INVESTIGATION OF THE FRIEDEL-CRAFTS REACTION OF THE CHLOROMETHYLATED COPOLYMER OF STYRENE-DIVINYLBENZENE

In the presence of Friedel-Crafts catalyst, the chloromethylated copolymer of styrene-divinylben-zene may react with each other and cross-link by itself Thus a new type of polymeric adsorbent wasobtained, and its structure was identified by its physical properties and infrared spectra. The Friedel-Crafts reaction is manifestly affected by the nature of the solvent, the kind and amount of catalystused, reaction temperature and reaction time, etc. The porous structure and physical properties of the adsorbent prepared have been investigatedsystematically. The adsorbent has high specific surface area (1000--1300m~2/g), porosity, narrowpore distribution,high skeleton density and good mechanical properties.     

HYDROLYSIS TRANSFORMATION OF A POLYSTYRENE-b-POLY(tert-BUTYL ACRYLATE) COPOLYMER AND MICELLIZATION PROPERTIES OF THE HYDROLYZED COPOLYMER

1. INTRODUCTION The association of amphiphilic block copolymers has been the subject of numerous studies for several decades due to the academic interest and industrial applications [1~7]. It is well-known that block copolymers exhibit interesting domain structures in the solid state and form micelle-like aggregates in selective solvent [8]. They have found many potential applications in drug delivery [9], extraction of proteins [10], corrosion protection [11] as well as removal of aromat…     

TRANSITION IN THE MELT OF FEP COPOLYMER

The nature of the transition in molten FEP copolymer was examined in relation to the enthalpy change, mechanical damping and melt viscosity. For a pre-heat-treated FEP copolymer sample a small endothermic peak appeared at 309—312 ℃in DSC trace with enthalpy change 0.03—0.05 cal/g. A peak was also detected in damping versus temperature curve at the same temperature range. The theological property of FEP copolymer melt was similar to that of liquid crystal, but no birefrigence was viewed in the melt. Therefore the transition was explained as the melting of small crystallites which persist in typical copolymer beyond its melting temperature. These crystallites can act as nuclei for crystallization upon cooling.     

NMR SPECTROSCOPIC STUDY ON COPOLYMER OF ETHYLENE-NORBORNENE

A series of ethylene-norbornene copolymers were synthesised using VO (OEt) Cl_2/Al_2Et_3Cl_3 catalytic system and their structure was characterized by ~1H-NMR, ~1H-~1HCOSY NMR and ~(13)C-NMR. Assignments of NMR spectra were given and discussed indetail.     

CHARACTERIZATION OF RADIATION GRAFT COPOLYMER OF INORGANIC COMPOUND ONTO ALKENE

ＣＨＡＲＡＣＴＥＲＩＺＡＴＩＯＮＯＦＲＡＤＩＡＴＩＯＮＧＲＡＦＴＣＯＰＯＬＹＭＥＲＯＦＩＮＯＲＧＡＮＩＣＣＯＭＰＯＵＮＤＯＮＴＯＡＬＫＥＮＥＺｈａｎｇＷａｎｘｉ；ＣｈｅＪｉｔａｉ；ＹａｎＭｅｉｌａｎ（ＣｈａｎｇｃｈｕｎｉｎｓｔｉｔｕｔｅｏｆＡｐｐｌｉ...     

THE STRUCTURE AND OPTICAL PROPERTIES OF COPOLYMER OF CHOLESTERIC ESTER

The structure and switching properties of liquid crystalline side chain copolymers of cholesteric ester of 1,2-hydroxypropyl 2,4-di-isocyanatoluene methylmethacrylate (PHCPM) have been studied in detail. The cholesteric mesophase of PHCPM is shown by polarizing microscopy, X-ray diffraction and selective light reflection. Solution of PHCPM in CHCl_3 is optically anisotropic; its optical properties were determined by specific rotation [α], circular dichroism (CD) and wide-angle hght scattering (WALS) methods.     

PREPARATION AND PROPERTIES OF SILICONE-ACRYLATE COPOLYMER LATEX

Silicone-acrylate copolymer latex was prepared through three different polymerization processes, i.e., the batch process, preemulsified monomer addition and the monomer addition process. The results revealed that the monomer addition process is a desirable approach to produce narrow particle size distribution latex with higher polymerization conversion and less amount of coagulum. The effect of silicone content on the glossiness and water absorption of latex film was investigated and the results showed that the glossiness of latex film is improved up to a silicone content of 10% of total monomers, but becomes impaired thereafter, whereas water absorption is reduced accordingly.     

