Polymeric pseudocrown ether resins containing azacrown and azathiacrown ethers: Synthesis and adsorption for metal ions

Eight novel polymeric pseudocrown ether (PPCE) resins containing azacrown and azathiacrown ethers were prepared by chemical reactions of the precursor of 1-chloro-2,3-epoxypropane, 1-(2-chloroethoxy)-2,3-epoxypropane, 1-chloro-2,3-epithiopropane, and 1-(2-chloroethoxy)-2,3-epithiopropane with triethylolamine or diethylolamine in the presence of NaH. The maximum adsorption capacities of PPCE resins for noble metals are 4.67 mmol Au/g-resin, 2.2 mmol Pd/g-resin, 0.7 mmol Pt/g-resin, and 7.3 mmol Ag/g-resin. The structure of PPCE resins were characterized by IR spectra and element analysis. The adsorption of PPCE resins for noble metals is jointly conducted by PPCE polymer backbone and the azacrown or azathiacrown cavity. The XPS study shows that there are strong complexion interactions between PPCE and Au(III) or Pd(II). © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 65:931–938, 1997     

Network crown ether resin with pendent sulfur ether group: Preparation,thermodegradation, and adsorption behavior

Network crown ether resin with the pendent sulfur ether group was prepared by ring‐opening copolymerization of 3‐thiopentyl glycidyl ether and diethylene glycol bisglycidyl ether with Na, NaOCH₂CH₂OCH₂CH₂OH, or BuLi as catalyst, respectively. The yield of network polymer and the conversion of functional monoepoxy monomer are varied from catalyst to catalyst, and the thermostability of the resin is related to the content of the sulfur ether group. The resins show high adsorption capacity toward Cu(II), Pb(II), especially, Hg(II) ions, but poor adsorption capacity toward Mg(II) ions. Corresponding thermodynamic parameter of Hg(II) ion was deduced, and could be expressed approximately with the Freundlich equation. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 87: 1445–1451, 2003     

Study on the adsorption properties of novel crown ether crosslinked chitosan for metal ions

We first synthesized N‐benzylidene chitosan (CTB) by the reaction of benzaldehyde with chitosan (CTS). Chitosan‐dibenzo‐18‐crown‐6 crown ether bearing Schiff‐base group (CTBD) and chitosan‐dibenzo‐18‐crown‐6 crown ether (CTSD) were prepared by the reaction of 4,4′‐dibromodibenzo‐18‐crown‐6 crown ether with CTB and CTS, respectively. Their structures were confirmed by Fourier transform infrared spectral analysis and X‐ray powder diffraction analysis. These novel crown ether crosslinked CTSs have space net structures with embedded crown ethers and contain the double structures and properties of CTS and crown ethers. They have stronger complexation with and better selectivity for metal ions than corresponding crown ethers and CTS. Moreover, these novel CTS derivatives can be used to separate and preconcentrate heavy or precious metal ions in aqueous environments. From this practical viewpoint, we studied the adsorption and selectivity properties of CTB, CTBD, and CTSD for Ag⁺, Cu²⁺, Pb²⁺, and Ni²⁺. The experimental results showed that CTBD had better adsorption properties and higher selectivity for metal ions than CTSD. For aqueous systems containing Pb²⁺–Ni²⁺ and Pb²⁺–Cu²⁺, the selectivity coefficients of CTSD and CTBD were K/Ni²⁺ = 24.4 and K/Cu²⁺ = 41.4 and K/Ni²⁺ = 35.5 and K/Cu²⁺ = 55.3, respectively. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 84: 29–34, 2002; DOI 10.1002/app.10180     

Synthesis and adsorption properties for metal ions of mesocyclic diamine‐grafted chitosan‐crown ether

A new type of grafted chitosan‐crown ether was synthesized using mesocyclic diamine crown ether as the grafting agent. The C2 amino group in chitosan was protected from the reaction between benzaldehyde and chitosan to form N‐benzylidene chitosan (CTB). After reaction with mesocyclic diamine crown ether of the epoxy propane group to give mesocyclic diamine‐N‐benzalidene chitosan (CTBA), the Schiff base was removed in a dilute ethanol hydrochloride solution to obtain chitosan‐crown ether (CTDA). Its structure was confirmed by FTIR spectra analysis and X‐ray diffraction analysis. Its static adsorption properties for Pb(II), Cu(II), Cd(II), and Cr(III) were studied. The experimental results showed that the grafted chitosan‐crown ether has high selectivity for the adsorption of Cu(II) in the presence of Pb(II), Cu(II), and Cd(II) and its adsorption selectivity is better than that of chitosan. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 75: 1255–1260, 2000     

