximum adsorption capacities of PMA and PVI were found to be 186.76 and 213.89 mg g^− 1, respectively, which are much higher than other adsorbents.     

Antimicrobial and biodegradable materials based on ε-caprolactone derivatives

Appropriate wound care is pivotal in preventing wound and postsurgery infections, which remain a serious clinical problem. In this study, we report the successful fabrication of antimicrobial and biodegradable materials for possible use in the medical field. Amino functionalized polycaprolactone (PCL [Poly(CL-co-ACL)]) was synthesized via ring opening polymerization. This polymer was then functionalized via the pendant amine to induce antimicrobial efficacy. This was done through the grafting of poly(lysine) onto the amine as well as the quaternization of the amine using alkyl halides. The chemical structures of the synthesized monomers and polymers were confirmed using nuclear magnetic resonance (¹H NMR and ¹³C NMR) spectroscopy and attenuated total reflection-Fourier transform infrared spectroscopy. The molecular weights of the polymers were determined using gel permeation chromatography. Nanofibre scaffolds were produced from the polymers using the electrospinning technique and these were characterized though scanning electron microscopy. The antimicrobial efficacy of the fabricated materials was tested against the Gram-positive (Staphylococcus aureus ATCC 25923) and Gram-negative (Pseudomonas aeruginosa ATCC 27853) bacteria using the disc diffusion and shake flask methods. The polymers demonstrated excellent antimicrobial efficacy. The fibers were exceptionally biodegradable which opens a lot of applications in the biomedical space.     

Semi-interpenetrating polymer networks composed of poly(l-lactide) and diisocyanate-bridged 4-arm star-shaped ɛ-caprolactone oligomers

Semi-interpenetrating polymer networks (semi-IPNs) were prepared by reactions of methylenediphenyl 4,4’-diisocyanate (MDI) and hydroxy-terminated 4-arm star-shaped ε-caprolactone oligomers (H4CLO_n's) with the degrees of polymerization per one arm, n = 3, 5 and 10 in the presence of poly(l-lactide) (PLA). Morphologies, thermal and mechanical properties of the MDI-bridged H4CLO_n (MH4CLO_n)/PLA semi-IPNs were evaluated by comparing with those of poly(?-caprolactone) (PCL)/PLA blends. Two tan δ peaks related to MH4CLO_n and PLA were observed in a dynamic mechanical curve of the semi-IPN. Although all the semi-IPNs and blends had micro-phase separated morphologies, the phase-separated droplets of MH4CLO₅/PLA 50/50 were much finer than those of PCL/PLA 50/50. Differential scanning calorimetry (DSC) analyses revealed that MH4CLO₃ and MH4CLO₅ are substantially amorphous, while MH4CLO₁₀ is semi-crystalline, and that cold crystallization of the PLA component of MH4CLO_n/PLA is more strongly disturbed for the semi-IPN with a smaller n value and more MH4CLO_n content. Tensile modulus, toughness and elongation at break of MH4CLO₅/PLA 50/50 semi-IPN were much higher than those of PCL/PLA 50/50 blend.     

On the role of aminolysis and transesterification in the synthesis of ɛ-caprolactone and L-lactide based polyurethanes

Summary Polyurethanes based on a 50/50 copoly(L-lactide/ɛ-caprolactone) prepolymer and butanediisocyanate were made. Chain extending a diisocyanate terminated prepolymer with butanediamine was not possible due to the susceptibility of the lactide bond to aminolysis. Chain extension with butanediol resulted in a polymer with poor mechanical properties due to transesterification. When the copolymer prepolymer was chain-extended with an isocyanate terminated block, transesterification with the chain-extender was avoided and the mechanical properties were increased. When the length of the hard segments was increased the mechanical properties increased further. A L-lactide/ɛ-caprolactone based polyurethane with a tensile strength and modulus of respectively 45 MPa and 60 MPa was made. The polymer contained no poly(L-lactide) crystals and was easy to process. Compared to the high molecular weight 50/50 copoly(L-lactide/ɛ-caprolactone) the polyurethane showed better mechanical properties, is expected to have the same adhesive properties and is expected to have a slower degradation rate. These factors makes this polymer excessively useful for in-vivo tissue engineering in for instance meniscal reconstruction material, nerve guide and artificial skin. Received: 12 March 1998/Revised version: 26 June 1998/Accepted: 26 June 1998     

