由A_2, B_2和BB’_2型单体合成超支化共聚物──Ⅳ.N-乙基乙二胺、4,4’-三亚甲基二哌啶与二乙烯基砜的共聚反应

将二官能度单体（Ａ_２）和三官能度单体（ＢＢ’２）反应合成超支化聚合物的方法推广应用于共聚反应．用Ａ２——二乙烯基砜（ＤＶ）,Ｂ２——４,４’－三亚甲基二哌啶（ＴＭ ＤＰ）和ＢＢ’２——Ｎ－乙基乙二胺（ＮＤＡ）单体直接反应合成了超支化共聚物．聚合反应时,ＴＭＤＰ和ＮＤＡ的仲胺基与ＤＶ的双键迅速加成,生成一种带有双键和伯胺基的ＡＢ’２型中间体,该中间体进一步聚合得到超支化聚砜胺．用Ｆｏｕｒｉｅｒ变换红外光谱（ＦＴＩＲ）,色－质联用谱（ＬＣ／ＭＳＤ）等测试手段验证了这一反应机理．产物的支化度随着ＴＭＤＰ与ＮＤＡ的加料比增大而减小,因而可通过这种共聚合方法来控制超支化聚合物的支化度．当ＴＭＤＰ与ＮＤＡ的加料比大于或等于４时,产物是半结晶的．     

疏水缔合聚丙烯酰胺的合成及溶液性能研究

水溶性疏水缔合聚合物是在聚合物亲水主链上引入极少量疏水基团(一般小于2ｍｏｌ%)而形成的一种新型水溶性聚合物[1]。由于这类聚合物具有独特的流变性能,因而备受学术界和工业界关注。目前已作为涂料增稠剂[2]和流变改性剂[3]得到了应用,而通过在部分水解聚丙烯酰胺(ＨＰＡＭ)的亲水主链上引入少量疏水单体而形成的疏水缔合聚丙烯酰胺(ＨＡＰＡＭ)则可望克服ＨＰＡＭ耐温、耐盐性差的缺陷[4]而作为新一代水溶性聚合物材料用于油气开采作业[5,6]。由于亲水单体和疏水单体的不相容性,通常通过在反应溶液中加入表面活性剂使亲水单体和疏水单体…     

超支化聚合物制备方法的研究进展

超支化聚合物是一类可以通过一步法来合成的具有高度支化结构的体型大分子.经过二十年的研究,超支化聚合物由于其独特的结构和性能特点以及可实现规模化生产的特点, 已经迅速成为一类重要的和具有广阔应用潜力的高分子材料.本文从单体类型的角度介绍了超支化聚合物的主要制备方法及其发展历程,主要涉及ABx型,AB*型,A2 B3型以及潜在ABx型单体(包括开环聚合和偶合单体法)等,同时论述了各制备方法的优点和局限性 .     

PS／PnBA／PEMA三元互贯网络聚合物（IPN）的合成及动态力学性能的研究

用分段乳液聚合的方式合成的聚苯乙烯／聚内烯酸正丁酯／聚甲基内烯酸乙酯三元互贯网络聚合物（Ｐ８／ＰｎＢＡ／ＰＥＭＡ三元ＩＰＮ）经动态力学谱分析发现：ＩＰＮ的动态力学性能除与单体的加料顺序、单体比例影响聚合物的相容性外，加料的间隔时间对聚合物的相容性有重大影响，①当Ｓ滴加完后再滴加ｎＢＡ的时间（ｔ＿１）＜７０ｍｉｎ，时，动态力学谱有分离的小峰，相容性不够好；②当１４０＞ｔ＿１＞７０ｍｉｎ，时，获得一单峰，三种聚合物达到热力学上的相容；③当１８０＞ｔ＿１＞１４０ｍｉｎ。时，同情况①；④当ｔ＿１＞１８０ｍｉｎ。时，同②。加完ｎＢＡ后，再滴加ＥＭＡ的时间（ｔ＿２）的改变亦有类似情况。此聚合方式及结果均为首次报道。     

在四官能团引发剂存在下的自缩合乙烯基聚合反应制备丙烯酸酯类超支化共聚物

超支化聚合物具有特殊的结构和性能 ,可通过一步法聚合直接制得 ,具有大规模工业应用前景 .近年来 ,超支化聚合物的研究已成为高分子科学的热门课题之一[1～ 3 ] .超支化聚合物的一个主要缺点是它的分子量分布比较宽 .Ｍ櫣ｌｌｅｒ[4] 等通过理论计算指出 ,在聚合体系中加入ｆ个功能基团的分子Ｂｆ[对自缩合乙烯基聚合反应 (ＳＣＶＰ) ,Ｂｆ为ｆ个引发基的引发剂 ;对ＡＢｘ 型单体的缩聚反应 ,为有ｆ个Ｂ官能团的分子 ],可以降低超支化聚合物的分子量分布 ,这一结果已被实验证实[5～ 7] .我们用ＭｏｎｔｅＣａｒｌｏ方法模拟了在多官能团引…     

