聚酰胺-胺型树枝状分子的合成及其荧光性质

以丙烯酸甲酯和乙二胺为原料通过Michael加成和酯氨解重复反应合成了以乙二胺为核的0.5～4.0G的半代和整代聚酰胺-胺树枝状分子。并用红外、紫外、荧光等对合成产物进行了表征。     

氨为核树状大分子聚酰胺-胺的制备与破乳性能

采用发散法以氨为核、甲醇为溶剂,交替与丙烯酸甲酯和乙二胺反应,合成了0．5-3．0代的树枝状大分子聚酰胺-胺,采用端基滴定分析对分子的结构进行了表征,并研究了它们对模拟原油乳液的破乳性能。结果表明：它们与以乙二胺为核心的树枝状大分子聚酰胺-胺所表现出来的趋势完全一致。     

新型聚酰胺-胺树状大分子的合成与表征

以1-萘胺为核,乙醇钠为催化剂,与丙烯酸甲酯反应生成0.5代1-萘胺核聚酰胺-胺树状分子,再与乙二胺反应合成了1.0代产物,重复以上两步反应,得4.0代产物。利用核磁共振、傅里叶变换红外光谱仪对产物结构进行表征、分析。对比分析聚酰胺-胺树状大分子与1-萘胺核聚酰胺-胺树状大分子的荧光性能,荧光发射波长从490 nm红移到520 nm。     

磁性聚酰胺-胺破乳剂的研制与性能评价

应用KH560对Fe_3O_4@SiO_2进行表面环氧化改性制备Fe_3O_4@SiO_2@Epoxy;其次分别以乙二胺、二乙烯三胺、三乙烯四胺为核,乙二胺、丙烯酸甲酯为原料,采用发散合成法合成了3种不同类型的聚酰胺-胺树枝状分子;应用开环加成反应将聚酰胺-胺整代产品嫁接到Fe_3O_4@SiO_2@Epoxy;应用酰胺化反应将聚酰胺-胺半代产品嫁接到Fe_3O_4@SiO_2@NH_2;应用红外光谱对中间体以及最终产品进行了红外结构表征,结果表明,得到的产品结构与预期产物结构相符。以O/W模拟原油乳液为研究对象,考察了聚酰胺-胺磁性破乳剂的破乳性能。结果表明,端基为胺基的磁性聚酰胺-胺破乳剂有较好的破乳效果,而端基为酯基的磁性聚酰胺-胺破乳剂基本无破乳效果;端基为胺基的磁性聚酰胺-胺破乳剂对O/W模拟原油的破乳性能随核分子结构、支化结构、破乳时间的增加,破乳剂的破乳性能均有所提高;在相同情况下,破乳性能以三乙烯四胺为核制备的磁性聚酰胺-胺材料最好;以二乙烯三胺为核制备的产品性能次之,以乙二胺为核制备的产品性能较差。     

树枝状聚酰胺-胺紫外光固化树脂的合成

采用发散法合成了以乙二胺为核的0.5 ～3.5代树枝状大分子聚酰胺-胺(PAMAM),研究了半代PAM-AM在酸性条件下的水解反应,用傅里叶变换红外光谱和核磁共振法对半代PAMAM和PAMAM水解酸进行了表征.通过丙烯酸羟乙酯与半代PAMAM水解酸的反应,合成了不需添加稀释剂,在紫外光作用下便能同化成膜的树枝状聚酰胺-...     

中国化学化工文献聚合物乳液题录

<正> 树枝状聚酰胺-胺对O/W型模拟原油乳液的破乳性能[刊]/王俊.陈红侠,于翠艳,杨锦宗(大连理工大学精细化工国家重点验室)//石油学报(石油加工).-2002,18(3).-60～64采用发散合成法以乙二胺为核、甲醇为溶剂,交替与丙烯酸甲酯和乙二胺反应,合成了支化代     

树枝状高分子聚酰胺-胺（PAMAM）对水杨酸增溶作用研究

本文用发散法合成了以乙二胺为核的聚酰胺胺（PAMAM0．5-4.5代），考察了不同分子代数、不同载体浓度的PAMAM对水杨酸的包载和增溶作用，结果表明：PAMAM分子对此类药物有着良好的增溶作用，其效果高代优于低代，整代优于半代，而半代的PAMAM有着单分子胶束的性质和载药量稳定的特点。结果表明PAMAM树枝状高分子作为弱酸性难溶性药物的载体有着良好的应用前景。     

