甲基丙烯酸烷基磺酸钠在嵌段聚醚氨酯膜上接枝聚合的研究

本文对两种新合成的亲水性单体,甲基丙烯酸已磺酸钠和甲基丙烯酸辛磺酸钠在聚醚氨酯膜上接枝聚合进行了研究。其反应分两步:首先,在过氧化氢存在下,将膜进行光氧化,引入过氧化氢基团;然后,在还原剂亚铁盐作用下,引发甲基丙烯酸烷基磺酸酯接枝聚合。单体浓度、亚铁盐浓度、反应温度对接枝速率均有影响。接枝膜与基膜相比,吸水率与抗凝血性能均有提高。辛酯接枝膜的抗凝血性能显得更好。用扫描电镜可观察到膜上接枝物的图象。     

铈盐引发聚醚氨酯膜上丙烯酰胺接枝聚合反应

由聚四亚甲基醚二醇、4,4′-二苯基甲烷二异氰酸酯与乙二胺或丁二醇扩链剂合成的聚醚氨酯薄膜,可顺利地在室温下用硝酸铈铵引发接枝丙烯酰胺共聚合反应,这可以从反应后的薄膜由起始时是透明的而变为不透明,也可以从接枝后的薄膜比基膜有较大的吸水率,以及从扫描电子显微镜观察到薄膜表面上有凸起图象的高分子链所证实,由于先发生接枝共聚合而后才是均聚反应,因而保证了接枝后的薄膜几乎不附着聚丙烯酰胺。     

聚醚的氧化及其接枝共聚合的研究

聚醚在空气氧化或在H_2O_2存在下的光氧化条件下,很容易被氧化成过氧化氢物。控制适度的氧化时间和过氧化氢物浓度,可避免发生链的断裂。聚醚过氧化氢物与亚铁盐或N,N-二甲基对甲苯胺作用,可在较低温度下引发烯类单体接枝共聚,并可避免均聚反应。接枝率随过氧化氢物浓度的增加而增加,随反应时间延长而提高,改变N,N-二甲基对甲苯胺的浓度,接枝率也随之改变。共聚产物分离提纯后,经IR光谱测定和元素分析,均证实了产物为一接枝共聚物。聚醚的氧化及接枝共聚的实验,为聚醚氨酯的氧化和接枝共聚的机理的研究,提供了基本数据。     

光引发丙烯酰胺在聚醚氨酯膜上的接枝聚合反应

本文研究了以二苯酮为光敏剂,在365nm光照下丙烯酰胺在聚醚氨酯表面的接枝聚合。研究了光照时间、单体浓度、二苯酮浓度对接枝率的影响。对产物作吸水性测定和扫描电镜观察,均证实是接枝共聚物。通过模型化合物的研究,认为激发三线态的二苯酮提取了聚醚氨酯中聚醚软段叔碳原子的氢和氨酯基氮原子上的氢,使这些部位产生自由基,引发单体接枝聚合。     

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。     

聚氧乙烯功能基复合修饰聚氨酯合成及其血液相容性研究（Ⅱ）—聚氨酯—接枝

采用以碘酸基为末端基的聚氧乙烯（PEO）接枝聚醚氨酯和氨基酸反应,将赖氨酸（Lys)和酪氨酸（Tyr)通过PEO为“间隔臂”固定在聚醚氨酯上,制备了氨基酸和PEO复合修饰的聚醚氨酯PEU－g-PEO-SO2Lys和PEU－g-PEO-SO2Tyr。通过血小板粘附试验对材料的体外抗凝血性进行 了初步评价。研究结果表明,采用具有选择性吸附纤溶酶原功能的赖氨酸和PEO复合修聚氨酯,不仅减少了材料表面血小板粘附量,而且减少了材料表面栓的形成量。     

聚氧乙烯功能基复合修饰聚氨酯合成及其血液相容性研究 (Ⅱ)──聚氨酯-接枝-聚氧乙烯氨基酸衍生物

采用以磺酸基为末端基的聚氧乙烯(PEO)接枝聚醚氨酯和氨基酸反应,将赖氨酸(Lys)和酪氨酸(Tyr)通过PEO为"间隔臂"固定在聚醚氨酯上,制备了氨基酸和PEO复合修饰的聚醚氨酯PEU-g-PEO-SO₂Lys和PEU-g-PEO-SO₂Tyr.通过血小板粘附试验对材料的体外抗凝血性进行了初步评价.研究结果表明,采用具有选择性吸附纤溶酶原功能的赖氨酸和PEO复合修饰聚氨酯,不仅减少了材料表面血小板粘附量,而且减少了材料表面血栓的形成量.     

铈离子氧化还原引发体系与铈离子引发接枝或嵌段共聚合研究的新进展

本文介绍Ce⁴⁺/酰胺引发体系;Ce⁴⁺/聚酰胺、带酰苯胺侧基的聚合物引发接枝共聚合;Ce⁴⁺/氨基甲酸酯引发体系;Ce⁴⁺/聚醚氨酯引发接枝共聚合;Ce⁴⁺/羰基化合物引发体系;Ce⁴⁺引发嵌段共聚合6个方面的研究新进展.     