Synthesis and characterization of four- and six-arm star-shaped poly(ε-caprolactone)-b-poly(N-vinylcaprolactam): Micellar and core degradation studies

Star-shaped copolymers with four and six poly(ε-caprolactone)-block-poly(N-vinylcaprolactam) (S(PCL-b-PNVCL)) arms were successfully synthesized by combining ring opening polymerization (ROP) of ε-caprolactone (CL) and reversible addition-fragmentation chain transfer (RAFT) polymerization of N-vinylcaprolactam (NVCL). The resulting star copolymers were characterized using ¹H NMR, GPC and UV–vis. The numbers of arms in the star-shaped PCL-b-PNVCL block copolymers were demonstrated using degradation studies under acidic conditions, and the individual PNVCL chains were characterized by GPC and ¹H NMR. In aqueous solution, star-shaped PCL-b-PNVCL block copolymers self-assembled into large aggregates or micelles with sizes varying from 54 to 300 nm, depending on the molecular weight of the copolymer and the relative lengths of the hydrophobic and hydrophilic segments. Micelles were characterized by atomic force microscopy (AFM), dynamic light scattering (DLS) and scanning electron microscopy (SEM).     

Synthesis and characterization of star-shaped block copolymer of poly-(?-caprolactone) and poly(ethyl ethylene phosphate) as drug carrier

A series of novel 4-arm biodegradable star block copolymers of poly(?-caprolactone) and poly(ethyl ethylene phosphate) were synthesized via ring-opening polymerization of 2-ethoxy-2-oxo-1,3,2-dioxaphospholane using hydroxyl terminated 4-arm star-shaped poly(?-caprolactone) and stannous octoate co-initiation system. Gel permeation chromatography (GPC), NMR and FT-IR were used to demonstrate the structure and analyze their compositions. The self-assembly behavior of these star-shaped copolymers in aqueous solution was studied by ¹H NMR and fluorescence technique, and the results indicated those copolymers formed nanoparticles in aqueous solution with hydrophobic poly(?-caprolactone) core and hydrophilic poly(ethyl ethylene phosphate) shell. The critical micelle concentration was relative to the length of poly(?-caprolactone) and poly(ethyl ethylene phosphate) block. Paclitaxel was encapsulated in the micelles and the release behavior demonstrated that a longer hydrophobic block resulted in slightly slower release rate from the micelles. These copolymer micelles were biocompatible and potential as drug-delivery vehicles for pharmaceutical application.     

Effects of pigmentation on siloxane–polyurethane coatings and their performance as fouling-release marine coatings

Siloxane–polyurethane paints were formulated and characterized for coating properties and performance as fouling-release (FR) marine coatings. Paints were formulated at 20 and 30 pigment volume concentrations with titanium dioxide, and aminopropyl-terminated poly(dimethylsiloxane) (APT-PDMS) loadings were varied from 0 to 30% based on binder mass. The coatings were characterized for water contact angle, surface energy (SE), gloss, and pseudobarnacle (PB) adhesion. The assessment of the FR performance compared with polyurethane (PU) and silicone standards through the use of laboratory biological assays was also performed. Biofilm retention and adhesion were conducted with the marine bacterium Cellulophaga lytica, and the microalgae diatom Navicula incerta. Live adult barnacle reattachment using Amphibalanus amphitrite was also performed. The pigmented coatings were found to have properties and FR performance similar to those prepared without pigment. However, a higher loading of PDMS was required, in some cases, to obtain the same properties as coatings prepared without pigment. These coatings rely on a self-stratification mechanism to bring the PDMS to the coating surface. The slight reduction in water contact angle (WCA) and increase in pseudobarnacle release force with pigmentation suggests that pigmentation slowed or interfered with the self-stratification mechanism. However, increasing the PDMS loading is an apparent method for overcoming this issue, allowing for coatings having similar properties as those of clear coatings and FR performance similar to those of silicone standard coatings.     