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     

Synthesis of chelate resins derived from furfural and their adsorption properties for metal ions

A series of new chelate resins were synthesized by ring‐opening polycondensation of the reaction mixture of furfural with diethanolamine, using sulfuric acid as a catalyst, and the resulting chelate resins were employed in the adsorption for metal ions Bi, In, Sn, V, Ga, Y, Ti, and Pb. The composition, structure, and properties of the resulting chelate resin were studied by means of fourier transform infrared (FTIR), electron paramagnetic resonance spectrum (EPR), and elemental analysis methods. Meanwhile, the adsorption properties of the resulting chelate resins for the above metal ions were investigated by inductively‐coupled plasma–atomic emission spectrometry (ICP‐AES) procedures. The results show that the resulting chelate resins hold the structure consisting of hydroxyl groups, amine groups, and conjugated π bonds, as well as more crosslinkages, and so they exhibit a good reactivity and chemical stability. The adsorption experiments show that the chelate resins could well adsorb V, Ga, Y, Ti, and Pb in a wider acidity range and exhibit a good adsorption selectivity. Particularly, the chelate resins could adsorb and desorb for Pb, Bi, In, V, Y, and Ti, quantitatively, in the given conditions. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 99: 1620–1626, 2006     

新型冠醚交联壳聚糖的合成

利用壳聚糖C2位上活泼氨基与苯甲醛反应,制得了保护氨基的Schiff碱壳聚糖（简称CTB）;再将合成的带有双活性基团的4,4‘-二溴二苯并18-冠-6冠醚与壳聚糖分子的羟基发生反应,得到二苯并18-冠-6冠醚交联的Schiff碱壳聚糖（简称CTBD）,在酸性条件下使CTBD脱去苯甲醛,制得二苯并18-冠-6冠醚交联壳聚糖（简称CTD）。其主要中间体及产物的结构经红外光谱、质谱、核磁共振动等进行了鉴定。     

开链冠醚衍生物的合成

开链冠醚基二芳醛在酸性条件下与氨基脲反应,合成了链状二芳醛缩氨脲类化合物,产率高达90%以上,产物由IR、MS和元素分析鉴定了其结构。     

碱金属离子在树脂上的动态吸附行为

选取4种Na型树脂（D001、D113、Ls-1000、Ls-5000）为吸附剂,通过动态吸附法研究其对碱金属混合溶液的动态吸附行为,重点考察了其中铷、铯的分离性能,并考察了溶液pH、溶液组成、流速及树脂类型等对分离性能的影响。研究发现,中性条件下对铷、铯的吸附量顺序为离子交换树脂>螯合树脂。强酸性树脂D001对碱金属离子的亲和顺序为Cs+>Rb+>K+>Li+,其余3种树脂均为Cs+相似文献   

以对氨基苯甲酸乙酯为端基的酰胺型开链冠醚的合成与表征

以对氨基苯甲酸乙酯为端基合成了3种酰胺型开链冠醚,并通过IR、^1HNMR、MS和元素分析确证了它们的结构.     

Synthesis and adsorption properties of metal ions of novel azacrown ether crosslinked chitosan

Azacrown ether chitosan (CTSC) was synthesized by the reaction of chitosan with N‐allyl benzo 15‐crown‐5 crown ether. Azacrown ether crosslinked chitosan (CCTSC) was prepared by the crosslinked reaction of CTSC and epichlorodydrin. Their structures were confirmed by infrared spectral analysis and X‐ray diffraction analysis. The adsorption properties of CTSC and CCTSC for metal ions were also investigated. The experimental results showed that the two chitosan derivatives not only had a good capacity to adsorb Pd²⁺ and Ag⁺ but also was highly selective for Pd²⁺ and Ag⁺ in the coexistence system containing other metal ions. At 20°C ± 1°C and pH = 4, the adsorption capacity of CTSC and CCTSC for Pd²⁺ was 186.1 and 173.1 mg/g, respectively; and for Ag⁺ was 90.2 and 56.5 mg/g, respectively. The selectivity coefficients were K = 6.99, K = ∞, K = 35.38, K = ∞ for CTSC and K = 10.66, K = ∞, K = 85.45, K = ∞ for CCTSC. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 2705–2709, 2006     

