一种水溶性荧光示踪共聚物(AM-AMCO)的合成及性能研究

本文采用乳液聚合方法,以丙烯酰胺和7-烯丙基氧-4-甲基香豆素作为单体,过硫酸铵-亚硫酸氢钠为氧化还原引发剂,合成了一种水溶性荧光示踪二元聚合物。考察了温度、单体浓度、体系pH和引发剂浓度等条件对聚合物表观粘度的影响,确定了最佳合成条件,并对聚合物结构进行了红外表征。紫外、荧光及耐温抗盐性研究结果表明了该二元聚合物可作为潜在的油田示踪剂,并具有良好的耐温抗盐性能。     

Synthesis of water-soluble carbon nanotubes via surface initiated redox polymerization and their tribological properties as water-based lubricant additive

Polyacrylamide (PAM)-grafted multi-walled carbon nanotubes (MWCNTs-g-PAM) which are dispersable in water were prepared by the surface initiated redox polymerization of acrylamide using ceric ammonium nitrate (CAN) as initiator. They are soluble in polar solvents such as water, tetrahydrofuran and acetone. The chemical structure of the resulting product and the quantities of grafted polymer were determined by FT-IR, TGA. TEM, and FE-SEM observations indicated that the nanotubes were coated with a PAM layer, exhibiting core-shell nanostructures, with the PAM chains as a brush-like or hairy shell, and the MWCNTs as a hard backbone. Furthermore, the tribological properties of the prepared MWCNTs-g-PAM composites as an additive in water were evaluated with a four-ball machine. The results confirmed that the composites exhibit good anti-wear and friction reduction properties as well as load-carrying capacity. This was attributed to the possibility of the composites acting as nanometer sized tiny bearings during lubrication.     

AM/AA/APEG/NANB共聚物的合成与性能研究

通过丙烯酰胺(AM),丙烯酸(AA),烯丙醇聚氧乙烯醚(APEG)和N,N-二烯丙基苄胺(NANB)制备共聚物P(AM/AA/APEG/NANB)。确定了最佳反应条件:m(AM)∶m(AA)=6.5∶3,APEG为5 wt%,NANB加量0.2 wt%,pH为7,反应温度40℃,引发剂0.4 wt%。通过IR和1H NMR确定了聚合物的分子结构,并对其进行性能测试。结果表明:2000 mg·L-1的AM/AA/APEG/NANB溶液具有较好的流变性能(120℃,粘度保留率:38.56%;1000 s-1,粘度保留率:17.93%)和抗盐性能(20 000 mg·L-1Na Cl,2000 mg·L-1Mg Cl2或Ca Cl2,粘度保留率分别为22.14%、18.34%和15.33%),且提高采收率可达16.12%。     

羟甲基化木质素磺酸盐添加剂对钻井液性能的影响

为了进一步优化木质素磺酸盐作为钻井液处理剂的效能,利用其与甲醛的羟甲基化反应制备了羟甲基化木质素磺酸盐;采用红外光谱仪、X射线粉末衍射仪、扫描电镜等分析了其结构;测定了改性前后的木质素磺酸盐对钻井液流变性、降滤失性、黏土水化膨胀抑制性等性能的影响.结果显示,改性后的羟甲基化木质素磺酸盐的整体结构变化不大,但羟基数量增加,与水的相溶性增强.与木质素磺酸盐相比,羟甲基化木质素磺酸盐在室温下对基浆有较强的提黏作用,经180℃高温老化后降黏、降滤失作用有所增强,形成的泥饼厚度降低,对黏土水化膨胀的抑制作用增强.     

