不同代数端羟基超支化聚酯及其二元共混物的流变行为

系统研究了消除热历史后的G1~G5端羟基超支化聚酯熔体及组分质量比为1∶1的二元共混物的流变行为。结果表明,无论是稳态剪切测试还是振荡测试,消除热历史后的G2~G5端羟基超支化聚酯熔体均表现为牛顿流体的流变行为。G3~G5端羟基超支化聚酯的流变行为均遵循Cox-Merz方程。G2端羟基超支化聚酯在振荡测试的高频区出现了剪切增稠现象。对于组分质量比为1∶1的低代/高代端羟基超支化聚酯二元共混物,无论是稳态剪切还是振荡剪切,只要一种组分是牛顿流体,那么二元共混体系也是牛顿流体。高代数组分决定了二元共混物的流变特性,而低代数组分主要影响二元共混物的黏度。     

Study on hyperbranched polyesters as rheological modifier for Spandex spinning solution

The rheological behavior of polyurethane (PU)/N,N‐dimethylformamide (DMF) spinning solutions with various contents of hyperbranched polyesters was studied using a RS150L‐controlled stress rotational rheometer. The results showed that the viscosity of the spinning solutions could be greatly reduced by adding hyperbranched polyesters even at 0.5 wt% loading. The zero‐shear viscosity of solutions with hyperbranched polyesters was much lower than that of pure PU/DMF solution, which indicated a lower degree of entanglement when solutions were in a static state. The apparent activation energy of viscous flow and the critical shear rate for shear thinning of solutions with hyperbranched polyesters were much lower than that for pure PU/DMF solution, which indicated a weaker entanglement structure formed. In addition, the effect of hyperbranched polyesters on the mechanical properties of Spandex fiber was discussed. Copyright © 2006 Society of Chemical Industry     

Investigation into the solution properties of hyperbranched polymer

The solution properties of hydroxyl terminated hyperbranched aliphatic polyesters and their acetyl derivatives have been studied by measuring viscosity parameters. The polarity of terminated groups of molecules is the most important factor affecting their properties. The intrinsic viscosity [η] cannot reflect the real monomolecular hydrodynamic volume of hydroxyl group-terminated hyperbranched polymer due to the strong intermolecular forces which lead to the formation of stable clusters. The intermolecular association constant K_M depends not only on molecular weight, but also on the polarity of end-groups. However, the dynamic contact concentration C_S can be determined accurately from reduced viscosity versus concentration plots. The reason why the intrinsic viscosity does not change linearly with the generation of the hyperbranched aliphatic polyesters is explained using ‘free-draining’ and ‘non-draining’ models. © 2001 Society of Chemical Industry     

A structure/function study of polyaminoamide dendrimers as silica scale growth inhibitors

Dendrimers have attracted immense attention during the last decade due to their interesting properties both from a basic and an applied research viewpoint. Encapsulation of metal nanoparticles for catalysis, drug delivery and light harvesting are only some applications of dendrimers that are breaking new ground. A novel application of dendrimer technology is described in the present paper that relates to industrial water treatment. Industrial water systems often suffer from undesirable inorganic deposits. These can form either in the bulk or on metallic surfaces, such as heat exchangers or pipelines. Silica (SiO₂) scale formation and deposition is a major problem in high‐silica‐containing cooling waters. Scale prevention rather than removal is highly desired. In this paper, benchtop screening tests on various silica inhibition chemistries are reported, with emphasis on materials with a dendrimeric structure. Specifically, the inhibition properties of commercially available STARBURST^® polyaminoamide (PAMAM) dendrimers generations 0.5, 1, 1.5, 2, and 2.5 are investigated in detail together with other commonly‐used scale inhibitors. Experimental results show that inhibition efficiency largely depends on structural features of PAMAM dendrimers such as generation number and nature of the end groups. PAMAM dendrimers are effective inhibitors of silica scale growth at 40 ppm dosage levels. PAMAM dendrimers also act as silica nucleators, forming SiO₂–PAMAM composites. This occurs because the SiO₂ formed by incomplete inhibition interacts with cationic PAMAM‐1 and ‐2. The general scope of silica formation and inhibition in industrial waters is also discussed. Copyright © 2005 Society of Chemical Industry     