Synthesis and evaluation of chitosan aryl azacrown ethers as adsorbents for metal ions

New azacrown ether chitosan derivatives (CTS–OC, CTS–NC) were synthesized by reaction of aryl mesocyclic diamine with the C6 hydroxyl group or C2 amino group in chitosan. Their structures were confirmed by elemental analysis, infrared spectra analysis, and X‐ray diffraction analysis. The adsorption and selectivity properties of the aryl azacrown ethers chitosan derivatives for Hg²⁺, Cd²⁺, Pb²⁺, Ag⁺, and Cr³⁺ were also investigated. The experimental results showed that the two chitosan–azacrown ethers have good adsorption capacity for Pb²⁺, Cd²⁺, and Hg²⁺. The adsorption capacity of CTS–OC are higher than that of CTS–NC for Pb²⁺ and Cd²⁺. The chitosan–azacrown ethers have high selectivity for the adsorption of Pb²⁺ and Hg²⁺ with the coexistence of Cd²⁺. The selectivity properties of CTS–OC are better than those of CTS–NC. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 77: 3093–3098, 2000     

Synthesis and characterization of polyacrylamide‐grafted coconut coir pith having carboxylate functional group and adsorption ability for heavy metal ions

The present investigation was undertaken to evaluate the effectiveness of a new adsorbent prepared from coconut coir pith (CP), a coir industry‐based lignocellulosic residue in removing metal ions from aqueous solutions. The adsorbent (PGCP‐COOH) having a carboxylate functional group at the chain end was prepared by grafting polyacrylamide onto CP using potassium peroxydisulphate as an initiator and in the presence of N,N′‐methylenebisacrylamide as a crosslinking agent. The adsorbent was characterized by infrared (IR) spectroscopy, thermogravimetry (TG), X‐ray diffraction (XRD) patterns, scanning electron microscopy (SEM), and potentiometric titration. The adsorbent exhibits very high adsorption potential for the removal of Pb(II), Hg(II), and Cd(II) ions from aqueous solutions. The optimum pH range for metal ion removal was found to be 6.0–8.0. The adsorption process follows a pseudo‐second‐order kinetic model. The adsorption capacities for Hg(II), Pb(II), and Cd(II) calculated using the Langmuir isotherm equation were 254.52, 189.49, and 63.72 mg g^?1, respectively. Adsorption isotherm experiments were also conducted for comparison with a commercial carboxylate form cation exchanger. Different industry wastewater samples were treated by the PGCP‐COOH to demonstrate its efficiency in removing heavy metals from wastewater. The reusability of the PGCP‐COOH was also demonstrated using 0.2M HCl. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 104: 3670–3681, 2007     

液晶冠醚的合成及在分析化学中的应用

讨论了近年来液晶冠醚的合成方法及其性质，并总结了其离子传输，分子识别以及在色谱分析，LB膜等方面的应用。     

Study of the synthesis of chitosan derivatives containing benzo‐21‐crown‐7 and their adsorption properties for metal ions

Three new chitosan crown ethers, N‐Schiff base‐type chitosan crown ethers (I, III), and N‐secondary amino type chitosan crown ether (II) were prepared. N‐Schiff base‐type chitosan crown ethers (I, III) were synthesized by the reaction of 4′‐formylbenzo‐21‐crown‐7 with chitosan or crosslinked chitosan. N‐Secondary amino type chitosan‐crown ether (II) was prepared through the reaction of N‐Schiff base type chitosan crown ether (I) with sodium brohydride. Their structures were characterized by elemental analysis, infrared spectra analysis, X‐ray diffraction analysis, and solid‐state ¹³C NMR analysis. In the infrared spectra, characteristic peaks of C?N stretch vibration appeared at 1636 cm^?1 for I and 1652 cm^?1 for II; characteristic peaks of N? H stretch vibration appeared at 1570 cm^?1 in II. The X‐ray diffraction analysis showed that the peaks at 2θ = 10° and 28° disappeared in chitosan derivatives I and III, respectively; the peak at 2θ = 10° disappeared and the peak at 2θ = 28° decreased in chitosan‐crown ether II; and the peak at 2θ = 20° decreased in all chitosan derivatives. In the solid‐state ¹³C NMR, characteristic aromatic carbon appeared at 129 ppm in all chitosan derivatives, and the characteristic peaks of carbon in C?N groups appeared at 151 ppm in chitosan crown ethers I and III. The adsorption and selectivity properties of I, II, and III for Pd²⁺, Au³⁺, Pt⁴⁺, Ag⁺, Cu²⁺, and Hg²⁺ were studied. Experimental results showed these adsorbents not only had good adsorption capacities for noble metal ions Pd²⁺, Au³⁺, Pt⁴⁺, and Ag⁺, but also high selectivity for the adsorption of Pd²⁺ with the coexistence of Cu²⁺ and Hg²⁺. Chitosan‐crown ether II only adsorbs Hg²⁺ and does not adsorbs Cu²⁺ in an aqueous system containing Pd²⁺, Cu²⁺, and Hg²⁺. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 83: 1886–1891, 2002     