树状桥联亚胺基吡啶-2-甲醛配体的合成与红外表征

以乙二胺和丙烯酸甲酯为原料,通过Michael加成和酰胺化缩合反应分别合成了0.5代聚酰胺-胺树状大分子PAMAM-Me和1.0代聚酰胺-胺树状大分子PAMAM-NH2,再利用PAMAM-NH2的端基与吡啶-2-甲醛进行希夫碱反应,制备了一种新型树枝状桥联亚胺基吡啶-2-甲醛配体,产率达到95%以上。作者还讨论了新型配体的合成及分离工艺条件,最后采用红外光谱法对配体的分子结构进行了表征。     

一种树枝型聚醚的合成及其防蜡性能研究

采用“发散法”合成了以乙二胺为核、端基为氨基的1．0G树枝状分子聚酰胺-胺（PAMAM）,利用聚酰胺-胺分子中氮原子上含有活泼氢原子的特点,在适宜的条件下,将其与环氧乙烷（EO）、环氧丙烷（PO）进行共聚,合成了一系列分子量不同而EO／PO值相同的二嵌段树枝型聚醚、分子量相同而PO／EO／PO值不同的三嵌段树枝型聚醚。采用倒杯法测定了系列树枝型聚醚的防蜡性能,结果表明：分子量为12240的二嵌段聚醚在浓度为2OOmg&#183;L^-1时,防蜡率达到了60．9％。同时,研究了树枝状聚醚的嵌段结构与防蜡性能的关系,得出了一些具有规律性的研究结果。     

树枝状高分子聚酰胺-胺(PAMAM)对水杨酸增溶作用研究

本文用发散法合成了以乙二胺为核的聚酰胺-胺(PAMAM 0.5-4.5代),考察了不同分子代数、不同载体浓度的PAMAM对水杨酸的包载和增溶作用,结果表明:PAMAM分子对此类药物有着良好的增溶作用,其效果高代优于低代,整代优于半代,而半代的PAMAM有着单分子胶束的性质和载药量稳定的特点。结果表明PAMAM树枝状高分子作为弱酸性难溶性药物的载体有着良好的应用前景。     

PAMAM树状大分子在水处理中的应用研究进展

PAMAM树状大分子具有特殊结构与性能,应用于水处理中,具有无毒和高效的特点。本文综述了PAMAM树状大分子在含重金属离子废水、染料废水、高硅水等水处理中的应用研究。PAMAM树状大分子在水处理中的处理效果受溶液的pH值、作用时间、树状大分子的代数等因素的影响,且在含重金属离子废水处理中可再生。最后探讨了PAMAM树状大分子在水处理应用中存在的问题,预测未来将通过改性PAMAM树状大分子或合成新树状大分子扩大其在水处理中的应用范围。     

树状分子PAMAM接枝改性纳米SiO2与尼龙6的原位复合

将树状分子PAMAM接枝改性的纳米Si02与尼龙6进行原位复合，测试了复合材料的各项性能，对树状分子改性无机纳米粒子进行了初步的探索。结果表明：PAMAM接枝改性纳米SiO2可以提高尼龙6的强度、刚性和非等温结晶能力，但材料的韧性在接枝PAMAM代数较高的情况下趋于降低，同时，基体的摩尔质量显著下降。     

Generational, skeletal and substitutional diversities in generation one poly(amidoamine) dendrimers

Structural deviations of ethylenediamine core polyamidoamine (PAMAM) dendrimers and derivatives can be defined as skeletal and/or substitutional diversities. Detailed analysis of dendrimer starting materials and derivatives is necessary to understand the intrinsic characteristics of commercial dendrimer materials and their variations related to subsequent surface modifications. In this paper, structural deviations of ethylenediamine core generation 1 PAMAM dendrimers (PAMAM_E1 or E1) are studied and determined in a frame of a systematic investigation using combined characterization techniques. A primary amine-terminated PAMAM dendrimer of generation 1 (E1.NH₂) was used as a starting material to synthesize glycidol (E1.N(Gly)OH) and acetamide-terminated (E1.NHAc) dendrimers. The purity and homogeneity of these dendrimers were extensively characterized by polyacrylamide gel electrophoresis (PAGE), capillary electrophoresis (CE), gel permeation chromatography (GPC), acid-base titration, nuclear magnetic resonance (NMR), matrix-assisted laser desorption ionization-time of flight (MALDI-TOF) and electrospray ionization (ESI) mass spectrometry. PAGE and CE studies showed that electrophoretic mobilities at pH 2.5 are in the order of E1.NH₂>E1.N(Gly)OH>E1.NHAc. Mass spectrometry and NMR investigations (¹H, ¹³C DEPT-135, and ¹³C NMR, COSY, HETCOR, NOESY) suggested that (a) the studied E1 dendrimers were generationally pure, (b) E1.NHAc and E1.N(Gly)OH dendrimers, and essentially had the same defects and skeletal diversity as E1.NH₂ did. The broad distribution of the main peak in the CE electropherogram of E1.N(Gly)OH revealed the incomplete hydroxylation of E1.NH₂ resulting in additional substitutional diversity between the dendrimer molecules. Potentiometric titration studies proved that overall numbers of terminal and tertiary amine groups also deviated from the theoretical values. NMR spectroscopy was applied for both qualitative and quantitative analysis of the structural defects of dendrimers and derivatives. E1.NH₂ and E1.NHAc exhibited only minor deviations from ideal structures and, respectively, displayed a narrow distribution; while E1.N(Gly)OH had a much broader distribution centered around 14±3 glycidol substituents. The study of structural variations in generation 1 PAMAMs provides new insights for the characterization of higher generation PAMAM dendrimers and derivatives both in terms of the skeletal deviations as well as other resulting diversities related to dendrimer surface functionalization.     