PAMAM树状大分子负载和释放阿霉素的耗散粒子动力学模拟

采用耗散粒子动力学模拟方法研究了药物输送载体聚酰胺-胺（PAMAM）树状大分子对抗癌药物阿霉素（DOX）的负载和释放行为。构建了PAMAM树状大分子的粗粒化模型,该模型能准确地重现树状大分子的构象性质。考察了PAMAM树状大分子代数（G）对DOX负载以及pH环境对DOX释放的影响。模拟结果表明,PAMAM树状大分子主要通过疏水作用将DOX包封于内部空腔,G6和G7 PAMAM树状大分子的负载能力较强,因为其孔隙率较高,内部有更多的疏水空腔。在低pH环境下,PAMAM树状大分子结构发生变化,DOX分子能快速地从其中释放,主要原因是PAMAM的伯胺、叔胺和DOX伯胺发生质子化,质子化基团间的静电排斥作用使得PAMAM树状大分子发生溶胀,导致其内部空腔暴露,促进了DOX的释放。本工作可以为基于树状大分子的药物输送体系的设计和优化提供参考。     

Binding properties of polyamidoamine dendrimers

Dendrimers are globular, hyperbranched polymers possessing a high concentration of surface functional groups and internal cavities. These unique features make them good host molecules for small ligands. To reveal relationships between dendrimer size and its encapsulating properties, the interactions of the fourth and the sixth generations of polyamidoamine dendrimers (PAMAM G4 and PAMAM G6) with a fluorescent dye 1‐anilinonaphthalene‐8‐sulfonate (ANS) were studied. Because ANS is a fluorescent molecule and its fluorescence is very sensitive to changes in its microenvironment, it was possible to use spectrofluorometric methods to evaluate the interactions with dendrimers. A double fluorometric titration method was used to estimate a binding constant and the number of binding centers. There were two types of dendrimer binding centers characterized by different affinity towards ANS. For PAMAM G4, the values of K_b and n for low‐affinity and high‐affinity sites equaled to 2.6 × 10⁵, 0.60 and 3.70 × 10⁶, 0.34, respectively, whereas in the case of PAMAM G6, these values equaled to 1.2 × 10⁵, 76.34 and 1.38 × 10⁶, 22.73. It was observed that the size of the dendrimer had a strong impact on the number of ANS molecules that interacted with dendrimers and their location within the macromolecule. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 2036–2040, 2007     

Synthesis of well‐defined dendritic hyperbranched polymers by iterative methodologies using living/controlled polymerizations

This review presents firstly the synthesis of various dendritic hyperbranched polymers with well‐defined structures by generation‐based growth methodologies using living/controlled polymerization. Secondly, the synthesis of dendritic hyperbranched poly(methyl methacrylate)s (PMMAs) and their functionalized block copolymers using a novel iterative methodology is described. The methodology involves a two‐reaction sequence in each iterative process: (a) a linking reaction of α‐functionalized living anionic PMMA with tert‐butyldimethylsilyloxymethylphenyl (SMP) groups with benzyl bromide (BnBr)‐chain‐end‐functionalized polymer and (b) a transformation reaction of the SMP groups into BnBr functions. This reaction sequence is repeated several times to construct high‐generation (maximum seventh generation) dendritic hyperbranched polymers. Similar branched architectural block copolymers have also been synthesized by the same iterative methodology using other α‐functionalized living anionic polymers. Surface structures of the resulting dendritic hyperbranched block copolymers composed of PMMA and poly(2‐(perfluorobutyl)ethyl methacrylate) segments have been characterized using X‐ray photoelectron spectroscopy and contact angle measurements. Solution behaviors of dendritic hyperbranched PMMAs with different generations and branch densities are discussed based on their intrinsic viscosities, g′ values and R_h values. Copyright © 2007 Society of Chemical Industry     

Facile and efficient synthesis of hyperbranched polyesters based on renewable castor oil

