聚双(6-咔唑基己氧基)磷腈的合成

以PCl5和NH4Cl为原料采用"一步法"合成了线型聚二氯磷腈(4);4与6-咔唑基己醇发生亲核取代反应合成了聚双(6-咔唑基己氧基)磷腈(5),其结构经1H NMR,31P NMR,IR和GPC表征。热分析结果表明,5具有良好的热稳定性和较高的玻璃化温度。     

聚双(对羟基苯甲酸甲酯)磷腈的合成及表征

通过一步法合成线性聚二氯磷腈(PDCP),并用对羟基苯甲酸甲酯与线性聚二氯磷腈(PDCP)反应合成聚双(对羟基苯甲酸甲酯)磷腈,运用~1HNMR、~(13)C NMR、~(31)P NMR及FT-IR对其结构进行了表征。DSC和TGA实验表明该聚合物的T_g有了明显的提高且具有较好的热稳定性。     

聚[(2-氯二乙氧基)x(三氟乙氧基)2-x]磷腈制备及核磁共振谱分析

以2-氯乙氧基乙醇、三氟乙醇和六氯环三聚磷腈为原料,合成2-氯二乙氧基和三氟乙氧基的混合取代聚磷腈。利用31P NMR对反应过程和聚合物的纯化过程进行跟踪,提供了六氯环三聚磷腈、聚二氯磷腈、以及这两种物质的2-氯二乙氧基、三氟乙氧基单一取代和共混取代产物的31P NMR谱图,并通过对这些核磁共振谱数据的对比分析。研究了聚合、取代反应进程和聚合物的提纯程度,建立了用31P NMR对其取代反应和纯化过程进行监测的方法。在以85%H3PO4为外标时,六氯环三聚磷腈的共振峰为δΡ21.30,聚二氯磷腈为δΡ16.61,三氟乙氧基取代环三聚磷腈是δΡ17.97,2-氯二乙氧基在不同位置上取代环三聚磷腈的共振峰是δΡ20.90、δΡ20.48和δΡ12.86处的三连峰,δΡ20.10、δΡ19.65和δΡ8.72处的五连峰则是2-氯二乙氧基和三氟乙氧基在不同位置上取代环三聚磷腈的共振峰,聚[(2-氯二乙氧基)x(三氟乙氧基)2-x]磷腈的共振峰是一个宽峰δΡ7.25。此外,δΡ-7.22对应聚二(2-氯二乙氧基)磷腈,δP-6.88对应聚二(三氟乙氧基)磷腈。对六氯环三聚磷腈和聚二氯磷腈而言,三氟乙氧基都是一种强的亲核取代基团,能够完全取代其上的氯,且取代产物易于通过丙酮-苯的溶解沉淀法去除小分子杂质而得到纯化,而2-氯二乙氧基能完全取代聚二氯磷腈上的氯,但对六氯环三聚磷腈只能部分取代,且须通过更多次的溶解沉淀才能从聚合物中去除杂质。     

聚对苯基苯酚取代磷腈的合成与表征

环状三聚六氯化磷腈在α-氯代萘中开环聚合得到聚氯化磷腈.后者与对苯基苯酚钠反应合成了标题聚合物.测定了该聚合物的IR、~1H NMR谱.GPC估计其数均分子量为6×10~4.扭辫分析表明,该聚合物的玻璃化转变温度与粘流温度分别为0℃和130℃,硫化温度为210℃.     

六(甲氧基乙氧基乙氧基)三聚磷腈的合成与表征

以六氯三聚磷腈和甲氧基乙氧基乙醇为主要原料,合成了全取代的六(甲氧基乙氧基乙氧基)三聚磷腈,并用IR、31P NMR、1HNMR、13C NMR、FABMS等现代谱学技术对其结构进行了表征。经生物活性试验证明,此化合物对腐生线虫Panagrellus redivivus具有一定的毒杀活性。     

生物可降解聚膦腈材料的功能化及研究进展

聚膦腈是一类主链由磷氮原子交替组成,每个磷原子带有两个有机官能团侧基的有机-无机杂化高分子,其化学结构强大的可设计性赋予了材料丰富的理化性能。作为生物学用途的聚膦腈材料,生物相容性、生物可降解性和功能化改性是实现其应用的关键因素。本文从数种功能化聚膦腈(如光致荧光、导电、聚膦腈-聚酯共聚物)的制备、聚膦腈的降解机理和降解行为调控,以及生物可降解聚膦腈作为组织工程支架材料、药物载体材料和基因转染材料等几个方面,较为全面地综述了聚膦腈生物医用高分子的研究进展。     

