Atom transfer radical polymerization of butadiene initiated by PhCH2Cl/MoCl3(OC8H17)2/PPh3

用苄基氯/辛醇取代的MoCl3/三苯基膦引发体系引发丁二烯聚合,得到聚合物相对分子质量、转化率与聚合时间呈线性关系.结果表明,该催化体系可实现丁二烯的ATRP反应.     

苄氯/MoCl3(OC8H17)2/PPh3引发丁二烯和苯乙烯的原子转移自由基共聚合

研究了以苄氯／MoCl3（OC8H17）2／PPh3,引发丁二烯和苯乙烯的原子转移自由基共聚合,所得聚合物的相对分子质量与转化率的增大呈线性增加,相对分子质量分布约2．0。紫外光谱分析表明,聚合机理符合原予转移自由基共聚合机理。差示扫描量热法分析表明,所得聚合物为无规共聚物。     

PhCH2CVMoCl3（OC8H17）2／PPh3催化丁二烯AT-RP反应

用苄基氯／辛醇取代的MoCl3／三苯基膦引发体系引发丁二烯聚合，得到聚合物相对分子质量、转化率与聚合时间呈线性关系。结果表明，该催化体系可实现丁二烯的AT-RP反应。     

CH_2CHCH_2Cl/MoO_2Cl_2/PPh_3引发丁二烯原子转移自由基聚合(英文)

以MoO2Cl2/PPh3为催化剂、CH2CHCH2Cl为引发剂,引发丁二烯进行原子转移自由基聚合,并用称量法、凝胶渗透色谱、核磁共振氢谱和傅里叶变换红外光谱对聚合产物的产率、相对分子质量及其分布和化学结构进行表征。结果表明,聚合产物的数均分子量与单体转化率呈线性增加关系,分子量分布较窄(1.4～1.6),聚合反应具有活性聚合特征,符合原子转移自由基聚合机理,所得聚丁二烯呈无规结构。     

原子转移自由基聚合研究进展

综述了原子转移自由基聚合的研究进展。     

原子转移自由基聚合研究进展

原子转移自由基聚合(ATRP)反应是实现活性聚合的一种颇为有效的途径,可以合成分子量可控、分子量分布窄的各种聚合物.介绍了ATRP的研究进展,包括ATRP反应的特点、聚合反应机理、应用、研究现状及前景展望.     

三氯乙酸引发的苯乙烯原子转移自由基聚合(英文)

采用三氯乙酸为引发剂,在ＣｕＣｌ／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。结果表明,聚苯乙烯的数均相对分子质量随单体转化率的提高呈线性增长,相对分子质量分布较窄（Ｍｗ／Ｍｎ＝１．３０～１．４０）。     

普通自由基引发剂存在下的原子转移自由基聚合(英文)

一种首先使聚合体系在６５～７０℃反应１０ｈ,然后再升温至１３０℃发生聚合反应的新聚合方法可以使苯乙烯在低的ＡＩＢＮ／ＣｕＣｌ２摩尔比下实现原子转移自由基聚合,而且苯乙烯活性聚合的可控程度与ＡＩＢＮ／ＣｕＣｌ２的摩尔比无关。     

Atom transfer radical polymerization of butadiene initiated by PhCH2Cl/MoCl3(OC8H15)2/PPh3

用苄基氯/辛醇取代的MoCl3/三苯基膦引发体系引发丁二烯聚合,得到聚合物相对分子质量、转化率与聚合时间呈线性关系.结果表明,该催化体系可实现丁二烯的ATRP反应.     

用偶氮二异丁腈/MoCl_3(OC_8H_(17))_2/三苯基膦催化苯乙烯-丁二烯反向原子转移自由基共聚合(英文)

以MoCl3(OC8H17)2/三苯基膦作为催化剂,用偶氮二异丁腈引发苯乙烯与丁二烯的反向原子转移自由基共聚合,分别通过称重法、凝胶渗透色谱分析及核磁共振分析对聚合物的产率、相对分子质量及其分布和结构进行了测定和表征。结果表明,所得聚合物的相对分子质量与单体转化率呈线性增加关系,相对分子质量分布较宽(多分散性指数为1.7～2.0),表明该反应具有活性特征。反应溶液的紫外可见光谱分析表明该聚合机理符合反向原子转移自由基共聚合机理。所得丁二烯-苯乙烯共聚物为无规共聚物。     

Atom transfer radical polymerization of butadiene using MoO2Cl2/PPh3 as the catalyst

