新型双向传输型区域规整噻吩嵌段共聚物的合成与研究

通过McCullough法制备出区域规整的HT3-十二烷基噻吩均聚物（HTP3DDT）及3-十二烷基噻吩-恶二唑嵌段共聚物（HT P3DDT-OXD）。利用NMR、GPC等方法对其结构进行了分析表征，均聚物和共聚物的紫外吸收和荧光发射最大波长分别为：387、326、435和463nm，分别发射出明亮的青光和青绿光。同时采用循环伏安法对其电化学性能进行了测定，发现3-十二烷基噻吩-恶二唑嵌段共聚物在正、负区域分别出现了氧化还原峰对，且负区域的一对氧化还原峰出现在较负的方向，具有较高的电子亲和势（-3．17eV），有利于电子从阴极的注入。结果表明：区域规整的3-十二烷基噻吩-恶二唑二元嵌段共聚物实现了集空穴、电子双向传输为一体的高性能的聚合物光电功能材料的性能要求。     

PBMA-b-PDMS-b-PBMA嵌段聚合物的合成与表征

以羟基封端的聚二甲基硅氧烷和α-溴代异丁酰溴为原料,制备了双官能度Br-PDMS-Br,并以此为大分子引发剂,CuCl和2,2’-联吡啶为催化剂,通过原子转移自由基聚合制备了聚甲基丙烯酸丁酯-聚二甲基硅氧烷-聚甲基丙烯酸丁酯(PBMA-b-PDMS-b-PBMA)三嵌段聚合物。利用傅里叶变换红外光谱仪(FT-IR)、核磁(1 H NMR)、凝胶渗透色谱分析仪(GPC)、热失重分析仪(TGA)、接触角测试仪、扫描电子显微镜(SEM)对三嵌段聚合物的结构及聚合反应进行了表征与测试。结果表明三嵌段聚合物具有较好的热稳定性、疏水性和微相分离。     

吡咯/3-氨基苯磺酸半导体共聚物纳米颗粒的制备

采用简单的化学氧化聚合法在无外加稳定剂的条件下成功地合成了自稳定性的吡咯/3-氨基苯磺酸半导体共聚物纳米颗粒.紫外和红外光谱的分析结果证实吡咯和3-氨基苯磺酸之间确实发生了共聚.3-氨基苯磺酸投量对共聚物颗粒的产率、电导率、尺寸及分布有明显影响.当其投量为30mol％时,共聚物颗粒表现出最小的平均粒径(约80nm)和相对较高的产率及电导率.电镜表征的结果表明共聚物纳米颗粒呈现不规则的粒状形貌且尺寸分布比较均一.共聚物纳米颗粒的形成和自稳定性与颗粒表面电负性磺酸基的静电排斥效应和亲水性有关.     

新型聚乳酸-聚酰亚胺嵌段共聚物的合成与表征

用氨基封端的PEG-800(ATPEG)与均苯四甲酸酐(PMDA)共聚得到一种新型的氨基封端的可溶性聚酰亚胺(PI)。氨基封端的PI在辛酸亚锡(Sn(Oct)2)的催化作用下引发丙交酯开环共聚,形成聚乳酸-聚酰亚胺(PLA-PI-PLA)嵌段共聚物。采用傅里叶变换红外光谱(FT-IR)、核磁氢谱(1H NMR)、凝胶渗透色谱(GPC)、水接触角等对PI和PLA-PI-PLA进行了表征。FT-IR、1H NMR、GPC的结果表明成功合成了PI及PLA-PI-PLA。水接触角结果显示PLA-PI-PLA相对于聚乳酸亲疏水性明显改善,同时PI主链上的酰亚胺环能在一定的条件下发生开环反应,可提供修饰聚乳酸材料的活性位点。     

