酯端基超支化聚(胺-酯)的合成与表征

以乙醇胺和丙烯酸甲酯为原料,通过Michael加成反应合成了N-羟乙基-3-胺基-N,N-二丙酸甲酯AB2单体,并采用FT IR1、H NMR和元素分析对单体的结构进行了表征;以丁二酸酐为反应中心核,N-羟乙基-3-胺基-N,N-二丙酸甲酯为单体,制得了1~5代酯端基超支化聚(胺-酯)。采用核磁共振法对1~5代酯端基超支化聚(胺-酯)的支化度进行了表征,结果表明,由于采取的是加入中心核并逐步加入单体的有核准一步缩聚法,所合成的超支化聚(胺-酯)具有较高的支化度;凝胶渗透色谱测定的结果表明,超支化聚(胺-酯)的相对分子质量分布较窄,具有单分散性;超支化聚(胺-酯)的粘度较低且在多种溶剂中均有较好的溶解性,分解温度均高于170°C,具有良好的热稳定性。     

超支化聚(胺-酯)对PVC力学及流变性能影响的研究

研究了超支化聚(胺-酯)对聚氯乙烯(PVC)力学性能和流变性能的影响。结果表明,超支化聚(胺-酯)能明显改善PVC的力学性能,加入3％第3代超支化聚(胺-酯)的PVC的拉伸强度和断裂伸长率分别达到55．47MPa和17．28％,分别比原来增加了31．14％和40．85％;少量超支化聚(胺-酯)可以大幅度降低PVC的粘度,随着超支化聚(胺-酯)加入量的增加,PVC粘度降低幅度增大。     

二茂铁端基修饰的超支化聚（胺-酯）的合成与表征

首先以二乙醇胺和丙烯酸甲酯为原料,通过Michael加成反应制备A2B型前驱单体N,N-二羟乙基-3-氨基丙烯酸甲酯,然后以三羟甲基丙烷为反应中心核,采用有核准一步法合成羟端基超支化聚(胺-酯)(HPAE);最后利用二茂铁甲酸对HPAE进行端基改性,得到了二茂铁端基修饰的超支化聚(胺-酯)(HPAE-Fc)。HPAE-Fc的合成条件:w(催化剂)=2.5%(相对于反应物总质量),反应温度为140℃,反应物投料比n(OH)∶n(二茂铁甲酸)为1∶0.8,反应时间为4 h。采用FTIR、1HNMR、UV-vis、DSC和羟值等手段对HPAE-Fc的结构进行了表征,表明二茂铁基团成功地接枝到了HPAE分子表面,接枝率达70%。     

超支化聚(酰胺-酯)的合成与改性

以邻苯二甲酸酐和二乙醇胺为原料,制得AB2型单体;加入三羟甲基丙烷为核,采用一步法合成了超支化聚(酰胺-酯),并用硬脂酸对所得聚合物进行封端改性.应用红外光谱对改性前后超支化聚合物进行了表征.结果表明,所合成的聚合物与理论结构相吻合,且硬脂酸与端羟基发生了酯化反应,成功地接到了聚合物上.     

超支化聚(酰胺-酯)的合成及其光致变色性能研究

采用丁二酸酐、三羟甲基氨基甲烷为主要原料,在冰水浴条件下合成AB_3型单体,然后进行熔融缩聚制得超支化聚(酰胺-酯)(HBP);再将含羧基的螺吡喃光致变色基元通过反应活性基团羧基与AB_3超支化聚合物末端羟基的反应而引入到AB_3超支化聚合物末端上,得到具有光致变色性能的超支化聚合物(MHBP)。利用红外、核磁等对其结构进行了表征,利用紫外可见分光谱对超支化聚合物光致变色性进行了研究。结果表明:MHBP同时具有超支化聚合物的性能和光致变色性能。     

多壁碳纳米管接枝超支化聚(胺-酯)

