Polyisobutylene supports—a non-polar hydrocarbon analog of PEG supports

Synthetic routes to terminally functionalized polyisobutylene oligomers useful as supports in synthesis and catalysis are discussed and described. Such hydrocarbon polymers serve as highly soluble non-polar analogs of well known poly(ethylene glycol) supports for synthesis and catalysis with the difference that they are separated after a reaction by an extraction with alkane solvent.     

Investigations of the Mechanism of Alternating Copolymerization with Charge-Transfer Interaction of the Monomers

The applicability of the method of Giese to the measurement of the influence of monomer reactivity is examined. The reaction of alkyl mercuric salts with sodium borohydride permits the production of alkyl (cyclohexyl and butyl) radicals. Since hydrogen radicals are present in high concentration, the addition of alkenes to the reaction mixture leads to radicals from the alkenes. Further addition of alkene (polymerization) can be nearly completely excluded in this way. The composition of the reaction products is determined by gas chromatography. The addition rate of the alkenes relative to styrene allows correlation with the e value of the Q-e scheme of Alfrey and Price. The method answers the question of how far addition of the monomer complex occurs in one step or as separate addition of both monomers during copolymerization in the presence of charge-transfer (CT) complexes of the monomers. The investigations are performed by using the styrene/acrylonitrile/ZnCl₂system, and it is demonstrated that the reactivity of the complexed     

Biocompatible,Hemocompatible and Antibacterial Acylated Dextran-g-polyisobutylene Graft Copolymers with Silver Nanoparticles

The novel amphiphilic acylated dextran-g-polyisobutylene(AcyDex-g-PIB) graft copolymers with different branch lengths(M_n,PIB,2600–5800 g/mol) and grafting numbers(G_N, 5–28 per 1000 Dex monosaccharide) were successfully synthesized via the nucleophilic substitution of the hydroxyl(―OH) side groups along AcyDex backbone by the living PIB-THF₄⁺ chains prepared through cationic polymerization. The crystallization of AcyDex backbone in AcyDex-g-PIB graft co...     

SiO2纳米粒子对受限流场下聚异丁烯/聚二甲基硅氧烷共混物相形态的影响

利用显微-光学剪切联用系统构造受限剪切环境,探讨了少量不同表面性质的SiO2纳米粒子的加入对聚异丁烯(PIB)/聚二甲基硅氧烷(PDMS)不相容共混体系分散相形态演变过程的影响.研究结果表明,少量疏水性SiO2纳米粒子的加入可抑制分散相液滴的凝聚,从而抑制珍珠链状及纤维状等超级相形态的形成,使共混物表现为近似本体流体的...     

Simultaneous measurements of velocity and stress distributions in polyisobutylenes using laser-Doppler velocimetry and flow induced birefringence

An experimental device was set up for the synchronous measurement of velocities and stresses in polyisobutylenes using laser-Doppler velocimetry (LDV) and the two-colour flow-induced birefringence method (FIB). The materials investigated are three low molecular polyisobutylenes. Velocity (LDV) and stress (FIB) measurements are performed in the flow entrance region and inside a slit die with a contraction ratio of 1:10. The behaviour of the polyisobutylenes is Newtonian under the flow conditions applied. Therefore, the stresses inside the fluids can be calculated and compared to the stresses experimentally determined. A good agreement in shear and elongational flows was found between the calculated (LDV) and directly measured stresses (FIB). This result demonstrates the applicability of the experimental setup as an optical rheometer that can preferentially be used to measure elongational properties of low viscous fluids.

