9,9-双（甲氧基甲基）芴的合成及其应用研究

9,9-双（甲氧基甲基）芴（BMMF）的合成分两步进行：首先,在乙醇钠催化剂的作用下,芴与多聚甲醛反应合成了中间体9,9-双（羟甲基）芴（BHMF）,然后以四丁基溴化铵（TBAB）为相转移催化剂,再与氯甲烷发生烷基化反应合成了9,9-双甲氧基甲基芴。用9,9-双（羟甲基）芴作外给电子体进行了丙烯聚合应用,实验结果表明：9,9-双（甲氧甲基）芴（BMMF）是聚丙烯Ziegler-Natta催化体系较好的外给电子体。     

2-丁二酸单乙酯酰基-9,9-双甲氧甲基芴的制备

以芴为主要原料,经过醚化、酯化和Friedel-Crafts酰基化等反应,合成出了9,9-双羟甲基芴、9,9-双甲氧甲基芴、丁二酸单乙酯和丁二酸单乙酯酰氯4种中间体,并最终合成出目的产物2-丁二酸单乙酯酰基-9,9-双甲氧甲基芴。采用核磁共振对中间体和目的产物的结构进行了表征和分析。最后以2-丁二酸单乙酯酰基-9,9-双甲氧甲基芴为内给电子体合成出新型聚丙烯催化剂,采用丙烯液相本体聚合的方法,对催化剂催化丙烯聚合反应的性能进行了评价。     

Synthesis and characterization of functionalized syndiotactic polystyrene copolymers

Functionalized syndiotactic polystyrene copolymers were synthesized and characterized. The syndiotactic polystyrene copolymers, poly(styrene‐co‐4‐methylstyrene) (sPSMS), were prepared by styrene with 4‐methylstyrene with a metallocene/methylaluminoxane catalyst. In addition, grafted copolymers, chemically grafted with isoprene onto an sPSMS backbone [poly(styrene‐co‐4‐methylstyrene)‐g‐polyisoprene (sPSMS‐g‐PIP)] were synthesized by anionic grafting polymerization with a metallation reagent. In this study, we also examined the effect of the degree of functionalization (epoxidation) on the polymer structure of the sPSMS‐g‐PIP copolymers. Experimental results indicate that the crystallinity of the sPSMS‐g‐PIP copolymer was lower than that of the ungrafted sPSMS copolymer. Moreover, the epoxy‐containing sPSMS‐g‐PIP copolymer effectively increased the thermal stability more than did the sPSMS‐g‐PIP copolymer alone. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 1038–1045, 2002     

9,9-双甲氧甲基芴的合成及其光谱分析

以芴为原料,在乙醇钠的催化下,经多聚甲醛羟甲基化反应合成了中间体9,9-双羟甲基芴,然后以四丁基溴化铵为相转移催化剂,再与氢氧化钠、碳酸二甲酯发生烷基化反应,合成了目标化合物。通过紫外光谱、红外光谱和核磁共振谱等分析测试手段对中间体和目标产物进行了结构表征并逐一归属。     

2-丁二酸单乙酯酰基-9，9-双甲氧甲基芴的合成与表征

以芴、多聚甲醛和乙醇钠等为主要原料,经过醚化、酯化和Friedel—Crafts酰基化等反应,合成了9,9-双羟甲基芴（BHMF）、9,9-双甲氧甲基芴（BMF）、丁二酸单乙酯和丁二酸单乙酯酰氯（ESC）这4种中间体,最终合成出目的产物2-丁二酸单乙酯酰基-9,9-双甲氧甲基芴,利用傅立叶红外光谱对中间体和目的产物结构进行了分析和表征。     

Imidazole functionalized polyaniline: Synthesis,characterization, and Cu (II) coordination studies

Polyaniline functionalized with imidazole as strategically designed receptor group in its backbone was synthesized for copper binding. The synthesized polymer has been characterized using FTIR, NMR, and UV‐Vis spectroscopic techniques. The addition of copper (II) to the polymer distinctly changes the properties such as crystallinity, molecular weight, aggregation, and electronic properties. XRD, DLS, SEM, and four‐point probe techniques have been used for study of these changes. It is observed that the secondary ion generated as a result of copper coordination results in the doping of the polyaniline backbone, which enhances the conductivity by one order of magnitude. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Acrylonitrile copolymers containing guanidine oligomer: Synthesis and use for the preparation of nonleaching antimicrobial acrylic fibers

