超支化分子桥联受阻酚抗氧化剂的合成与表征

以正十八胺为核的1.0代超支化大分子和β-(3,5-二叔丁基-4-羟基苯基)丙酰氯为原料,通过酰胺化缩合反应,合成了一种具有长链烷基和2个受阻酚基团的新型超支化分子桥联受阻酚类抗氧化剂.通过正交实验确定了超支化分子桥联受阻酚类抗氧化剂的最佳合成体系为:3,5-丙酰氯为酰化剂、K_2CO_3为缚酸剂、苯和水为反应溶剂.通过条件优化实验确定了超支化分子桥联受阻酚类抗氧化剂的最佳合成条件为:3,5-丙酰氯与1.0代超支化大分子的物质的量比为6∶1、反应温度为25 ℃、反应时间为12 h、体系苯与水体积比为6∶1、3,5-丙酰氯与缚酸剂K_2CO_3的物质的量比为1∶1,在此条件下,超支化分子桥联受阻酚类抗氧化剂的收率高达75.5%.FT-IR和1H NMR证实了合成抗氧化剂的化学结构与其理论结构相符.超支化分子桥联受阻酚类抗氧化剂在聚乙烯树脂中的抗氧化性能优于抗氧化剂1076,且随着烷基链长度的增加,抗氧化性能增强.     

氢键作用对端羟基超支化聚酯熔体流变性能的影响

以三羟甲基丙烷(TMP)为核,二羟甲基丙酸(DMPA)为支化单体,通过熔融缩聚法合成了第一至五代端羟基脂肪族超支化聚酯,采用旋转流变仪系统地研究了氢键作用对端羟基超支化聚酯熔体流变性能的影响.结果表明,与高代数超支化聚酯相比,低代数超支化聚酯的线性黏弹区较窄,松弛时间更长.无论是稳态剪切测试还是振荡测试,第一、二代端羟基超支化聚酯熔体均表现出假塑性流体的剪切变稀行为,而第三至五代端羟基超支化聚酯熔体则表现为牛顿流体的流变行为.端羟基超支化聚酯的流变行为均不遵循Cox-Merz方程.温度谱的测定发现,低代数超支化聚酯相对于高代数的结晶度更高.流变测试中所出现的现象都与分子间的氢键作用密切相关.     

含芴共轭单元的超支化聚合物的合成及表征

以芴和季戊四醇为初始物,分别合成了具有芴共轭单元和季戊四醇多臂结构的两种聚合单体,进一步采用Suzuki反应合成出一种结构新颖的部分共轭结构的超支化聚合物.利用紫外吸收光谱和荧光发射光谱对聚合物予以表征,结果表明,超支化聚合物具有与模型化合物分子相似的发光行为,既可以发出纯正的蓝光,又表现出支化结构对荧光发射的影响.差...     

端丙烯酸酯基超支化聚(酯-胺)的结构分析及光固化

近年来 ,具有树枝状结构的超支化聚合物因其独特的物理化学性质而得到广泛关注[1,2 ] .超支化聚合物主要采用 3种途径合成 ,( 1 )ABn(n >2 )型及潜ABn 型单体的聚合 ;( 2 )由A2 与Bn 型单体直接聚合 ;( 3)先由特定的单体对原位形成ABn型中间体后再聚合 .其中后两种方法可直接采用商业化原料 ,因此更具有实用价值 .目前 ,基于途径 ( 2 )已合成出超支化聚酰胺[3 ] 、聚醚[4] 、聚酰亚胺[5] 和共轭聚合物[6] 等 ,但该途径容易生成凝胶化产物 ,通过控制反应物浓度、在凝胶点之前停止反应等 ,可得到溶解型超支化产物 .由于超支化聚合物具有低…     

超支化PAMAM桥联乙烯齐聚用镍系催化剂的合成与表征

以系列直链脂肪胺为核的低代超支化聚酰胺-胺(PAMAM)和水杨醛为原料,通过席夫碱反应制备系列新型超支化PAMAM桥联水杨醛亚胺配体;以无水Ni Cl2为络合试剂,通过络合反应合成系列超支化PAMAM桥联镍催化剂,采用FT-IR和1H NMR证实合成的系列新型配体和镍系催化剂的结构与其理论结构相符.对系列超支化PAMAM桥联镍催化剂催化乙烯齐聚的性能进行了研究,结果表明,超支化PAMAM桥联镍系催化剂配体骨架烷基链长度对其催化活性和选择性影响较小,助催化剂和溶剂影响较大;倍半乙基氯化铝为助催化剂,甲苯为溶剂时,聚合活性较高,产物中C8以上的高碳产物的含量最高;其中以十四胺为核的超支化PAMAM桥联镍催化剂为主催化剂、倍半乙基氯化铝为助催化剂、甲苯为溶剂时,催化乙烯齐聚活性高达1.96×106 g/(mol·h),齐聚产物中C8以上的高碳产物含量为98.77%.     

