NOVEL AMPHIPHILIC FLUORESCENT GRAFT COPOLYMER： SYNTHESIS, CHARACTERIZATION AND ENCAPSULATION OF A HYDROPHOBIC AGENT

Novel amphiphilic fluorescent graft copolymer （PVP-PyAHy） was successfully synthesized by the free radical copolymerization of hydrophobic monomer N-（1-pyrenebutyryl）-N＇-acryloyl hydrazide （PyAHy） with hydrophilic precursor polymers of vinyl-functionalized poly（N-vinylpyrrolidone） （PVP） in DMF. The copolymer is amphiphilic and has intrinsic fluorescence. FT-IR, ^1H-NMR, TEM, gel permeation chromatography-multi-angle laser light scattering, UV-Vis spectroscopy and fluorescence spectroscopy were used to characterize this copolymer. The TEM observation shows that the copolymer PVP-PyAHy forms micelles in aqueous solution. Results of fluorometric measurements illustrate that the critical micelle concentration （CMC） value of PVP-PyAHy in aqueous solution is about 0.90 mg/mL. To examine the encapsulation ability of the copolymer in aqueous media, methyl yellow was employed as a model hydrophobic agent. The loading level of the polymer to methyl yellow is 8.8 mg/g. The cytotoxicity assays for Madin Darby Canine Kidney （MDCK） cells shows good biocompatibility of PVP-PyAHy in vitro. These results suggest the potential of this copolymer PVP-PyAHy as drugs delivery carrier and fluorescent tracer.     

聚对二氧环己酮/聚乙二醇两亲性聚合物共网络的合成与表征

以辛酸亚锡为催化剂,季戊四醇(PTOL)为引发剂,引发对二氧环己酮(PDO)单体开环聚合,合成了以PTOL为核的四臂聚对二氧环己酮(4s-PPDO).通过直接将4s-PPDO预聚物和聚乙二醇(PEG)于熔点以上、惰性气体保护下与偶联剂甲苯二异氰酸酯(TDI)交联共聚得到聚对二氧环己酮/聚乙二醇(PPDO-b-PEG)两亲性共网络聚合物(PPDO-PEG APCNs).研究了两亲性聚合物共网络结构、配比组成、溶剂种类等对聚合物溶胀率的影响,结果表明APCNs在不同类型的溶剂中表现出不同的溶胀行为,可以通过调节偶联剂的用量及PPDO/PEG的投料比来满足不同的实际需求.通过示差扫描量热分析(DSC)详细研究APCNs的结晶性能,证实交联反应降低APCNs的结晶度和结晶尺寸.     

新型大分子席夫碱配合物的合成和表征

本文用胺基封端聚四氢呋喃(Mn=862)与水杨醛反应，生成新型席夫碱遥爪配体，再与金属离子(Fe³⁺, Co²⁺, Cu²⁺)反应，得到新型大分子席夫碱配合物。用IR、ESR、UV、循环伏安法、拉伸和动态粘弹谱等表征手段对配合物进行了研究。证明所得配合物的配位结构与血红蛋白分子的功能片段的配位结构相似，钴配合物具有与血红蛋白分子相近的可逆化学吸附功能。     

水溶性聚合物和两亲聚合物 16.聚苯乙烯/聚丙烯酰胺嵌段聚合物的合成和表征

采用聚偶氮酯引发剂,合成了聚苯乙烯/聚丙烯酰胺嵌段聚合物(PSt/PAM)。考察了含偶氮基聚苯乙烯预聚物(pre-PSt)在1,4-二氧六环中引发AM的聚合反应行为,讨论了影响第二单体转化率和聚苯乙烯均聚物含量的因素。用元素分析、溶解性、红外光谱、DSC、TG和裂解色谱表征了PSt/PAM嵌段聚合物。     

结肠酶特异响应性两亲高分子载体的合成和表征

合成了一种可在结肠部位被特异酶解的两亲性嵌段高分子,由聚丙交酯(PLA)疏水嵌段和聚乙二醇(PEG)亲水嵌段组成,两者通过5,5′-偶氮二水杨酸(OLZ)偶联,其中的偶氮键可被结肠部位的偶氮还原酶特异酶解.利用FTIR、NMR和GPC等方法表征了共聚物的结构,并通过透射电镜(TEM)和动态光散射(DLS)等方法研究了该高分子载体在水溶液中的组装行为.结果表明MPEG-OLZ-b-PLA可在水介质中形成尺寸在30nm左右的球形胶束,并在大鼠全盲肠提取液中被特异性酶解。     

