超支化聚胺-酯改性聚硅氧烷及纳米银导电胶的制备与性能

利用端羟基超支化聚胺-酯(HBP3-OH)与马来酸酐的酯化反应,合成了含双键的超支化聚胺-酯(HBP3-MA),并用红外光谱和核磁共振光谱对HBP3-MA进行了表征.将HBP3-MA作为改性剂,液体硅橡胶为基体,镀银铜粉为导电填料,制备了改性硅橡胶导电复合材料.HBP3-MA参与到液体硅橡胶的固化,采用示差扫描量热仪(DSC)对复合体系的固化条件进行了研究.采用原位还原法在复合体系中生成纳米银,利用透射电子显微镜(TEM)、扫描电子显微镜(SEM)对银纳米粒子的形貌和复合体系的结构进行了表征,探讨了纳米粒子增强复合物体系导电性的机理,即银纳米粒子具有低温烧结的特性,固化时可在镀银铜粉表面烧结,降低了镀银铜粉之间的接触电阻.最后,对导电复合材料的导电性能和粘结性能进行了研究.研究发现,当醋酸银用量为4.4份时,导电复合材料的体积电阻率和剪切强度均达到最佳值,分别为3.6×10-3Ω·cm和0.32 MPa.     

超支化聚胺-酯改性聚二甲基硅氧烷微流控芯片的紫外检测应用

采用超支化聚胺-酯对经过氧气氛处理的PDMS微流控芯片表面进行改性.成功地将超支化聚胺-酯涂覆到PDMS表面,使其表面的接触角由108°±1°降到32°±20°,改善了其亲水性;改性过后通道内的电渗流得到了有效抑制,远低于未改性通道内的电渗流.同时,将芯片通过专门设计的通道与毛细管连接在一起,在紫外检测波长214nm,...     

线性聚胺介导的SiO2 杂化纳米粒子的仿生合成

我们报道了在环境条件下采用简单的线性聚胺作为仿生结构导向剂快速可控的合成了聚合物杂化的SiO2纳米粒子。采用TEM, EDX, FT IR, TGA等方法对所合成的纳米粒子的形态、结构和组成进行了详细表征。另外,我们也发现纳米粒子的形成强烈依赖于体系中SiO2的矿化反应时间。所合成的杂化纳米粒子预期将在催化和生物医学等领域具有重要的应用价     

基于超支化温敏聚合物制备温敏金纳米粒子

通过对不同分子量的超支化聚乙烯亚胺(hyperbranched polyethyleni mine,HPEI)的端基进行部分或完全异丁酰胺(isobutyric amide,IBAm)化,可以制备一系列具有不同低临界溶解温度(Lower Critical SolutionTemperature,LCST)的超支化温敏聚合物HPEI-IBAm。通过离子键或氢键之间的相互作用,所得超支化温敏聚合物可以吸附于柠檬酸钠还原并稳定的14nm的金纳米粒子(AuNP)的表面,从而得到具有温敏性质的金纳米粒子。所得温敏金的LCST都低于其相应的温敏聚合物,其差值在0.8至6℃之间。在pH值为9.18的缓冲溶液中,通过改变所用聚合物的分子量以及异丁酰胺基团的取代度,所得温敏金的LCST可控制在21.7~48.2℃之间。此外,所得温敏金的LCST也是pH值敏感的,通过溶液pH值的改变,所得温敏金的LCST值可以在更宽的范围内调节。增加溶液的碱性,LCST可能变化不大或降低,减小溶液的碱性会使LCST升高,直到消失。在偏酸的条件下,所得金复合物通常发生聚集,变得不稳定。此外,溶液中的盐度对所得温敏金的LCST也有影响,氯化钠和硫酸钠会降低其LCST,尤其是硫酸钠的效果更显著。     