采用混酸氧化,使碳纳米管表面产生羧基,再分别以接出法(grafting from)的方式在碳纳米管表面长出超支化大分子;以接入法(grafting to)的方式将由一步法合成的超支化聚(胺-酯)通过酯化反应接枝到碳纳米管表面。通过SEM、FTIR、TGA-DSC以及XRD等表征手段并结合酸碱滴定法测定修饰后碳纳米管表面的羟基密度,对功能化修饰的碳纳米管进行分析。结果表明,分别以grafting from和grafting to方式接枝超支化聚(胺-酯)后,碳纳米管的羟基密度分别为24.74 mmol/g和20.04 mmol/g,修饰后的碳纳米管分散性能明显提高,同时末端丰富的官能团为碳纳米管的进一步功能化修饰创造了条件。     

两亲性超支化聚（胺-酯）对PVC／PP共混体系的增容作用

研究了两亲性超支化聚（胺-酯）（A-HPAE）对PVC／PP共混体系的增容作用，讨论了其用量对PVC／A-HPAE／PP共混体系力学性能和复数黏度的影响。结果表明，在PVC／PP共混物中加入2份（质量份，下同）A-HPAE时，能很好地改善共混体系的相容性，使共混物的拉伸强度和断裂伸长率分别达到26．18mPa和18．72％，比未加的分别提高了107．67％和34．68％；共混体系的绝对复数黏度随着A-HPAE用量的增大而降低；扫描电子显微镜分析表明，A-HPAE增强了PVC和PP之间的界面黏结作用，减小了共混体系中分散相的尺寸。     

超支化聚(酯-酰胺)对超高摩尔质量聚乙烯的加工流动改性

采用超支化聚合物(HBP)改善超高摩尔质量聚乙烯(UHMWPE)的加工流动性。在摩尔质量为200万级的UHMWPE中加入3％的HBP,可使其熔融扭矩值下降约85％;对混合熔体的形态分析证明,HBP分子更易于在混合熔体的表面富集;初步认为HBP通过降低混合熔体的表观粘度来改善UHMWPE的加工流动性。     

超支化聚(酰胺-酯)的合成及性能研究

以丁二酸酐和二乙醇胺为起始原料经加成反应合成新型AB2型单体,在溶液中采用“准 一步法”自缩聚反应合成超支化聚(酰胺-酯),使用傅里叶变换红外光谱、乌式粘度计、差热-热重联 用分析仪等测试分析超支化酰胺类聚合物的结构、粘度及热性能,红外光谱图分析进一步证实了聚合 物的超支化结构。实验表明封端剂对超支化聚合物的粘度有较大影响,封端产品粘度在0．019- 0．057 dL／g范围之间,而未封端产品粘度为0．146 dL／g。热分析中,超支化聚(酰胺-酯)的Td(热分 解温度)为316．3℃,Tg(玻璃态转化温度)为270℃;结果表明,超支化聚(酰胺-酯)具有较低的比浓 对数粘度、良好的溶解性和热稳定性等特点。     

一种超支化聚(酰胺-酯)的合成及性能研究

以二异丙醇胺和六氢化苯二甲酸酐为原料,合成AB2型单体DH;DH和过量的二异丙醇胺在共沸带水剂-二甲苯中进行缩聚反应,合成超支化聚（酰胺-酯）。同时利用傅立叶红外光谱、化学滴定法和凝胶渗透色谱对DH和超支化聚（酰胺-酯）进行表征,并对超支化聚（酰胺-酯）的热稳定性、溶解性和流变性进行了研究。研究结果表明：超支化聚（酰胺-酯）具有较好的热稳定性,加热到300℃,超支化（酰胺-酯）才出现明显的失重;超支化聚（酰胺-酯）具有良好的溶解性能,能溶于醇类、酮类、四氢呋喃等极性溶剂,溶解度参数δ值为21．85～26．29（J／cm^3）^0.5;相对线型高分子,超支化聚（酰胺-酯）具有较好的流变性,在四氢呋喃溶液中,质量浓度高达40％时,黏度仅为6．61mPa·s。     

Upgrading of MUF adhesives for particleboard production using oligomers of hyperbranched poly(amine-ester)

