Modified kaolinites‐polyalkyl methacrylate nanocomposites: Exploring relations between solubility parameters and thermal properties for in situ solution polymerization

Poly(methyl methacrylate) (PMMA), poly(ethyl methacrylate) (PEMA), and their nanocomposites (Kao‐PMMAs and Kao‐PEMAs) with various kaolinite intercalation compounds were prepared in several solution polymerization media in order to examine relations between solubility parameters of polymerization medium including monomer and solvent/solvents and of intercalating agents and thermal properties of the resultant materials. The measurements of X‐ray diffraction, scanning electron microscopy, transmission electron microscopy, thermogravimetry/derivative thermogravimetry, and differential scanning calorimetry were used to characterize these materials. The increase in solubility parameter of polymerization medium improved thermal decomposition temperatures of PEMA and Kao‐PEMAs when it usually induced a decrease in those of PMMA and Kao‐PMMAs and in glass transition temperatures of all materials. These results were also examined in respect of the effects of hydrogen bonding and dispersion components of solubility parameters of intercalating agents on the thermal properties of these materials. POLYM. COMPOS., 37:2333–2341, 2016. © 2015 Society of Plastics Engineers     

纳米零价铁强化高岭石去除水中Cr(VI)及机制研究

纳米零价铁(nZVI)作为一种治理重金属、核素污染物的环保材料而被广泛关注,而黏土矿物作为常见的重金属吸附材料虽成本低廉、来源广泛,但去除性能又普遍有限。通过液相还原法制备nZVI/高岭石复合材料来强化高岭石去除水中Cr(VI)的性能,利用X射线衍射仪(XRD)、扫描电子显微镜(SEM)和透射电子显微镜(TEM)技术对其结构进行表征,考察了Cr(VI)初始浓度、nZVI/高岭石投加量、温度等条件对Cr(VI)去除率的影响,并探讨了其对水中Cr(VI)的去除能力及机制。结果表明,nZVI/高岭石中的nZVI结晶度低,粒径在50~100 nm,nZVI/高岭石在60 min时对Cr(VI)的去除率达91.7%,分别比nZVI和高岭石提高了2.7倍和18.5倍。nZVI/高岭石对Cr(VI)的去除动力学符合准二级动力学模型,表观反应活化能为27.97 kJ/mol,去除是吸附、还原和共沉淀共同作用的结果。通过nZVI强化可提升高岭土在水处理和环境修复中的应用前景。     

国际家居及个人护理品品牌故事

对国际著名家用品及个人护理品的品牌公司进行了介绍，包括联合利华、欧莱雅、花王、资生堂、汉高、利高曼、威娜和拜尔斯道夫，并简要讲述了其品牌故事。     

Determination of average molecular weight of commercial surfactants: Alkylpolyglucosides and fatty alcohol ethoxylates

A quick and simple method, based on elemental and moisture analyses, is proposed for estimating the mean molecular weight of alkylpolyglucosides and fatty alcohol ethoxylates, which are nonionic surfactants that are attracting growing interest for their ease of biodegradation. Analyses for the water content and the elemental composition were carried out for three alkylpolyglucosides (Henkel-Cognis): Glucopon 215, Glucopon 600, and Glucopon 650, as well as for five fattyalcohol ethoxylates (Kao Corporation): FINDET 10/15, FINDET 10/18, FINDEt 1214N/16, FINDET 1214N/23, and FINDET 1618/A18. Application of the method requires knowing the mean number of carbons in the fatty acid chains of the surfactant. This number, in the case of the alkylpolyglucosides assayed here, has been determined experimentally by high-performance liquid chromatography.     

国内外烷基多苷的研究开发和生产现状

由葡萄糖和脂肪醇合成新型非离子表面活性剂烷基多苷的技术路线有两步法和直接法两种。由于两步法存在产品质量不高、工艺流程长和能耗高等缺点,烷基多苷合成技术的研究重点已转向直接法。国外主要生产烷基多苷的公司有Henkel、P&G、Kao、Huls和Seppic等,主要采用直接法,生产规模较大。国内直接法技术也已成熟,但生产厂家多数采用两步法,生产规模小,产品质量不高。国内总生产能力约6000t/a,而实际产量约1200t/a。今后烷基多苷的研究应致力于提高质量、降低成本、增加品种和扩大应用领域。     

New detergent mechanism with use of novel alkaline cellulose

Microscopic studies of naturally soiled cotton undershirts showed that there was sebum in the microscopic spaces in the interior of the cotton fibers. Ordinary detergents did not remove this soil satisfactorily, although they readily removed sebum on the exterior of the fibers. Alkaline cellulase, which was compatible with the alkaline ingredients of detergents and which interacted selectively with celluloses in interfiber space in the interior of fiber, effectively removed sebum soil in the interfiber spaces in the presence of usual detergent ingredients. The removal of soil by the hydrolysis of the amorphous regions of fibers with cellulase is a new detergent mechanism. To whom correspondence should be addressed at: Plant Manager, Kawasaki Plant, Kao Corp., 1-2, Ukishimacho, Kawasaki, Kanagawa 210, Japan.     

