聚(苯乙烯-丙烯酸)-氯化铜配合物膜的合成及表征

将聚(苯乙烯-丙烯酸)(PSAA)(MW＝3500)与氯化铜在异丙醇溶液中反应得到一种配位聚合物膜--聚(苯乙烯-丙烯酸)-氯化铜(PSAA-Cu(Ⅱ))．以ESR，FT-IR，XPS，电导率，元素分析及DMTA等方法对此配合物膜进行表征，确定了组成与结构．结果表明，配位聚合物的中心离子Cu^2 与二个链节单元上的羧基发生配位，从而引起进一步的交联作用，导致玻璃化转变温度和耐热性能的提高．     

引发甲基丙烯酸甲酯聚合的聚丙烯酰胺－氯化铜配合物膜催化剂表征

考察甲基丙烯酸甲酯在室温Ｎａ２ＳＯ３水溶液的聚合能力，发现在该溶液添加聚丙烯酰胺（ＰＡＡｍ）－氯化铜（ＣｕＣｌ２）配合物膜以组成ＰＡＡｍ－ＣｕＣｌ２膜／Ｎａ２ＳＯ３催化引发系是必不可少的，采用ＥＳＲ、ＩＲ、ＸＰＳ和电导率等手段研究该体系催化剂的表面结构，结果表明，膜的单位面积平均含铜量在一定范围内和配位体种类等对催化活性有显著影响，即催化性能与催化剂的表面结构紧密相关。     

取代茚基稀土配合物/添加剂体系催化丙烯腈聚合

研究了取代茚基稀土配合物 /添加剂体系对丙烯腈的聚合 ,发现季胺盐及芳氧钠是取代茚基二价稀土配合物催化丙烯腈聚合的有效添加剂 ,其中Me3NC1 6 H33Br效果最好 ,5种二价稀土配合物 (C5H9C9H6 ) 2 Yb (THF) 2 ,(C5H9C9H6 ) 2 Sm (THF) 2 ,KSm (C5H9C9H6 ) 3(THF) 3,(PhCH2 C9H6 ) 2 Sm(THF) 2 和 (CH3CH2 C9H6 ) 2 Sm (THF) 2 与Me3NC1 6 H33Br构成的催化体系对于丙烯腈聚合都显示出好的催化活性。对(C5H9C9H6 ) 2 Yb(THF) 2 /Me3NC1 6 H33Br体系而言 ,在丙烯腈中当催化剂用量为 2× 10 - 5mol·g - 1时 ,丙烯腈聚合的最大转化率为 61%。     

二（2,6—二叔丁基—4—甲基苯氧基）钐配合物催化丙烯腈聚合

首次报道用稀土有机配合物作为单组份催化剂催化丙烯腈聚合，研究了聚合条件对标题化合物的催化活性和所得聚丙烯腈的分子量及其结构的影响。     

引发甲基丙烯酸甲酯聚合的聚丙烯酰胺－氯化铜配合物膜催化剂表征

考察甲基丙烯酸甲酯在室温Ｎａ２ＳＯ３水溶液的聚合能力，发现在该溶液添加聚丙烯酰胺（ＰＡＡｍ）－氯化铜（ＣｕＣｌ２）配合物膜以组成ＰＡＡｍ－ＣｕＣｌ２膜／Ｎａ２ＳＯ３催化引发体系是必不可少的．采用ＥＳＲ、ＩＲ、ＸＰＳ和电导率等手段研究该体系催化剂的表面结构．结果表明，膜的单位面积平均含铜量在一定范围内和配位体种类等对催化活性有显著影响，即催化性能与催化剂的表面结构紧密相关．     

二价芳氧钐配合物催化苯乙烯聚合

二价芳氧钐配合物催化苯乙烯聚合齐贵中扈晶余＊沈琪（中国科学院长春应用化学研究所稀土化学与物理开放实验室长春１３００２２）（苏州大学化学系苏州）关键词钐配合物，苯乙烯，聚合１９９６－０５－１８收稿，１９９６－１０－３０修回国家科委攀登计划及国家自然科学...     

