梳形接枝共聚物的合成(Ⅱ)——载体化钌卡宾络合物催化降冰片烯基聚苯乙烯的开环岐化聚合

由石油化工副产C₅馏份提取双环戊二烯(DCPD)、以聚合物负载三氟化硼为催化剂进行DCPD与烯丙基氯(AC)的Diels-Alder反应合成5-氯甲基-2-降冰片烯(NBCH₂Cl),经锂代反应后用以引发苯乙烯的活性阴离子聚合合成了降冰片烯(NB)基聚苯乙烯(PS)大分子环烯单体NB-PS,在聚合物负载钌卡宾络合物[RuCl₂(PPh₃)₂(=C=CHtBu)]催化(引发)作用下进行大分子单体NB-PS的开环歧化聚合(ROMP)合成了梳形接枝共聚物PNB-g-PS.实验结果表明所合成聚合物负载硼、钌络合物催化剂的性能均明显优于对应非负载体.讨论了上述催化剂的聚合物载体效应的机理及温度、溶剂等对活性阴离子聚合反应的影响.     

活性开环歧化合法合成带羧酸酯基功能高分子

由石油化工C5馏分提取得到的粗产品双环戊二烯(DCPD,83.9%)经精馏制成高纯度双环戊二烯(98.9%),解聚后制成环戊二烯(CPD).以CPD、丙烯酸叔丁酯(tBA)为原料经Diels-Alder反应合成得到了一种带叔丁氧羰基的降冰片烯衍生物-2-叔丁氧羰基-5-降冰片烯(BOCN).以钌卡宾络合物RuCl2(PCy3)2(=CHPh)为引发剂进行所合成降冰片烯基单体BOCN的活性开环歧化聚合(ROMP)反应,合成得到一种具有受控分子量及窄分子量分布的带羧酸酯基的反应性高分子.     

双环戊二烯开环歧化聚合反应及合成聚合物性能研究

采用WCl6－ArOH／Et2AlCl（ArOH：2，6-二叔丁基对甲苯酚）催化体系进行了双环戊二烯的开环歧化聚合反应，考察了单体纯度以及催化体系支载化对聚合反应和合成聚合物性能的影响。在极限聚合浓度下，研究了单体与主、助催化剂摩尔比等因素对聚合反应及合成聚合物性能的影响。实验结果表明：单体纯度越高所得聚合物的机械性能越好；催化体系经聚合物支载化后能显著提高催化体系的催化聚合活性及合成聚合物的机械性能。     

卟啉降冰片烯聚合物的合成、表征及性质研究

本文设计合成了卟啉的降冰片烯单体,采用Grubbs催化剂与长链烷基的降冰片烯单体开环易位聚合,直接得到了卟啉降冰片烯聚合物,通过紫外-可见吸收光谱、荧光光谱、电化学等手段研究了卟啉降冰片烯聚合物的性质,与小分子单体相比,所得卟啉高分子共聚物相当好地保持了卟啉应有的光物理、电化学等特性.     

以二氟烷基磺酸修饰的聚降冰片烯为基础的聚合物电解质薄膜的制备

合成了一种新型的二氟烷基磺酰氟单体2-（双环[2.2.1]庚-5-烯-2）-1,1-二氟-2-甲氧基丙基-1-磺酰氟.首先利用二氟甲基2-吡啶基砜和2-乙酰基-5-降冰片烯发生亲核加成反应,在低温下用三氟甲磺酸甲酯保护加成产物中的羟基,之后在KOH/MeOH的条件下脱去吡啶基,得到的二氟亚磺酸盐和Slectfluor试剂反应制得想要的二氟烷基磺酰氟单体.这种新型的二氟烷基磺酰氟单体和不同比例的降冰片烯单体在Grubbs第二代催化剂存在条件下进行开环烯烃复分解聚合（ROMP）,所得的聚合物在碱性条件下水解,再用稀盐酸处理最终制得新型的含有二氟烷基磺酸的聚合物电解质膜.这些新型的聚合物电解质膜具有中等的室温质子电导（12～49mS/cm）.     

钌催化降冰片烯开环移位聚合的研究

CpRuCl(PPh~3)~2/O~2和CH~3OCH~2CH~2CpRuCl(PPh~3)~2/O~2体系对降冰片(NBE)开环移位聚合(ROMP)有活性,降冰片烯的转化率和聚降冰片烯主链双键顺反比与气氛催化剂摩尔比及催化剂本身性质有关。在实验的基础上提出了钌催化降冰片烯开环移位聚合的可能机理。     

降冰片烯开环易位聚合反应的分子量及分子量分布控制

使用Grubbs催化剂催化降冰片烯单体进行开环易位聚合反应, 研究了催化剂搅拌溶解时间、聚合反应的溶剂极性和三苯基膦的加入等反应条件对降冰片烯单体ROMP反应分子量及分子量分布的影响, 从而得到降冰片烯ROMP反应的最佳条件.     