Influence of constituents on thermal properties of polymethacrylate derivatives–clay materials

In this study, the solution‐mixing method was used to prepare polymethacrylate derivatives' (PaMAs) nanocomposites with kaolinite. It was observed that the resultant materials could include exfoliated, intercalated, and undispersed kaolinite depending on their XRD patterns. TEM micrographs also revealed that platy and tube structures of kaolinite and their stacked form would disperse in the PaMAs. Therefore, they were called PaMAs–kaolinite materials with mixed morphology. The effects caused by different types of PaMA, solvent, and clay (sepiolite and kaolinite) on the thermal properties of these materials were examined. When the thermal stability of the materials was compared on the basis of the functional groups in the PaMAs, it was seen that the materials of the linear PaMAs with kaolinite usually had better thermal stability than that of the ring PaMAs and also seen that the thermal stability of Kao‐PaMAs increased from PMMA to poly(ethyl methacrylate) (PEMA) and poly(butyl methacrylate) for linear PaMAs. The solvent type affected the thermal stability and the glass transition temperature of the PaMAs. It was found that THF is the most suitable solvent for increasing thermal stability of the PaMAs in the presence of kaolinite; however, it is difficult to say the same about their T_g temperatures. In addition, the thermal stabilities of PEMA and poly(2‐hydroxylethyl methacrylate) were higher in the presence of kaolinite in comparison with sepiolite. The results obtained in this study were explained by the utilization of the relationships among their solubility parameters and of the interactions among the PaMAs, clays, the modifier (octadecylamine) and solvents. POLYM. COMPOS., 2011. © 2011 Society of Plastics Engineers     

Hemostatic activities of nano/microporous bilayer dressings in a femoral artery bleeding rat model

Recently, an effective hemostatic dressing requirement has become a major problem in both the military and civilian world. Available hemostatic agents are too expensive, ineffective, unsafe, or complicated to use. Here, we evaluated the hemostatic efficacy of a nano/micro bilayer hemostatic dressing including a porous sublayer from chitosan (CTS) and bacterial cellulose (BC) and a nanofibrillar upper layer from silk fibroin (SF). In addition, several active agents rolled in coagulation cascade [vitamin K (Vit K), protamine sulfate (PS), kaolin (Kao), etc.] were doped to the sublayer of bilayer hemostatic agent and their activities were compared via in vivo and in vitro tests. Lactate dehydrogenase (LDH) activity test results demonstrated that BC/CTS, SF‐coated BC/CTS, and Vit K K/BC/CTS, SF/phosphatidylcholine (PC)‐coated BC/CTS showed higher LDH activity compared to standard gauze (p < 0.005). In a femoral artery bleeding rat model, SF‐coated PS/BC/CTS significantly reduced bleeding time (80 ± 0.3 s) compared to standard gauze and kaolin‐doped group (p < 0.005). Blood loss and mortality rate with 2.3 g and 37.5% SF‐coated BC/CTS and SF‐coated PS/BC/CTS showed increased efficacy in achieving hemostasis compared to standard gauze. All the prepared hemostatic dressings except for kaolin‐doped BC/CTS and standard gauze induced no inflammatory reaction in the tissue. All these data suggest that active agent‐doped BC/CTS/SF‐based bilayer hemostatic dressings have a great influence on the resulting hemostatic action. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43657.     

Synthesis,Characterization and Material Application of Poly(Urea-Imide)s,Part 1

Poly(urea-imide)s (PUIs) were prepared by Diels-Alder (DA) intermolecular polymerization of hexamethylenebis(2-furanmethylurea) (BFU) (1) with various bismaleimides (2a-f). The DA reaction was carried out using 1,4-dioxane as solvent, as well as in bulk, followed by aromatization (dehydration) of poly(tetrahydro phthalimide) intermediates (3a-f) in the presence of acetic anhydride. All the PUIs (3a-f, 4a-f and 5a-f) were characterized by elemental analysis, IR spectral studies and thermogravimetrically. BFU (1) and bismaleimides (2a-f) were polymerized (at 145 ± 10°C) by in situ DA intermolecular reaction into moderately thermally stable PUIs (5a-f), glass fiber and carbon fiber composites without evolution of any byproducts. The prepared composites were characterized by chemical resistance and mechanical properties.     