Preparation of star-shaped and hyperbranched polyester modified acrylate resin and study on properties of its waterborne coating——Part Ⅰ.Synthesis of star-shaped and hyperbranched polymer and its influencing factors

用树枝状超支化聚酯BoltornTM H20 (B-OH)与叔碳酸缩水甘油酯(E10P)进行阳离子开环接枝聚合,合成了星形超枝化聚合物B-PE 10P,研究了聚合反应条件对单体E10P转化率的影响,确定了较佳反应条件为∶n(E10P)∶n(—OH)=30,n [BF3O(C2H5)2]∶n(—OH)=1.0,以质量分数7.5％的二氧六环为溶剂,反应温度40℃,反应时间15h.通过FT-IR和1H-NMR对合成的星形超支化聚合物B-PE10P进行了表征,计算了B-PE10P支链的平均聚合度及其数均分子量分别为22.1和8.2×104.     

Synthesis of poly(ε-caprolactone)-based polyurethane semi-interpenetrating polymer networks as scaffolds for skin tissue regeneration

A new biodegradable poly(ε-caprolactone)-polyurethane semi-interpenetrating polymer network (PCL-PU-semi-IPNs) was synthesized through the reaction of hydroxyl-terminated four-armed star-shaped PCL, 1,4-diisocyanatobutane, and ethylenediamine. Afterwards, the three-dimensional (3D) porous structure of the polymer was prepared through particulate leaching and freeze-drying methods. The chemical structure of star-shaped block PCL-PU polymer was confirmed by ¹H NMR and IR spectroscopy. The morphology of the fabricated PCL-PU-semi IPN scaffolds was identified by scanning electron microscopy. Results indicated that lower polymer concentration can lead to formation of an isolated pore with a small size, while increasing polymer concentration increases the pore size. Fibroblast cells culturing on the scaffold suggests that the fabricated PU-based scaffold is biocompatible and can be considered as a suitable scaffold material for skin tissue engineering applications.     

Application of zirconium (IV) acetylacetonate to the copolymerization of glycolide with ɛ-caprolactone and lactide

Summary A study on the copolymerization of glycolide with lactide and glycolide with ɛ-caprolactone was performed in the presence of zirconium (IV) acetylacetonate at moderate temperatures (100° and 150°C). Zirconium acetylacetonate appeared to be an efficient initiator of copolymerization. The obtained polymers were characterized by high molecular weights. Considerable influence of transesterification on the polymer chain microstructure was found. Received: 13 October 1998/Revised version: 4 January 1999/Accepted: 4 January 1999     

Biodegradable elastic photocured polyesters based on adipic acid, 4-hydroxycinnamic acid and poly(ε-caprolactone) diols

A novel series of photocurable biodegradable polyesters (CAC/PCL) were synthesized by a high-temperature solution polycondensation of poly(ε-caprolactone) (PCL) diols varying molecular weight (M_W; 1250, 2000, 3000) and a diacyl chloride of 4,4′-(adipoyldioxy)dicinnamic acid (CAC) as a chain extender derived from adipic acid and 4-hydroxycinnamic acid. The resulting polyesters were photocured by the ultraviolet (UV) light irradiation in order to prepare elastic polyester with enhanced thermal and mechanical properties. The effects of photocuring by the UV light irradiation on the thermal, tensile and hydrolytic properties of the CAC/PCL were examined. DSC indicated that the melting temperatures and the crystallinities are decreased by the photocuring. The tensile properties of the photocured CAC/PCL films depended on the M_W of PCL-diols and photocured time. The CAC/PCL1250 films photocured for 10-60 min exhibited a strength-at-break of 3.1-4.7 MPa and an elongation-at-break of 640-1500%, and recovered very rapidly to the original size from 90 to 300% extension. Enzymatic degradation was performed in the phosphate buffer solution (pH 7.2) with Ps. cepacia lipase at 37 °C and evaluated by the weight loss. Non-photocured CAC/PCL films were degraded very rapidly and the weight loss after 3 h incubation was more than 60%. The weight loss of the photocured films decreased remarkably with increasing the photocuring time due to the increase of cross-linking density, while it increased with increasing the M_W of PCL-diols. The photocured CAC/PCL1250 film is promising as a novel biodegradable elastomer for biomedical applications as well as environmental applications.     