半代聚酰胺-胺树状聚合物的酸性水解及性能研究

采用发散法合成了以乙二胺为核的半代聚酰胺-胺(PAMAM),研究了其在酸性条件下的水解反应,采用傅立叶变换红外光谱和核磁共振法对PAMAM水解酸进行了表征.测定了半代PAMAM水解酸的溶解性、熔点、热稳定性等性能,并对其性能变化的规律进行了探讨.通过丙烯酸羟乙酯与半代PAMAM水解酸的反应,合成了在紫外光作用下能固化成...     

酯端基型聚酰胺胺树形高分子对聚(3-羟基丁酸戊酸共聚酯)结晶性能的影响

采用不同比例G3.5酯端基类型的聚酰胺胺(PAMAM)树形高分子氯仿溶液与聚(3-羟基丁酸酯-co-3-羟基戊酸酯)(PHBV)树脂氯仿溶液进行共混并流延成膜,采用差示扫描量热分析、偏光显微镜以及拉伸和直角撕裂等方式对制备的PHBV/PAMAM复合膜进行表征。结果表明,随着PAMAM树形高分子的加入,PHBV/PAMAM复合膜的玻璃化转变温度（Tg）越来越明显,初步表明其韧性增强; G3.5 PAMAM树形高分子的加入,可使PHBV的结晶度由61.70 %先下降至24.02 %,并逐渐下降,最后至结晶消失; PAMAM树形高分子的加入可使PHBV的直角撕裂强度大幅度提高,最高可由8.90 kN/m提高到22.10 kN/m;当PAMAM树形高分子含量为2.0份时,增韧效果最好。     

Spectroelectrochemical analysis of ion-transfer and adsorption of the PAMAM dendrimer at a polarized liquid|liquid interface

The interfacial behavior of the fourth generation polyamidoamine (G4 PAMAM) dendrimer at a water|1,2-dichloroethane (DCE) interface was studied by cyclic voltammetry and potential modulated fluorescence (PMF) spectroscopy. Irregular voltammetric responses were observed at positively polarized interfaces. The cyclic voltammogram was strongly dependent on pH and on the concentrations of the G4 PAMAM dendrimer and the organic supporting electrolyte. PMF spectroscopy was successfully used to analyze the interfacial mechanism of the dendrimer by adding an anionic porphyrin derivative as a fluorescent probe. The results of the PMF measurements demonstrated that the G4 PAMAM dendrimer was transferred across the interface, a process that was accompanied by an adsorption step at pH 7. In contrast, under alkaline conditions, the adsorption process did not seem to be involved in the interfacial behavior.     

一种聚酰胺胺-苯甲醛树状大分子的合成及其荧光性能

首先以乙二胺为中心核,丙烯酸甲酯为支化单体合成了2.0代的聚酰胺胺树状大分子(PAMAM G 2.0),然后同苯甲醛在60℃水浴恒温反应48 h,得到了一种聚酰胺胺-苯甲醛树状大分子,用FTIR1、HNMR和13CNMR表征了合成产物的分子结构,结果和设计一致。该树状大分子能溶解于三氯甲烷,不溶于水、环己烷。对其荧光性能进行了研究,结果表明,溶液中的Fe3+对聚酰胺胺-苯甲醛树状大分子的荧光具有猝灭效应,并且荧光发射峰从436 nm红移到458 nm;溶液中的Zn2+对聚酰胺胺-苯甲醛树状大分子的荧光具有增强作用,同时荧光发射峰从436 nm蓝移到402 nm。     