Oligomeric precursors of poly(amine-ester) were synthesized by a two-step condensation reaction of succinic anhydride with diethanolamine under mild conditions. The oligomers formed were characterized at each synthesis step using matrix-assisted laser desorption/ionization time of flight (MALDI-TOF) mass spectrometry. This showed that after step (1), the condensation adduct of both reactants (206?Da) was the main product mixed to high proportion of unreacted diethanolamine (106?Da). After step (2), the adduct at 206?Da decreased substantially, while other compounds at 275, 292, and 375?Da started to increase along with the appearance of a new compound at 392?Da. This indicates that the reaction proceeds slowly under these conditions to give higher branched oligomers (HP). In addition, some cyclic compounds were also identified by the 188, 275, and 375?Da peaks. MALDI-TOF of the melamine–urea–formaldehyde (MUF) resin before and after reaction with the hyperbranched oligomers mix showed clear indication of the coreaction of simple melamine–formaldehyde oligomers with several of the hyperbranched oligomers previously identified. Addition of small proportions of a mixture of the formed HP oligomers to a MUF adhesive improved the internal bond (IB) strength, both dry and wet, of wood particleboards bonded with it. The results obtained indicate that the addition of these HP oligomers can improve the dry IB strength by 17–24% according to conditions of preparation and the wet IB strength by as much as 47% when compared to the control sample.     

The synthesis of hyperbranched poly (amine-ester) and study on the properties of its UV-curing film

Firstly, the monomer of N, N-diethylol-3-amine methylpropionate was obtained via Michael addition of methyl acrylate and diethanolamine. Then the hyperbranched poly (amine-ester) (HBPE) was synthesized through pentaerythritol as core molecules and monomer as AB₂. HBPE was characterized by Fourier transform-infrared spectroscopy, hydrogen nuclear magnetic resonance (¹H-NMR) and elemental analysis. Methyl tetrahydrophthalic anhydride (MTHPA) is grafted to the hydroxyl groups of HBPE and then glycidyl methacrylate (GMA) is introduced to the structure of HBPE, which is obtained by the UV-curable hyperbranched prepolymer (HBPE-MTHPA-GMA). Ultraviolet-differential scanning calorimeter showed that the HBPE-MTHPA-GMA has high photocuring speed under photoinitiator. Furthermore, the films also show good impact strength, outstanding adhesive force and primary thermal stability.     

Reaction and characterization of crosslinking hyperbranched poly(amine-ester) with succine anhydride

Basing on hydroxyl terminated hyperbranched poly(amine-ester)s (HPAEs), the cross-linking reactions and preparation of ester-crosslinked HPAE films were investigated using succine anhydride (SA) as crosslink reagent. It was proved that the cross-linking reaction between HPAE and SA followed a two-step mechanism. This mechanism provides an efficient route to prepare HPAE/SA cross-linked films, in which, the precursor films were prepared by casting HPAE/SA solution at a lower temperature, and then curing the films at a higher temperature. By varying SA content, the solid HPAE/SA films with different cross-linking degrees were prepared successfully. The highest tensile strength of the cross-linked film could reach 59.60 MPa. With all water contact angle smaller than 74.3°, the crosslinked films demonstrated good hydrophilic properties. __________ Translated from Journal of East University of Science and Technology (Natural Science Edition), 2006, 32(10): 1,164–1,168 [译自: 华东理工大学学报 (自然科学版)]     

Postgrafting of vinyl polymers onto hyperbranched poly(amidoamine)-grafted nano-sized silica surface

To prepare polymer-grafted nano-sized silica with hydrophilic core and hydrophobic shell and with higher percentage of grafting, the postgraft polymerization of vinyl polymers onto hyperbranched poly(amidoamine)-grafted (PAMAM-grafted) nano-sized silica initiated by the system consisting of Mo(CO)₆ and terminal trichloroacetyl groups of PAMAM-grafted silica was investigated. The introduction of trichloroacetyl groups onto PAMAM-grafted silica surfaces was readily achieved by the reaction of trichloroacetyl isocyanate with terminal amino groups of PAMAM-grafted silica. It was found that the polymerization of vinyl monomers, such as methyl methacrylate (MMA), styrene, and glycidyl methacrylate (GMA) was successfully initiated by the system consisting of Mo(CO)₆ and terminal trichloroacetyl groups of PAMAM-grafted silica. In the polymerization, the corresponding vinyl polymers were effectively postgrafted onto PAMAM-grafted silica, based on the propagation of polymer from surface radicals formed by the reaction of terminal trichloroacetyl groups with Mo(CO)₆: the percentage of PMMA postgrafting onto PAMAM-grafted silica reached to 400% after 30 min, but the formation of gel was observed after 35 min. The formation of gel tends to decrease by use of hyperbranched PAMAM-grafted silica with higher percentage of grafting. The vinyl polymer-postgrafted nano-sized silica gave a stable colloidal dispersion in various organic solvents.     