溶剂手性转移法制备超支化共轭聚合物手性荧光纳米粒子

通过Suzuki缩合反应制备了一系列新型不同超支化结构的9,9-二辛基芴-联二噻吩交替共聚物(HF8T2s).以手性溶剂(R)-(+)-/(S)-(-)-柠檬烯为手性源,在三氯甲烷/((R)-(+)-或(S)-(-)-)柠檬烯/甲醇混合溶剂体系里,通过溶剂手性转移技术,制备了分别以三苯胺、三苯基苯和螺二芴为支化单元的超支化聚(9,9-二辛基芴-联二噻吩)手性荧光纳米粒子.在混合溶剂中形成的荧光纳米粒子的手性来源于手性溶剂(R)-(+)-/(S)-(-)-柠檬烯.以三苯胺为支化单元时,支化单元的含量为4.56%时聚合物的手性信号最强,支化单元的含量为6.76%时聚合物的手性信号消失.以三苯基苯和螺二芴为支化单元时,支化单元的含量分别为1.85%(三苯基苯)和1.78%(螺二芴)时聚合物的手性信号最强,支化单元的含量较高(三苯基苯:4.68%和6.56%,螺二芴:4.54%和6.54%)时聚合物的手性信号消失.以超支化聚合物HF8T2-TRA2(三苯胺为支化单元,支化单元含量为1.90%)为例,考察了超支化聚合物重复单元浓度、弱溶剂的种类、弱溶剂与手性溶剂比例和(R)-(+)-柠檬烯与(S)-(-)-柠檬烯比例对超支化聚合物圆二色谱光谱强度的影响.当超支化聚合物重复单元浓度为5.0×10-5mol/L,使用甲醇为弱溶剂,三氯甲烷/((R)-(+)-或(S)-(-)-)柠檬烯/甲醇之间的配比为0.3∶1.8∶0.9(V/V/V)时,超支化聚合物圆二色谱光谱强度最强.在三氯甲烷/((R)-(+)-或(S)-(-)-)柠檬烯/甲醇(0.3∶1.8∶0.9(V/V/V))混合溶剂中,聚合物重复单元浓度为5.0×10-5mol/L,超支化聚合物在350～550 nm有较强的紫外吸收,在450～700 nm有较强的荧光发射,组装成的荧光纳米粒子尺寸约为500～2000 nm.     

超支化聚(胺酯)的分子设计及其制备

以丙烯酸甲酯和二乙醇胺为原料由Michael加成反应制得N ,N 二羟乙基 3 胺基丙酸甲酯单体 ,再用“准一步法”和“发散法”使之与 1 ,1 ,1 三羟甲基丙烷 (核 )反应合成一种新型超支化聚 (胺 酯 ) .以核磁共振和元素分析方法对N ,N 二羟乙基 3 胺基丙酸甲酯单体的分子结构进行了表征 .GPC测定表明合成的超支化聚 (胺 酯 )分子量分布窄 ,具有单分散性 ;粘度小于同分子量的线形分子 ;耐热性能较好 ,失重温度高于2 0 0℃ .     

超支化聚合物为模板Ag纳米簇的制备

超支化聚（胺-酯）;Ag纳米簇;模板合成     

水分散超支化共轭聚合物纳米粒子的制备及其对苦味酸的高灵敏荧光检测

采用Suzuki细乳液聚合以及后功能化反应,制备了季铵盐末端的水分散超支化共轭聚合物纳米粒子(HCPN-QA),用于高灵敏度和高选择性的检测2,4,6-三硝基苯酚(PA).带正电荷的季铵盐端基以及疏水的超支化共轭聚合物核心,使HCPN-QA对水中呈酸性的PA产生静电吸引与疏水富集的协同作用,产生高度灵敏的荧光猝灭响应,检测限达到0.18μg/L,猝灭常数达到6.36×10~7 L/mol,相比于有机相分散的超支化共轭聚合物纳米粒子HCPN-OMe,HCPN-QA检测限低了4个数量级,猝灭常数高出3个数量级.通过研究HCPN-QA粒径对PA检测灵敏度的影响,发现纳米粒子粒径对PA的检测灵敏度影响很小.并且,HCPN-QA对PA的猝灭响应显著高于TNT及其他硝基爆炸物,表现出很好的选择性以及竞争选择性.此外,HCPN-QA检测试纸对PA固体颗粒的检测表现出很高的灵敏度,检测限达到66 pg/mm~2.     