树形聚醚的合成及其应用

树形聚合物高度支化,与线形结构的聚合物相比具有较低的粘度及良好的溶解性,而且其单分子尺寸通常在纳米尺度,在多方面具有广阔的应用前景。树形聚合物通常分为3种,即树枝状聚合物、超支化聚合物和树枝化聚合物。作为树形聚合物的主要一类,树形聚醚由于其良好的化学、物理稳定性,良好的水及有机溶剂的溶解性,以及生物相容性等诸多优点,其合成及应用研究得到了广泛重视。本文对不同种类树形聚醚的合成及其应用作一详尽的综述,包括树枝状聚醚、树枝化聚醚及超支化聚醚3种主要类型,同时报道了作者等在该领域的最新研究进展,并对该领域的研究进行了相应的展望。     

超支化聚缩水甘油醚研究进展

超支化聚缩水甘油醚(HPG)是一种分子内部为醚键,分子周围有大量羟基的超支化聚合物.这些结构特点使超支化聚缩水甘油醚在催化剂载体、生物医药、聚合物电解质等领域具有重要意义.本文介绍了超支化聚缩水甘油醚的合成方法及其功能化的研究进展,并简要分析了其发展前景.     

超支化聚醚的合成与应用

超支化聚醚以其独特的结构与性能而成为高分子研究的热点。本文对近年来HBPE的合成方法及应用研究进行了综述。目前超支化聚醚的制备方法主要包括在缩合反应、开环聚合反应、及质子转移等其它聚合反应。超支化聚醚的应用研究领域非常广阔,主要包括聚合物电解质、生物医药、无机物表面改性、荧光功能高分子材料、聚合物改性以及负载、液晶、水凝胶等其它功能材料方面显示出了巨大的应用潜力。本文还对超支化聚醚今后的应用前景进行了展望。     

由苯-1，2，4-三羧酸-1，2—酐和羟乙基哌嗪合成酰胺键、叔氨和酯键交替排列的水溶性超支化聚合物

基于官能团非等活性原理，由商品化多组分单体一步法合成了超支化聚合物． 用苯—1，2，4-三羧酸—1，2酐(BTAA)与羟乙基哌嗪(HEPZ)为原料，利用氨基和羟 基反应活性不同，制备了结构非对称超支化聚酰胺—酯．分别用红外、核磁共振确 定了所得聚合物的结构．该聚合物分子骨架中含有交替排列的酰胺键、叔氨和酯键 ，易溶于水．本合成方法原料易得、工艺简单，适合大量制备超支化聚合物．     

两亲性超支化聚合物的研究进展

两亲性超支化聚合物作为一种新型功能性材料.近年来引起了人们的广泛关注.两亲性超支化聚合物的合成丰要是利用不同亲水性的链段对超支化聚合物端基进行改性,或者首先在超支化聚合物末端产生活性位点,再利用超支化分f作为大分子引发剂引发烯类单体进行斤环聚合、原子转移自由基聚合等得到以超支化聚合物为核的两亲性超支化共聚物;这些分子由...     

Synthesis and characterization of a flame retardant hyperbranched polyether

<正>A brominated hyperbranched polyether has been synthesized from cyanuric chloride and sodium salt of tetrabromobisphenol-A by an A_2+B_3 approach.The synthesized polyether was characterized by ~1H-NMR,~(13)C-NMR,UV, FTIR spectroscopy and X-ray diffraction studies,measurements of solution viscosity,molecular weight and solubility and elemental and thermogravimetric analyses.The flame retardancy of the synthesized polyether and its blends with commercially available plasticized poly(vinyl chloride)(PVC) and low density polyethylene(LDPE) was investigated by measurements of limiting oxygen index(LOI) value and thermogravimetric analysis.The properties are compared with a non-halogenated similar type of bisphenol-A based aromatic polyether after blending at different dose levels with the same base polymers.The LOI values of these blends indicated that these hyperbranched polyethers acted as flame retardant additives,and antimony trioxide had prominent synergistic effect with the bromo hyperbranched polyether for the above base polymers,and an increment of 4 to 6 units in LOI values was observed.     