Nonleaching acrylic fibers with permanent antibacterial activity were prepared via a combination of copolymerization and a wet‐blend‐spinning method. Specifically, poly[acrylonitrile‐co‐modified poly(hexamethylene guanidine hydrochloride)] [poly(AN‐co‐M‐PHMG)] copolymers containing a covalently connected antibacterial guanidine oligomer were first synthesized via the precipitation copolymerization of acrylonitrile (AN) with a modified poly(hexamethylene guanidine hydrochloride) (M‐PHMG) macromonomer in water. Then, modified acrylic fibers were prepared from a mixture of the copolymer and commercial fiber‐grade AN terpolymer via a wet‐spinning process with dimethyl sulfoxide as the solvent. The influences of the reaction time, temperature, pH value of the medium, and amount of initiator on the copolymerization and the effect of the copolymer content on the mechanical properties and antibacterial activity of the modified acrylic fibers were investigated in detail. The results show that the M‐PHMG macromonomer exhibited a lower reactivity than AN. The poly(AN‐co‐M‐PHMG) copolymer with a PHMG content of 5.49% and an intrinsic viscosity of 11.2 dL/g could be synthesized under optimized conditions. With increasing copolymer content, the tensile strength of the modified acrylic fibers decreased slightly, and the antibacterial activity increased. The modified acrylic fibers with a copolymer content of 50% (i.e., a PHMG content of 2.75%) exhibited both good mechanical properties and excellent antibacterial activity. The additional antibacterial function would surely enlarge the applications of the fiber. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Polymer electrolytes based on poly(ethylene glycol) and cyanoresin

Polymer electrolytes based on a mixed polymer matrix consisting of poly(ethylene glycol) (PEG) and cyanoresins with lithium salt and plasticizer were prepared with an in situ blending process to improve both the mechanical properties and the ionic conductivity (σ). The PEG/lithium perchlorate (LiClO₄) complexes, including blends of cyanoethyl pullulan (CRS) and cyanoethyl poly(vinyl alcohol) (CRV), exhibited higher σ's than a simple PEG/LiClO₄ complex when the blend compositions of CRS/CRV were 5 : 5 or 3 : 7 or than CRV alone. When the CRS/CRV blend was compared with a copolymer of cyanoethyl pullulan and cyanoethyl poly(vinyl alcohol) (CRM) in the same molar ratio, the σ values of the polymer electrolytes containing the CRM copolymer series were slightly higher than those of the CRS/CRV blends containing PEG/LiClO₄ complexes. Moreover, the addition of cyanoresin to PEG/LiClO₄/(ethylene carbonate–propylene carbonate) polymer electrolytes provided better thermal stability and dynamic mechanical properties. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 2402–2408, 2007     

Synthesis and characterization of N‐ and O‐alkylated poly[aniline‐co‐N‐(2‐hydroxyethyl) aniline]

Poly[aniline‐co‐N‐(2‐hydroxyethyl) aniline] was synthesized in an aqueous hydrochloric acid medium with a determined feed ratio by chemical oxidative polymerization. This polymer was used as a functional conducting polymer intermediate because of its side‐group reactivity. To synthesize the alkyl‐substituted copolymer, the initial copolymer was reacted with NaH to obtain the N‐ and O‐anionic copolymer after the reaction with octadecyl bromide to prepare the octadecyl‐substituted polymer. The microstructure of the obtained polymers was characterized by Fourier transform infrared spectroscopy, ¹H‐NMR, and X‐ray diffraction. The thermal behavior of the polymers was investigated by thermogravimetric analysis and differential scanning calorimetry. The morphology of obtained copolymers was studied by scanning electron microscopy. The cyclic voltammetry investigation showed the electroactivity of poly [aniline‐co‐N‐(2‐hydroxyethyl) aniline] and N and O‐alkylated poly[aniline‐co‐N‐(2‐hydroxyethyl) aniline]. The conductivities of the polymers were 5 × 10^?5 S/cm for poly[aniline‐co‐N‐(2‐hydroxyethyl) aniline] and 5 ×10^?7 S/cm for the octadecyl‐substituted copolymer. The conductivity measurements were performed with a four‐point probe method. The solubility of the initial copolymer in common organic solvents such as N‐methyl‐2‐pyrrolidone and dimethylformamide was greater than polyaniline. The alkylated copolymer was mainly soluble in nonpolar solvents such as n‐hexane and cyclohexane. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

