具有血液相容性的嵌段聚酯-聚醚接枝共聚物的合成

本文研究了嵌段聚酯-聚醚膜经紫外光活化后,于水溶液中铈盐引发亲水性单体丙烯酰胺在其表面上接枝共聚合反应。同时对接枝物进行了证实和表征。并通过活体动物血液灌流实验表明,此接枝共聚物具有良好的血液相容性。     

壳多糖与丙烯酸丁酯的乳液接枝共聚研究

以十二烷基苯磺酸钠为乳化剂，过硫酸钾－亚硫酸氢钠为引发剂，研究了壳多糖与丙烯酸丁醋的乳液共聚合，结果表明当［Ｋ２Ｓ２Ｏ８］＝［ＮａＨＳＯ３］＝２．５７×１０－３ｍｏｌ·１－１，［ＢＡ］＝０．６８ｍｏｌ．１－１，［Ｃｈｉｔｏｓａｎ］＝１９．２ｇ·ｌ－１，在７０℃下反应５小时，共聚反应的接技率和接枝效率均较高．用红外光谱，差热分析，Ｘ射线衍射，扫描电镜对接技共聚物进行了表征，此外测试了共聚物胶乳成膜的机械性能，表明用丙烯酸丁酯对壳多糖进行接枝改性，可提高壳多糖的韧性，扩大其应用范围．     

N-甲基丙烯酰-N′-甲基哌嗪在嵌段聚醚氨酯膜上的Co~(60)-γ辐射接枝的研究

<正> 用亲水性单体对嵌段聚醚氨酯(SPEU)膜接枝共聚以改善其抗凝血性能,在医用材料的研究中已引起普遍重视,但由于一般化学方法接枝引发系统中带入的小分子常常对产品的医用性质造成不利的影响。我们曾报道通过Co~(60)-γ射线预辐照法用亲水性单体对以PTMG;MDI与不同的二胺类扩链剂制备的SPEU膜接枝共聚。本文在此基础上选用了两种单体AMP和MAMP。     

聚醚氨酯的氧化及其接枝共聚合的研究

本文研究了在聚醚氨酯表面上进行接枝共聚合的新方法。首先在聚醚氨酯薄膜上通过过氧化氢光氧化引入过氧化氢基,然后在还原剂亚铁盐或N,N-二甲基对甲苯胺的作用下引发丙烯酰胺接枝共聚合,反应具有低温快速的特点。产物经吸水性实验及扫描电子显微镜观察均证实了是一接枝共聚物。通过模型化合物的研究证明,接枝反应具有较高的选择性,接枝共聚占优势地发生在聚醚软段上,接枝地点很可能就在醚键旁的α-碳原子上。     

N-甲基丙烯酰-N′-甲基哌嗪在嵌段聚醚氨酯膜上的Co60-γ辐射接枝的研究

The graft copolymerization of N-methacryl-N'-methyl-opiperazine onto segmented polye-therurethane (SPEU) film by Go⁶⁰-r-preirradiation has been studied. It is found that the grafting time varies with structure of different chain extenders. The grafted substrated become opaque, the contact angle drops down and from SEM photographs with salient micrograph showing grafts of macrochain on the surface of SPEU film.     

两亲接枝共聚物PS-g-N-PEO的合成及表面性能研究——铸膜溶剂及浓度的影响

采用大分子单体法合成了一系列聚苯乙烯接枝壬基酚聚氧乙烯 (PS g NPEO)两亲共聚物 ,采用溶液铸膜法将其在PET表面制膜 ,并利用扫描电子显微镜 (SEM) ,X射线光电子能谱 (XPS) ,衰减全反射红外光谱(ATR)和水接触角 (CA)等手段研究了共聚物组成、铸膜溶剂及浓度对共聚物膜表面形貌、组成及水浸润性能的影响 .结果表明 ,两亲接枝共聚物在不同条件下可形成规则的表面微孔 ,共聚物中NPEO含量越高 ,共聚物膜表面微孔孔径越大 ,对应的水接触角越小 .以THF为铸膜溶剂时 ,制膜浓度越大 ,共聚物膜表面微孔孔径越大 ,对应的水接触角越小 ;而以甲苯为溶剂时 ,制膜浓度对共聚物膜表面形貌影响不大 ,但水接触角要较THF体系显著降低 ,水接触角与浓度关系与THF体系相反 ,制膜浓度越大 ,对应的水接触角越大 .制膜浓度相同时 ,THF作溶剂 ,共聚物膜微孔较大 ,表面亲水组分含量较低 ;以甲苯为溶剂 ,微孔较密 ,表面亲水组分较高 .     

甲基丙烯酸聚乙二醇单甲醚酯在聚(醚-氨酯)表面的臭氧化接枝

甲基丙烯酸聚乙二醇单甲醚酯在聚（醚 氨酯）表面的臭氧化接枝王晨晖王安锋车波周彩华苏琳丽林思聪（南京大学高分子科学与工程系生物材料分子工程与控制释放分子工程室南京２１００９３）王炳坤（南京大学环境科学系南京２１００９３）关键词臭氧化，表面接枝，大...     