具有可控温敏相变行为的四氢呋喃-缩水甘油超支化共聚醚的合成

采用四氢呋喃(THF)和缩水甘油(glycidol)进行阳离子开环共聚,一步合成了主链中含有柔性聚四氢呋喃线型链段的温敏性超支化共聚醚.采用定量13C-NMR确定了共聚醚的超支化结构,同时计算了其支化度.利用体积排除色谱-多角度激光光散射(SEC-MALLS)对聚合物分子量及分布进行了表征.紫外-可见光光谱(UV)测试发现共聚醚水溶液透过率在最低临界溶解温度(LCST)附近呈现剧烈变化,但是其相变速率缓慢,相变平衡时间可达30 min;且聚合物溶液的相变速率和紫外光透过率变化具有温度依赖性.采用透射电镜(TEM)对相变过程观察后发现,这种缓慢相变过程是由于超支化共聚醚组装形成的胶束随温度升高发生不同程度聚集所致.     

Synthesis of novel multi-arm star azobenzene side-chain liquid crystalline copolymers with a hyperbranched core

A series of novel multi-arm star side-chain liquid crystalline (LC) copolymers with hyperbranched core moieties were synthesized by atom transfer radical polymerization (ATRP) using a multi-functional hyperbranched polyether as the initiator and chlorobenzene as the solvent. The multi-functional hyperbranched polyether initiator was prepared from poly(3-ethyl-3-(hydroxymethyl)oxetane) (PEHO) and 2-bromo-2-methylpropionyl bromide. The azobenzene side-chain liquid crystalline arms were designed to have an LC conformation of poly[6-(4-methoxy-4^′-oxy-azobenzene)hexyl methacrylate] with different molecular weights. Their characterization was performed with ¹H NMR, size exclusion chromatograph (SEC), differential scanning calorimetry (DSC) and thermal polarized optical microscopy (POM). The multi-arm star side-chain liquid crystalline copolymers exhibited a smectic and a nematic phase, and the phase transition temperatures from the smectic to the nematic phase and from the nematic to isotropic phase increased with increasing the molecular weight of the multi-arm star side-chain liquid crystalline copolymers from 1.78 × 10⁴ to 9.07 × 10⁴.     

Supramolecular self-assembly of inclusion complexes of a multiarm hyperbranched polyether with cyclodextrins

A new class of crystalline inclusion complexes of a multiarm hyperbranched polyether combined with various cyclodextrins (CDs) was successfully prepared. Using self-condensing ring-opening polymerization, a kind of multiarm polyether with a hyperbranched poly(3-ethyl-3-oxetanemethanol) core and multiple linear poly(ethylene glycol) (PEG) arms was obtained. It has been found that this kind of hyperbranched polyether can be dissolved in water. Adding alpha-CDs to the multiarm hyperbranched polyether solution, molecular recognition results in the formation of crystalline inclusion complexes based on the noncovalent interactions between the linear PEG arms of the polyether particles and the alpha-CDs. These multiarm polyether inclusion complexes have been well characterized. Interestingly, quite different from inclusion complexes of CDs and linear polymeric guests, the complexes of the multiarm hyperbranched polyether with alpha-CDs show a novel lamellar morphology. The experimental results validate that the resultant lamellar crystals have a juxtaposed structure. In addition, the formation mechanism of these inclusion complexes of a multiarm polyether with alpha-CDs has also been well described. Besides the role of displacement of associated water molecules and the presence of hydrogen bonding between CDs in channel structure CD inclusion complexes, the noncovalent intermolecular forces between CDs and polymers also play an important role in the formation of complex architectures.     

Backbone-thermoresponsive hyperbranched polyethers

A new type of materials, the backbone-thermoresponsive hyperbranched polyether, was successfully synthesized by proton-transfer polymerization of 1,4-butanediol diglycidyl ether and various triols, and the lower critical solution temperature (LCST) values can be readily adjusted from 19.0 to 40.3 degrees C by changing the hydrophilic/hydrophobic balance of BDE and triols.     

十八烷基超支化有机物的合成

以十八胺、丙烯酸甲酯为原料,甲醇为溶剂通过迈克尔加成反应制备了0.5G(Generation)超支化有机物,再以0.5G为原料与乙二胺通过酰胺化缩合反应制备了1.0G超支化有机物.并对1.0G进行了合成条件探索,最佳反应条件为n(乙二胺)∶n(0.5G)=60∶1,反应温度60℃,反应时间24 h,产物的产率为99.11%,同时采用红外光谱对两种超支化分子进行了结构表征.     