聚丙烯催化剂内给电子体9,9-双(苯甲酸甲酯基)芴的合成与表征

以自制的9,9-双羟甲基芴(BHMF)和苯甲酰氯为原料,以三乙胺为吸收剂合成了9,9-双(苯甲酸甲酯基)芴,采用了红外光谱和核磁共振氢谱等分析测试手段对产品进行了结构表征并逐一归属。考察了原料配比、反应时间、反应温度及吸收剂用量等因素对9,9-双(苯甲酸甲酯基)芴收率的影响。实验结果表明,最佳工艺条件为:0.1 mol BHMF,n(BHMF)∶n(苯甲酰氯)=1.0∶3.0,三乙胺吸收剂为60 mL,反应温度10℃,反应时间4.0 h,在此条件下9,9-双(苯甲酸甲酯基)芴收率可达85.4%。     

2,7-二溴-9,9-双(4-氨基苯基)芴的合成及精制研究

以2,7-二溴-9-芴酮和苯胺盐酸盐为原料,以甲苯为溶剂,亚硫酸氢钠为助催化剂,在氮气保护一定温度下催化合成9,9-双(4-氨基苯基)-2,7-二溴芴。粗产品采用重结晶的方法进行精制,精制溶剂选用甲苯与无水乙醇的混合液,重结晶产品经抽滤、干燥等处理得到相应的精制产品,并对产品进行了红外核磁等表征。产品通过液相测定纯度为99.50%,精制后产品收率为67.91%。     

Construction of inter-chain polymers and the investigation into Friedel–Crafts alkylation of styrene–acrylonitrile copolymers with chloroprene rubber and characterization

In this study, the Friedel–Crafts alkylation was realized in a solvent free processing of styrene–acrylonitrile copolymers/chloroprene rubber (SAN/CR) molten blending which contributes the formation of SAN-co-CR co-polymers and improved compatibility between SAN and CR. The properties of several Lewis acid compounds were tested as catalysts among which AlCl₃ was the most efficient. The effects of blending temperature and time on the co-polymer formation in situ were also investigated. The methodology of weighing and Fourier transform infrared analyses indicated that the reaction degree increases with increasing blending temperature and time in the ranges of this study. The micro-structures and reaction mechanisms of the resulted SAN-co-CR polymers and morphological structures of SAN/CR/AlCl₃ blends were characterized as well by differential scanning calorimetry, FT-IR spectra, GPC and scanning electron microscopy. The results showed that the inter-facial reactions between SAN and CR have been effectively improved. Moreover, the inter-chain structure of SAN-co-CR co-polymers was proposed which is different from general grafting or blocking co-polymers.     

Demulsification efficiency of some novel styrene/maleic anhydride ester copolymers

Four demulsifiers were prepared in three steps. In the first step, styrene and maleic anhydride were copolymerized. In the second step, a long‐chain alcohol (dodecanol) was reacted with the prepared copolymer to form the monoesterified copolymer. In the final step, the resulting product was further esterified with poly(propylene oxide) (PPO)–poly(ethylene oxide) (PEO) block copolymers of different molecular weights (1.1, 2.5, 3.0, 5.0, and 8.0 × 10³) and different PPO/PEO ratios. The demulsification efficiency of these demulsifiers was investigated with the bottle test (Sany glass). The effects of the molecular weight and ratio of the PPO–PEO block copolymers on the demulsification efficiency were studied. The demulsification efficiency could be enhanced from 66% by an individual demulsifier to 100% by demulsifier blends. The surface‐active and thermodynamic properties of the prepared demulsifiers were measured at 25, 35, and 45°C. The kinematics of the demulsification process were photographed with a binocular microscope. The demulsification mechanism was found to occur in three stages, that is, adsorption and flocculation, coalescence, and channel formation followed by separation. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Conjugated polymers with anionic dyes: Synthesis,properties, and sensing ability for nucleosides,DNA, and BSA