Synthesis and characterization of Poloxamer 188-grafted heparin copolymer

Background: Poloxamer 188 is a safe biocompatible polymer that can be used in protein drug delivery system. Aim: In this study, a new heparin–poloxamer 188 conjugate (HP) was synthesized and its physicochemical properties were investigated. HP structure was confirmed by Fourier transform infrared spectroscopy (FTIR) and Hydrogen-1 nuclear magnetic resonance spectroscopy (¹H-NMR). Content of the conjugated heparin was analyzed using Toluidine Blue. The critical micelle concentration (CMC) of the copolymer was determined by a fluorescence probe technique. The effect of HP on the gelation of poloxamer 188 was characterized by the rheological properties of the HP–poloxamer hydrogels. Solubility and viscosity of HP were also evaluated compared with poloxamer 188. Results: From the results, the solubility of the conjugated heparin was increased compared with free heparin. The content of heparin in HP copolymer was 62.9%. The CMC of HP and poloxamer 188 were 0.483 and 0.743 mg/mL, respectively. The gelation temperature of 0.4 g/mL HP was 43.5°C, whereas that of the same concentration of poloxamer 188 was 37.3°C. With HP content in poloxamer 188 solution increasing, a V-shape change of gelation temperature was observed. Conclusion: Considering the importance of poloxamer 188 in functional material, HP may prove to be a facile temperature-sensitive material for protein drug-targeted therapy.     

PSS-VS共聚物掺杂PEDOT的合成与表征

以苯乙烯磺酸钠(SSS)和乙烯磺酸钠(SVS)的共聚物PSS-VS为掺杂剂,过硫酸铵(APS)为氧化剂,采用化学氧化法制备了PEDOT/PSS-VS分散体,研究了PSS-VS的共聚比、分子量和用量等因素对PEDOT/PSS-VS导电性能及平均粒径的影响,分析了PEDOT/PSS-VS粒子形成过程。结果表明,SSS/SVS共聚摩尔比为5/5,单体与APS摩尔比为60时制得的PSS-VS掺杂PEDOT具有较好的导电性和分散稳定性,SO3-/EDOT=2,APS/EDOT=1.5,PEDOT/PSS-VS固含量为2.8%时制得的PEDOT/PSS-VS电导率可达11.74S/cm,分散体平均粒径为447nm。     

一种新型红色长余辉材料的制备及其发光性能

采用高温固相法制备出Sr3Al2O6∶Eu3x+红色荧光材料,可被可见光激发。在392和463nm激发下的线状发射峰,可归属为Eu3+离子的5DJ(J=0,1,2,3)→7FJ(J=0,1,2,3,4,5)跃迁,以612和617nm附近对应于5D0→7F2的电偶极跃迁发光最强。随着Eu3+掺杂量的增加,612nm附近发射峰相对减弱,而617nm处的发射峰相对增强,当x值为0.16时,样品发光强度最大。将所制样品与蓝、紫色长余辉材料混合,在停止光照后,利用长余辉材料所发出的光作为激发光源,使样品能够继续发射红光,从而得到一种新型的红色长余辉材料。     

Synthesis and characterization of novel biodegradable tetra-amino-terminated PLGA telechelic copolymer

A new method for the synthesis of biodegradable multifunctional group-terminated copolymers is explored, by which a series of novel biodegradable tetra-amino-terminated PLGA telechelic copolymers are synthesized for the first time. The composition, structure, and thermal property of the telechelic copolymer were characterized by FTIR, NMR, GPC, and MDSC. The results show that by careful selection of the synthesis parameters, tetra-amino-terminated PLGA telechelic copolymer with desired molecular weight and glass transition temperature can be prepared. This versatile synthetic platform can provide a large family of biodegradable, tetra-amino-terminated telechelic copolymers with tunable physiochemical and biological properties useful for the preparation of network biodegradable polyester elastomer with tailorable properties.     