聚对二氧环己酮/聚乙二醇多嵌段共聚物的合成与表征

首先合成双端羟基的聚对二氧环己酮预聚物(PPDO)和双端羧基的聚乙二醇预聚物(PEG),然后以丁二酸酐/二环己基碳二亚胺(DCC)将PPDO与PEG偶联共聚,得到PPDO/PEG多嵌段共聚物.通过1H-NMR和GPC表征了聚合物的结构和分子量.采用差示扫描量热法(DSC)和热重分析(TGA)研究了共聚物的结晶性能和热稳定性.用透析法制备了共聚物纳米粒子,并用动态光散射(DLS)表征了共聚物纳米粒子的粒径及分散度,结果表明,随着共聚物亲水链段PEG含量的增加,其纳米粒子更易形成,粒子粒径随共聚物分子量增大而增大.     

含偶氮苯两亲性ABA三嵌段共聚物合成与自组装研究

利用原子转移自由基聚合(ATRP)制备了中间链段含对氰基偶氮苯尾挂液晶基元的PMAA-b-PMAZOCN-b-PMAA两亲性三嵌段共聚物.首先合成了含有偶氮苯液晶基元的甲基丙烯酸酯单体;再使用小分子双端引发剂,以对壬基联二吡啶、溴化亚铜为催化剂,通过ATRP反应制备了含偶氮苯液晶侧基的双端大分子引发剂.进一步以氯化亚铜为催化剂,用该大分子引发剂引发甲基丙烯酸叔丁酯聚合,制备了结构规则的PtBMA-b-PMAZOCN-PtBMA三嵌段共聚物.通过在三氟乙酸作用下的选择性水解,将PtBMA段中的甲基丙烯酸叔丁酯单体单元转化为甲基丙烯酸,得到了两端亲水,中间疏水的两亲性ABA三嵌段共聚物.用1H-NMR、GPC、PLM、DSC等对产物进行了表征.并利用溶剂诱导微相分离的方法,研究了该共聚物在THF/水混合溶剂中的自组装行为.TEM结果显示,在采用的亲疏水链段比例的条件下,得到了囊泡结构.囊泡结构的平均直径在300~500 nm.在固态下经过紫外光照射,囊泡结构转变为实心胶体球.     

偶氮苯功能化两亲性共聚物的合成与其纳米聚集体光响应行为的研究

以4,4'-二羟乙氧基偶氮苯(BHEAZO)为引发剂引发对二氧环己酮(PDO)开环聚合,与羧基化的单羟甲基聚乙二醇(mPEG)偶联,制备了具有光响应性的两亲性三嵌段共聚物mPEG-BHEAZO-PPDO-mPEG,并对其纳米聚集体的光响应行为进行了研究.采用紫外可见光谱(UV-Vis Spectroscopy)研究了纳米聚集体水溶液的吸光度随着光照时间的变化;用动态光散射(DLS)研究了辐射波长对纳米聚集体的粒径及粒径分布的影响;结合透射电子显微镜(TEM)的研究结果,提出了对纳米聚集体在不同波长光照下聚集行为改变的机理,即反式结构共平面的共轭体系更易形成稳定的低能级电子离域状态,从而使得纳米聚集体之间通过π-π堆积作用形成微聚集现象.     

STATISTICS OF A NOVEL CLASS OF LIQUID CRYSTAL POLYMERS

A novel class of the liquid crystal polymers with mesogens laterally attached to flexible main chain backbones has been synthesized recently by us. While the flexible backbones tend to take configuration of maximum entropy the mesogenic side groups tend to orientate because of the anisotropie soft dispersion forces. A mean field theory is presented to describe the competition between these two trends which makes it possible for this class of polymers to show anisotropic (liquid crystal) phase within certain temperature range where the polymer main chains and the side chain mesogens will take approximately parallel arrangement, which is different from the normal side chain liquid crystal polymers. The temperature range of the liquid crystal phase, its ordering and phase transition all depend on the flexibility of the backbone, the strengthof the anisotropic forces of the side groups and the hinge elasticity. The results show that the liquid crystalisotropic phase transition is of the first order. The phase diagram, i. e. the dependence of the transition temperature on the structure of the polymers is also given.     

