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JOURNAL OF POLYMER RESEARCH · 2023 ·Vol. 31 ·期 1 ·1-9 · IF 2.8

Efficient ring-opening polymerization of epsilon-caprolactone catalyzed by iron(III) chloride under mild reaction conditions

Wu Hai-Bo,Zhou Xian-Tai,Zhou Xiao-Wu,Fang Yan-Xiong

As a biodegradable polyester, the commercialized synthesis protocol of poly(ε-caprolactone) (PCL) under mild conditions is of great significance and attractive. Herein, the ring-opening polymerization (ROP) of ε-caprolactone (ε-CL) using FeCl 3 catalyst and benzyl alcohol (BnOH) as the initiator was developed. FeCl 3 has been proved to be an efficient catalyst for the ROP of ε-CL under mild conditions. The conversion of ε-CL to PCL was 98.8% at 60 °C within 4 h, with number-average molecular weight ( M n) and dispersity (PDI) of 1.65 × 10 4  g/mol and 1.28, respectively. Moreover, a coordination-insertion ring-opening polymerization mechanism mediated by FeCl 3 was proposed. Overall, this work is expected to provide a feasible industrial method for the preparation of PCL from the direct aerobic oxidation of cyclohexanone.

研究领域: 材料科学 · 化学工程
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POLYMER TESTING · 2020 · IF 3.275

Determination of residual monomers in poly(lactide-co-ε-caprolactone) using gas chromatography

Lidong Feng,Sheng Xiang,Yanlong Liu,Xinchao Bian,Gao Li,Xuesi Chen

An analytical method was developed to quantitatively determine residual monomers, namely, lactide (LA) and ε -caprolactone (CL), in poly(lactide- co - ε -caprolactone) (PLCL) using an internal-standard method of gas chromatography (GC). PLCL and diphenyl ether (DPE) as an internal standard were initially dissolved in dichloromethane (DCM), and then PLCL was precipitated in cyclohexane. The residual LA and CL monomers in PLCL, as well as DPE, were extracted into cyclohexane from the polymer solution. The resulting solution was directly injected into a GC system. This method was practical for measuring the residual LA and CL contents in PLCL. The relative standard deviation ( RSD ) ( n  = 5) denoting the repeatability of this method was less than 5.6% and 4.3% for the LA and CL measurements, respectively, indicating that the method was sufficiently precise. The recovery rate of standard addition was 96.5%–101.5% and 98.4%–104.2% for the determination of LA and CL in PLCL, respectively. The RSD of the recovery of standard addition ( n  = 5) was not more than 2.0%, indicating that the method was sufficiently accurate.

CAS / MDL: 101-84-8
研究领域: 分析化学 · 高分子材料科学 · 医学材料
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Polymer Chemistry · 2014 ·Vol. 5 ·期 8 ·3098-3106 · IF 5.368

o-Benzenedisulfonimide as a recyclable cationic organocatalyst for the controlled/living ring-opening polymerization of δ-valerolactone and ε-caprolactone

Yu Jin,Yufeng Ji,Xiaojiang He,Suli Kan,Haidong Xia,Binqi Liang,Jia Chen,Hao Wu,Kai Guo,Zhenjiang Li

o-Benzenedisulfonimide (OBS) was demonstrated for the first time to be a safe, recyclable, and water-tolerant Brønsted acidic catalyst for the ring-opening polymerization (ROP) of δ-valerolactone and ε-caprolactone using benzyl alcohol as the initiator. The polymerizations proceeded to afford poly(δ-valerolactone) and poly(ε-caprolactone) with controlled molecular weights and narrow polydispersities. The kinetics and chain extension experiments were carried out to confirm the controlled/living fashion of the polymerizations. In addition, 1H NMR and MALDI-TOF MS measurements strongly indicated that the initiator residue was incorporated into the obtained polymers. Furthermore, well-defined poly(δ-valerolactone)-block-poly(ε-caprolactone) has been successfully synthesized via OBS-catalyzed ROP.