Synthesis,characterization and performance evaluation of long chain methacrylate-octene copolymer for lubricant formulation

Abstract

In this study, the authors synthesized myristyl methacrylate monomers by esterification reaction of methacrylic acid and myristyl alcohol using conc. H₂SO₄ as catalyst. Homopolymer of the prepared ester was synthesized and a series of copolymers were prepared by varying the ratio between the ester and 1-octene by free radical polymerization using azobisisobutyronitrile as initiator. All the synthesized polymers were characterized by spectral studies (FT-IR and NMR) and their average molecular weights were determined by gel permeation chromatography (GPC). Thermogravimetric analysis (TGA) was selected as the method to investigate the thermal behavior of the polymers at high temperature. Performances of the polymers as additives, and their responses as flow improvers and viscosity modifiers in the base fluid were carefully assessed by standard methods in terms of pour point and viscosity index. In addition, photo micrographic image was employed to examine the wax crystallization behavior of the additives. The results of the experimental work showed that although the copolymers were thermally more stable than the homopolymer, the latter showed better flow improving efficiency and induced better viscosity modification. The viscosity modification and the pour point performance of the additives also depend on the concentration of the additives in the base fluid.     

Synthesis and characterization of a thiazolo[5,4-d]thiazole-based copolymer for high performance polymer solar cells

A highly processable, new semiconducting polymer, PCDTTz, based on alternating thiazolothiazole and carbazole units was synthesized. The new polymer exhibited a field-effect carrier mobility of up to 3.8 × 10(-3) cm(2) V(-1) s(-1) and bulk heterojunction solar cells made from PCDTTz produced a power conversion efficiency of 4.88% under AM 1.5 G (100 mW cm(-2)) conditions.     

Synthesis and ferromagnetic properties of composites of a water-soluble polyaniline copolymer containing iron oxide

Composites of water-soluble conducting polyaniline copolymers, poly(aniline-co-aminobenzenesulfonic acid) (PAOABSA), containing γ-Fe₂O₃magnetic particles with nanometer size, were synthesized by a chemical method. The ferromagnetic properties of the resulting PAOABSA composites were measured as a function of the pH value of the reaction solution, the sulfonated degree of the copolymer, and the concentration of FeCl₂. The structure of the composites was characterized by means of elemental analysis, FTIR, XPS, and X-ray diffraction. It was found that increasing the pH value of the reaction solution and the concentration of FeCl₂ is favorable for an enhancement of the saturated magnetization. As high as 33.2 emu/g of saturated magnetization for the PAOABSA composites was observed. No hysteresis loop (i.e. H_c = 0) was observed, which is independent of the preparation conditions. Structure characterizations show that iron oxide existing in the composite is mainly γ- Fe₂O₃, which is responsible for the ferromagnetic properties of the PAOABSA composites, whereas γ- Fe₂O₃ magnetic particles nanometer in size (∼85 nm) may be attributed to a lower coercive force (i.e. H_c = 0) of the composites. © 1998 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 36: 2749–2755, 1998     

Controlled synthesis and evaluation of cyanate ester/epoxy copolymer system for high temperature molding compounds

Epoxy molding compounds (EMCs) have become an integral component for high power electronics to work under harsh environment nowadays. For high temperature operation, polymer networks with high glass transition temperature (T_g) are required to ensure device stability. In this work, high T_g polymers were designed via controlled incorporation of in situ formed and thermally stable triazine structures into epoxy matrix. Reactions involved in the copolymer system of cyanate ester and epoxy (CE/EP) were investigated. Increasing ratio of cyanate ester dramatically promoted T_g of the copolymer up to 275 °C with improved heat resistance. High temperature aging and moisture absorption tests revealed that hydrolysis of polycyanurate network and rearrangement of cyanurate occurred during aging, especially for copolymers with higher than 75% of cyanate ester. Based on thermal properties and aging performance, the composition of CE/EP system was optimized. The formulated bisphenol A cyanate ester and biphenyl epoxy copolymer system has great potential to be applied as high temperature encapsulation materials in electronic packaging. © 2018 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2018 , 56, 1337–1345     

Synthesis and functionalization of a highly fluorescent and completely water-soluble poly(para-phenyleneethynylene) copolymer for bioconjugation

Bioconjugation of a highly fluorescent water-soluble poly(para-phenyleneethynylene) (PPE) copolymer with ionic and non-ionic side chains is achieved by means of chain-end modification, providing a design principle for biosensor development.     

Benzimidazolyl functionalized ionic liquids as an additive for high performance dye-sensitized solar cells

Benzimidazolyl functionalized ionic liquids were synthesized and applied as additives for dye-sensitized solar cells. The fabricated devices show an overall power conversion efficiency of ~7.79% under AM 1.5 radiation (50 mW cm(-2)), and an excellent long-term stability.     