Hyperbranched polyesters with thioether linkages were facilely prepared from methyl 10‐undecenoate, a castor oil‐derived renewable chemical. The monomer was obtained in excellent yield through thiol–ene click chemistry in the presence of catalytic amounts of photoinitiator under UV irradiation. Subsequent bulk polycondensation via a transesterification process catalyzed by Ti(OBu)₄, Sb₂O₃ or Zn(OAc)₂ gave hyperbranched polyesters with high molecular weights and unusual crystalline properties. The degree of branching in the range 0.45 ? 0.54 calculated from quantitative ¹³C NMR spectroscopy and low inherent viscosities of 0.16 ? 0.25 dL g^?1 strongly confirmed the hyperbranched structures of the resultant polymers. © 2012 Society of Chemical Industry     

New coating systems based on vinyl ether‐ and oxetane‐modified hyperbranched polyesters

A series of hyperbranched aliphatic‐aromatic polyesters has been synthesized which contain vinyl ether or oxetane functionalities as curable groups. We investigated the curing behavior of these multifunctional polymers in the presence of reactive diluents in order to analyze the possibility of their application in high solids coatings. The vinyl ether‐modified hyperbranched polyesters with a high degree of modification yield the best coatings. Furthermore, coating systems containing vinyl ether‐modified hyperbranched polyesters and triethyleneglycol divinyl ether (DVE‐3) as reactive diluent showed a better performance compared to those containing 4‐hydroxybutyl vinyl ether (HBVE). Real time FT‐IR studies revealed a high conversion of functional groups (76%) for the cationic curing with DVE‐3. On the other hand, the curing reaction of the functional hyperbranched polymers without the presence of any reactive diluent stopped at 32% conversion of functional groups due to the reduced mobility of the polymer. The vinyl ether‐modified hyperbranched polyester could be cured also radically in the presence of diethyl maleate (DEM) as reactive diluent, whereas the curing of the oxetane‐modified polyesters was very slow and incomplete in all attempts.     

A study of antimicrobial property of textile fabric treated with modified dendrimers

Dendrimers have been used as a vehicle to develop the antimicrobial properties of textile fabrics. We have taken advantage of the large number of functional groups present in the regular and highly branched three‐dimensional architecture of dendrimers. In this study, the poly(amidoamine) (PAMAM) G‐3 dendrimer was modified to provide antimicrobial properties. Following a procedure similar to what is suggested in the literature, PAMAM (G3) with primary amine end groups was converted into ammonium functionalities. The modification was then confirmed by FTIR and ¹³C‐NMR analysis. Dendrimers have unique properties owing to their globular shape and tunable cavities, this allows them to form complexes with a variety of ions and compounds; and also act as a template to fabricate metal nanoparticles. AgNO₃–PAMAM (G3) complex as well as a MesoSilver–PAMAM (G3) complex were formed and these modified dendrimers were characterized by a UV–Visible spectrophotometer to study the complex formation. Modified dendrimers were applied to the Cotton/Nylon blend fabric. SEM and EDX analysis were performed to study the dispersion of silver nanoparticles onto the fabric. An antimicrobial test of the treated‐fabric against Staphylococcus aureus exhibited significant biocidal activities for each type of modified‐dendrimer. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Rheological behavior in the molten state and solution of hyperbranched polyester of fourth and fifth generation

The rheological behavior in the molten state and solution of hyperbranched polyol polyesters (HBPs) obtained by one step (HBP4, HBP5), step by step (HBP4P, HBP5P), and combination of both (HBP1‐4, HBP1‐5) was studied. Under conditions of dynamic oscillatory shear, all HBPs presented a shear‐thinning behavior and under steady shear they showed a Newtonian behavior. Also, the steady shear viscosities decreased with increasing temperature. The behavior of HBPs was mainly viscous, except for the HBP4P that showed higher storage modulus and reduction of complex viscosity when increasing the angular frequency. The HBPs presented higher complex viscosity than steady shear and they did not follow the Cox‐Merz rule. The HBPs in solution presented a plateau region at shear rate lower than 40 s⁻¹ but a shear‐thickening behavior at shear rate higher than 40 s⁻¹. The viscosities of HBPs in solution (in the plateau region) and molten state increase in the following order: HBP5P > HBP1‐5 > HBP4P > HBP1‐4 > HBP4 > HBP5. These results are not in agreement with the values of the number average molar mass obtained by vapor pressure osmometry due to different interaction between HBPs molecules. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