双吡唑亚胺镍/甲基铝氧烷催化降冰片烯的聚合

合成了两种双吡唑亚胺镍配合物: 双-N-(苯基-1-3,5-二甲基吡唑基亚甲基)苯基亚胺二溴化镍(Cat.1)和双-4-甲氧基-N-(苯基-1-3,5-二甲基吡唑基亚甲基)苯基亚胺二溴化镍(Cat.2). 研究了Cat.1/MAO和Cat.2/MAO催化体系对降冰片烯(NBE)单体聚合的催化性能, 考察了各种聚合条件, 如温度、Al/Ni摩尔比及催化剂浓度对降冰片烯的催化效率、单体转化率、聚合物分子量及分子量分布的影响. 研究结果表明, Cat.1/MAO和Cat.2/MAO催化体系对降冰片烯聚合具有较高的催化效率, 可达到105 g PNBE/(mol Ni)数量级, 所得聚降冰片烯(PNBE)的重均分子量在105以上, 分子量分布指数在2左右. 聚合产物的1H NMR和FTIR谱分析结果表明, 该聚合反应是以单体的乙烯基加成聚合机理进行的.     

氯乙酸降冰片烯甲酯制备方法的改进

在环烯烃开环歧化聚合反应(ROMP)中,降冰片烯类是一类应用的最多的单体。为合成具有高反应活性的单体,选择双环戊二烯与烯丙醇隔绝空气下的Diels-Alder反应,产物与α-氯代乙酰氯反应得到氯乙酸降冰片烯甲酯,在实验中对反应的温度、时间、比例等条件进行进一步精确。     

结构规整的高密度两亲性接枝聚合物刷的合成及其自组装研究

大分子单体通过两种可控聚合方法, 即开环易位聚合(ROMP)和原子转移自由基聚合(ATRP)的联用, 合成一种新型两亲性接枝聚合物刷. 具有高环张力的降冰片烯单侧链大分子单体norbornene-graft-poly(ε-caprolactone)/Br (PCL- NBE-Br)首先进行ROMP反应, 生成聚合物主链, 每个单体单元上含有一条PCL链和一个溴官能团; 然后用含溴的ROMP聚合物poly(norbornene)-graft-poly(ε-caprolactone)/Br (PCL-PNBE-Br)作为大分子引发剂引发单体2-(dimethyl- amino)ethyl methacrylate)的ATRP反应, 生成结构明确的高密度两亲性接枝聚合物刷poly(norbornene)-graft-poly(ε- caprolactone)/poly(2-(dimethylamino)ethyl methacrylate) (PCL-PNBE-PDMAEMA), 其主链每个单体单元上均含有一条疏水性PCL接枝链和一条亲水性PDMAEMA接枝链. 最后, 研究此类高密度两亲性接枝聚合物刷的自组装行为, 用动态激光光散射(DLS)研究其在混合溶剂(THF/H2O)中的胶束行为, 考察胶束溶液的浓度以及不同长度的亲水性接枝链对胶束尺寸的影响; 利用透射电镜(TEM)观察胶束为球形, 具有类似线团或草莓状的形态.     

SYNTHESIS OF A COMB GRAFT COPOLYMER VIA RING OPENING METATHESIS POLYMERIZATION CATALYZED BY SUPPORTED RHUTHENIUM CARBENE COMPLEX

Comb graft copolymers (CGC), a special kind of the hyper-branched polymer series, have unique and excellent properties [1,2]. Synthesizing CGC via ring opening metathesis polymerization (ROMP) of cycloolefinyl macromonomer catalyzed (initiated) by the molybdenum carbene complex (Schrock complex) is a newly-developed method [3,4]. Though showing excellent catalytic behavior the complex has the disadvantage of highly moisture and oxygen sensitive and is hence operation-inconvenient. We repor…     

SYNTHESIS OF A COMB GRAFT COPOLYMER VIA RING OPENING METATHESIS POLYMERIZATION CATALYZED BY SUPPORTED RHUTHENIUM CARBENE COMPLEX

5－Chloromethyl-2-norbornene was synthesized via Diels-alder reaction of cyclopentadiene and allyl chloride using a polymer supported boron trifluoride as the catalyst,and was then lithiated and used to initiate a livcing anionic polymerization of styrene to prepare a macromonome,5-polystryl-2-norbornene NB-PS,Comb graft copolymer PNB-g-PS was synthesized via ring opening metathesis polymerization of the macromonomer under the catalysis of ruthenium carbene complex RuCl2(PPh3)2(=CCHtBu)and its polymer supported correspondent.Experimetal results showed that the behavior of both the supported boron and supported ruthenium catalysts are superior to their unsupported counterparts.The possible promotion mechanism of the tailor-made supports is discussed.     