Atom transfer radical polymerization has been used to successfully synthesize polybutadiene. This was achieved by using MoO₂Cl₂/triphenyl phosphine as the catalyst and the various organic halide compounds such as methyl‐2‐chloropropionate, CCl₄, 1,4‐dichloromethyl benzene, 1‐phenylethyl chloride, and benzyl chloride as initiators. The monomer conversion increased up to 50% with polymerization time. The polydispersity indices of the polymers were as high as above 1.5. However, the polymerizations were controlled and the polydispersity indices of the polymers were less than 1.5 throughout the polymerizationin reverse atom transfer radical polymerization. The chemical structure of the polymer obtained was characterized by ¹HNMR and FTIR. The valency states of molybdenum in this reactive system were detected by UV–vis spectra. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 104: 3517–3522, 2007     

Reverse atom transfer radical polymerization of styrene initiated with AIBN/Ni ( naph ) 2/PPh3 catalyst system

以AIBN/Ni(naph),/PPh3为均相引发剂引发苯乙烯聚合,所得试样相对分子质量与转化率呈线性增加,相对分子质量分布约为1.5.紫外光谱分析表明,聚合机理为反向原子转移自由基聚合.     

添加剂对MoCl3(OC8H17)2-Al(OPhCH3)(i-Bu)2催化丁二烯聚合的影响

研究了3种添加剂对钼系催化丁二烯聚合活性和产物相对分子质量及其分布的影响.结果显示,3种添加剂都能使体系的聚合活性提高;加入方式以Al(OPhCH,3)(i-Bu)2-MoCl3(OC8H17)2-添加剂为好.三者对聚合物的1,2-结构含量均无太大影响.其中α-氯代甲基丙酸酯使产物相对分子质量下降、相对分子质量分布变宽,因此其可在适当范围内用作相对分子质量调节剂.     

Atom transfer radical polymerization of styrene initiated by bromoacetylated syndiotactic polystyrene macroinitiator

Atom transfer radical polymerization of styrene was conducted with bromoacetylated syndiotactic polystyrene as macroinitiator and copper bromide combined with N,N,N′,N′,N′‐pentamethyldiethylenetriamine as catalyst. A two‐stage process has been developed to synthesize the macroinitiator. First, syndiotactic polystyrene (sPS) was functionalized in the side phenyl rings with acetyl groups using the Friedel–Crafts reaction; second, the acetyl groups were converted to bromoacetyl groups by an acid‐catalyzed halogenation reaction. The initiator was found to be active in the polymerization of styrene, leading to the production of graft chains with well‐defined structure. The molecular weight and molecular weight distribution of the graft chains were determined using gel permeation chromatography after cleaving from the sPS backbone using peroxide acid oxidation followed by hydrazine‐catalyzed hydrolysis. The results indicated that the polymerization process was characteristic of a ‘living’ nature. Copyright © 2007 Society of Chemical Industry     

均相Nd(vers)3/Al(i-Bu)2H/Al(i-Bu)2Cl催化聚合异戊二烯

采用A l(i-Bu)2C l(简称C l)、Nd(vers)3(简称Nd)和A l(i-Bu)2H(简称A l)在少量异戊二烯(Ip)存在下,Nd与A l在50℃下反应后,再与C l作用,可配制成均相高效催化剂体系。考察了Nd和A l二组分陈化时间、Nd和A l、C l三组分陈化时间、A l/Nd(摩尔比)、C l/Nd(摩尔比)、聚合温度及溶剂对催化剂相态和Ip聚合的影响。结果表明,上述反应因素对催化剂的相态和产物微观结构均无影响,聚异戊二烯(PI)的顺式-1,4-结构摩尔分数在95.0%以上;Nd和A l二组分陈化时间应控制在10 m in之内;Nd、A l和C l三组分陈化时间对PI收率无影响。当A l/Nd为15或C l/Nd为1.0时,均相Nd/A l/C l催化剂体系仍具有高的聚合活性。当聚合温度为30~70℃时,提高温度可提高PI收率;以环己烷替代或部分替代己烷可提高PI收率。     

Atom transfer radical polymerization of styrene initiated by 2-(4-chloromethyl-phenyl)-benzoxazole with high activity and fluorescent property

Functionalized polystyrene (PSt) was synthesized utilizing atom transfer radical polymerization (ATRP), which was conducted by using 2-(4-chloromethyl-phenyl)-benzoxazole (CMPB) as initiator, CuCl/PMDETA as catalyst, and cyclohexanone as solvent. The mechanism of ATRP was proved by characterizing the structure of PSt via ¹H NMR and preparing of PSt-b-PMMA block copolymer. The polymerization showed first order with respect to monomer concentration and relatively narrow polydispersity (M_w/M_n range from 1.30 to 1.50). Factors such as different reaction temperatures, mole ratio of monomer to initiator and so on, which can affect the ATRP system, were discussed in the paper. Moreover, CMPB showed high activity and could initiate styrene polymerization even at ambient temperature. The optical property of initiator was well preserved in the obtained PSt, and the end-functionalized PSt exhibited strong fluorescent emission at 351 nm.