The reaction of N-(2,4-dinitrophenyl)pyridinium chloride (salt[Cl⁻]) with sodium salts of anionic dyes, such as acid red 52 (AR52), acid violet 49 (AV49), and coomassie brilliant blue G-250 (CBBG250) involves an anion exchange between the chloride anion of salt(Cl⁻) and sulfonium anion of the dyes, resulting in the generation of novel Zincke salts, namely, salt(AR52), salt(AV49), and salt(CBBG250), respectively. Reactions of salt(AR52), salt(AV49), and salt(CBBG250) with piperazine in the absence of catalysts resulted in the opening of the pyridinium ring to yield ionic polymers comprising units of 5-piperazinium-2,4-dienylideneammonium and the corresponding dye anion, namely polymer(AR52), polymer(AV49), and polymer(SBBG250), respectively. The corresponding model compounds for the polymers were also synthesized by reacting salt(AR52), salt(AV49), and salt(CBBG250) with piperidine. Polymer(AV49) and polymer(SBBG250) were found to be suitable for the detection of nucleosides, DNA, and proteins, realized by monitoring the changes in their UV–vis absorption spectra, arising from the anionic dyes within the polymers. The polymers and the model compounds were electrochemically oxidized in solution.     

新型二醚类给电子体DMMF的合成研究及结构表征

以工业芴为原料,经甲醛羟甲基化反应合成了9,9-双(羟甲基)芴,再以NaH为催化剂,与CH3I发生烷基化反应得到了目标产物9,9-双(甲氧基甲基)芴(DMMF),产品收率可达80.0%以上。采用红外光谱和核磁共振谱等分析测试手段对产品进行了结构表征并逐一归属。实验结果表明,该方法是一种实用的制备DMMF的简便方法。     

Synthesis,characterization, and in vitro biocompatibility study of novel disulfide cross‐linked hydrogels based on poly(amic acid)

In this study, novel disulfide cross‐linked hydrogels were designed and synthesized. First, ethylenediaminetetraacetic dianhydride reacted with butanediamine and amino‐terminated polyethylene glycol via N‐acylation reaction to give biocompatible poly(amic acid) (PAA) with pendant carboxyl groups; then, the amino groups of cystamine reacted with carboxyl groups of PAA to generate disulfide cross‐linked network polymer (PAA‐SS). Fourier transform infrared spectroscopy, ¹H nuclear magnetic resonance imaging, gel permeation chromatography with multiangle laser light scattering, potentiometric titration, rheology, hydrolytic degradation, morphology, porosity, and in vitro biocompatibility studies were used to qualitatively and quantitatively characterize the obtained polymers. The results indicated that the equilibrium swelling ratio of the PAA‐SS decreased with the increase in Rm. The PAA‐SS provided good mechanical strength to maintain their integrity, and the storage modules (G′) of the hydrogels can be adjusted by Rm. The PAA‐SS presented co‐continuum pores, and the pore size correlated with the cross‐linking degree. The degradation of PAA‐SS could be controlled by regulating the concentration of dithiothreitol. Particularly, the PAA‐SS possessed an excellent biocompatibility, as the average proliferating rate of osteoblasts on PAA‐SS was appreciably higher than that on PAA and glass coverslips. In conclusion, the above obtained results demonstrate that the performance of the PAA‐SS outbalance and facilitate the application in biomedical region, particularly in bone tissue regeneration. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40930.     

Multiple morphologies of a poly(methyl methacrylate)-block-poly(N,N-dimethyl aminoethyl methacrylate) copolymer with pH-responsiveness and thermoresponsiveness

We successfully prepared a series of pH-responsive and thermoresponsive poly(methyl methacrylate) (PMMA)-block-poly(N,N-dimethyl aminoethyl methacrylate (PDMAEMA) copolymers via reversible addition–fragmentation chain-transfer polymerization with PMMA as a macro chain-transfer agent. Control over the chain length of PDMAEMA allowed the morphological transformation of PMMA-b-PDMAEMA. The critical water content and critical micelle concentration also depended on the length of the PDMAEMA block. UV–visible and fluorescence spectrum analyses indicated that the PMMA-b-PDMAEMA copolymer exhibited a lower critical solution temperature type phase transition in water. The particle size of PMMA-b-PDMAEMA was dominated by the pH value, as evidenced by dynamic light scattering and transmission electron microscopy. In addition, the PMMA-b-PDMAEMA copolymers exhibited good reversible thermoresponsive behavior between 33 and 38°C. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47972.     