研究领域: 高分子化学 · 材料科学
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ORGANOMETALLICS · 2019 · IF 4.1

Aluminum Complexes Bearing Bidentate Amido–Phosphine Ligands for Ring-Opening Polymerization of ε-Caprolactone: Steric Effect on Coordination Chemistry and Reactivity

Chuanzhi Wei,Binghao Han,Dejuan Zheng,Quande Zheng,Shaofeng Liu,Zhibo Li

The aluminum complexes LAlMe2 (Al1–Al5: LH = 2,6-(R1)2-4-R2-C6H2NHCH2C6H4-2-PPh2; Al1, R1 = H, R2 = H; Al2, R1 = Me, R2 = H; Al3, R1 = iPr, R2 = H; Al4, R1 = Ph2CH, R2 = iPr; Al5, R1 = Cl, R2 = H) have been synthesized and characterized by elemental analysis and 1H, 13C, and 31P NMR. NMR analysis in solution reveals an interesting hemilabile coordination of the soft P donor. The molecular structures of Al2–Al4 were defined by X-ray diffraction studies, showing a distorted-tetrahedral geometry around the aluminum center in all structures. Careful comparison of these crystal structures suggested that different substituents on the ligands could lead to unignorable changed coordination environments around the Al center, thus affecting their catalytic properties. In the presence of BnOH, complexes Al1–Al5 efficiently catalyzed the ring-opening polymerization (ROP) of ε-caprolactone (ε-CL) with high conversions in a controlled manner, and high molecular weights (Mn up to 118.6 kg mol–1) of polycaprolactones (PCLs) were readily prepared. Immortal polymerizations by Al4 having bulky Ph2CH groups were also studied with up to 20 equiv of alcohols and 2000 equiv of monomers, without sacrificing polymerization control.

CAS / MDL: 502-44-3
研究领域: 化学 · 材料科学
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Journal of Industrial Textiles · 2025 · IF 2

Electrospun nanofber membranes for complete leukocyte removal in blood filtration: Pore size optimization and performance evaluation

Hongyan Wu,Wenna Xing,Chuyan Zheng,Liuyao Wang,Jialu Li

The safety of blood transfusions faces significant challenges due to the presence of leukocytes, which can trigger severe immune responses and facilitate virus transmission. Existing leukocyte reduction filters, predominantly composed of melt-blown nonwovens, encounter difficulties in completely eliminating leukocytes for specific patient populations such as organ transplant recipients. This research introduces electrospun membranes composed of PBS and CS/PBS nanofiber membranes as a novel filtration material. Through the optimization of electrospinning parameters (including voltage, receiving distance, and solution volume), membranes with adjustable pore sizes ranging from 1.3 to 2.1 μm and substantial specific surface areas were developed. Blood filtration trials revealed that nanofiber membranes with an optimal pore size range of 1.9–2.1 μm achieved complete leukocyte removal while preserving a red blood cell (RBC) recovery rate of 87.72%–90.65%. In comparison to conventional filters, these electrospun nanofiber membranes present a promising strategy for highly efficient leukocyte depletion, catering to the demands of critical transfusion scenarios.

研究领域: 生物医学工程 · 纳米技术 · 输血医学 · 材料科学 · 免疫学
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JOURNAL OF CHEMICAL AND ENGINEERING DATA · 2018 · IF 2.196

Measurement and Correlation for Solubilities of Succinic Acid and Glutaric Acid in ε-Caprolactone + Acetic Acid Mixtures and ε-Caprolactone + Cyclohexanone Mixtures

Weiping Luo,Xiuqing Li,Dong Ruan,Kaili Xie,Bao Tao,Cancheng Guo

By using the method of dynamic laser, the solubilities of succinic acid and glutaric acid in ε-caprolactone + acetic acid mixtures and ε-caprolactone + cyclohexanone mixtures were determined under atmospheric pressure. The experimental temperature ranged from 293.35 to 340.65 K, and the mass fraction of ε-caprolactone in the solvent mixtures ranged from 0.0 to 1.0, respectively. It was found that with the increase of the temperature at constant concentration, the measured solubilities of succinic acid and glutaric acid in ε-caprolactone + acetic acid mixtures and ε-caprolactone + cyclohexanone mixtures would increase. Moreover, when the mass fraction of ε-caprolactone in ε-caprolactone + acetic acid mixtures increases at the same temperature, the measured solubilities of succinic acid and glutaric acid would decrease. However, it would increase as the mass fraction of ε-caprolactone increases for the system of ε-caprolactone + cyclohexanone at the same temperature. The experimental data were correlated by using the modified nonrandom two liquid activity coefficient model. The maximum value of average relative deviation was 1.50%.