预氧化聚烯烃膜的表面光接枝聚合

将经表面热氧化的聚丙烯和聚乙烯膜在不加敏化剂的情况下,通过紫外光照射与光稳定剂甲基丙烯酸(2,2,6,6-四甲基哌啶)酯进行接枝聚合,以改善膜的光稳定性。研究了各种因素,包括热氧化时间,光照射时间、单体浓度及溶剂等对表面预氧化膜的光接枝含量的影响。实验结果表明,常用的有机溶剂除酮类外均不能使膜接枝;接枝以后膜的光稳定性有很大的提高。     

硝化纤维素与甲基丙烯酸甲酯的均相接枝共聚

借助付里叶红外光谱、Ｘ－射线衍射以及电子显微技术，结合化学提纯方法，检测纤维素分子中主要基团、分子取向度和超分子结构形态等方面的变化，考察了均相条件下硝化纤维素与甲基丙烯酸甲酯接枝共聚物的形成与发生接枝共聚反应的部位，探索均相接枝的可能反应机理。     

Porous copolymer film materials by using free radical copolymerization and its side reaction product, homopolymer, as template

The present report introduces a simple and novel strategy for producing an ordered porous copolymer film material by using its side reaction product, homopolymer, in free radical copolymerization as template. In general, homopolymers are side products in free radical copolymerization, but herein we try to make good use of them (e.g. PMMA). In this paper, we optimized the graft copolymerization of gelatin and MMA via traditional free radical initiation. PMMA is a side product and act as a template to create ordered nanoporous structure. Furthermore, this approach has been successfully extended to chitosan-g-PMMA and gelatin-g-PS systems. The present novel approach provides a new opportunity by using the side product in copolymerization to fabricate ordered porous structure film materials. The porous gelatin-g-PMMA film is especially suitable as surfaces for cell growth due to its good biocompatibility, mechanical properties and multilayer structure.     

GRAFT COPOLYMERIZATION OF ACRYLAMIDE ONTO POLYPROPYLENE FILMS BY PLASMA TECHNIQUE

The graft copolymerization of acrylamide onto polypropylene (PP) Film was carried out by using a capacitively coupled rf plasma apparatus with external plate electrodes. The relationship between the surface structure of the Ar plasma-treated PP films and the extent of grafting of acrylamide on the films was studied through observing the effects of discharge power and exposure time on the relative content of free-radical on the film surface. Meanwhile, the wettability and surface energy of the PP film were measured.     

Functionalization of polyethylene surface using plasma-induced graft copolymerization of acrylic acid

Plasma-induced graft copolymerization of acrylic acid onto PE films was investigated. The influence of plasma treatment power, pressure, time, graft copolymerization time, and monomer concentration on polymerization yield was determined. A chemical shift of the Cls signal of Ar plasma treated and untreated PE films was revealed by ESCA, which also verified the presence of grafted PAAc. An increase in graft polymerization yield with plasma treatment time and power was found. Both the plasma treated film and the subsequently grafted film were shown to be hydrophilic. Only the grafted film, however, shows an invariably low contact angle. The decomposition of peroxides upon heating was followed by a simple first-order reaction. © 1993 John Wiley & Sons, Inc.     

聚四氟乙烯-丙烯酸辐射接枝共聚中盐酸效应的研究

<正> 聚四氟乙烯(以下简称F4)辐射接枝改进粘结性能是一种较好的方法,已有不少报道。七十年代初,已有聚烯烃等辐射接枝中酸效应的研究,表明无机酸能提高接枝速度。 众所周知,F4不耐高能射线,在通常条件下,很小的辐射剂量即引起它的物理机械     

Surface modification of SPEU films by ozone induced graft copolymerization to improve hemocompatibility

Surface modification of segmented poly(ether urethane) (SPEU) by graft copolymerization with N,N′-dimethyl-N-methacryloyloxyethyl-N-(3-sulfopropyl) ammonium (DMMSA), a zwitterionic sulfobetaine structure, was conducted. A simple two-step procedure for grafting of DMMSA onto the surface of SPEU film was used. The surface was first treated with ozone to introduce active hydroperoxide groups. The active surface was then exposed to the DMMSA solution in the sealed tube. Grafted SPEU film was characterized by ATR–FTIR, XPS and contact angle measurement. ATR–FTIR and XPS investigations confirmed the graft copolymerization. The monomer concentration, copolymerization temperature and time were varied to maximize the efficiency of DMMSA grafting. The equilibrium water content (EWC) and contact angle measurements showed that the hydrophilicity of the film had been greatly improved. The blood compatibility of the grafted films was evaluated by platelet adhesion in platelet rich plasma (PRP), deposits in blood control and protein adsorption in bovine fibrinogen using SPEU film as the control. No platelet adhesion and no thrombus were observed for the grafted films incubated in PRP for 300 min and in blood for 120 min, respectively. The protein adsorption was reduced on the grafted films after incubation in bovine fibrinogen for 120 min. These results proved that improved blood compatibility was obtained by grafting this new zwitterionic sulfobetaine structure monomer onto SPEU film.     