Hyperbranched polycarbosiloxane with dendritic boron cores: Synthesis,characterization, and structure regulation

The synthesis, characterization, and structure regulation of hyperbranched polycarbosiloxane with dendritic boron cores were realized in this paper. First, dendritic boron core was synthesized via hydroboration with borane dimethylsulfide and bis(allyloxy)dimethylsilane. Then, the hyperbranched polycarbosiloxanes with dendritic boron cores were synthesized via hydrosilylation with AB₂ type monomer of bis(allyloxy)methylsilane and dendritic boron cores. The molecular structures of the dendritic boron core and resulting hyperbranched polymers were characterized by using Fourier transform infrared spectroscopy, ¹H nuclear magnetic resonance, and ¹³C nuclear magnetic resonance spectroscopies. Size exclusion chromatography/multiangle laser light scattering analysis reveals that the structures of hyperbranched polycarbosiloxane can be regulated effectively by incorporation of functional dendritic boron cores. Compared with hyperbranched polycarbosiloxane of the same molecular weight level, the hyperbranched polycarbosiloxane with dendritic boron cores presents narrower molecular weight distribution as well as much smaller hydrodynamic radius and intrinsic viscosity. Thermalgravimetric analyzer analysis indicates that both the decomposition temperature and ceramic yields are increased as the results of the incorporation of dendritic boron cores into hyperbranched polycarbosiloxane. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 3930–3941, 2006     

Physical, thermal, dielectric and chemical properties of a hyperbranched polyether and its linear analog

The hyperbranched and the linear polyethers were prepared by one-pot nucleophilic displacement polymerization technique using cyanuric chloride and aromatic diol as reported earlier. The physical, thermal, dielectric and chemical properties of the hyperbranched polyether and its linear analog have been studied. The amorphous character of both the polyethers was observed in XRD study. The solubility studies showed that the hyperbranched polyether has relatively higher solubility in different solvents compared to its linear analog. The thermal properties of both polymers have been studied by thermogravimetric (TG) and differential scanning calorimetric (DSC) analyses. The chemical resistance tests indicated that both polyethers are very good chemical resistances except in dilute aqueous alkali solution. The dielectric properties such as dielectric constant and loss factor for both polyethers have also been studied with respect to changes of frequency (50-500 kHz) and temperature (303-343 K).     

Hyperbranched polyesters: synthesis, characterization, and molecular simulations

New types of hyperbranched polyesters were synthesized by the reaction of 2,2-bis(hydroxymethyl) propionic acid as an AB2-type monomer with pentaerythritol, trimethylol propane, or glycerol as the core moiety. The obtained globular networks were characterized by NMR and MALDI-TOF spectroscopic techniques. Molecular weights determined by MALDI-TOF were confirmed by gel permeation chromatography. Fourier transform infrared (FTIR) spectroscopy was used for the quantitative evaluation of hydrogen bonding as well as to study the structure-property relationship. To investigate the changes and types of intermolecular H-bonding interactions in hyperbranched polyesters with a variation in molecular structure, the deconvolution of FTIR spectra was carried out using Origin 6.0 software through the Gaussian curve-fitting method. Molecular simulations were performed through molecular mechanics and molecular dynamics (MD) calculations using the DISCOVER module. Cohesive energy density, solubility parameters, and surface properties of the hyperbranched polyesters were calculated. Further, vibrational analysis was computed using MD simulations for all the hyperbranched polyesters developed in this work.     

超支化聚醚涂层毛细管柱在线推扫富集检测6种有机磷农药

合成了3种不同支化度的超支化聚醚,采用化学键合的方法将其涂覆于石英毛细管电泳柱内壁,制备了一种新型的毛细管电泳涂层柱。利用该涂层柱通过胶束电动毛细管色谱在线推扫富集技术对6种有机磷农药进行了富集和检测。结果表明:由于超支化聚醚涂层柱显著降低了电渗流,其富集倍数远高于未涂层柱,有效提高了检测的灵敏度。其中支化度为0.43的S3涂层柱的富集倍数高达530倍,是未涂层柱的4倍。利用S3涂层柱建立了分析6种有机磷农药的方法,检出限为0.03～0.08mg/L;加标回收率为85.8%～104.6%;RSD为3.0%～8.4%。此超支化聚醚涂层柱的稳定性良好。