侧链准聚轮烷的制备及表征--葫芦脲[6]与聚[4-乙烯基-溴(N-正丁基)吡啶季铵盐]的超分子自组装

通过葫芦[6]脲(CB[6])与聚[4乙烯基溴(N正丁基)吡啶季铵盐](P4VBuBr,2)在水溶液中于室温下进行超分子自组装,得到一类超分子聚合物———准聚轮烷.通过1HNMR、IR、元素分析对其结构进行了表征,证实CB[6]位于2的侧基脂肪链上,通过非共价键与2结合,并且CB[6]与2重复单元的结合摩尔比分别为0.28∶1、0.2∶1、0.1∶1;通过X射线粉末衍射(XRD)、热重分析(TGA)、紫外可见吸收(UVVis)对其性质进行了研究,证实了准聚轮烷比相应的聚合物2有更高的热稳定性、更强的UVVis吸收以及较高的结晶能力;热分解温度随着准轮烷中CB[6]含量的增加而逐渐提高;NaBr是准聚轮烷的优良的沉淀剂.     

以环糊精为核的星形高分子合成及其温度、pH敏感性研究

以不同用量的氯乙酰氯与 β 环糊精反应 ,得到含有不同酰化度的氯乙酰化 β 环糊精 ,以此化合物为引发剂 ,采用原子转移自由基 (ATRP)引发甲基丙烯酸N ,N 二甲氨基乙酯 (DMAEMA)聚合 ,得到温度及pH敏感的以 β 环糊精为核的星形聚合物 .通过红外光谱、1 3C NMR、1 H NMR和氯元素滴定分析确定了酰化后的 β 环糊精的结构 ,并采用红外光谱、1 H NMR、元素分析、DSC表征了以 β 环糊精分子为核的星形聚甲基丙烯酸N ,N 二甲氨基乙酯的大分子结构 ,紫外光谱研究表明聚合物水溶液具有明显的温度和pH敏感性 .     

SYNTHESIS AND PROPERTIES OF NOVEL POLY(IMINO KETONE)S AS HIGH-PERFORMANCE POLYMERS

Di(4-bromophenyl)ketone and various aromatic diamines as the monomers,a series of novel poly(imino ketone)s (PIKs)have been synthesized via palladium-catalyzed aryl amination,which is Hartwig-Buchwald polycondensation reaction.The structures of PIKs are characterized by means of elemental analysis,FT-IR,~1H-NMR and UV-Vis spectroscopy. The results show a good agreement with the proposed structure.The general properties of PIKs are studied by DSC,TG and wide-angle X-ray diffraction,the solubility behavior...     

侧链含氨基的PLGA-(PEGA-SP)_n共聚物的合成与表征

以聚乙二醇(PEG)和N -苄氧羰基 -L- 天冬氨酸酐为原料,通过溶液缩聚法制备了聚(聚乙二醇 -co -L -天冬氨酸)交替预聚物(PEG- ASP) n;进一步以辛酸亚锡为催化剂、(PEG- ASP) n 为共引发剂引发D ,L- LA和GA开环共聚合成了带有侧氨基功能基团的PLGA (PEG- ASP) n 共聚物.用GPC、FT -IR、1 H -NMR、DSC等研究了共聚物的结构和性能.结果表明,共聚物表现为典型的无定形聚合物;(PEG- ASP) n 的含量对共聚物的性能有显著影响,随(PEG- ASP) n 含量增加,共聚物的亲水性增强,玻璃化转变温度(Tg)下降;以Pd(5wt% ) C为催化剂,采用催化加氢方法可完全脱除共聚物侧氨基上的保护基团;脱除侧氨基上的保护基团后,共聚物的分子量和Tg 值均略有增大,亲水性有所提高.     

SYNTHESIS AND CHARACTERIZATION OF POLY{4-[2-(tert-BUTYLDIMETHYLSILOXY)ETHYL]STYRENE} AND ITS HYDROLYSIS DERIVATIVE

The living cationic polymerization of 4-[2-(tert-butyldimethylsiloxy)ethyl]styrene(TBDMES)was studied in methylcyclohexane(MeChx)/methylchloride(MeC1)(50/50 V/V)solvent mixture at-80℃.The initiator 1,1- diphenylethylene(DPE)capped 2-chloro-2,4,4-trimethylpentane(TMPCl)was formed in situ in conjunction with titanium tetrachloride(TiCl_4).The Lewis acidity of TiCl_4 was decreased by the addition of titanium(IV)isopropoxide(Ti(OiPr)_4)to accomplish living polymerization of TBDMES.Hydrolysis of poly(TBDMES)i...     