树形分子的制备及对量子点荧光性能的影响

采用发散法合成了以乙醇胺为初始核的扇形树枝状化合物PAMAM,用核磁共振法（^1H NMR和^13C NMR）对G1．0—NH2,G1．0-SH进行了表征,证实了其结构;并用荧光分光光度计检测了PAMAM对CdTe量子点水溶液的荧光性质的影响。发现PAMAM树形分子可增强CdTe—TGA量子点的荧光,不同浓度的PAMAM对量子点荧光性能的影响不同。     

Preparation and characterization of hyperbranched polyester capillary columns used for the separation of basic proteins

A series of hyperbranched polyesters with pentaerythritol as the core were synthesized and coated on the inner surface of fused‐silica capillaries by chemical bonding. Three kinds of basic proteins were selected for studying the behavior of the adsorption to fused‐silica capillaries. Comparative studies of the coating materials were conducted, and the experimental results showed that the coated columns with hyperbranched polyesters could suppress the electroosmotic flow greatly and effectively prevent adsorption in the pH range of 4–6; they were superior to capillaries coated with traditional hydroxypropyl cellulose. Furthermore, research was conducted to study the effect of hyperbranched polyester generation on the column efficiency. The results showed that higher column efficiency was obtained on a capillary column coated with the sixth generation of the hyperbranched polyester at pH 5.0. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

端苯基超支化聚酯对PET结晶行为和构象的影响

采用差示扫描量热法(DSC)和衰减全反射傅里叶变换红外光谱(ATR-FTIR)研究了不同代数和含量的端苯基超支化聚酯(HBP)对聚对苯二甲酸乙二醇酯(PET)结晶行为和构象的影响,计算了晶带与内标峰的吸光度比值以及左右式构象的相对含量.其中975 cm?1和1340 cm?1处的吸收峰归属于反式构象,1370 cm?1处归属于左右式构象,793 cm?1和873 cm?1处的吸收峰为内标峰.结果表明,6%的第三代超支化聚酯对PET的结晶促进能力最强.随着超支化聚酯含量或代数的增加,各吸光度比值基本上都呈现出先增大后减小的趋势,左右式构象的含量则表现出先减小后增大的趋势.端苯基超支化聚酯既可以充当成核剂,又可以充当结晶促进剂,因而可以促进PET结晶.     

树枝状大分子聚酰胺胺对布洛芬的增溶性能研究

采用发散合成法,合成了系列以乙二胺为核的树枝状大分子聚酰胺 胺(PAMAM)和三羟基氨基甲烷改性的聚酰胺 胺,用紫外 可见分光光度计测定了树枝状大分子对布洛芬的增溶能力。结果表明:两类树枝状大分子对布洛芬的增溶量均高于传统的表面活性剂SDS,而且增溶能力均随代数的增加而增加;在引入羟基后,PAMAM增溶能力明显提高,作为一种新型的药物输送剂,显示了良好的应用前景。     

Boltorn型超支化聚酯的合成与表征

以季戊四醇(PEL)、三羟甲基丙烷(TMP)和2,2-二羟甲基丙酸(DMPA)为原料,合成了3种端羟基超支化聚酯(HBPE),即分别是以PEL为核的HBPE、以TMP为核的HBPE和无核的HBPE。采用FTIR、13C NMR、GPC等方法对其结构进行了表征,3种HBPE的Fréchet支化度分别为41.86%,41.49%和39.77%,而Frey支化度分别为32.29%,31.37%和23.11%。研究了中心核分子对HBPE的溶解性、特性黏度的影响。结果表明,随着核分子官能度的增加,HBPE的溶解性变好,特性黏度增加,支化度(DB)增加,分子量多,分散系数(PD I)变小。     