新型环三磷腈大分子的合成与性能研究

以六对羧基苯氧基环三磷腈为原料,通过羧基活化与缩合反应合成了一种新型的环三磷腈生物大分子(1),其结构经1H NMR,13C NMR,IR和MS表征。用UV,分子荧光光谱仪和共聚焦激光显微镜研究了1的水解性能和荧光性能。结果表明,1既具有生物可降解性,又具有荧光特性。     

聚[(四氟丙氧基)2-x(三氟乙氧基)x]膦腈合成和气体分离性能研究

以六氯环三聚磷腈为原料通过真空热开环聚合制得线型聚二氯磷腈(PDCP),再通过对PDCP进行亲核取代合成制备了新的聚膦腈类高分子--聚[(四氟丙氧基)2-x(三氟乙氧基).]膦腈,聚合物经过四氢呋喃-苯反复溶解-沉淀得到纯化产物.通过31P-NMR、1H-NMR和FTIR对其结构进行了表征;DSC法测定其玻璃化转变温度...     

六(乙氧基吡咯烷酮)三聚磷腈的合成与表征

以N-羟乙基吡咯烷酮与氢化钠作用生成相应的钠盐,再将此钠盐与六氯三聚磷腈(HCCP)发生亲核取代反应,合成了六(乙氧基吡咯烷酮)三聚磷腈,用IR、31P NMR、1H NMR、13C NMR、DEPT、FABMS等现代谱学技术对其结构进行了表征。生物活性试验表明,此化合物1mg/mL时对腐生线虫Panagrellus redivivus的72h致死率为52·7%。     

聚[(甲氧基乙氧基乙氧基)1.0(乙氧基吡咯烷酮)1.0]膦腈的合成及性能研究

用三氯化铝催化六氯三聚膦腈开环聚合制得线性聚二氯膦腈(PDCP), 通过PDCP磷原子上的亲核取代反应, 合成了新的水溶性高分子聚[(甲氧基乙氧基乙氧基)_1.0(乙氧基吡咯烷酮)_1.0]膦腈(P3), 用³¹P NMR, ¹H NMR, ¹³C NMR和IR对其结构进行了确证, 用DSC测定了其玻璃化转变温度T_g和熔融温度T_m, 用蒸汽压渗透法(VPO)测定了其数均分子量. 改进了聚二(乙氧基吡咯烷酮)膦腈(P2)的合成方法. 体外降解实验表明, P3具有和P2类似的pH响应性降解行为, 降解速率在pH=5.0时最快, 而在pH=7.4和8.0时较慢. P3在所测试的3个pH缓冲溶液中均比P2降解慢. 用³¹P NMR、薄层色谱(TLC)和滴定法对降解产物进行了检测, 初步推断了P3在不同pH介质中的水解机理, 其在pH=5.0的缓冲溶液中的降解, 除侧链断裂外, 聚膦腈的骨架也裂解; 而在pH=7.4和8.0时的降解仅为侧链的断裂. 用噻唑蓝(MTT)比色法进行的体外细胞毒性评价实验表明, P3及其在pH=5.0的缓冲溶液中降解49 d后的产物均对细胞表现出了很好的生物相容性, 而且其降解产物在浓度为800 μg/mL时还表现出一定的促进细胞增殖作用.     

Synthesis of biodegradable poly (methylparaben/glycine ethyl ester) phosphazene and further research of its degradation in vitro

Polydichlorophosphazene(PDCP)was synthesized from PCl5 and NH4Cl via a one-pot approach,and then further reacted with glycine ethyl ester and methylparaben via a two-step nucleophilic substitution approach to give poly(methylparaben/glycine ethyl ester)phosphazene(PMGP),which was a kind of mix-substituted biodegradable polymer.NMR and FT-IR were used to characterize its structure.A series of experiments were conducted to study the effects of the ratio of methylparaben to glycine ethyl ester and the experime...     

可生物降解聚[(对羟基苯甲酸甲酯/甘氨酸乙酯)膦腈]的合成及其体外降解

以PCl5和NH4Cl为原料,利用一锅法制备了聚二氯膦腈,通过两步亲核取代反应,分别以甘氨酸乙酯和对羟基苯甲酸甲酯为亲核试剂,合成了混合取代可生物降解聚[(对羟基苯甲酸甲酯/甘氨酸乙酯)膦腈].用核磁共振波谱及红外光谱等对产物结构进行了表征.研究了甘氨酸乙酯和对羟基苯甲酸甲酯的比例及外界环境对所制备的聚膦腈降解性能的影响,并进行了体外降解实验.研究结果表明,通过改变甘氨酸乙酯和对羟基苯甲酸甲酯的比例,可获得一种降解速率可调节的生物降解膦腈聚合物.     