研究领域: 化学工程 · 物理化学
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JOURNAL OF CHEMICAL AND ENGINEERING DATA · 2016 · IF 1.835

Measurement and Correlation for Solubilities of Adipic Acid in Acetic Acid + ε-Caprolactone Mixtures and Cyclohexanone + ε-Caprolactone Mixtures

Weiping Luo,Dong Ruan,Dawei Liu,Kaili Xie,Xiuqing Li,Wei Deng,Cancheng Guo

The solubilities of adipic acid in acetic acid + ε-caprolactone mixtures and in cyclohexanone + ε-caprolactone mixtures were measured by using the method of dynamic laser under atmospheric pressure. The experimental temperature ranged from 305.55 to 343.15 K, and the mass fraction of ε-caprolactone in the solvent mixtures ranged from 0.100 to 1.000, respectively. It was found that with the increasing of mass fraction of ε-caprolactone in solvent mixtures (0.100 to 1.000), the measured solubilities of adipic acid in acetic acid + ε-caprolactone mixtures decreased at the same temperature. However, in cyclohexanone + ε-caprolactone mixtures, the solubility showed an opposite trend with the increasing of mass fraction of ε-caprolactone in solvent mixtures. The experimental data were correlated by the modified NRTL activity coefficient model, and the values of the solubility calculated showed good agreement with the experimental observations.

研究领域: 化学工程 · 物理化学
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Frontiers of Chemical Science and Engineering · 2011 ·Vol. 5 ·期 4 ·409-415 · IF 0

Synthesis of depsipeptides from L-amino acids and lactones

Cao Hongfei,Feng Yakai,Wang Heyun,Zhang Li,Khan Musammir,Guo Jintang

By using the corresponding L -amino acid sodium as initiator, ɛ -caprolactone-depsipeptides CL-Ala and CL-Leu were prepared by the reactions of ɛ -caprolactone (CL) with L -alanine and L -leucine, respectively, and p -dioxanone-depsipeptide (PDO-Leu) was prepared by the reaction of p -dioxanone (PDO) with L leucine. Two poly( ɛ -caprolactone) oligomers (PCL-Ala and PCL-Leu) of different molecular weights with depsipeptide unit were synthesized by controlling the feed ratio of L -amino acid sodium and CL. The presence of the depsipeptide structure in these obtained products was confirmed by 1 H NMR spectra and the molecular weight of the poly( ɛ -caprolactone) oligomers was measured by gel permeation chromatography (GPC). These products contain a hydroxyl group and a carboxyl group in one molecule, which means they could act as bifunctional monomers for further polymerization to prepare high molecular weight polymers. By this way, the depsipeptide unit could be introduced into the polymers and the biodegradation rates of the novel polymers could be well controlled in vivo by the tailored molecular structures.

研究领域: 有机化学 · 高分子化学 · 生物材料学
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REACTIVE & FUNCTIONAL POLYMERS · 2021 · IF 3.975

Hydrophilic and degradable polylactones via copolymerization of ε-caprolactone and oxo-crown ether catalyzed by a bifunctional organic base

Zhitao Hu,Xiaohui Cao,Huahua Huang,Yongming Chen

Poly( ε -caprolactone) (PCL) has been one of the most important biomaterials, but its instinct hydrophobicity and slow biodegradation limit its broad applications. Herein, copolymerization of CL and a hydrophilic macrolactone, 2-oxo-15-crown-5 ether (O15C), was achieved through ring opening polymerization catalyzed by 1,5,7-triazabicyclo[4.4.0]dec-5-ene (TBD) using benzyl alcohol as the initiator at room temperature . A series of poly(CL- co -O15C) copolymers with different O15C contents were prepared by simply tuning the feeding ratio of [CL]/[O15C]. They showed molecular weights ranging from 11.0 to 20.6 kg mol −1 , and polydispersity index between 1.4 and 1.6, characterized by SEC (Size Exclusion Chromatography). Analysis of 1 H NMR indicated that the copolymers belong to a random copolymer structure. The introduction of O15C had a significant influence on thermal stability, hydrophilicity and degradability of the copolymers. With increasing the O15C content, the crystalline ability of PCL segment among the copolymers reduced, while the hydrophilic property was improved obviously. Through hydrolysis experiment, the poly(CL- co -O15C) with O15C content of 38 mol% exhibited a much faster degradable rate than that of the copolymer with O15C content of 10 mol%. Therefore, copolymerization of CL with a crown ether monomer via organic catalyst mediated ROP will be a feasible strategy for modification of polyester materials.