Hyperbranched polyesters with internal and exo‐presented hydrogen‐bond acidic sensor groups for surface acoustic wave sensors

Three hyperbranched aromatic polyesters carrying both internal and exo‐presented hydrogen‐bond acidic phenol, carboxylic acid, or mixed phenol/acetoxy groups were coated onto 500 MHz surface acoustic wave (SAW) sensor platforms, and sensor responses to the nerve agent simulant dimethyl methylphosphonate (DMMP) and the explosives simulant dinitrotoluene (DNT) were studied. All three hyperbranched polyesters gave strong responses to DMMP, and the hyperbranched polyester carrying carboxylic acid groups gave a particularly strong response. The hyperbranched polyester carrying phenol groups gave the best response to DNT of the three polymers studied. The DMMP and DNT responses of the three hyperbranched polyesters were also compared with hyperbranched SAW sensor polymers carrying exo‐presented phenolic sensor groups only, and also with linear SAW sensor polymers carrying phenolic sensor groups. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

超支化聚酯在环氧树脂改性中的应用

超支化聚合物是一类具有三维树形结构的高度支化的大分子。由于其独特的结构和性能以及可实现工业化生产的潜力,超支化聚合物已经成为高分子材料领域研究的热点之一,并且得到了越来越多的关注。作为一类非常重要的超支化聚合物,超支化聚酯(HBPE)引起了研究人员的极大兴趣。目前,HBPE已经在众多领域获得应用,特别是在环氧树脂改性中的研究发展迅速。综述了HBPE作为改性剂在环氧树脂中的应用研究进展,同时对HBPE在环氧树脂和其他热固性树脂改性中的应用研究方向作了展望。     

Studies on the complexation between generation‐4.5 methyl ester‐terminated poly(amidoamine) dendrimer and Pd2+ ions in methanol

Poly(amidoamine) (PAMAM) dendrimers have attracted attention because of their well‐defined molecule structures and chemical versatility, which also complicate the mechanism of interactions between metal ions and PAMAM dendrimers. To further understand the complexation of dendrimers with metal ions, the interactions between Pd²⁺ ions and G4.5‐COOCH₃ PAMAM dendrimers were investigated by UV‐vis and FTIR spectrophotometric method. The results show that the addition of K₂PdCl₄ results in covalent attachment of the PdCl alcoholysis product of this complex to tertiary amines within the dendrimers under the appropriate conditions. This process was also supported by X‐ray photoelectron spectroscopy data of the new complex which indicated a 1 : 3 Pd/Cl ratio. The maximum loading of 80 Pd²⁺ ions within the G4.5‐COOCH₃ dendrimers and the best pH value of 8.3 for complexation system are also obtained. Details regarding the Pd species present in solution of different chemical environments are reported. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Grafting and phosphonic acid functionalization of hyperbranched polyamidoamine polymer onto ultrafine silica

In this study, grafting of hyperbranched polyamidoamine (PAMAM) polymer onto ultrafine silica followed by functionalization via the introduction of phosphonic acid groups into the branch ends was performed. First, an initiating site was incorporated into the silica surface by reacting the silica silanol group with 3‐aminopropyltriethoxysilane, producing amino‐functionalized silica. The free amine group content was altered by varying the ratio of methanol to water in the hydrolysis step of the silanization reaction. Grafting of PAMAM was attained by three rounds of sequential Michael addition of silica amino groups to methyl acrylate and amidation of the resulting terminal methyl ester groups with ethylenediamine. Completion of the grafting reaction in each step was clearly confirmed using FTIR analysis. Excessive ethylenediamine and unattached hyperbranched PAMAM present in the reaction product were removed by dialysis with a molecular weight cutoff of 6000–7000 Daltons. However, the amino group content determined in each step was found to be significantly lower than theoretically expected, perhaps indicative of side reactions and, in later stages, steric hindrance. The resultant hyperbranched PAMAM‐grafted onto silica was functionalized by phosphorylation of the terminal amino groups by a Mannich type reaction, producing the phosphorylated hyperbranched PAMAM‐grafted silica. Then its application on cotton fabric to produce fire‐retardant cellulose was tentatively investigated. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008