SBS与甲基丙烯酸丁酯本体接枝反应的研究

本文研究了以过氧化苯甲酰(BPO)为引发剂,甲基丙烯酸丁酯(BMA)既作溶剂又作为单体与苯乙烯-丁二烯嵌段共聚物(SBS)进行接枝共聚反应。用红外光谱、核磁共振谱及透射电镜表征了接枝共聚物(SBS-g-BMA)的组成及结构,讨论了时间、温度及SBS和BPO的用量对接枝的影响。     

利用大分子单体技术合成接枝共聚物

大分子单体和小分子共单体共聚是合成接枝共聚物的重要途径之一。本文综述了大分子单体通过各种聚合方式(自由基共聚、离子型共聚、配位共聚、基团转移共聚和逐步共聚)和普通小分子单体的共聚反应,详细讨论了大分子单体和小分子单体的自由基共聚反应动力学,并简要介绍了接枝共聚物的应用背景。     

Synthesis and Biomedical Properties of Poly-[(Ethylene-Vinylalcohol)-g-Acrylamide]

This paper deals with the graft copolymerization of acrylamide (AM) onto ethylene-vinyl alcohol copolymer (EVAL) film initiated by cerium(IV) ion. It was found that both the chemical and diffusion factors had influences on the graft reaction. The reaction was initiated on the surface and then penetrated inward as the grafting percentage was increased. The permeability of urea through the grafted EVAL film was improved compared to that of the original film as was the blood compatibility.     

STUDIES ON THE OXIDATION AND GRAFT COPOLYMERIZATION OF POLY(ETHER-URETHANE)

A new method of graft copolymerization of acrylamide (AAM) on poly(ether-urethane) (PEU) which was prepared from poly(tetramethylene ether) glycol (PTMG), 4,4'-diphenylmethane diisocyanate (MDI) and ethylene diamine or butanediol extender was investigated. Hydroperoxide group was first introduced onto the surface of PEU through photo-oxidation in the presence of hydrogen peroxide, then it was reacted with ferrous ion or N,N-dimethyl toluidine (DMT) to initiate AAM graft copolymerization on PEU surface. The graft reaction could be carried out effectively at low temperature. The formation of graft copolymer has been verified by its water absorption % and the scanning electron microscopy photographs. Some model compounds of PEU soft segment and hard segment were synthesized in order to clarify the site of graft reaction. The results of oxida-tion and graft copolymerization of model compounds showed that this graft copolymerization possesses higher selectivity, and it takes place predominately at the polyether segments, because the ether linkage in soft segment is very sensitive to oxidation and can form hydroperoxide easily. Thus, the grafting site appears to be at α-carbon of the ether linkage.     

三价锰离子引发烯类单体在聚乙烯醇上接枝聚合的研究

<正> 无论是淀粉;纤维素,还是聚乙烯醇(PVA)的接枝反应,Ce(Ⅳ)被认为是一个十分有效的引发剂,已有较详尽的研究。与Ce(Ⅳ)相类似,Mn(Ⅲ)也可以和一些高聚物组成氧化还原引发体系,由此产生自由基,引发烯类单体在高分子主干上进行接枝聚合。Ranby等人,以焦磷酸络合的三价锰离子引发烯类单体在纤维素和淀粉的接枝反应中,获得了高效的接枝产物。有用这种引发体系在淀粉上接枝丙烯腈获得吸水276     

可聚合的光引发转移终止剂合成接枝共聚物

采用一种可聚合的光引发转移终止剂 ,2 N ,N 二乙基二硫代氨基甲酰氧基乙酸 β 甲基丙烯酰氧基乙酯 (MAEDCA) ,通过两种途径制备了含有聚甲基丙烯酸甲酯 (PMMA)和聚苯乙烯 (PSt)链段的接枝共聚物 .其一是将MAEDCA作为引发剂 ,在紫外光照射下引发MMA聚合 ,得到大分子单体 ,通过大分子单体与St的共聚合得到 .考察了所用大分子单体的分子量和浓度对共聚合的影响 .其二是将MAEDCA作为单体与MMA共聚得到侧链上含有N ,N 二乙基二硫代氨基甲酰氧基 (DC)基团的无规共聚物 ,P(MMA co MAEDCA) .在紫外光照射下 ,P(MMA co MAEDCA)作为大分子引发剂引发St聚合 ,得到P(MMA co MAEDCA) g PSt的共聚物 ,研究了接枝共聚合过程的活性自由基聚合特征