大分子引发－转移－终止剂

大分子引发－转移－终止剂杨文君，李俊柏，沈家骢（青岛化工学院橡塑工程研究所，青岛，２６６０４２）（吉林大学化学系，长春，１３００２３）关键词聚苯乙烯，聚丙烯酰胺，嵌段共聚，扩链反应，引发－转移－终止剂含有二乙基二硫代氨基甲酸基的有机硫化物或大分子，在...     

聚对苯二甲酸乙二醇酯和聚对苯二甲酸丁二醇酯化学扩链反应

综述了用于聚对苯二甲酸乙二醇酯（ＰＥＴ）、聚对苯二甲酸丁二醇酯（ＰＢＴ）化学扩链反应的羧基加成型和羟基加成型扩链剂，以及缩合型扩链反应、羧基加成型扩链反应和羟基加成型扩链反应、羧羟基同时加成型扩链反应。讨论了扩链反应、反应特性和扩链产物的性能，并简要介绍了国内研究概况。参考文献２０篇。     

以双硫酯为链转移剂的活性自由基聚合

合成并研究了两种双硫酯链转移剂的纯化方法 ,进行了多种单体以双硫酯为链转移剂的活性自由基聚合及嵌段共聚 .发现以PhC(S)SC(CH3) 2 Ph为链转移剂的效果比PhC(S)SCH(CH3)Ph好 ,聚合产物的多分散性系数较小 .引发剂与链转移剂的摩尔数比为 1∶3 5～ 1∶4 2时 ,得到多分散性系数小 ,实测分子量与理论分子量相近的聚合产物 .聚合物的分子量随时间和转化率的增加而增加 ,加入第二单体形成嵌段共聚物 ,具有活性聚合特征 .聚甲基丙烯酸酯大分子引发剂引发丙烯酸酯单体聚合时 ,聚合速度最快 .     

Modification of poly(propylene carbonate) with chain extender ADR-4368 to improve its thermal,barrier, and mechanical properties

Melt blending with the application of epoxy compound ADR-4368 as a chain extender was used to chemically modify polypropylene carbonate (PPC). ¹H nuclear magnetic resonance spectroscopy (¹H NMR), thermogravimetric analysis (TGA), differential scanning calorimetry (DSC), and tests using a universal material testing machine, a gas permeability tester, a water vapor permeability tester and other instruments were used to assess changes in the chemical structure, thermal and mechanical properties, and barrier efficacy of PPC before and after modification.The epoxy group in ADR-4368 reacted with the terminal hydroxyl group in PPC, considerably enhancing its mechanical properties, thermal stability and barrier efficacy to O₂ and CO₂. With the addition of 1% ADR-4368, the glass transition temperature of PPC was increased from 17 °C to 26.9 °C, while the thermal decomposition temperature (T_−5%) of PPC was increased from 177.3 °C to 240.6 °C. Moreover, the tensile strength of the modified PPC was improved from 3.3 MPa to 20.7 MPa.     

PREPARATION OF PERFLUOROOCTANOYL-MODIFIED POLY(VINYL-ALCOHOL)S AND THEIR ADSORPTION AT AN AIR-WATER INTERFACE

Perfluorooctanoyl modified poly(vinyl alcohol)s (FPVA) were prepared by means of substituting a small amountof hydroxyl groups on the backbone of poly(vinyl alcohol), for which the initial degree of polymerization is equal to 1750.The substitution extent, defined by the number of substituting units in a chain, for the four FPVA samples was in the range of0.5-5 perfluorooctanoyl groups per chain. The FPVA samples with the highest substitution extent still had good solubility inwater. It was shown by experimental measurement at 30.0±0.1℃ that the surface tension of the aqueous solution of thehighest substituted FPVA decreased to 16.6 mN/In at a higher concentration, e.g about 0.1 g/mL. Obviously,macromolecules of FPVA exhibit a very strong tendency to adsorb at the air-water interface, because the hydrophobicperfluorooctanoyl groups in FPVA have a very high surface activity as they are in small molecular fluorinated surfactants.The chain conformation of such a model polymer adsorbed on the air-water interface was also discussed.     

A Germanate Compound Constructed from Dissymmetric Ge7 Chains and Metal Complexes

Abstract. A novel germanate compound, |[Ni(dien)₂]₃(H₂O)₃|[Ge₇O₁₃F₅]₂(designated JU‐85, dien = diethylenetriamine), was solvothermally synthesized. The structure of JU‐85 was determined by single‐crystal X‐ray diffraction and further characterized by powder X‐ray diffraction, inductively coupled plasma, infrared spectroscopy, elemental analysis, and thermogravimetric analysis. JU‐85 has dissymmetric chains constructed from diagonally linked Ge₇ building units and various Ni(dien)₂²⁺ complexes formed in situ during the synthesis. Compared with its structural analogue, FJ‐6, JU‐85 contains less complex cations and different host‐guest assembly. Besides the diagonal linkage in JU‐85, other dissymmetric linkages of Ge₇ building units were enumerated, which could be used as the stereogenic centers for the design of novel chiral germanate compounds.     

Chain Conformation and Local Rigidity of Soluble Polyimides(Ⅱ): Isomerized Polyimides in THF

Two soluble isomerized polyimides(PIs)synthesized from 2,2′-bis(3,4-dicarboxyphenyl)hexafluoropropane dianhydride(6FDA)with either 2,2′-dimethylbenzidine(2,2′-DMB)or 3,3′-DMB were investigated by means...     

Three Octacyanometallate‐Based LnIII–MV (Ln = La,Ce; M = Mo,W) Bimetallic Assemblies with a One‐Dimensional Rope‐Ladder Chain Structure

Three octacyanometallate‐based hetero‐bimetallic complexes, [Ln(H₂O)₄(CH₃CN)₂][M(CN)₈] · CH₃CN [Ln = La, M = Mo( 1 ), W( 2 ); Ln = Ce, M = W( 3 )], were synthesized and characterized structurally. Single‐crystal X‐ray analysis reveals that 1 – 3 are isomorphous and consist of infinite one‐dimensional (1D) 3,3 rope‐ladder chains, in which the 12‐membered puckered square Ln₂M₂(CN)₄ is the basic building unit. The 1D chains are further linked through interchain hydrogen bonds, resulting in a three‐dimensional (3D) supramolecular network.     

A stochastic model for the HIV epidemic in homosexual populations involving age and race

In this paper, we derive a stochastic model for the HIV epidemic in homosexual populations involving age and race. To account for effects of different mixing patterns, a low risk selection rule is introduced. The model is then formulated in terms of chain multinomial distributions by means of which the means are derived. Some simulation studies by computer indicate clearly that age and race have a significant impact on the HIV epidemic.