Soluble polyisobutylene-supported reusable catalysts for olefin cyclopropanation

Polyisobutylene oligomers (PIB) have been used as soluble supports for the immobilization of cyclopropanation catalysts. In addition to simple carboxylate ligands, chiral bisoxazolines have been successfully attached to these heptane-soluble polymers. Their use and recovery has been investigated using cyclopropanation of styrene as an example. An achiral PIB-bound Rh(II) catalyst showed good activity and could be easily recycled nine times using a liquid-liquid biphasic separation technique. PIB-supported bisoxazoline ligands for Cu(I) catalysts were also prepared. These chiral catalysts showed good catalytic activity and stereoselectivity. A chiral ligand prepared from phenylglycine provided the most effective stereocontrol and gave the trans- and cis-cyclopropanation products in 94% ee and 68% ee, respectively. All three PIB-bound chiral bisoxazoline-Cu(I) catalysts prepared could be reused five to six times.     

MeOH/BF_3体系引发异丁烯阳离子聚合反应中水含量及聚合温度的影响

研究了水含量和聚合反应温度Tp 对MeOH BF3体系引发异丁烯 (IB)阳离子聚合反应的转化率、产物的分子量及分子量分布的影响 ,求出在不同水含量条件下的Tp 对聚合物分子量影响的数学方程及相应的聚合度活化能Ep ,以期对体系中存在的微量水加以充分利用 .结果表明 ,[H2 O]和Tp 两者共同影响IB阳离子聚合反应过程及产物的分子参数 .当Tp 由 - 10 0℃升高至 - 5 0℃时 ,聚合转化率先增加到一定值后再减小 ,在- 80℃～ - 70℃范围内出现峰值 .在 [H2 O]较低时 ,Tp 明显影响着聚合产物的分子量及分子量分布 ,Tp 越低 ,分子量越高 ,分子量分布越窄 ;在 [H2 O]较高时 ,Tp 对分子量的影响程度较小 ,说明此时水对聚合反应的影响更为突出 .体系中水含量增大对IB阳离子聚合反应呈现不利作用 ,当 [H2 O]由 1 5× 10 - 3mol L增加至 4 6×10 - 3mol L时 ,Ep 由 - 4 0kJ mol增大至 - 17kJ mol ,说明随着 [H2 O]增大 ,水的负面效应更加明显 ,既促进副反应 ,又阻碍链增长反应 ,增长活化能增大 ,聚合物分子量降低 ,分子量分布变宽 .水的负面作用也随着Tp 升高而变得明显 .     

聚异丁烯基生物惰性弹性体的研究进展

聚异丁烯由于其全饱和结构,有且仅存在碳氢键,所以聚异丁烯基材料大多具有良好的生物稳定性和相容性。近年来关于聚异丁烯基生物惰性弹性体的研究取得了许多的进展,包括PIB-poly(methyl methacrylate)(PMMA)用于骨关节粘合剂、PIB-cyanoacrylate (CA)用于腰椎间盘替换、基于PIB的两亲网络(APNs)用于免疫隔离膜、聚异丁烯基聚氨酯(PU)及聚脲的发展。另外,在poly(styrene-b-isobutylene-b-styrene)(SIBS)生物医用材料方面也取得了重要进展,其中包括SIBS应用于药物释放载体、青光眼导流管、心脏瓣膜以及人工血管等方面。最后,本文也对聚异丁烯基生物惰性弹性体的未来发展进行了展望。     

烯烃可控/活性正离子聚合新方法与新工艺及其应用

<正>离子聚合是高分子科学中重要的聚合方法之一,也是制备聚异丁烯或丁基橡胶等关键材料不可或缺的聚合方法.本文总结了异丁烯、苯乙烯及其衍生物等单体可控/活性正离子聚合的新引发体系、聚合反应特征的调节与转化、水相介质中正离子聚合新方法与新工艺、微观分子混合与正离子聚合新工艺及其用于设计合成异丁烯基聚合物.这些方法与技术是发展高效节能与绿色减排先进聚合物生产技术的重要途径,部分研究成果已在产业化中得到应用与验证.发展可控/活性正离子聚合新体系、新方法与新工艺,为实现绿色低碳高分子化工过程及相关产品工程(新结构、新功能、高性能与高品质)提供了新思路与新技术.