二茚基钇-铝双金属配合物催化丙烯腈聚合

丙烯腈 (AN)聚合通常采用自由基和阴离子聚合两种 .它们存在催化剂活性低 ,用量大等缺点 .关于丙烯腈的配位聚合研究报道则较少 .最近 ,有报道发现二价稀土化合物可以催化丙烯腈聚合 ,但催化活性较低[1 ,2 ] .本文以二茚基钇 -铝双金属配合物 (C9H7) 2 Y(μ- Et) 2 Al Et2(以下以 Y- Al代表 )为 AN聚合催化剂 ,发现它单独可以催化 AN聚合 .当外加酚钠(Ph ONa)时 ,可以大大提高聚丙烯腈 (PAN)的产率及分子量 .研究了单体浓度、催化剂浓度、温度、时间等对 AN聚合的影响 ,并对其引发机理进行了研究 .Y- Al的合成及聚合方法见文献 [3…     

聚(苯乙烯-丙烯酸)载体铁邻菲啰啉(5-硝基邻菲啰啉)配合物的合成及其对丁二烯聚合的催化活性

合成了不同邻菲啰啉(phen)含量的聚(苯乙烯-丙烯酸)载体铁邻菲啰啉配合物(SAAC·Fe·phen)和不同5-硝基邻菲啰啉(Nphen)含量的聚(苯乙烯-丙烯酸)载体铁5-硝基邻菲啰啉配合物(SAAC·Fe·Nphen)。元素分析和红外结果证明SAAC·Fe·phen具有下面的结构:SAAC·Fe·phen-(i-Bu)_3Al二元体系的催化效率是SAAC·Fe-phen-(i-Bu)_3Al三元体系的2倍,是小分子铁的400倍。在SAAC·Fe·phen和SAAC·Fe·Nphen体系中,当phen(或N pnen)/Fe的摩尔比为0.7左右时催化活性最高。催化活性随着Al/Fe摩尔比的增大而升高,但当Al/Fe摩尔比大于70以上活性趋于恒定,和小分子铁催化荆相比这种高分子铁催化剂可以提高聚合温度。     

η6-苯乙烯二羰基(三苯基膦)铬配合物的合成与聚合

以η＾６－苯乙烯三羰基铬为原料,通过多步配体取代反应,合成了金属有机单体η＾６－苯乙烯二羰基（三苯基膦）铬配合物,经元素分析,ＩＲ和＾１Ｈ－ＮＭＲ进行了结构分析。研究了它在自由基引发下的聚合反应,结果表明强电子给体三苯基膦取代羰基配体可以改善配合物的聚合活性。     

二（叔丁基环戊二烯基）钕甲基配合物催化丙烯腈聚合

二（叔丁基环戊二烯基）钕甲基配合物催化丙烯腈聚合任劲松，扈晶余，沈琪（中国科学院长春应用化学研究所稀土化学与物理开放实验室长春１３００２２）（苏州大学化学系苏州）关键词丙烯腈，配位聚合，钕配合物丙烯腈聚合通常采用ＢＦ＿３、ＴｉＣｌ＿４、过氧化苯甲酰￣...     

海藻酸酮膜表面的配位结构及催化MMA聚合的性能

将海藻酸钠(SA)与CuCl2.2H2反应得到一种配位聚合物海藻酸酮(Cu-An)。以ESR、电导率、IR和SPS方法对此配位聚合物进行表征,确定了组成与结构：同时研究了甲基丙烯酸甲酯(MMA)在该配位聚合物膜、HSO3^-和水体系催化引发作用下的聚合反应历程。结果表明,配位聚合物的中心离子Cu^2^+与两个海藻酸(An)链节单元上的两个羧羟基氧原子和两个离解氢原子的羧羟基氧原子以共价型配位,配位数为4.MMA在上述的催化引发体系中是按照自由基加聚反应历程进行聚合的,PMMA呈无规结构。Cu-An在催化引发体系中起着催化剂的配位催化作用。     