蒽醌冠醚双功能化杯[4]芳烃的合成与表征

以对叔丁基杯[4]芳烃为原料,经碱催化两步合成了26,28-双（2-亚甲基蒽醌）-5,11,17,23-四叔丁基杯[4]-25,27-冠-6。产物经IR、1HNMR表征和元素分析表征,该衍生物为锥形结构并与设计思想一致。     

芘冠醚双功能化杯[4]芳烃的合成与表征

以杯[4]芳烃为原料,经碱催化合成了26,28-双(1-乙酰基芘)-5,11,17,23-四叔丁基杯[4]-冠-6,产物结构经IR、1HNMR和元素分析表征。该衍生物为锥形结构。     

Preparation and adsorption behavior for metal of chitosan crosslinked by dihydroxy azacrown ether

A new type of crosslinked chitosan was prepared using Dihydroxy azacrown ether as the crosslinking agent. Its structure was confirmed by elemental analysis, Fourier transform infrared (FTIR) spectra analysis, solid‐state ¹³C nuclear magnetic resonance (NMR) analysis, and X‐ray diffraction analysis. Its static adsorption properties for Ag⁺, Cd²⁺, Hg²⁺, and Co²⁺ were studied. The experimental results showed that the Dihydroxy azacrown ether crosslinked chitosan has good adsorption capacities and high selectivity for adsorption of Ag⁺ with the coexistence of Hg²⁺ and Co²⁺. The selectivity coefficients of crosslinked chitosan are k/ = 5.47, k/ = 4.64, respectively. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 85: 530–535, 2002     

Addition‐cure phenolic resins based on propargyl ether functional novolacs: synthesis,curing and properties

Thermosetting phenolic resins, bearing varying extents of propargyl ether groups (PN resins), have been synthesized by the Williamson reaction of a novolac with propargyl bromide and the products characterized. The resin precursors were cured through Claisen rearrangement of the propargyl ether groups and thermal polymerization. The activation energy for thermal cure is substantially lower than that of model bispropargyl ether compounds but is quite independent of the degree of functionalization. The isothermal cure profile, extrapolated from non‐isothermal DSC kinetics studies is consistent with the results from DMA studies. The mechanical properties of glass composites of the resins, of varying propargyl contents, reveal good consolidation of the interphases, evident from the initial gain in both interlaminar shear strength (ILSS) and flexural strength. The benefits of better resin–reinforcement interactions are not retained on crosslinking the resin further, wherein the composite fails by a combination of fibre debonding and brittle fracture of the matrix. Although the resins show better thermal stability than cured resoles, a higher extent of propargylation is detrimental for the thermal stability. Resins with moderate propargylation show good mechanical and thermal properties. © 2001 Society of Chemical Industry     

Effective adsorption of phenolic compounds by functional group modified resins: behavior and mechanism

A series of functional hyper-crosslinked resins were successfully synthesized by incorporating amino, hydroxyl, and complex functional groups into post-crosslinked polymer. Possessing high specific surface area and effective functional groups, the newly synthesized resins showed excellent adsorption capacity toward various phenolic compounds. HC-IT displayed huge advantage over the others. Its adsorption capacity for salicylic acid was up to 336 mg/g, which was 3.01–6.64 times higher than that of the commercial resins and 2.33 times higher than its non-functionalized precursor HCLR (144 mg/g). The improved adsorption capacity was attributed to its high specific surface area, good polarity, and proper pore structure.