Styrene‐butadiene‐styrene copolymer compatibilized interfacial modified multiwalled carbon nanotubes with mechanical and piezoresistive properties

In this study, styrene‐butadiene‐styrene tri‐block copolymer/multiwalled carbon nanotubes (SBS/MWNTs) were prepared by means of a solution blending method. To enhance the compatibility between SBS and MWNTs, the SBS grafted MWNTs (SBS‐g‐MWNTs) were used to replace MWNTs. The MWNTs were chemically hydroxylated by the dissolved KOH solution with ethanol as solvent and then reacted with 3‐Aminopropyltriethoxysilane (APTES) to functionalize them with amino groups (MWNT‐NH₂). The SBS‐g‐MWNTs were finally obtained by the reaction of MWNT‐NH₂ and maleic anhydride grafted SBS (MAH‐g‐SBS). The SBS‐g‐MWNTs were characterized by X‐ray photoelectron spectroscopy (XPS), Fourier transform‐infrared spectroscopy (FT‐IR), transmission electron microscopy (TEM), scanning electron microscope (SEM), and thermogravimetric analysis (TGA). The results showed that the SBS molecules were homogeneously bonded onto the surface of the MWNTs, leading to an improvement of the mechanical and electrical properties of SBS/SBS‐g‐MWNTs composites due to the excellent interfacial adhesion and dispersion of SBS‐g‐MWNTs in SBS. A series of continuous tests were carried out to explore the electrical‐mechanical properties of the SBS/SBS‐g‐MWNTs composites. We found out that, near the percolation threshold, the well‐dispersed SBS/SBS‐g‐MWNTs composites showed good piezoresistive characteristics and small mechanical destructions for the development of little deformation under vertical pressure. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 42945.     

Environmentally responsive amphiphilic cationic block copolymers synthesized by 2,2,6,6‐Tetramethylpiperidinyloxy mediated living free‐radical polymerization

Polychloromethylstyrene (PCMS)‐block‐polystyrene (PS) copolymers were prepared by controlled free‐radical polymerization in the presence of 2,2,6,6‐tetramethylpiperidinooxy and 2,2′‐azobisisobutyronitrile (AIBN) initiator. The PCMS‐b‐PS copolymers had narrow molecular weight distributions, and the block lengths were controlled by the reaction time and the molar ratios of chloromethylstyrene/AIBN and styrene/PCMS macroinitiator. The block copolymers were further quaternized with triethylamine. The amphiphilic cationic block copolymers formed colloidal particles; the effects of the pH value, salt concentration, and solvent polarity on the particle size were investigated with a dynamic light scattering analyzer. The average colloid size increased with increasing pH value and salt concentration. This implied that the colloid formed a protonated hydrophilic shell and hydrophobic styrene core in water. Furthermore, with the addition of tetrahydrofuran to the aqueous solution, the styrene segments in the core could be inverted to the outside of the colloid. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Thermal and gas permeation properties of copolymers derived from 3‐methacryloxypropyltris(trimethylsiloxy)silane and adamantyl group‐containing methacrylate derivatives

Novel copolymer membranes derived from three types of adamantyl group‐containing methacrylate derivatives and 3‐methacryloxypropyltris(trimethylsiloxy)silane (SiMA) were synthesized via free radical polymerization. The thermal and permeation properties of these copolymer membranes were investigated. Copolymer membranes with less than 11.9 mol % adamantane content exhibited good membrane forming abilities that are suitable for permeation measurement. The decomposition temperature of all copolymers increased up to approximately 40–80°C with increasing adamantane content compared with poly(SiMA). Moreover, the glass transition temperature (T_g) of all copolymers increased up to approximately 46–60°C with increasing adamantane content compared with the theoretical value, which was estimated from Fox equation. 1‐Adamantyl methacrylate copolymer had the highest fractional free volume among the three types of adamantly group‐containing methacrylate derivatives. The gas permeability coefficient of this copolymer increased by 22–45% with increasing adamantane content compared with that of poly(SiMA). © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43129.