聚丙烯酰胺-CuCl~2膜表面结构及对醋酸乙烯酯 聚合催化性能研究

根据IR,ESR,XPS和电导率的测试结果推定,在催化剂聚丙烯酰胺-CuCl~2膜表面上,1个Cu^2^+与聚丙烯酰胺4个链节单元配位,产生σ配位键而交联,形成疏水性的聚丙烯酰胺-Cu(Ⅱ)配位聚合物膜.从该膜的X射线光电子能谱中的Shake-up效应得知,膜表面的Cu^2^+具有高自旋态电子构型,其缺位处与醋酸乙烯酯,Na~2SO~3配位活化,并产生自由基氢,从而在室温Na~2SO~3水溶液体系(pH=7)中能催化引发醋酸乙烯酯按自由基加聚反应历程进行聚合,诱导期3min20s,得率75%。     

Synthesis and characterization of multiarm (Benzoin-PS)m-polyDVB star polymer as a polymeric photoinitiator for polymerization of acrylates and methacrylates

In this study, a new benzoin-based multi-arm star polymer was synthesized by using ATRP, and characterization was achieved by spectrophotometric and chromatographic methods. Obtained multiarm (Benzoin-PS)_m-polyDVB star polymer was employed as a polymeric photoinitiator for polymerization of methacrylates and acrylates. Photophysical properties of this initiator were determined by fluorescence and phosphorescence measurements, the phosphorescence lifetime was calculated as 29 ms hence the lowest triplet state nature was n-π* character, and laser flash photolysis technique was additionally used to get more information about triplet state and triplet lifetime which was calculated as 1.34 ms. Photokinetics of difunctional acrylate such as HDDA was studied with a multi-arm (Benzoin-PS)_m-polyDVB star polymeric initiator using Photo-DSC.     

Viscosity effects in cobaloxime‐mediated catalytic chain‐transfer polymerization of methacrylates

The effect of bulk viscosity on the cobaloxime‐mediated catalytic chain‐transfer polymerization of methacrylates at 60 °C was investigated by both the addition of high molecular weight poly(methyl methacrylate) to methyl methacrylate polymerization and the dilution of benzyl methacrylate polymerization by toluene. The results indicate that the bulk viscosity is not directly linked to the chain‐transfer activity. The previously measured relationship between chain‐transfer‐rate coefficient and monomer viscosity therefore probably reflects changes at the molecular level. However, the results in this article do not necessarily disprove a diffusion‐controlled reaction rate because cobaloxime diffusion is expected to scale with the monomer friction coefficient rather than bulk viscosity. Considering the published data, to date we are not able to distinguish between a diffusion‐controlled reaction rate or a mechanism directly affected by the methacrylate substituent. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 782–792, 2002; DOI 10.1002/pola.10152     

Criteria for the preparation of cross-linked poly(meth)acrylate microparticles by solution free radical polymerization

Cross-linked polymer microparticles (CPMs) with nanoscopic size were synthesized from the free radical polymerization of acrylate/diacrylate mixtures or of their methacrylate counterparts. The syntheses were carried out in solution, and the study of the influence of the solvent on the CPM characteristics led to the definition of reliable criteria for the obtention of true, soluble, individualized microgels and for avoiding macro-gelation, when starting from any desired monomer combination. Two main parameters could be pointed out: first, the probability of propagation of the growing radicals, q, (or the kinetic chain length λ = 1/1 − q) that must be kept below a certain threshold value in order to prevent macrogelation; q may be adjusted by playing on the monomer, initiator and transfer agent concentrations. The second essential criterion is the ability of the copolymer for auto-stabilization in the chosen solvent (that may be adjusted by the use of a suitable stabilizing co-monomer in case the quality of the solvent would not be sufficient), in order to avoid flocculation and interparticular reactions. By controlling these two parameters, the preparation of CPMs becomes possible over a wide range of concentration and composition.     