叶酸受体靶向的聚乳酸共聚物的合成及性质

用氨基被保护的4-羟基-脯氨酸与L-丙交酯共聚合,得到含有活性氨基作为侧基的聚合物主链(PLLA-Hpr),通过DDC将叶酸与聚合物中的氨基反应,制得叶酸偶联的脯氨酸一乳酸共聚物(FA-PLLA-Hpr).采用1H-NMR、FT-IR确证了共聚物的结构,对比研究了共聚物的亲水性.结果表明成功地制备了叶酸受体靶向的聚乳酸共聚物.这种共聚物有望作为药物缓释领域的肿瘤靶向材料.     

新型含铱共聚物的合成及表征

利用2-对甲苯基吡啶(ptpy)、对乙烯基苯甲酸(VBA)和三水合氯化铱(IrCl_3·H_2O)配位,得到了铱配合物单体Ir(ptpy)_2(VBA),再将其与乙烯基咔唑共聚制得了一种含铱配合物的新型聚合物.通过元素分析、FT-IR光谱和~1H NMR谱等对Ir(ptpy)-2(VBA)和聚合物的结构进行了表征.凝胶色谱仪(GPC)测试结果表明,聚合物的数均分子量(Mn)为8230.此外还研究了Ir(ptpy)_2(VBA)和聚合物的紫外-可见(UV-vis)吸收光谱和光致发光(PL)光谱.光致发光光谱测试结果表明,聚合物在固态时,主体咔唑基团向客体铱配合物基团有着较为有效的能量转移.聚合物在501nm处有较强的金属配合物三重态的磷光发射峰,是一种绿色磷光材料.     

Synthesis and characterization of new precursors to nearly stoichiometric SiC ceramics: Part 1 The copolymer route

Organosilicon polymers with a (C/Si (atomic ratio)<1.28) exhibiting Si–Si and Si–CH2–Si linkages in their backbone have been prepared and characterized by multinuclear magnetic resonance and infrared spectroscopies, size exclusion chromatography and thermogravimetric analysis. These precursors give SiC ceramics with a C/Si (atomic ratio)1.14 and a relatively low oxygen content (between 1.5–3 at %).     

己二酸-1,4-丁二醇-尿素共聚物的合成与表征

以己二酸、1,4-丁二醇和尿素为原料,在氩气环境下,通过高温熔融缩聚反应合成了一种新型可降解的己二酸-丁二醇-尿素共聚物,并对反应时间、催化剂种类及其用量、原料配比、反应温度等因素对聚合产物的影响进行了研究。采用红外光谱(FT-IR)、核磁共振(1H-NMR)、凝胶渗透色谱(GPC)、热重分析(TG)、差示量热扫描(DSC)对产物的结构与性能进行了表征。结果表明,当丁二醇和尿素的总量与己二酸(n(丁二醇+尿素)∶n(己二酸))的摩尔比为1.16∶1,丁二醇和尿素(n(1,4-丁二醇)∶n(尿素))的摩尔比为5∶1,最高反应温度为220℃,二月桂酸二丁基锡为催化剂且用量为原料总量的0.03%,总反应时间10h,所得到产物的重均分子量(Mw)可达12700,其颜色、热稳定性和降解性能等较好。     

Synthesis, characterization, photophysics and electroluminescence based on a series of pyran-containing emitters

Four unsymmetric as well as symmetric carbazole or oxadiazole modified pyran-containing compounds have been synthesized and characterized. These compounds are 4-(dicyanomethylene)-2-methyl-6-(4-(carbazolo-9-yl)phenyl)-4H-pyran (10), 4-(dicyanomethylene)-2,6-bis(4-(carbazolo-9-yl)phenyl)-4H-pyran (11), 4-(dicyanomethylene)-2-methyl-6-(4-tert-phenyl)-1,3,4-oxdiazole-4-phenyl)-4H-pyran (12), and 4-(dicyanomethylene)-2,6-bis(4-tert-phenyl)-1,3,4-oxdiazole-4-phenyl-4H-pyran (13). Photoluminescent measurements indicated that their maximal emissions can be tuned from 543 to 590 nm in acetone solution. Electroluminescent studies based on these compounds as dopants resulted in greenish yellow light emission. It was found that the device based on the bis-condensed symmetric compound (11) with the configuration of indium tin oxide / Copper (II) phthalocyanine (5 nm) / N,N′-bis-(1-naphthl)-diphenyl-1,1′-biphenyl-4,4′-diamine (40 nm) / compound (11) : tris-(8-quinolinolato)aluminium (Alq₃) (1%) (30 nm) / 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline (5 nm) / Alq₃ (40 nm) / Mg : Ag (9 : 1) (200 nm) / Ag (80 nm) has achieved the highest luminance (6869 cd/m²) and efficiency (1.32 lm/W and 2.52 cd/A) among the four emitters.     