Synthesis of poly(norbornene-g-ɛ-caprolactone) copolymers by sequential controlled ring opening polymerization

Summary Poly(norbornene-g-ɛ-caprolactone) copolymers have been prepared by the “grafting from” technique. Well controlled polynorbornene containing 5% acetate pendant groups has been firstly synthesized by ruthenium complex-mediated ring opening metathesis polymerization. The acetate groups have been derivatized into aluminum alkoxides by hydrolysis into alcohol followed by reaction of the alcohol with triethylaluminum. The two polymerization steps are under complete control, so that graft copolymers have been synthesized with a narrow molecular weight distribution and are free from any detectable traces of the parent homopolymers as stated by selective fractionation experiments. These original copolymers have been characterized by SEC, FTIR, ¹H NMR, DSC, TGA. Received: 28 January 1998/Revised version: 14 April 1998/Accepted: 14 April 1998     

Effect of poly(ε-caprolactone) and titanium (IV) dioxide content on the UV and hydrolytic degradation of poly(lactic acid)/poly(ε-caprolactone) blends

The effect of accelerated weathering degradation on the properties of poly(lactic acid) (PLA)/poly(ε-caprolactone) (PCL) blends and PLA/PCL/titanium (IV) dioxide (TiO₂) nanocomposites are presented in this paper. The results show that both polymers are susceptible to weathering degradation, but their degradation rates are different and are also influenced by the presence of TiO₂ in the samples. Visual, microscopic and atomic force microsocpy observations of the surface after accelerated weathering tests confirmed that degradation occurred faster in the PLA/PCL blends than in the PLA/PCL/TiO₂ nanocomposites. The X-ray diffraction results showed the degradation of PCL in the disappearance of its characteristic peaks over weathering time, and also confirmed that PLA lost its amorphous character and developed crystals from the shorter chains formed as a result of degradative chain scission. It was further observed that the presence of TiO₂ retarded the degradation of both PLA and PCL. These results were supported by the differential scanning calorimetry results. The thermogravimetric analysis results confirmed that that PLA and PCL respectively influenced each other's thermal degradation, and that TiO₂ played a role in the thermal degradation of both PLA and PCL. The tensile properties of both PLA/PCL and PLA/PCL/TiO₂ were significantly reduced through weathering exposure and the incorporation of TiO₂.     

Fabrication of star-shaped, thermo-sensitive poly(N-isopropylacrylamide)-cholic acid-poly(?-caprolactone) copolymers and their self-assembled micelles as drug carriers

Novel star-shaped copolymers, comprised of a thermo-sensitive poly(N-isopropylacrylamide) (PNIPAAm) segment and three hydrophobic poly(?-caprolactone) (PCL) arms were fabricated. The copolymers were prepared by stannous octoate (Sn(Oct)₂) catalyzed ring-opening polymerization of ?-caprolactone (CL) using cholic acid functionalized PNIPAAm as the macroinitiator. The lower critical solution temperatures (LCST) of the copolymer solutions are attractively close to the nominal physiologic temperature at around 37 °C. The in vitro cytotoxicity test indicated no apparent cytotoxicity. The amphiphilic star-shaped copolymers were capable of self-assembling into spherical micelles in water at room temperature, and they possessed low critical micelle concentrations (CMCs) of 3 ∼ 8 mg/L in aqueous solution determined by fluorescence spectroscopy using pyrene as a probe. Transmission electron microscopy (TEM) measurement showed that the micelles exhibited a spherical shape with a size range of 30 ∼ 75 nm in diameter. In addition, the anticancer drug, methotrexate (MTX) can be loaded effectively in the polymeric micelles and its release was temperature-stimulated, which suggests that these materials have good potential as “intelligent” drug carriers.     