两亲性嵌段共聚物mPEG-b-PCL/FA的合成及其药物释放性能

以苯甲醇为引发剂,在辛酸亚锡催化下引发ε-环己内酯(ε-CL )开环聚合,合成了聚己内酯(PCL).分别利用端甲氧基聚乙二醇(mPEG)、PCL及叶酸(FA)与三氯三嚎中不同的氯反应,得到两亲性嵌段共聚物mPEG-b-PCL/FA;采用傅立叶变换红外光谱仪和核磁共振谱仪等表征了mPEG-b-PCL/FA的组成和结构;采...     

An amphiphilic graft copolymer as a surface-modifying additive for poly(methyl methacrylate)

An amphiphilic graft copolymer was prepared by transesterification of poly(2-ethylhexyl acrylate-co-methyl methacrylate) with poly(ethylene glycol) monomethyl ether (MPEG2000). The grafting reaction was performed in melt at 155°C. The purified graft copolymer was blended into poly(methyl methacrylate) in concentrations of 1.5-30 wt %, either by mixing in chloroform solution or by melt mixing by means of a twin-screw extruder or a Brabender blender. Films of the blends were prepared by solution casting onto glass plates or by hot pressing between polished Al plates. At concentrations up to 20% of the graft copolymer homogeneous blends were obtained. At higher concentrations the blends were heterogeneous, and side-chain crystallinity was detectable by DSC analysis. The surface properties of the films were studied by measurements of water contact angles. The surface accumulation of the graft copolymer was demonstrated as a large increase in the wetting angle hysteresis, and found to depend on the procedure for film preparation as well as the casting substrate. © 1995 John Wiley & Sons, Inc.     

磺丁基醚-β-环糊精手性流动相添加剂法分离兰索拉唑对映体

采用磺丁基醚-β-环糊精(SBE-β-CD)为手性流动相添加剂,建立了兰索拉唑对映体的高效液相色谱分离分析方法.对影响兰索拉唑对映体分离的主要因素:环糊精种类和浓度、缓冲溶液pH以及有机改性剂种类和含量进行考察.确定最优色谱条件:色谱柱为Spherigel C18 (150 mm×4.6 mm,5 μm),流动相为V(乙腈):V(水相)=20:80(水相含10 mmol/L SBE-β-CD、 10 mmol/L NaH2PO4缓冲液、 pH 2.5),流速为0.9 mL/min,检测波长为288 nm.在此条件下,兰索拉唑对映体的保留时间分别为14.4和15.8 min,分离度为2.0.两对映体质量浓度在0.2～50 μg/mL范围内线性关系良好(r≥0.9996),保留时间的RSD分别为0.27%和0.26%,峰面积的RSD分别为0.65%和0.68%.     

Function and performance of silicone copolymer (VI). Synthesis and novel solution behavior of water-soluble polysiloxanes with different hydrophiles

Silicone surfactants containing different pendant hydrophilic groups such as diethanol tertiary amine (SHE, nonionic), diethanol methyl quaternary amine (cationic) and triethyl quaternary amine (cationic) have been synthesized and characterized by ¹H and ¹³C NMR and gel permeation chromatography. The solution behavior of these novel surfactants has also been investigated by surface tension measurement and a fluorescence method. It has been observed that the surface tension of these surfactants decreases as a function of time at a very low polymer concentration (1 × 10⁻⁴ wt%). At higher concentration (0.1 wt%), the equilibrium surface tensions reached very low values compared to that of typical polymer surfactants, for example, poly(ethylene oxide–propylene oxide) block copolymer (EPE0.8). In addition, the low I ₁/I ₃ values of these silicone surfactants indicate the formation of polymer aggregates in aqueous solution, and an extremely low I ₁/I ₃ value of SHE (1.06) compared to other polymeric surfactants (EPE0.8) and conventional surfactants [poly(ethylene glycol n-nonyl phenyl ethers), cetyltrimethylammonium bromide, and sodium dodecyl sulfate] indicates its stronger hydrophobicity. Received: 15 May 2000 Accepted: 18 October 2000     