Synthesis of polyphosphates by the polyaddition of bisphenol-S diglycidyl ether and aryl phosphorodichloridates

In this study, we synthesized polyphosphates with reactive pendant chloromethyl groups by an addition reaction of the diglycidyl ether of bisphenol-S (bisphenol-S epoxy, BPSE) with aryl phosphorodichloridates. The polyphosphates obtained were characterized by IR, ¹H NMR spectra, elemental analysis, TGA, DSC, X-ray diffraction, and molar mass measurement. The polyaddition proceeded very smoothly in aromatic solvents catalyzed by quaternary ammonium or phosphonium salts such as tetrabutylammonium bromide and tetrabutylphosphonium bromide to produce a polymer having a high molecular weight. Polymer B, containing a bromine atom in the phenyl ring side chain, has the higher T_g value (T_g = 58°C) than the polyphosphate derived from phenoxy dichlorophosphate (PDCP). Polymer A derived from PDCP begins to lose 10% of its mass at 278°C, and the mass percentage remaining at 700°C is 44% under nitrogen. X-ray diffraction patterns revealed that all the subsequent polyphosphates are amorphous. © 1997 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 35 : 2365–2369, 1997     

一种超支化聚硅烷的合成和性能

近年来,光电高分子的研究由于其在发光二极管、太阳能电池、光信息材料、传感器等方面的潜在应用而得到了广泛重视[1].自从英国剑桥大学Cavendish实验室的Burroughes等首次发现聚对亚苯基亚乙烯基的电致发光现象以来[2],共轭聚合物作为发光材料的研究迅速引起了人们的注意[3~5]     

Main-chain,syndioregic, high-glass transition temperature polymer for nonlinear optics: Synthesis and characterization

A new main-chain syndioregic (head-to-head) NLO polymer was synthesized. The glass transition temperature of high molecular weight polymer was found to be 208°C, and the polymer has minimal weight loss at temperatures to at least 250°C owing to the incorporation of hydrogen bonding moieties and rigid bridging groups. The polymer was further characterized using nuclear magnetic resonance (NMR) and Fourier transform infrared spectroscopy (FTIR). The study of the nonlinear optical properties of this polymer are in progress. © 1993 John Wiley & Sons, Inc.     

咪草烟分子印迹聚合物的制备及其选择性吸附性能的研究

以丙烯酸为聚合单体,TMPTA为交联剂,AIBN为引发剂,咪草烟为模板分子,采用在低温光聚合的方法,制备了对咪草烟分子具有选择性识别能力的分子印迹聚合物．通过IR和HPLC表征,咪草烟分子印迹聚合物对咪草烟分子具有良好的识别作用．     

Synthesis and characterization of amphiphilic star copolymer of beta-cyclodextrin and polypropylene oxide and their application as nanocarriers

The present study was aimed at synthesizing and characterizing star copolymers of ??-cyclodextrin and exploring their application as nanocarriers. The copolymers of ??-cyclodextrin and polypropylene oxide were synthesized by using ring opening polymerization, catalyzed by base, under high temperature and pressure. The polymers of different molecular weight were synthesized by increasing chain length of polypropylene oxide at optimized temperature, pressure and concentration of catalyst. The structure of synthesized polymer was confirmed by IR and NMR. Molecular weight and molecular weight distribution was evaluated by hydroxyl number and gel permeation chromatography respectively. Amphiphilic nature of the polymers was evaluated by determining the solubility in water and different organic solvents. For the evaluation of polymer as a nanocarrier, Ibuprofen was selected as model drug. Loading efficiency and release of Ibuprofen from the complex were also investigated. It was observed that, with increase in the molecular weight of the polymers, loading capacity was increased.     

Preparation and Cytotoxicity of Novel Aliphatic Polycarbonate Synthesized from Dihydroxyacetone

A new cyclic carbonate, 2,2-ethylenedioxypropane-l,3-diol carbonate (EOPDC), was synthesized through a two-step reaction from dihydroxyacetone dimer, and polymerized in bulk initiated by Sn(Oct)2 to give a high molecular weight polycarbonate. The structure of monomer and the polymer were characterized by FT-1R, ^1H NMR, ^13C NMR. The cytotoxicity of the obtained polycarbonate was investigated by MTT assay.     

以亲核取代反应制备质子交换膜用磺化聚酰亚胺

本文先通过缩合反应合成羟端基的二酰亚胺单体, 然后利用亲核缩聚反应, 与4,4′-二氯二苯砜及3,3′-二磺酸钠基-4,4′-二氯二苯砜共聚, 制备聚合物. 该合成路线反应周期短, 对温度和溶剂等条件要求不高, 简便易得.