超支化聚酯的合成与应用——纳米银粒子的制备与表征

超支化聚酯的合成与应用——纳米银粒子的制备与表征;超支化聚酯;纳米银;稳定剂;光还原     

AB2型超支化聚(胺-酯)活性端羟基与乙酸酐的功能化反应

以二乙醇胺和丙烯酸甲酯为原料合成了具有端羟基的AB2型超支化聚（胺－酯）。研究了超支化聚（胺－酯）端羟基与乙酸酐的功能化反应，分析了温度和搅拌对该反应动力学的影响。实验结果表明：超支化聚（胺－酯）端羟基与乙酸酐的酯化反应动力学偏离二级反应，用反常扩散理论对这一实验现象进行了解释。     

Preparation and stability of copper particles formed using the template of hyperbranched poly(amine-ester)

The sixth-generation hydroxyl-ended hyperbranched poly(amine-ester) (G6-OH) was investigated as template in formation and stabilization of copper nanoparticles. Ultra-violet spectra and transmission electron microscope were adopted to characterize absorption properties of G6-OH(Cu²⁺)_n complex and the morphology of the formed particles (G6-OH(Cu)_n), respectively. The template and stabilization functions of G6-OH were compared with di-block copolymer micelles and dendrimers having similar structure. It was found that the hyperbranched polymers could act as the templates for the preparation of copper particles. The size of the formed copper particles increased with Cu²⁺/Gn-OH molar ratio. Besides, the oxygen influenced the chemistry stability of copper particles greatly.     

Preparation and pervaporation properties of crosslinked hyperbranched poly(amine-ester) membranes

Crosslinked hyperbranched poly(amine-ester) (HPAE) membranes were prepared by crosslinking its terminal hydroxyl groups with glutaraldehyde (GA). The crosslinked HPAE membranes showed high reactivity and good hydrophilicity. The crosslinking degree was investigated by Fourier transformation infrared spectra (FT-IR). Atom force microscope (AFM) and scanning electron microscope (SEM) reveals that the crosslinked HPAE films have smooth surfaces, dense and homogenous matrices. The swelling degree of the membrane was higher in water than that in isopropanol. From the permeation of pure water through the HPAE membrane, the effect of hydroxyl/aldehyde group ratio on the permeation flux and separation factor was investigated. The results indicated that the permeation flux increase was accompanied with the separation factor decrease if the water concentration increased in the feed solution.     

由A2和CB2型单体合成端羟基超支化聚(脲-氨酯)

超支化聚合物是一类高度支化的具有三维椭球状立体构造的大分子[1]. 由于具有传统线型聚合物所没有的低熔体粘度、高流变性、良好的溶解性及大量末端官能团等一系列独特的物理化学特性, 超支化聚合物自 20世纪 80年代末在杜邦公司诞生以来[2]便很快成为高分子科学界研究的一个热点[3～7], 预计其将在医药载体、大分子建筑"砌块"、催化剂和流变添加剂等诸多领域得到广泛应用[8].     

New Phase Transfer Agent for Dye： Application for Hyperbranched Poly （ester-amine）

Hydrophilic hyperbranched poly(ester-amine) (HPEA) synthesized from diethanolamine and methyl acrylate was used as phase transfer agent for the first time to transfer methyl orange(MO) from water into chloroform. This process was quantified by UV-Vis spectra. A possible mechanism was put forward based on the formation of amphiphilic aggregates.     

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.     

NOVEL HYPERBRANCHED POLY（AMINE-ESTER） FILMS： PREPARATION,CHARACTERIZATION AND PROPERTIES

Crosslinked film of hyperbranched poly(amine-ester) (HPAE) was prepared by crosslinking its terminal hydroxyl groups with glutaraldehyde (GA). Atom force microscope (AFM) and scanning electron microscope (SEM) reveals that they have smooth surfaces, dense and homogenous matrices. It was found that the water static contact angle is smaller than 41.7°, the tensile strength is higher than 8.9 MPa, the elongation at break is higher than 5.1%, the swelling degree is higher than 42% in water, and the Bovine hemoglobin (Hb) adsorption is relatively low. These results indicate that the crosslinked HPAE films might have some potential applications in many areas.     