Synergistic Extraction of Am(III) and Eu(III) by Tris(2‐pyridylmethyl)Amine with Various Anions in 1,2‐Dichloroethane

The extraction equilibria of Am(III) and Eu(III) by using a tripodal ligand, tris(2‐pyridylmethyl)amine (tpa), with various lipophilic anions have been investigated. The extractability of both Am(III) and Eu(III) was increased by the combination of tpa and counteranions due to a synergistic effect. The separation factors between Am(III) and Eu(III) were also increased from 7.6 to 49 by the combination of counteranions and organic solvents. The extraction equilibria of Am(III) and Eu(III) with tpa in 1,2‐dichloroethane were determined by slope analysis. It was found that three anions and one molecule of the ligand coordinated to Am(III) and Eu(III) was extracted regardless of the anions.     

Synthese und Reaktionen von β-Campholenverbindungen

Synthesis and Reactions of β-Campholene Compounds In contrast to the well known α-campholenic ( B ) and fencholenic compounds ( C ) little is known about β-campholenic derivatives ( A ) because of their difficult accessibilitiy. β-Campholenic compounds ( A ) can be obtained: (1) by Baeyer-Villiger oxidation of camphor via lactone 7 and β-dihydrocampholenic lactone ( 5 ); (2) by Beckmann fragmentation of camphor oxime via α-( 2 ) and β-campholenic nitril ( 3 ) and the lactone 5 ; and ( 3 ) by acid catalysed rearrangement of α-campholenic derivatives ( B , 17a , b ). The β-analogous brahmanol ( 14 ) can be synthesized by the reaction of the β-campholenic bromide ( 11 ) with methyl diethyl malonate or by rearrangement of brahmanol.     

The Film Properties of Waterborne Polyurethane Modified by Epoxidized Soybean Oil and Styrene

The waterborne polyurethane (WPU) modified by epoxidized soybean oil (ESO) and styrene (St) (WPU-ESO-St) was synthesized by free-radical emulsion polymerization using styrene (St) as a monomer, and azodiisobutyronitrile (AIBN) as initiator. The research on the mechanical properties of the film showed that with the increasing of the [NCO]/[OH] ratio, the contents of ESO, DAAM and the St, the tensile strength increased, and elongation at break decreased. The surface morphology of the film was characterized by atomic force microscopy (AFM). The glass transition temperature (Tg) of the film was characterized by differential scanning calorimetry (DSC) analysis.     

(R)-9-[2-(二乙氧基磷酰甲氧)丙基]腺嘌呤合成过程中催化剂的优选

目的:(R)-9-[2-(二乙氧基磷酰甲氧)丙基]腺嘌呤(3)合成过程中的催化剂优选。方法:以亚磷酸二乙酯和多聚甲醛经缩合、酯化得到对甲苯磺酸羟甲基磷酸二乙基酯(1)。另以(R)-1,2-亚丙基碳酸酯与腺嘌呤反应得到9-(2-羟丙基)腺嘌呤(2),在(1)与(2)缩合得到(3)的反应中对四种催化剂进行实验对比。结果:优选催化剂为叔丁醇锂的无水DMF溶液,降低成本和污染。结论:合成得到(3),产率提高到40.5%。     

Separation and Recovery of Silver(I) Ions from Base Metal Ions by Thiourea- or Urea-Formaldehyde Chelating Resin

Abstract

In the present work, thiourea-formaldehyde (TF) and urea-formaldehyde (UF) chelating resins have been synthesized and they have been used in the adsorptions of Ag(I), Cu(II), and Zn(II) metal ions by batch and column methods. The effect of initial acidity of Ag(I) solution and the adsorption capacities of TF and UF resins by batch method and the separation of Ag(I) ions from Cu(II) and Zn(II) base metal ions by the column method were examined experimentally. The adsorption capacities of TF and UF resins were found as 58.14 and 47.39 mg Ag(I)/g by batch method and 30.7 and 4.66 mg Ag(I)/g, 0.80 and 0.121 mg Cu(II)/g, and under 0.002 mg Zn(II)/g by the column method, respectively. It was found that Ag(I) ions showed higher affinity towards TF resin than UF resin, compared with Cu(II) or Zn(II) ions, and Ag(I) could be separated more effectively by TF resin from Cu(II)and Zn(II) ions.     

Preparation and properties of polyurethane acrylates modified by saturated alcohols

Polyurethane acrylates (PUAs) modified by saturated alcohols were synthesized by saturated alcohols, isophorone diisocyanate (IPDI), 2-hydroxyethyl acrylate (HEA) and polycaprolactone triol (PCL). The molecular structures were identified by Fourier transform infrared (FTIR) spectroscopy. Real time infrared (RTIR) spectroscopy was used to investigate the conversion vs. irradiation time plots of photopolymerization of synthesized PUAs. The volume shrinkage was measured by using laser displacement sensor (LDS). The adhesion in the glass, polycarbonate (PC) and polyvinyl chloride (PVC) substrates was tested by the laser micrometer and universal testing machine. The glass-transition temperature (Tg) and storage modulus (E′) were measured by dynamic mechanical analysis (DMA). The pendulum hardness, pencil hardness and flexibility were also tested. The results showed that the synthesized PUAs had low volume shrinkage and excellent adhesion in glass, PC and PVC substrates.     