新型聚氨酯基液晶光定向层材料的合成与性能研究

设计并合成了一种新的二醇单体 5 羟基 1 ,3 间苯二甲酸二 (2 羟基 )乙酯 [Di(2 hydroxyethyl) 5 hydroxylisophthalate,DHHI],并用各种手段对其进行了表征 .DHHI与二苯基甲烷 4 ,4′ 二异氰酸酯 (MDI)溶液聚合得到一种侧链含有酚羟基的先驱聚合物PU OH ,通过肉桂酰氯的功能化反应制备出新型光敏聚氨酯 (PU CI) .用示差扫描量热分析 (DSC) ,红外光谱 (FT IR) ,紫外可见光谱 (UV Vis)等对PU CI进行了表征 .研究表明 ,PU CI在紫外光的照射下可发生环 (2 +2 )加成反应 .PU CI经线性偏振光聚合技术 (LPP)处理制成液晶光定向层 ,采用向列型液晶 5CB组装成液晶盒 ,在偏光显微镜下可以观察到均匀的液晶取向 ,表明该聚合物膜具有很好的液晶定向能力 ,是一类具有潜在应用价值的新型液晶光定向层材料     

可溶性聚酰亚胺类偶氮高分子的合成与表征

用聚合物的后重氮偶合方法合成了以可溶性聚酰亚胺为主链 ,偶氮生色团为侧基的新型偶氮高分子 ,并通过引入线性长链烷烃侧基来提高聚合物的溶解性 .采用红外光谱、氢核磁共振、紫外光谱和热分析等手段 ,对产物的结构、热性能及光学性能等进行了表征 .该聚合物膜在氩离子干涉激光的照射下形成正弦波形的表面起伏光栅 ,起伏深度可达 2 0 0nm .     

新型热反应大分子单体的合成与表征

溶液法合成了一些低分子量的羟端基低聚苯醚砜,并由相转移催化剂将之转为热反应大分子单体——α,ω-双甲基丙烯酸聚苯醚砜酯;用FTIR、~1H-NMR对其结构进行了表征,GPC、VPO对其分子量进行了分析和测定;用DSC、DTA对聚苯醚砜双烯大分子单体的转变温度、热反应过程进行了测定和分析。     

SYNTHESIS OF AMPHIPHILIC COPOLYMERS BASED ON ACRYLATES BY FREE-RADICAL POLYMERIZATION AND THEIR APPLICATION IN ALKYD EMULSIONS

Novel amphiphilic copolymers which contained poly(ethylene glycol) side-chain, long-chain alkyl pendant groups, and carboxyl groups have been synthesized by the conventional free-radical copolymerization of special monomers. The products were characterized by analysis of Fourier transform infrared spectroscopy (FT-IR), Gel Permeation Chromatography (GPC), and ¹H NMR. Based on the measurement of surface tension of aqueous copolymer solutions with various concentrations at an air/water interface, the critical micelle concentrations (CMC) was found to be lower along with the increase of copolymer concentration. Experimental results showed that CMC of this kind of amphiphilic polymer appeared in the range of 0.01～0.1 g/L. The amphiphilic polymer was mixed with an anionic surfactant (SDBS) in different proportions at aqueous solution and then successfully used in the preparation of alkyd emulsions. The results were compared with those of alkyd emulsions without polymeric surfactant. Steric stabilization of amphiphilic polymer was investigated by the observation of the stability of alkyd emulsions. The emulsions were stable after resting at ambient temperature for four months.     

SYNTHESIS OF A NOVEL CHELATING RESIN WITH HETEROCYCLIC RING OF S AND N

1.INTRODUCTIONThechelatingresinswithheterocyclicringofsulfur,oxygen,andnitrogenhaveexcellentadsorptionformetallicionsespeciallyfornoblemetallicions[1~3].Generally,theabove-mentionedresinsweresynthesizedbythereactionsofchloromethylatedpolystyrenewithheterocycliccompoundsinthepresenceofbase[3].Inthispaper,anewmethodforpreparingchelatingresincontaining2-amino-3-thiazoline(ATZ)wasreported.Thedetailedreactionscan2.EXPERIMENTAL2.1MaterialsEPSandBEPSweresynthesizedaccordingtothemethodde…