两亲性超支化聚砜胺对染料的可逆高装载

采用戊酰氯、壬酰氯和棕榈酰氯对超支化聚砜胺(HPSA)进行封端,合成了3种不同烷基末端的两亲性核壳型超支化聚砜胺,并将其用于小分子装载.发现它们对刚果红(CR)、甲基橙(MO)、虎红(RB)等水溶性染料具有很强的装载能力,且对同种染料的封装载荷随着末端亲油性烷基链的增长而增大.对于末端为棕榈酰基的HPSA-PC,平均每个大分子可以捕捉CR和MO分子的数目分别高达41.8和19.4个,远高于已报道的树枝状聚合物和超支化聚合物对这些染料的封装载荷.这主要是聚砜胺内核的高度亲水性及其与亲油性烷基外壳的极性差所致.与已报道的聚合物不同,两亲性超支化聚砜胺装载的染料用纯水洗涤可以释放出来.这种高装载性能和可逆性赋予超支化聚砜胺在药物释放、分子识别和分离以及纳米催化剂和纳米涂料等领域具有广阔的应用前景.     

超支化聚酯酰胺的合成及在聚碳酸酯加工中的应用

以1,2,4-偏苯三羧酸酐(BTAA)和乙醇胺(EMA)为原料,分别采用"二步法"和"一步法"熔融缩聚制备了端羧基超支化聚酯酰胺(HBPEA).第1步利用官能团非等活性原理,在乙醇溶剂中由BTAA中高活性的酸酐基团与EMA中高活性的氨基反应原位生成含1个羟基和2个羧基的AB_2中间体,蒸除乙醇后,再第2步熔融缩聚得到超支化聚酯酰胺,可避免聚合过程中发生凝胶.为便于工业化应用,还采用BTAA与EMA经"一步"熔融缩聚制备了端羧基超支化聚酯酰胺.分别采用核磁共振(NMR)、乌氏黏度计、示差扫描量热仪(DSC)、热失重分析仪(TGA)以及阿贝折射仪等对2种方法所制备的目标产物化学结构和特性黏度等各项性能进行了表征,结果表明:所得聚酯酰胺具有超支化结构,特性黏数为0.12~0.15 d L/g,支化度为0.64~0.65,在350oC之前未发生热失重,玻璃化转变温度为125~126oC,折射率为1.57~1.58,与聚碳酸酯(PC)相近.因此将其作为加工助剂用于PC塑料体系的加工.超支化聚酯酰胺的加入,不仅能改善PC的加工流动性,同时还能改善制品的机械性能和表面光洁度,且不会引起PC色泽的变化.     

通过A2+B3反应制备超支化聚芳醚酮荧光材料

用3-二甲氨基苯酚与超支化聚芳醚酮(HPETFDEK-F)的末端氟发生反应,制得荧光超支化聚芳醚酮(FHPETFDEK).采用1HNMR,FTIR,DSC和TGA等方法对所得到的聚合物结构和热性能进行了表征.研究了FHPETFDEK的紫外吸收及荧光发射光谱,发现其具有荧光行为.     

Reactive Blends of Poly(phenylene sulfide)/Hyperbranched Poly(phenylene sulfide)

Summary: Polymer blends consisting of linear poly(phenylene sulfide) (PPS) and hyperbranched PPS (HPPS) were obtained in melt. The solid-state properties of PPS and their blends were investigated by scanning electron microscopy (SEM), thermogravimetric analyzer (TGA), extraction measurement, differential scanning calorimetry (DSC) and dynamical mechanical analysis (DMA). Blends prepared by melt mixing turned out to be reactive as shown by the TGA and extraction measurement. SEM indicated that no phase separation occurs in PPS/HPPS blends. The degree of crystallization of the blends decreased with increasing HPPS content. Both the storage modulus and loss modulus increased as HPPS content increasing.