高枝化聚合物的最新研究进展

高枝化聚合物（dendrigraft）是树枝状聚合物（dendrimer）家族中的新成员,其合成、性质及应用的研究方兴未艾。本文重点介绍了高枝化聚合物的合成方法：偶联法、引发法、大单体法;前两者是发散式聚合法,而后者是收敛式聚合方法。高枝化聚合物与本家族其它聚合物相比：形态上,它的重复单元是侧链聚合物（而非单体）;结构...     

单体极性对甲基丙烯酸甲酯/丙烯酸丁酯/甲基丙烯酸钠无皂乳液共聚合的影响

研究了少量甲基丙烯酸钠（ＮａＭＡ）存在下单体极性对甲基丙烯酸甲酯（ＭＭＡ）／丙烯酸丁酯（ＢＡ）无皂乳液共聚合的影响．单体极性降低，使粒径减小、聚合速率提高、乳液表面张力和粘度降低、粒子表面电荷密度增大、聚合物分子量提高．ＭＭＡ／ＮａＭＡ无皂乳液聚合物只呈现一个玻璃化温度Ｔｇ，ＢＡ／ＮａＭＡ无皂乳液聚合物呈现两个Ｔｇ，ＭＭＡ／ＢＡ比为２∶１～１∶２的ＭＭＡ／ＢＡ／ＮａＭＡ无皂乳液聚合物呈现四个Ｔｇ，这是由于粒子外面相对富含ＯＳＯ－３和ＣＯＯ－基聚合物的亚层溶解了较多的水，使ＢＡ向粒子中心扩散，ＭＭＡ向外扩散，造成组成差异和相分离而引起的．     

单体极性对甲基丙烯酸甲酯／丙烯酸丁酯／甲基丙烯酸钠无皂乳液共聚？…

研究了少量甲基丙烯酸钠存在下单体极性对甲基丙烯酸甲酯／丙烯酸丁酯无皂乳液共聚合的影响。单体极性降低，使粒径减小，聚合整编提高，乳液表面张力和粘度降低，粒子表面电荷密度增大，聚合物分子量提高。ＭＭＡ／ＮａＭＡ无皂乳液聚合物只呈现一个玻璃化温度Ｔｇ，ＢＡ／ＮａＭＡ无皂乳液聚合物呈现两个Ｔｇ，ＭＭＡ／ＢＡ比为２：１－１：２的ＭＭＡ／ＢＡ／ＮａＭＡ无皂乳液聚合物呈现四个Ｔｇ，这是由于粒子外机相对富含ＯＳＯ     

几种反应型相容剂及其在聚合物共混改性中的应用

反应型增容已经成为提高聚合物相容的一个重要手段。甲基丙烯酸缩水甘油配(GMA)、马来酸酐(MAH)和丙烯酸(AA)作为主要的接枝单体己得到广泛应用。本文从GMA、MAH和AA官能化聚合物的作用机理，以及他们作为反应型相容剂，通过“原位”反应增容聚合物共混体系，提高聚合物合金的相容性两个方面，介绍了国内外在反应型增容这一领域内所取得的进展。     

单电子转移活性自由基聚合制备支化聚丙烯酸甲酯的研究

以丙烯酸2-(2-溴异丁酰氧基)乙酯(BIEA)为引发剂单体(inimer),丙烯酸甲酯(MA)为单体,Cu0/CuBr2和N,N,N',N″,N″-五甲基二亚乙基三胺(PMDETA)为催化体系,二甲亚砜(DMSO)为溶剂,在常温(25℃)下通过单电子转移活性自由基聚合(SET-LRP)合成支化聚丙烯酸甲酯.聚合反应过程中,采用气相色谱(GC)、核磁共振(1H-NMR)和三检测体积排除色谱(TD-SEC)等测试手段跟踪分析和表征支化聚合物的结构.研究结果表明,采用SET-LRP方法,铜粉作为催化剂,常温下聚合反应就能快速进行,130 min之内MA的转化率已达99%以上,制备出高分子量支化聚合物.随着反应的不断进行,聚合物支化程度不断提高,相比较同分子量下的线型聚合物其黏度不断下降,Mark-Houwink特征常数α最小可达0.290.此外,低分子量聚合物组分随着反应不断减少,在高单体转化率下,聚合体系中以高支化度的聚丙烯酸甲酯为主.     