无光敏剂光引发亲水性单体在嵌段聚醚氨酯膜上接枝聚合的研究

<正> 嵌段聚醚氨酯(SPEU)是一类应用广泛的医用高分子材料。用亲水性单体进行表面接枝改性,已有不少研究,接枝聚合方法有铈盐引发、辐射引发以及光敏引发等。 本文研究一种新的接枝方法,不加光敏剂,用紫外光照射,直接引发亲水性单体接枝于SPEU膜上、接枝的单体有丙烯酰胺(AAM)与N,N-二甲基丙烯酰胺(DMAA),从接枝前后膜的性能变化可以证实接枝反应的发生。文中研究了反应条件与单体结构对接枝率的影响,并通过模型化合物,对接枝部位进行了研究。     

以乙烯基酯树脂为多元醇制备聚氨酯硬质泡沫塑料的研究

研究了用乙烯基酯树脂（ＶＥＲ）直接代替通常的聚醚或聚酯型多元醇制备聚氨酯（ＰＵ）硬质泡沫塑料的可能性。实验结果表明,发泡配方中促进氨酯化反应的催化剂Ｎ,Ｎ－二甲基环己胺能与ＢＰＯ复合形成室温引发体系,加速ＶＢＲ的共聚合反应,影响了ＰＵ硬质泡沫塑料形成过程中的发泡与凝胶反应,导致泡了孔骨架基材的交联密度较低,泡孔结构不规整,并显示出较差的物理性能。以ＡＩＢＮ为引发剂时,反应初期主要进行氨酯化反应;仅     

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.     

GRAFTING OF ACRYLAMIDE ONTO SURFACE OF COPOLYMERS CONTAINING P-TOLYLCARBAMOYL PENDANT GROUP INITIATED WITH CERIC SALT

Two copolymers containing p-tolylcarbamoyl pendant group poly (MAMT-co-VAc) and poly(MAMT-co-MA) were synthesized f and the graft copolymerization of AAM onto these two func-tional copolymers films initiated with ceric salt were carried out in aqueous solution for variousperiods at 30℃. The formation of graft copolymer was verified by water absorption, ESCA andSEM photographs. Based on the results of the study of the initiation mechanism of model com-pounds and ceric salt systems, the reaction mechanism of the graft copolymerization initiated withceric salt was proposed.     

STUDIES ON THE OXIDATION AND GRAFT COPOLYMERIZATION OF POLYETHERS

Polyethers could form hydroperoxide under air-oxidation or photo-oxidation in the presence of H_2O_2. The scission of ether linkage induced by moderate oxidation was prevented by controlling the reaction time and hydroperoxide concentration. The oxidation rate was affected by the end groups of polyethers. The decreasing order of oxidation rate for various poly(tetramethylene ether) glycol derivatives having different end groups are as follows: poly(tetramethylene ether) glycol (PTMG)>poly(tetramethylene ether)acetate (PTMGAC) >poly(tetramethylene ether) phenyl carbamate (PTMGPC). The urethane end groups in PTMGPC increase the resistance toward oxidation. Polyether hydroperoxide reacts with ferrous ion or N,N-dimethyl toluidine (DMT) to form polymericoxy radical which then initiates the graft copolymerization of vinyl monomers at low temperature, and was devoid of homopolymerization. The copolymer after separation and purification was proved to be a graft one by IR analysis and elemental analysis.     

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...     

铈离子引发N-对甲苯基丙烯酰胺类聚合物膜上丙烯酰胺接枝共聚合的研究

合成了NTAAM,NTMAAM,NPMAAM功能单体,发现这类功能单体与铈离子组成的体系能引发丙烯酰胺聚合,带有这类功能单体的聚合物和共聚物铸成的膜,能用铈离子引发丙烯酰胺接枝共聚合。这可从反应后的膜比基膜有较大的吸水率、与水有较小的接触角,也可从扫描电子显微镜观察到表面上有凸起图象的高分子链,以及从膜表面的X射线光电子能谱所证实。同时研究了共聚物膜的组成、反应条件对接枝共聚合的影响。     

Amphiphilic segmented polyurethanes as surface modifying additives

Amphiphilic segmented polyetherurethanes were prepared from methylene diphenylene diisocyanate (MDI), poly(ethylene glycol) 1500 (PEG), and a fatty acid monoglyceride as a chain extender. The polymers were not soluble in water or methanol, but dissolved readily in organic solvents. The amphiphilic properties were demonstrated as a large hysteresis in the water contact angles, exceeding 110°. The amphiphilic polymers were shown to modify the surface properties of a poly(ether urethane) (PEU) and a poly(ether urethane urea) (PEUU) when added in 1–10 wt %, presumably due to migration of the additive to the surface. The surfaces of particularly the PEU blends became highly amphiphilic, exhibiting contact angles hystereses up to 90–100°. A surface saturation effect was observed at 5% added amphiphilic polymer. A difference in the behavior of PEU and PEUU was ascribed to differences in solubility of the additive in the matrix. On long-term exposure to water the PEUU blends increased their amphiphilic behavior.     

Parameters affecting transition temperatures of poly(lactic acid‐co‐polydiols) copolymer‐based polyester urethanes and their shape memory behavior

A series of polyester urethanes (PEUs) comprising poly(lactic acid‐co‐polydiol) copolymers as a soft segment, 4,4′‐diphenylmethane diisocyanate (MDI) and 1,4‐butanediol (BDO) as a hard segment were systematically synthesized. Soft segments, which were block copolymers of L ‐lactide (LA) and polydiols such as poly(ethylene glycol) and poly(trimethylene ether glycol), were prepared via ring opening polymerization. Glass transition temperatures (T_g) of the obtained PEUs were found strongly dependent on properties of copolymer soft segments. By simply changing composition ratio, type and molecular weight of polydiols in the soft segment preparation step, T_g of PEU can be varied in the broad range of 0–57°C. The synthesized PEUs exhibited shape memory behavior at their transition temperatures. PEUs with hard segment ratio higher than 65 mole percent showed good shape recovery. These findings suggested that it is important to manipulate molecular structure of the copolymer soft segment for a desirable transition temperature and design optimal soft to hard segment ratio in PEU for good shape recovery. Copyright © 2011 John Wiley & Sons, Ltd.