室温原子转移自由基聚合（RT—ATRP）在合成嵌段共聚物中的应用研究进展

室温原子转移自由基聚合较普通自由基聚合有多方面的优点。综述了室温原子转移自由基聚合在合成油溶性、水溶性及两亲嵌段共聚物方面的研究和应用,对室温原子转移自由基聚合及其在合成嵌段共聚物的应用作了展望。     

用ATRP法合成SBS的接枝共聚物

以溴化的SBS(Br-SBS)为大分子引发剂,甲基丙烯酸甲酯为接枝单体,CuBr为催化剂,联二吡啶为配位剂,苯甲醚为溶剂,通过原子转移自由基聚合反应(ATRP)得到SBS—g—PMMA．用FTIR．^1-NMR GCP等分析方法对其结构进行了表征,并讨论了合成条件对反应的影响．     

铜(Ⅱ)-甲基咪唑配合物的合成、结构表征及其在ATRP中的催化活性

以甲基咪唑为配体,合成铜(Ⅱ)-甲基咪唑配合物,并通过元素分析、红外光谱、DSC等进行分析表征.将该配合物作为催化剂成功地进行了MMA的ATRP反应,和苯乙烯的嵌段聚合,证实该化合物作为ATRP催化剂具有催化活性.     

Reverse atom transfer radical polymerization of methyl methacrylate initiated by AIBN/FeCl3/isophthalic acid system

The reverse ATRP of MMA using AIBN/FeCl₃/ isophthalic acid as the initiating system was successfully performed. The new initiating system can be used to synthesize PMMA with high molecular weight and narrow polydis- persity index. The polymerization shows ‘living’/controlled characteristics. Compared with other initiating system used in reverse ATRP, the easy availability and non-toxicity of isophthalic acid make it very attractive.     

聚丙烯酸乙酯-g-聚甲基丙烯酸甲酯接枝共聚物的合成

丙烯酸乙酯与2-溴丙烯酸乙酯乳液共聚合制备了聚(丙烯酸乙酯-co-2-溴丙烯酸乙酯)无规共聚物，用该共聚物作为原子转移自由基聚合的大分子引发剂，进行了甲基丙烯酸甲酯的接枝聚合，制备了聚丙烯酸乙酯-g-聚甲基丙烯酸甲酯接枝共聚物。接枝共聚物的分子量随单体转化率的上升而线性增加。     

温度对RBr/CuBr/2, 2′-联吡啶引发的苯乙烯原子转移自由基聚合的影响

分别采用溴化苄、２－溴丙二酸二乙酯和２－溴－２－甲基丙二酸二乙酯作引发剂,在ＣｕＢｒ／２,２‘－联吡啶配位化合物催化下,进行了苯乙烯的原子转移自由基聚合,在９０￣１３０℃范围内研究了温度对聚合反应级所得聚合物相对分子质量及其分布的影响。实验发现,在温度为１１０℃时聚合速率最大。     

多卤化物引发苯乙烯原子转移自由基聚合官能度的研究

以四氯化碳和三氯乙酸甲酯分别与苯乙烯（St）发生原子转移自由基加成反应,合成了多官能卤化物1-苯基-1,3,3,3-四氯丙烷(TCPP)和2,2,4-三氯-4-苯基丁酸甲酯(MTCPB),然后分别以TCPP和MTCPB为引发剂、氯化亚铜为催化剂、2,2'-联吡啶为配体,进行St的原子转移自由基聚合反应。采用核磁氢谱和凝胶渗透色谱对聚合物结构和分子量进行分析表征,结果表明：聚合物分子量与单体转化率之间存在较好的线性关系;TCPP和MTCPB都是St原子转移自由基聚合的双官能度引发剂。     

Preparation of Chitosan-g-PAMPS in H2O/scCO2 Inverse Emulsion

Chitosan(CS)was successfully modified in supercritical carbon dioxide(scCO2)by grafting method to enhance its water solubility.In this work,a three-arm star-like fluorinated polymer was synthesized by atom transfer radical polymerization(ATRP)method and applied as a surfactant in supercritical carbon dioxide(scCO2).Then 2-acrylamido-2-methyl propane sulfonic acid(AMPS)was grafted onto CS(CS-g-PAMPS)in H2O/scCO2inverse emulsion.The effects of mass ratio of water and surfactants(R w/s)and pressure of scCO2on the grafting reaction were investigated.The grafting rate,particle size,and dispersity in water of CS-g-PAMPS varied greatly as R w/s and pressure of scCO2changed.It could be found that the value of R w/s at 12 and the pressure of scCO2at 30 MPa were the optimum conditions for the grafting reaction.CS-g-PAMPS prepared in this reaction system has higher grafting rate,smaller particle sizes,and better dispersity in water than those prepared via conventional methods.     

一种原位生成的原子转移自由基聚合的新型引发剂

通过元素溴与偶氮二异丁腈（AIBN）在二甲基甲酰胺（DMF）中反应合成了一种新型的原子转移自由基聚合（ATRP）引发剂α-溴代异丁腈（B IBN）,B IBN的DMF溶液（B IBN-DMF）可直接作为引发剂引发甲基丙烯酸甲酯和苯乙烯的原子转移自由基聚合.考察了B IBN-DMF分别与不同的催化体系CuB r/PMDETA,FeC l2.4H2O/MA5-DETA及FeC l2.4H2O/PPh3等相匹配时聚合的情况.动力学研究表明：以ln（[M]0/[M]）对反应时间作图,图线呈直线,证明聚合反应过程符合一级反应动力学.聚合产物分子量分布窄（Mw/Mn=1.1-1.3）.实验结果证实反应具有良好的可控性,不经分离可直接使用B IBN的DMF溶液,B IBN-DMF作为引发剂引发ATRP是一种高效而便捷的方法.     

Water Repellent Finishing on Cotton Fabric via Atom Transfer Radical Polymerization

In order to enhance the water repellence property of cotton fabric, cotton fabric was grafted using hexafluorobutyl methacrylate( HFMT) monomer via atom transfer radical polymerization( ATRP) method. Water repellent cotton fabric was successfully prepared, and characterized by scanning electron microscopy( SEM),Fourier transform infrared spectroscopy( FTIR), and X-ray photoelectron spectroscopy( XPS). The SEM images of the HFMT-treated cotton displayed significant difference from the untreated one. FT-IR characterization of the HFMTtreated cotton indicated that HFMT was successfully grafted onto the surface of the cotton fabric. XPS analysis indicated that the fluorine element of the HFMT-treated cotton existing on the surface of the cotton fabric. The surface contact angle test as well as the water repellence rating test showed that the water repellence of the HFMTtreated cotton fabric was much better than that of the untreated cotton fabric. The surface contact angle of the HFMT-treated cotton fabric could reach( 132. 4 ± 2. 2) °,and the water repellence rating could achieve grade 3. The washing durability of the HFMT-treated fabric was also investigated. The surface contact angle of the HFMTtreated cotton fabric could reach( 121. 1 ± 2. 1) ° after 20 washing times. Furthermore, the whiteness, air permeability, breaking strength,and breaking elongation of the HFMT-treated cotton fabric decreased slightly compared with the untreated cotton fabric.Finally,cotton fabric with good water repellence property and excellent washing durability could be obtained with little effect on the intrinsic properties of cotton fabric.