Control of polymer topology through transition-metal catalysis: synthesis of hyperbranched polymers by cobalt-mediated free radical polymerization

A novel approach was demonstrated for the synthesis of hyperbranched polymers by direct free radical polymerization of divinyl monomers controlled by a cobalt chain transfer catalyst (1). By controlling the competition between propagation and chain transfer with 1, the free radical polymerization of ethylene glycol dimethacrylate (3) afforded soluble hyperbranched polymers in one pot. The structure of the hyperbranched polymers was confirmed by (1)H and (13)C NMR. The molecular weight and intrinsic viscosity of the hyperbranched polymers were measured by matrix-assisted laser desorption ionization (MALDI) mass spectrometry and size exclusion chromatography (SEC) equipped with triple detectors. The intrinsic viscosities of the hyperbranched polymers are much lower than those of their linear analogues and do not show molecular weight dependence. The unique structure and properties of these hyperbranched polymers combined with the commercial availability of many divinyl monomers and the robustness of free radical polymerization make this new approach attractive for the preparation of new functional materials.     

可控降解超支化聚碳硅氮烷的合成与表征

通过锂化四甲基二乙烯基二硅氮烷分别与甲基氢二氯硅烷和二甲基氢氯硅烷的亲核取代反应合成了AB4和AB2型单体AB4M和AB2M,两种单体通过Karstedt催化剂催化的硅氢加成反应分别生成聚碳硅氮烷PAB4M和PAB2M.单体和聚合物的结构通过FT-IR、1H-NMR、13C-NMR、29Si-NMR和体积排除色谱-多角度激光光散射联用(SEC-MALLS)技术进行了表征,结果表明,单体的结构与设计结构相符合;单体聚合时主要以α-硅氢加成方式为主;聚合物具有超支化结构并由N(Si—C)3链节和大量端基双键组成.PAB4M和PAB2M的重均分子量分别为7800和5860g/mol,分子量分布系数分别为2·54和2·31·对PAB4M稳定性的初步研究表明,该聚合物对氯硅烷和在中性条件下对水稳定,但在HCl水溶液中可以降解,且通过控制HCl浓度可以调节其降解速度,从而实现对其控制降解.     

超支化聚合物研究进展

超支化聚合物由于具有高度文化三维球状结构以及众多的端基,因此显示出与相应线型分子截然不同的性质,如低粘度、无链缠结和良好的溶解性.本文讨论了超支化聚合物的特性与表征,对合成超支化聚合物所用单体以及产物作了详细介绍,旨在引起对该领域的兴趣.     

Aliphatic Hyperbranched Poly（amido amine）s （PAMAMs） ： Preparation and Modification

A series of water soluble aliphatic hyperbranched poly(amido amine)s(PAMAMs) with the same or similar chemical structure of poly(amido amine) dendrimer was successfully synthesized from commercially available AB and Cn types of monomers by one-pot polymerization via the couple-monomer methodology(CMM). The AB type monomer used in this paper was methyl acrylate, and Cn monomers were multi-amino compounds such as ethylenediamine (EDA), diethylenetriamine (DETA), triethylenetetraamine (TETA). tetraethylenepentaamine (TEPA) and pentaethylenehexamine (PEHA). The reaction mechanism was investigated by means of the mass spectra of the reaction intermediates. Adjusting the feed ratio of AB to Cn. hyperbranched polymers with different terminal groups and properties were obtained. FTIR, NMR, DSC. and TGA were used to characterize the polymers. It was found that the polymers‘ properties such as solubility, thermal behaviour and encapsulation capability varied with changing the feed ratio of AB to Cn. Benzoyl and palmitoyl groups were introduced into these macromolecules by acidylation to form amphiphilic hyperbranched polymers which have a high capability to encapsulate water soluble dyes such as Congo red. It is expected that the hyperbranched PAMAMs can play an important role in the industrial applications, such as coatings, cross-linking and phase-transferring agents because of their versatility and availability.     

三元非等活性自缩合乙烯基聚合体系的Z均回转半径

利用Monte Carlo模拟方法研究了由单体、引发单体和引发核组成的三元自缩合乙烯基聚合反应体系. 重点考察了两类活性基团反应活性的差异、引发单体分数、引发核的配比及活性基团数等因素对体系中无核和有核两类超支化高分子Z均回转半径的影响. 结果表明, 这些因素对超支化高分子的结构和尺度影响显著, 因而通过调节有关参数可以实现对超支化高分子结构和尺度的调控.     