SYNTHESIS OF A NEW SILICONE-CONTAINING BISMALEIMIDE COPOLYMER RESIN

A copolymer of bismaleimide-diallylbisphenol A-diphenylsilandiol was synthesized andthe copolymerization was studied by using N-phenylmaleimide, bisphenol A and diphenyl-silandiol as model compounds. The copolymer could be well cured around 200℃, andthe cured resins had good thermal stability In the range of 170-210℃, a higher curingtemperature was favorable to obtain more thermal stable resin by reducing the content ofdiphenylsilandiol cyclo-homopolymer in resin which would spoil its thermal stability     

THE RHEO-OPTICAL FTIR STUDY OF POLYESTERPOLYETHER SEGMENTED COPOLYMER

The polyester-polyetber segmented copolymer has been investigated by rheo-optical FTIR during stretehing for the informastion on strain induced crystallizatinn of soft segment chains, hard and soft chain orientation.At room temperature 15℃, the soft segment chains of polyester-polyether being to crystallize at 220% strain and the degree of crystallixation increa(?)e with draw ratio, but there will not be any soft segment chains crystallization above 21℃even at bigber strain. The average orientation of hard segment chains are higher than that of the soft chain at high strain level, both are positive oriented into the stretching direction at allover strain level. This indicates that the b(?)d (?)ent ch(?)ins are dispersed into the elastomeric phase and without forming spherulite.     

STUDY ON THE SWELLING BEHAVIOUR OF COPOLYMER HYDROGEL

The states of water in poly (N-vinylpyrrolidone-methylmethacrylate) and poly (N-vinylpyrroli-done-2-hydroxyethyl methacrylate) hydrogels have been studied by means of DSC. The effect ofpolmer structure on equilibrium swelling extent of water has been examined. It was found that thestate of water and the water content in different hydrogels were dependent on the kind of monomer used,the component of copolymer, the sequence distribution of the monomer unit and the degree of cross-linking (including chemical and physical) to a great extent. The equilibrium water content of thehydrogel may be regarded as the sum of the different state of swollen water contents of the hydrogel.Based on these, a semiempirical formula used to estimate the equilibrium water content of the copolymerhydrogels was presented.     

药物包载对两亲嵌段共聚物胶束形态的影响

以聚(ε-己内酯-b-L-丙交酯)/聚乙二醇单甲醚(P(CL-b-LLA)-b-mPEG)和聚(ε-己内酯-b-D,L-丙交酯)/聚乙二醇单甲醚(P(CL-b-DLLA)-b-mPEG)两种两亲嵌段共聚物为载体,选择了物理状态完全不同、而疏水性相近的吲哚美辛和维生素E为模型药物,研究了药物包载对高分子胶束形态的影响.发现两种药物在高分子胶束内部的增溶均会导致胶束形态发生显著改变,变化行为与胶束内核的结晶性和药物疏水性有关.另外,还研究了两种嵌段共聚物的载药性能,发现非结晶性疏水内核共聚物的药物包载率明显大于可结晶疏水内核的共聚物.     

核中含有羧基官能团的聚合物胶束的高效制备

通过化学交联反应诱导胶束化以较高的效率制备了PMCC(聚合物的质量浓度高达50 g/L). 首先制备嵌段共聚物聚苯乙烯-b-聚丙烯酸(PS-b-PAA), 然后对PAA嵌段中的羧基实行酰氯化, 在酰氯化产物聚苯乙烯-b-聚丙烯酰氯(PS-b-PACl)的共同溶剂二氯甲烷中加入交联剂乙二醇交联PACl嵌段. 交联反应使得PACl嵌段聚集, 同时, PS嵌段的保护作用使得PACl嵌段的聚集在有限个分子链间发生, 从而生成以PS为壳, 以含有羧基官能团的聚丙烯酸酯交联网络为核的PMCC.     

聚乙二醇-聚谷氨酸-聚丙氨酸三嵌段共聚物的合成及其胶束的pH-响应性药物控制释放

通过大分子引发剂ω-胺基-α-甲氧基聚乙二醇引发N-羧基-α-氨基环内酸酐开环聚合和酸性水解制备了一种具有pH-响应性的三嵌段共聚物聚乙二醇-聚谷氨酸-聚丙氨酸(mPEG-PLGA-PLAA).通过核磁共振、ζ-电势、动态光散射、电子显微镜等手段表征了此类三嵌段共聚物的自组装过程及所形成胶束的pH-响应性.使用圆二色谱和红外光谱,分析了胶束结构随环境pH值转变过程中聚氨基酸链段二级结构的变化.以阿霉素作为模型药物,研究了三嵌段共聚物的载药能力和在不同pH条件下的药物释放能力.在碱性条件下,PLGA链段去质子化,链段从疏水性变为亲水性,胶束中间层由于水合作用变得松散,药物释放速率增加;在酸性条件下,PLGA链段质子化,不带电荷,与阿霉素药物分子间的静电相互作用消失.同时,PLGA链段α-螺旋含量增加,形成由链内氢键维持的刚性棒状结构,将链段周围包埋的药物分子"挤出",加速了药物的释放.     