Aureole nanofibers by electrospinning of PAMAM‐PEO solution

Poly(amido amine) (PAMAM) dendrimer‐polyethylene oxide (PEO) nanofibers as dendrimeric‐polymeric composite nanofibers were prepared via electrospinning of PEO solution containing PAMAM dendrimer. The resultant fibers were characterized by means of transmission electron microscopy (TEM), differential scanning calorimetry (DSC), and thermogravimetric analysis (TGA). The morphology and thermal properties of PEO nanofibers with and without PAMAM dendrimer were compared and the effect of PAMAM concentration on morphology and thermal properties of the resultant fibers was studied. The fibers had a size range of about 400–1300 nanometer in diameter with aureole morphology in most regions. The phase change temperature, phase transition heat, and the crystallinity of the produced composite fibers were determined by DSC analyses. TGA was also used to confirm the presence of PAMAM and to determine the amount of it within the fibers. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Novel Poly(EThyleneAmidoAmine) (PETAA) dendrimers produced through a unique and highly efficient synthesis

Polyamidoamine (PAMAM) dendrimers have unique attributes that have led to their use in a wide variety of biomedical applications. However, the complex synthesis of this polymer leads to variations in the structure and consistency of the final product, and makes scale-up of manufacturing difficult. This has limited the clinical translation of PAMAM-based materials. Here we describe a rapid and highly efficient two-step method for the synthesis of novel Poly(EThyleneAmidoAmine) (PETAA) dendrimers that have many of the favorable characteristics of PAMAM dendrimers. Generation 0 (G0) to 5 (G5) PETAA dendrimers were synthesized using a 3-(bis(2-(2,2,2,-trifluoroacetamido)ethyl)amino)propanoic acid AB₂ (compound 1) building block via a divergent approach. An ethylenediamine core was coupled with the AB₂ building block via O-(7-Azabenzotriazol-1-yl)N,N,N’,N’-tetramethyluronium hexafluorophosphate (HATU) in the presence of diisopropylethyl amine to give a G0 trifluoroacetamide surface dendrimer. The G0 amine surface dendrimer was then obtained by treating the G0 trifluoroacetamide surface dendrimer with potassium carbonate. Repetitions of these two coupling/deprotection reactions were then used to build the dendrimer by coupling the surface amino groups to the carboxyl moiety of the AB₂ building block, followed by the deprotection step with potassium carbonate. The resulting PETAA dendrimers have the same number of surface primary amino groups, the same number of chemical bonds between the dendrimer core and the surface, and the same number of tertiary amino groups throughout the structures as similar generations of PAMAM dendrimers. In contrast, the structure of the PETAA dendrimers is more complete and more uniform than PAMAM dendrimers, especially at higher generations. This unique synthetic process for PETAA dendrimers also offers the potential for large-scale production, therefore providing inherently more uniform and complete structures for exacting biomedical applications.     

Gelation and swelling behavior of end-linked hydrogels prepared from linear poly(ethylene glycol) and poly(amidoamine) dendrimers

Linear α,ω di-epoxide-terminated poly(ethylene glycol) of molar mass 4000 g mol⁻¹ was end-linked with amine-terminated poly(amidoamine) (PAMAM) dendrimers of generations 0, 2, and 4 in water to prepare architecturally well-defined copolymer hydrogels. The gelation and equilibrium swelling of the gels in water were characterized while systematically varying the polymer concentration at preparation, dendrimer generation, and mole ratio of dendrimer endgroups to PEG endgroups. The Ahmad-Rolfes-Stepto (ARS) theory of non-linear polymerization was applied to predict conditions favoring gelation, and to estimate the extent of reaction of amine and epoxide groups. Hydrogels having a large stoichiometric excess of amines over epoxides exhibited “superabsorbent” behavior upon extraction and equilibrium swelling in pure water. The mole ratio of amines to epoxides (equivalently, the mass fraction of dendrimers) was the most important factor governing superabsorbent behavior, although the polymer volume fraction at crosslinking and dendrimer generation also affected swelling to a lesser extent. The superabsorbency arises in part from protonation of the dendrimer amine endgroups at external pH = 7, which is supported by the drastic shrinkage of the most highly swelling gels in aqueous NH₄OH at pH = 11. Equilibrium swelling at pH = 7 was noticeably enhanced in gels having a high soluble fraction and high mass fraction of dendrimers. End-linking of linear polymer precursors to PAMAM dendrimers can potentially produce novel copolymer gels that combine attractive properties of the linear precursors with high swelling and pH-responsive behavior of PAMAM-containing networks.