Synthesis and characterization of cellulose nanowhisker-reinforced-poly(ε-caprolactone) scaffold for tissue-engineering applications

Poly(ε-caprolactone) (PCL) is a bioresorbable and biocompatible polymer with assorted medical applications. However, remarkable hydrophobicity and nonosteoconductivity have stood as a barrier to limit its applications. The present study aims to modify the bulk characteristics of PCL to develop a polymeric scaffold with adequate structural and mechanical properties to support regenerated tissues. For this purpose, functionalized bacterial cellulose nanowhiskers (BCNW-g-βCD-PCL₂₀₀₀) are synthesized. Reinforcing PCL matrix with 4 wt % of the nanowhiskers resulted in a bionanocomposite with promoted bulk properties. Compared to neat PCL, the obtained bionanocomposite shows improvements of 115 and 51% in tensile strength and Young's modulus, respectively; 20% increase in hydrophilicity; 7% increase in degradation rate; and 6% decrease in crystallinity. Gas foaming/combined particulate leaching technique is used to develop highly porous structures of 86–95% porosity with interconnected macropores of mean pore diameters of 250–420 μm. Porous scaffolds showed compression modulus values of 5.3–9.1 MPa and would have promising applications in regenerative medicine. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2020 , 137, 48481.     

Effects of Poly(ϵ-caprolactone) on Structure and Properties of Poly(lactic acid)/Poly(ϵ-caprolactone) Meltblown Nonwoven

To obtain flexile poly(lactic acid)-based melt-blown nonwoven filtration material, poly(lactic acid)/poly(?-caprolactone) melt-blown nonwoven with various components were melt-spun by melt-blown processing in the Melt-blown Experiment Line. The 3 wt.% tributyl citrate to poly(?-caprolactone) was added in the composites as compatibilizer. The effect of poly(?-caprolactone) on the structure, morphology, mechanical and filtration properties of poly(lactic acid)/poly(?-caprolactone) melt-blown nonwoven was reported. Scanning electron microscopy micrographs revealed good dispersion of the additive in the fiber webs. The crystallinity of melt-blown webs with poly(?-caprolactone) was more than that of poly(lactic acid) alone. The tensile strength, ductility and air permeability of poly(lactic acid) melt-blown nonwovens were enhanced significantly. The input of poly(?-caprolactone) increased the diameter of fibers and decreased the filtration efficiency of poly(lactic acid)/poly(?-caprolactone) melt-blown nonwoven.     

In situ photocrosslinkable nanohybrids based on poly(ε-caprolactone fumarate)/polyhedral oligomeric silsesquioxane: synthesis and characterization

Two types of biodegradable, in situ photocrosslinkable macromers were synthesized consisting a linear copolyester i.e., PCLF based on fumaric acid (FA) and poly(ε-caprolactone diol) (PCL diol), and its nanohybrid counterpart (POSS-PCLF) composed of FA, PCL diol and polyhedral oligomeric silsesquioxane (POSS). Chemical structure of the macromers was characterized by ¹HNMR and FTIR spectroscopy. The synthesized macromers were photocrosslinked by visible light irradiation in the presence of camphorquinone and N,N’-dimethylaminoethyl methacrylate as a photoinitiator and accelerator, respectively. Photocrosslinking characteristics of the compositions were investigated as a function of the initial PCL diol molecular weight, presence of POSS nanoparticles or N-vinylpyrrolidone (NVP, as a reactive diluent) by tracing degree of conversion by FTIR spectroscopy, equilibrium swelling studies. Thermal and dynamical properties of the macromers and the resulting networks were studied by TGA, DSC and DMA techniques pre- and post-photocrosslinking. In contrast to the self-crosslinkability of the macromers, the crosslinking reaction was promoted more efficiently in the presence of NVP as a reactive diluent. This scrutiny showed that there is an optimum point for POSS concentration to obtain the maximum improvement in the network properties.