新型聚2,4-二乙烯基3-十二烷基噻吩-1,3,4-噁二唑交替共聚物的合成、表征及性能研究

采用Heck偶合法首次合成了新型的含有空穴传输单元3-十二烷基噻吩和电子传输单元1,3,4-噁二唑的低带隙能的聚2,4-二乙烯基-3-十二烷基噻吩-1,3,4-噁二唑共轭聚合物(P3DDTV-OXD).并且通过1H-NMR、FT-IR、凝胶色谱(GPC)、UV-vis光谱、荧光光谱(PL)、循环伏安(CV)法对所合成的共聚物进行了分析表征.与规整的聚3-十二烷基噻吩均聚物(P3DDT)相比,共聚物的UV最大吸收波长和Pl最大发射波长明显蓝移,具有强烈的蓝色荧光,且电子亲和势较高,同时拥有空穴和电子传输能力,实现了电荷在分子内的双向传输.     

淀粉与丙烯酸乙酯接枝共聚物的合成与表征

以硝酸铈铵(CAN)为引发剂,研究了丙烯酸乙酯(EA)与玉米淀粉接枝共聚体系的自由基引发反应规律.实验结果得到较佳的反应条件为:单体浓度1.4939mol/L,引发剂浓度0.0293mol/L,AGU浓度1.1075mol/L,硝酸浓度0.02 mol/L,反应温度50℃,反应时间3h.在以上的反应条件下,转化率(C)可达98.64％,接枝率(G)可达34.92％,接枝效率(GE)可达74.55％.通过对接枝共聚产物的红外分析、核磁共振波谱分析、DSC分析及电镜扫描分析对产物进行了表征.结果表明,EA与淀粉发生了接枝共聚反应.     

Synthesis and photoluminescence properties of Ho3+ doped LaAlO3 nanoparticles

Nanosized particles with different Ho3+ concentrations were synthesized in LaAlO3 lattices using a simple Pechini-type sol-gel method. X-ray diffraction measurements were used to investigate the structural composition and the effects of holmium dopant concentration on LaAlO3:Ho3+ crystal formation. Field-emission scanning-electron microscopy images confirm the formation of approximately spherical particles with an average size about 100 nm. The photoluminescence results yielded optimal holmium ion concentration in LaAlO3 host matrices was about 3% in mol equivalent. The mechanism that are responsible for the photoluminescence emission processes discussed with the help of Ho3+-ion Dieke energy level diagram. Power dependent slope measurements were performed to identify up-conversion photoluminescence process involved in LaAlO3:Ho3+.     

含磷阻燃共聚热塑性聚酯弹性体的合成及表征

通过熔融缩聚的方法合成阻燃性TPEE;对比了阻燃剂直接添加和以丁二醇溶液方式添加对最终产物性能的影响,并通过DSC、FT-IR、NMR等手段对合成的阻燃TPEE进行表征.DSC 结果表明添加2-羟乙基苯基次磷酸(CEPPA)后共聚物熔点等变小,但软段熔点并无太大变化;FT-IR结果显示添加CEPPA后共聚物出现新吸收峰935cm-1(P-O-C),其它特征基团吸收峰的位置和强度均发生明显改变,并随添加量的不同而不同;NMR结果表明CEPPA加入后,各质子峰有明显变化.