Graft polymerization of epoxide and alternating graft copolymerization of epoxide–acid anhydride onto a polystyrene backbone having an aminimide moiety

Graft polymerization of glycidyl phenyl ether (GPE) and alternating graft copolymerization of GPE–succinic anhydride (SA) onto a polymer‐supported aminimide were examined. The polymer‐supported aminimide was synthesized by radical polymerization of 1,1‐dimethyl‐1‐(2‐hydroxy‐3‐(4‐vinylbenzyloxy)propyl)amine 2‐benzoylimide, which was prepared by the reaction of methyl benzoate with equimolar amounts of 1,1‐dimethyl hydrazine and 4‐glycidylmethylstyrene. This aminimide could initiate the polymerization of GPE and alternating copolymerization of GPE with SA to give the corresponding graft copolymers. © 1999 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 37: 1041–1048, 1999     

Controlled cationic ring‐opening polymerization of cyclic thiocarbonates with ester groups

This work deals with the cationic ring‐opening polymerization of the cyclic thiocarbonates 5‐benzoyloxymethyl‐5‐methyl‐1,3‐dioxane‐2‐thione ( 1 ), 5,5‐dimethyl‐1,3‐dioxane‐2‐thione ( 2 ), and 4‐benzoyloxymethyl‐1,3‐dioxane‐2‐thione ( 3 ). The polymerization was carried out with 2 mol % trifluoromethanesulfonic acid, methyl trifluoromethanesulfonate, boron trifluoride etherate, or triethyloxonium tetrafluoroborate as the initiator to afford the polythiocarbonate with a narrow molecular weight distribution accompanying isomerization of the thiocarbonate group. The molecular weight of the obtained polymer could be controlled by the feed ratio of the monomer to the initiator and increased when the second monomer was added to the polymerization mixture after the quantitative consumption of the monomer in the first stage. The block copolymerization of 2 and 3 was also achieved, and this supported the idea that the cationic ring‐opening polymerization of these monomers proceeded via a living process. The order of the polymerization rate was 3 > 2 > 1 . The cationic ring‐opening polymerization of 1 and 3 involved the neighboring group participation of ester groups according to the polymerization rate and molecular orbital calculations with the ab initio method. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 185–195, 2003     

原子转移自由基法合成八臂星型聚苯乙烯

设计合成了星型聚合物引发剂四(2,2-二氯乙酸)季戊四醇酯(TDCAP), 并通过原子转移自由基聚合合成了八臂星型聚苯乙烯. 用FTIR, 1H NMR和GPC等手段对引发剂和星型高分子的结构进行了表征.     

Poly(silmethylene)-based polymer blends. I. In situ polymerization of 1,3-disilacyclobutanes in silicon-based polymers

The in situ polymerization of 1,1,3,3-tetraphenyl-1,3-disilacyclobutane with or without a catalyst in flexible organo-silicon polymers was demonstrated to provide poly(silmethylene)-based polymer blends. An alternative route, which implies preparation of blends via synthesis of a flexible polymer in the presence of a rigid polymer, was also promising. The resulting polymer blends were characterized by DSC, dynamic mechanical analysis, and solvent extraction. No chemical interaction is observed between component polymers of blends prepared by the in situ bulk polymerization method while formation of block or graft copolymers comprising poly(diphenylsilmethylene) and flexible polymers is suggested when in situ copper-catalyzed polymerization was employed. A morphological difference between samples synthesized by the different methods was suggested by microscopic observation. © 1997 John Wiley & Sons, Inc.     

Controlled Radical Polymerization of Methyl Methacrylate Catalyzed by Hybrid Supported Iron Catalyst

A supported iron catalyst, which was prepared by anchoring FeCl2/FeCl3 on the cross-linking macroporous polyacrylate ion exchange resin, was evaluated via the controlled radical polymerization. When a small amount of CuCl2/ Me6TREN was added, the controllability of the polymerization over the iron-mediated catalyst was significantly improved（Mw/Mn = 1.23-1.73 ）, affording a polymer with a low residual metal via a simple catalyst separation procedure. After suitable regeneration, the supported iron catalyst could also he recycled. UV-Vis analysis showed that the additional copper catalyst could facilitate the radical deactivation process.     

旋光性聚{(+)-甲基丙烯酸-2,5-二[4′-((S)-2-甲基丁氧基)苯基]苄酯}的合成与表征

设计、合成了一个带有横挂三联苯侧基的手性乙烯基单体——(+)-甲基丙烯酸-2,5-二[4′-((S)-2-甲基丁氧基)苯基]苄酯,进行了普通自由基和原子转移自由基聚合反应.所得聚合物具有比单体低30°左右的比旋光度,且在侧基的紫外吸收处呈现明显不同于单体的Cotton效应,说明其主链可能形成了具有相反旋光方向的螺旋构象.在所研究范围内,聚合条件对聚合物的旋光度没有明显的影响.在分子量较小时,聚合物的比旋光度随着分子量的增加而降低,说明主链螺旋构象的贡献在增大,而当分子量达到一定值后,聚合物的比旋光度不再随分子量的增加而显著变化.