树状化-线形两亲嵌段聚合物的合成及自组装研究

合成了缩酮保护的一代甲基丙烯酸羟乙酯单体DHEMA(G1),通过顺序ATRP聚合方法,制备得到大分子引发剂PDHEMA(G1)-Br,再引发苯乙烯单体得到一代嵌段聚合物PDHEMA(G1)-b-PS.以PDHEMA(G1)-b-PS为反应前体,通过重复的缩酮保护和脱保护反应,进一步得到了二代和三代的树状化-线形两亲嵌段...     

pH值响应性超支化多臂共聚物的合成及其自组装行为研究

以超支化双硫酯为链转移剂,偶氮二异丁腈(AIBN)为引发剂,采用可逆加成-断裂链转移(RAFT)活性自由基聚合方法,合成了以超支化聚酯(Boltorn H20)为核,聚丙烯酸为臂的两亲性超支化多臂共聚物(H20-star-PAA),并通过紫外分光光度计、动态光散射(DLS)和透射电子显微镜(TEM)对它在水溶液中的pH响应的自组装行为进行了研究.结果表明,在稀溶液条件下,H20-star-PAA始终以单分子胶束的形式存在,随着溶液pH的降低,胶束的PAA壳层会逐步塌缩,导致胶束尺寸减小;而在浓溶液条件下,当溶液的pH较低时,单分子胶束会进一步聚集形成多分子胶束.     

Thermoresponsive micelles from Jeffamine-b-poly(L-glutamic acid) double hydrophilic block copolymers

Double hydrophilic block copolymers (DHBC) consisting of a Jeffamine block, a statistical copolymer based on ethylene oxide and propylene oxide units possessing a lower critical solution temperature (LCST) of 30 degrees C in water, and poly(L-glutamic acid) as a pH-responsive block were synthesized by ring-opening polymerization of gamma-benzyl-L-glutamate N-carboxyanhydride using an amino-terminated Jeffamine macroinitiator, followed by hydrolysis. This DHBC proved thermoresponsive as evidenced by dynamic light scattering and small-angle neutron scattering experiments. Spherical micelles with a Jeffamine core and a poly(L-glutamic acid) corona were formed above the LCST of Jeffamine. The size of the core of such micelles decreased with increasing temperature, with complete core dehydration being achieved at 66 degrees C. Such behavior, commonly observed for thermosensitive homopolymers forming mesoglobules, is thus demonstrated here for a DHBC that self-assembles to generate thermoresponsive micelles of high colloidal stability.     

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。     

化学酶法合成五嵌段聚合物及其自组装行为的研究

用酶促开环聚合与ATRP方法相结合,制备了聚甲基丙烯酸六氟丁酯-聚己内酯-聚乙二醇-聚己内酯-聚甲基丙烯酸六氟丁酯(PHFMA-b-PCL-b-PEG-b-PCL-b-PHFMA)五嵌段聚合物.首先用Novozym e 435作为催化剂合成了聚己内酯-聚乙二醇-聚己内酯三嵌段聚合物,然后通过端基官能化法合成了大分子引发剂,并用其引发甲基丙烯酸六氟丁酯(HFMA)的ATRP反应,合成了五嵌段聚合物.通过核磁和GPC证明了大分子引发剂和五嵌段共聚物的结构,五嵌段共聚物的GPC分析表明这种合成方法的可行.共聚物胶束的直径和大小通过动态光散射方法和原子力显微镜测试,五嵌段共聚物在水中的的自组装行为也被研究.结果证明胶束是球形,其平均直径为77 nm.聚合物在四氢呋喃中的浓度对聚合物的聚集形貌有很大的影响.     

Influence of Mixed Common Solvent on the Co-assembled Morphology of PS-b-PEO and CdS Quantum Dots

The hybrid structures of polystyrene-b-poly(ethylene oxide)(PS-b-PEO) block copolymer and inorganic nanoparticles with good stability and biocompatibility have potential applications in drug delivery and bioimaging. Spherical co-assemblies of PS120-b-PEO318 and oleylamine-capped Cd S quantum dots(QDs) are produced successfully in this work by adding water to a mixed common solvent, such as N,N-dimethylmethanamide(DMF)/chloroform, DMF/tetrahydrofuran(THF), or DMF/toluene. The energy dispersive X-ray(EDX) spectrum indicates that QDs are located at the interface between the core and shell of the spherical co-assemblies. The co-assembly process during water addition is traced by transmission electron microscopy(TEM) and turbidity measurement. Spherical co-assemblies are formed through budding from bilayers of the block copolymer and QDs. The morphology of the co-assemblies is related to the miscibility of the QD-dispersing solvents with water and the morphology changes from a spherical to a vesicle-like structure with DMF/toluene. Increasing THF content in the mixed solvent causes morphological transitions from spherical co-assemblies to multi-branched cylinders and micelles where QDs are located in the central core. Increasing chloroform content yields vesicle-like structures with protruding rods on the surface. The mechanism of the morphological transitions is also discussed in detail.