Polyisobutene/polycyclohexyl methacrylate interpenetrating polymer networks

Interpenetrating polymer networks (IPNs) combining polyisobutene (PIB) and poly(cyclohexyl methacrylate) (PCHMA) networks were prepared using an in situ strategy. PIB networks were formed by alcohol-isocyanate addition between the hydroxyl end groups of telechelic dihydroxypolyisobutene and an isocyanate cross-linker, catalyzed by dibutyltindilaurate (DBTDL). PCHMA networks were obtained from free-radical copolymerization of cyclohexyl methacrylate (CHMA) with ethylene glycol bismethacrylate (EGDM) in the presence of dicyclohexyl peroxydicarbonate (DCPD) as the initiator. The network formations into the IPN architecture were followed by FTIR spectroscopy. In a large composition range, transparent IPNs exhibit two mechanical relaxation temperatures as determined by dynamic mechanical thermal analysis (DMTA), corresponding to those of a PIB enriched phase and of one interpenetrating phase containing the PCHMA network. This morphology was confirmed by IPN surface analysis by AFM. As expected, mechanical properties of PIB networks are improved by the presence of PCHMA network in such IPN architectures.     

纳米聚丙烯酸酯改性纳米Mg(OH)_2及其在LDPE中的应用

采用纳米聚丙烯酸酯乳液改性纳米Mg(OH)2,通过单螺杆挤出机制备了纳米Mg(OH)2/低密度聚乙烯(LDPE)复合材料,利用红外光谱、扫描电镜、透射电镜等方法对改性前后的Mg(OH)2及Mg(OH)2/LDPE复合材料进行了表征。结果表明:纳米Mg(OH)2表面经纳米聚丙烯酸酯乳液改性后吸附上了一层聚丙烯酸酯;纳米聚丙烯酸酯乳液改性提高了纳米Mg(OH)2的热稳定性,分解温度提高了27℃;改性纳米Mg(OH)2在LDPE基体中分散更为均匀;改性纳米Mg(OH)2的用量为LDPE的15%时复,合材料的拉伸强度比纯LDPE提高了6.5%。     

Synthesis and characterization of poly(N-(2-(thiophen-3-yl)methylcarbonyloxyethyl)maleimide) and its spectroelectrochemical properties

A new monomer; N-(2-(thiophen-3-yl)methylcarbonyloxyethyl) maleimide (NMT) was synthesized. The chemical structure of the monomer was characterized by Nuclear Magnetic Resonance (¹H-NMR) and Fourier Transform Infrared (FTIR) Spectroscopy. Electrochemical polymerization of NMT was performed in acetonitrile (AN)/borontrifloride ethylether (BFEE) solvent mixture (1:1, v/v) where tetrabutylammonium tetrafluoroborate (TBAFB) was utilized as the supporting electrolyte. The resulting conducting polymer was characterized by Fourier Transform Infrared (FTIR) Spectroscopy, thermal analyses and Scanning Electron Microscopy (SEM). Electrical conductivity was measured by the four-probe technique. The spectroelectrochemical behavior and switching ability of P(NMT) film were investigated by UV–Vis spectrophotometry. P(NMT) revealed color changes between yellow and blue in the reduced and oxidized states respectively.     

Preparation and characterization of bioinert amphiphilic P(VDF-co-CTFE)-g-POEM graft copolymer

ABSTRACT

Hydrophobic poly (vinylidene fluoride-co-chlorotrifluoroethylene) P(VDF-co-CTFE) was used as the polymer backbone to graft poly (oxyethylene methacrylate) (POEM) by atom transfer radical polymerization. Synthesis of graft P(VDF-co-CTFE)-g-POEM copolymer was confirmed by fourier transfer infrared spectroscopy (FTIR) and proton nuclear magnetic resonance (¹H-NMR). The hydrophilicty of grafted membrane increased with increasing ingrafting of POEM as characterized by contact angle measurement. Transmission electronmicroscopy (TEM) study reveals the microphase separated morphology of P(VDF-co-CTFE)-g-POEM copolymer. Adhesion of gram-positive and negative bacteria and mouse embryonic fibroblast (MEF) cell on the membrane surface were observed by SEM that showed the enhancement of bioinert properties with the increase in the POEM grafting. Bioinert properties were further confirmed by protein adsorption behavior.