Using hyperbranched macromers as crosslinkers of methacrylic networks prepared by photopolymerization

Hyperbranched polymers were modified with terminal methacryloyl groups to be used as crosslinkers. The photoinitiated polymerization of several methacrylic monomers was examined in the presence of the hyperbranched macromers and bis-(2,4,6-trimethylbenzoyl)-phenylphosphine oxide (Irgacure 819^®) as a photoinitiator, upon UV irradiation. The photopolymerization kinetics was systematically studied by fluorescence and photoDSC in real time and in situ. Six types of monofunctional methacrylic monomers, two types of difunctional methacrylic monomers and four types of (meth)acrylate-modified hyperbranched macromers with different structures were employed for series of photopolymerization reactions. The incorporation of the hyperbranched macromers allows to increase the conversion at gelation and thus, final conversion. This behaviour is dependent on monomer and macromer nature and has been explained as due to an increase of the free volume fraction and confirmed by fluorescence. The results indicate that H-bonding and π-stacking induce self-assembly of hyperbranched macromers leading to reaction induced phase separation at the highest concentration of hyperbranched macromer used.     

Hyperbranched copolymers made from A2, B2 and type monomers (iv)--Copolymerization of divinyl sulfone with 4, 4′-trimethylenedipiperidine and N-ethylethylenediamine

The new approach for synthesis of hyperbranched polymers from commercially available A2 and type monomers was extended to synthesize hyperbranched copolymers. In this work, hyperbranched copoly(sulfone-amine) was prepared by copolymerization of divinyl sulfone (A2) with 4,4′-trimethylenedipiperidine (B2) and N-ethylethylenediamine ( ). During the reaction, secon-dary-amino groups of B2 and monomers react rapidly with vinyl groups of A2 monomers within 35 s, generating a type of intermediate containing one vinyl group and two reactive hydrogen atoms. Now the intermediates can be regarded as a new type monomer, which further polymerizes to form hyperbranched copoly(sulfone-amine). The polymerization mechanism was investigated with FTIR and LC-MSD. The degree of branching (DB) of hyperbranched copolymers increased with decreasing the ratio of 4, 4′-trimethylenedipiperidine to N-ethylethyl- enediamine, so DB can be controlled. When the initial mole ratio of B2 to was equal to or higher than four, r≥4, resulted copolymers were semi-crystalline, while copolymers with r＜3 were amorphous.     

Synthesis of a novel one‐pot approach of hyperbranched polyurethanes and their properties

A new method for the synthesis of hyperbranched polymers involving the use of AB_x macromonomers containing linear units have been investigated. Two types of novel hyperbranched polyurethanes have been synthesized by a one‐pot approach. The structures of monomers and polymers were characterized by elemental analysis, ¹H NMR, ¹³C NMR, Fourier transform infrared spectroscopy, gel permeation chromatography, and thermogravimetric analysis. The hyperbranched polymers have been proven to be extremely soluble in a wide range of solvents. Polymer electrolytes were prepared with hyperbranched polymer, linear polymer as the host, and lithium perchlorate (LiClO₄) as the ion source. Analysis of the isotherm conductivity dependence of the ion concentration indicated that these hyperbranched polymers could function as a “solvent” for the lithium salt. The conductivity increased with the increasing concentration of hyperbranched polymers in the host polymer. © 2001 John Wiley & Sons, Inc. J Polym Sci Part A: Polym Chem 40: 344–350, 2002     

Synthesis and characterization of hyperbranched polymers with increased chemical versatility for imprint lithographic resists

Hyperbranched polymers were prepared from a variety of mono‐ and difunctional monomers and used in the development of novel UV‐imprint lithography (UV‐IL) resists. The unique physical and chemical properties of these hyperbranched materials significantly increase the range of molecular systems that could be imprinted. Traditional challenges, such as the use of monomers that have low boiling points or the use of insoluble/highly crystalline momomers, are overcome by the preparation of hyperbranched polymers that incorporate these repeat units. In addition, the low viscosity of the hyperbranched macromolecules and the large number of reactive chain ends overcome many difficulties that are traditionally associated with the use of polymeric materials as imprint resists. Hyperbranched polymers containing up to 12 mol % pendant vinyl groups, needed for secondary crosslinking during imprinting, were prepared with a wide range of repeat unit structures and successfully imprinted with features from tens of microns to ∼ 100 nm. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 6238–6254, 2008