Quinone transfer radical polymerization (QTRP) of styrene: Catalysis by different metal complexes

Styrene has been polymerized by a Quinone Transfer Radical Polymerization (QTRP) based on the redox reaction of an ortho‐quinone and a metal catalyst. Several metal acetylacetonates have been tested in this work. The radical polymerization of styrene is largely controlled when phenanthrenequinone (PhQ) is used with catalytic amounts of Co(acac)₂, Ni(acac)₂, Mn(acac)_{2 or 3}, and Al(acac)₃. As a rule, in the presence of all these metallic complexes, the polystyrene molar mass increases with the monomer conversion, and polydispersity (M_w/M_n) is in the 1.3–1.6 range (at least until 40% monomer conversion). Styrene polymerization has also been resumed by polystyrene chains prepared by QTRP. In the specific case of manganese acetylacetonates, an amine or phosphine ligand has to be added for the control to be effective. Finally, two mechanistic hypotheses have been proposed, depending on whether the oxidation state of the metal can be easily changed or not. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 2723‐2733, 2005     

电化学聚合漆酚及其钬配合物研究

提纯过的漆酚在Na2 SO4的乙醇 /水溶液中用恒电位法 ,以铂为研究电极 ,其电位不能低于 0 6 80V(vs.SCE)进行电化学聚合 ,获得电化学聚合漆酚(EPU) ,探讨了其较适宜的聚合方式及反应条件 .利用EPU与氯化钬的异丙醇溶液作用 ,得到聚合漆酚钬配合物 (EPU -Ho3 + ) .采用红外光谱、紫外 -可见光光谱、XPS光电子能谱、动态机械热分析 (DMTA)、差热 -热重 (DTA -TG)以及磁化率等手段进行表征 ,确定其每个钬离子与EPU分子中三个链节单元的羟基发生配位 .研究结果表明 ,钬含量达 14 0 8% ,配合物的电阻为 1 3× 10 11Ω(EPU为 7 9× 10 10 Ω) ,出现反铁磁性相互作用 ,因配位作用而使配合物进一步交联 ,导致玻璃化转变温度和耐热性能得到提高 .     

Novel miktofunctional initiator for the preparation of an ABC‐type miktoarm star polymer via a combination of controlled polymerization techniques

An ABC‐type miktoarm star polymer was prepared with a core‐out method via a combination of ring‐opening polymerization (ROP), stable free‐radical polymerization (SFRP), and atom transfer radical polymerization (ATRP). First, ROP of ϵ‐caprolactone was carried out with a miktofunctional initiator, 2‐(2‐bromo‐2‐methyl‐propionyloxymethyl)‐3‐hydroxy‐2‐methyl‐propionic acid 2‐phenyl‐2‐(2,2,6,6‐tetramethyl‐piperidin‐1‐yl oxy)‐ethyl ester, at 110 °C. Second, previously obtained poly(ϵ‐caprolactone) (PCL) was used as a macroinitiator for SFRP of styrene at 125 °C. As a third step, this PCL–polystyrene (PSt) precursor with a bromine functionality in the core was used as a macroinitiator for ATRP of tert‐butyl acrylate in the presence of Cu(I)Br and pentamethyldiethylenetriamine at 100 °C. This produced an ABC‐type miktoarm star polymer [PCL–PSt–poly(tert‐butyl acrylate)] with a controlled molecular weight and a moderate polydispersity (weight‐average molecular weight/number‐average molecular weight < 1.37). The obtained polymers were characterized with gel permeation chromatography and ¹H NMR. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 4228–4236, 2004     

4-溴苯酚的酶催化聚合及其抗自由基性能

在有机溶剂和缓冲溶液的混合体系中对4-溴苯酚的酶催化聚合反应进行了研究;利用红外光谱分析了产物的分子结构.结果表明,有机溶剂与缓冲溶液配比对反应产率和产物分子量影响较大.以乙醇为有机溶剂,当其与磷酸盐缓冲溶液(pH=7)体积比为1∶3时,反应产率较高,而聚合产物的分子量随反应体系中乙醇含量的增加呈上升趋势.与此同时,4-溴苯酚聚合物分子链含有苯-苯连接和苯-氧连接两种结构;4-溴苯酚聚合物的热分解温度在250℃左右,具有较好的热稳定性;且其对1,1-二苯基-2-三硝基苯肼(DPPH)自由基和2,2′-联氮双(3-乙基苯并噻唑啉-6-磺酸)二铵盐(ABTS)阳离子自由基均表现出明显的抑制作用.