Boric acid as a mobile phase additive for high performance liquid chromatography separation of ribose, arabinose and ribulose

A new high performance liquid chromatographic (HPLC) method is described for the analysis of ribose, arabinose and ribulose mixtures obtained from (bio)chemical isomerization processes. These processes gain importance since the molecules can be used for the synthesis of antiviral therapeutics. The HPLC method uses boric acid as a mobile phase additive to enhance the separation on an Aminex HPX-87K column. By complexing with boric acid, the carbohydrates become negatively charged, thus elute faster from the column by means of ion exlusion and are separated because the complexation capacity with boric acid differs from one carbohydrate to another. Excellent separation between ribose, ribulose and arabinose was achieved with concentrations between 0.1 and 10 gL(-1) of discrete sugar.     

Preparation of stationary phases for reversed-phase high-performance liquid chromatography using thermal treatments at high temperature

Batches of poly(methyloctylsiloxane) (PMOS)-loaded silica were prepared by deposition from a solution of PMOS into the pores of HPLC silica. Portions of PMOS-loaded silica were subjected to a thermal treatment at 100 degrees C for 24h (condition 1) in a tube furnace under a nitrogen atmosphere. After that, the material was heated for 4h at higher temperatures (150-400 degrees C) (condition 2). Heating at higher temperatures produces polymer bilayers. Non-immobilized and thermally treated stationary phases were characterized by percent carbon, (29)Si cross-polarization magic angle spinning nuclear magnetic resonance spectroscopy and reversed-phase chromatographic performance. The results show that thermal treatment between 150 and 300 degrees C accelerates the immobilization process, possibly due to some bond breaking of the polysiloxane, with formation of strong linkages to the surface of the support, resulting in more complete coverage of the silica. The chromatographic results show an improvement of efficiency with the increase of the temperature of condition 2 up to 300 degrees C and an increase in the resolution of the components, mainly for the phase heated at 300 degrees C. Such results demonstrate that a two-step thermal treatment (100 degrees C then 150-300 degrees C) produces stationary phases with good properties for use in reversed-phase high-performance liquid chromatography.     

Radiation synthesis of a water-soluble temperature sensitive polymer, activated copolymer and applications in immobilization of proteins

In this work the radiation polymerization of N-isopropylacrylamide (NIPAAM) in aqueous solutions has been carried out and a water-soluble, temperature sensitive polymer and copolymer were obtained by using γ-rays from Co-60 source at room temperature. We have gained the optimum dose and dose—rate of radiation synthesis of linear polyNIPAAM through determining conversion yield and viscosity. In order to immobilize protein (BSA) and enzyme (HRP) into this water-soluble polymer, we prepared an activated copolymer, poly ( N-isopropylacrylamide-co-N-acryloxysuccinimide). The BSA and HRP has been immobilized onto the activated copolymer. The BSA (HRP) / copolymer conjugates still kept the original thermally sensitive properties of the linear polyNIPAAM. The conjugation yield of BSA to the activated copolymer decreased with increasing of dose. The thermal stability of the immobilized HRP was stable at 0 °C for a long time and has, at least, 4 days stability at room temperature. Immobilized HRP activity was lowered when the temperature was raised above its LCST. This phenomenon was reversible and the immobilized HRP regained activity below its LCST. The optimum pH of the immobilized HRP shifted from ca.5 upward to ca.7.     

Synthesis of copolymer electrolytes based on polysiloxane and their high temperature durability analysis for solvent-free dye-sensitized solar cells

The present work develops a new type of solvent-free copolymer electrolyte based on polysiloxane for dye-sensitized solar cells (DSSCs). The electrolyte is characterized by conductivity measurements, hydrogen-1 nuclear magnetic resonance spectroscopy, rheology, and DSSC performance. Repeated units of the ethylene oxide on methylhydrosiloxane show plasticizing effects and enhanced durability of the DSSCs. DSSC employing the polysiloxane electrolytes show no energy conversion efficiency decay after 16 days test at room temperature and yields a conversion efficiency of 1.5% during long-term stability measurement at 90 °C under white light irradiation of 100 mW cm⁻². The new solvent-free polysiloxane copolymer electrolyte can be good candidate for next generation DSSC.