研究领域: 材料科学 · 生物医学工程
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EUROPEAN POLYMER JOURNAL · 2023 · IF 6

Fast and living ring-opening polymerization of ε‑caprolactone by aluminum complexes bearing amino-quinoline ligands

Mengting Zang,Wenyao Cao,Xingwang Zhang,Shaofeng Liu,Zhibo Li

Catalysts drive innovation in sustainable polymers because of their reactivity and selectivity. In this context, the synthesis and characterization of a series of Al complexes ( Al1  −  Al5 ) bearing N,N-bidentate amino-quinoline ligands are described, as well as their applications in ring-opening polymerization (ROP) of ε -caprolactone ( ε -CL). The amido-coordination Al complexes were directly synthesized by reactions of imino-quinoline compounds with AlMe 3 via methyl migration from Al to the carbon atom of imine, as indicated by both NMR spectroscopy and X-ray diffraction. In the presence of BnOH, complexes Al1  −  Al5 showed significant reactivity for ROP of ε -CL with good control over molar mass ( M n ) and dispersity ( Đ < 1.2), and polycaprolactones (PCLs) with high molecular weights ( M n up to 129 kDa) were readily synthesized. Remarkably, immortal catalysis with excess of BnOH (up to 20 equiv. to Al) was achieved to prepare PCLs with predictable M n s, low dispersities, and end groups using an extremely low loading of Al complex (0.05 mol% to ε -CL monomer).

CAS / MDL: 502-44-3
研究领域: 高分子化学 · 催化化学
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JOURNAL OF HAZARDOUS MATERIALS · 2025 · IF 11.3

Nanoplastics and microplastics released from an enzyme-embedded biodegradable polyester during hydrolysis

Ling Ma,Zi-Yang Fan,Wen-Qian Lian,Xin-Feng Wei,Rui-Ying Bao,Wei Yang

Embedding enzyme in biodegradable polyester accelerates hydrolysis in environments it ends up, but the release of microplastics (MPs) and nanoplastics (NPs) during this process remains underexplored. This work investigated the evolution of MPs and NPs released from poly(ε-caprolactone) (PCL) with embedded Lipase PS. The embedded enzyme significantly accelerated hydrolysis, causing the PCL film to disappear within 96 h. Notably, the formation rates and quantities of MPs and NPs were much higher compared to film with external enzyme. At 96 h, MPs (3.55 ×10 5 particles/mL) was 2.4 times, and NPs (4.65 ×10 7 particles/mL) was an order of magnitude higher than that with external enzyme. After 130 days, although both quantities and average size of MPs and NPs decreased due to only 90.6 % of enzymes were detected leaking, they did not completely disappear. The quantities of MPs and NPs were comparable to that with external enzyme, and the average size of MPs remained 1 μm. The simultaneous erosion inside film macroscopically, and severe chain cleavage microscopically, contributed to feasible film disintegration and formation of high amounts MPs and NPs. These findings underscore the importance of managing the release of MPs and NPs during the hydrolysis of enzyme-embedded biodegradable polyesters to ensure safety and mitigate environmental impact.

CAS / MDL: 51649-83-3
研究领域: 环境科学 · 材料科学 · 生物学
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JOURNAL OF POLYMER SCIENCE PART A-POLYMER CHEMISTRY · 2013 ·Vol. 52 ·期 2 ·188-199 · IF 3.543

Synthesis and pH-responsive assembly of methoxy poly(ethylene glycol)-b-poly(ε-caprolactone) with pendant carboxyl groups

Yan Zhang,Jinhong Li,Zhengzhen Du,Meidong Lang

pH-responsive methoxy poly(ethylene glycol)- b -poly(ε-caprolactone) bearing pendant carboxyl groups mPEG- b -P(2-CCL- co -6-CCL) was synthesized based on our newly monomer benzyloxycarbonylmethly functionalized ε-caprolactone. Their structure was confirmed by 1 H NMR, 13 C NMR, and Fourier transform infrared spectrum spectra. In addition, SEC results indicated that the copolymers had a relatively narrow polydispersity. WXRD and DSC demonstrated that the introduction of carboxymethyl groups had significant effect on the crystallinity of the copolymers. Furthermore, the solution behavior of mPEG- b -P(2-CCL- co -6-CCL) has been studied by various methods. The results indicated that mPEG- b -P(2-CCL- co -6-CCL) had a rich pH-responsive behavior and the micelles could be formed by pH induction, and the mPEG- b -P(2-CCL- co -6-CCL) could existed as unimers, micelles or large aggregates in different pH range accordingly. The mechanism of which was supposed to depend on the counteraction between the hydrophobic interaction from PCL and the ionization of the carboxyl groups along the polymer chain. Moreover, the mPEG- b -P(2-CCL- co -6-CCL) copolymers displayed good biocompatibility according to the preliminary cytotoxicity study. © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2014 , 52 , 188–199

CAS / MDL: 5437-45-6 937-14-4
研究领域: 高分子化学 · 生物材料 · 药物递送
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