树枝状聚（胺-酯）的功能化及其荧光性能研究

以乙二胺(EDA)、三羟甲基丙烷三丙烯酸酯(TMPTA)和苯甲醛(BZA)为原料,合成了聚(胺-酯)-苯甲醛树枝状大分子(PAE-BZA),产率为60.82%,色谱纯度为65.27%。用IR、1HNMR和13CNMR表征了它的结构;并测定了PAE-BZA的荧光性能;考察了不同浓度PAE-BZA、不同溶剂及n(Sn2+)/n(PAE-BZA)对其荧光性能的影响。结果表明,丙酮为溶剂时,0.5 mmol/L PAE-BZA荧光强度最强;以丙酮、甲醇、DMSO、DMF和乙醇等为溶剂,PAE-BZA在乙醇中的荧光强度最强。随着n(Sn2+)/n(PAE-BZA)增加,PAE-BZA的荧光强度先减弱后增强,且Sn2+与PAE-BZA络合顺序是由外围的N原子逐步向内部的N原子络合。     

Facile preparation of highly luminescent CdTe quantum dots within hyperbranched poly(amidoamine)s and their application in bio-imaging

A new strategy for facile preparation of highly luminescent CdTe quantum dots (QDs) within amine-terminated hyperbranched poly(amidoamine)s (HPAMAM) was proposed in this paper. CdTe precursors were first prepared by adding NaHTe to aqueous Cd²⁺ chelated by 3-mercaptopropionic sodium (MPA-Na), and then HPAMAM was introduced to stabilize the CdTe precursors. After microwave irradiation, highly fluorescent and stable CdTe QDs stabilized by MPA-Na and HPAMAM were obtained. The CdTe QDs showed a high quantum yield (QY) up to 58%. By preparing CdTe QDs within HPAMAM, the biocompatibility properties of HPAMAM and the optical, electrical properties of CdTe QDs can be combined, endowing the CdTe QDs with biocompatibility. The resulting CdTe QDs can be directly used in biomedical fields, and their potential application in bio-imaging was investigated.     

Synthesis and characterization of hyperbranched poly(silyl ester)s

Hyperbranched poly(silyl ester)s were synthesized via the A₂ + B₄ route by the polycondensation reaction. The solid poly(silyl ester) was obtained by the reaction of di‐tert‐butyl adipate and 1,3‐tetramethyl‐1,3‐bis‐β(methyl‐dicholorosilyl)ethyl disiloxane. The oligomers with tert‐butyl terminal groups were obtained via the A₂ + B₂ route by the reaction of 1,5‐dichloro‐1,1,5,5‐tetramethyl‐3,3‐diphenyl‐trisi1oxane with excess amount of di‐tert‐butyl adipate. The viscous fluid and soft solid poly(silyl ester)s were obtained by the reaction of the oligomers as big monomers with 1,3‐tetramethyl‐1,3‐bis‐β(methyl‐dicholorosilyl)ethyl disiloxane. The polymers were characterized by ¹H NMR, IR, and UV spectroscopies, differential scanning calorimetry (DSC), and thermogravimetric analysis (TGA). The ¹H NMR and IR analysis proved the existence of the branched structures in the polymers. The glass transition temperatures (T_g's) of the viscous fluid and soft solid polymers were below room temperature. The T_g of the solid poly(silyl ester) was not found below room temperature but a temperature for the transition in the liquid crystalline phase was found at 42°C. Thermal decomposition of the soft solid and solid poly(silyl ester)s started at about 130°C and for the others it started at about 200°C. The obtained hyperbranched polymers did not decompose completely at 700°C. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 3430–3436, 2006     

Synthesis and characterization of hyperbranched aromatic poly(ester-imide)s

The synthesis and characterization of hyperbranched aromatic poly(ester-imide)s are described. A variety of AB₂ monomers, N-[3- or 4-bis(4-acetoxyphenyl)toluoyl]-4-carboxyl-phthalimide and N-{3- or 4-[1,1-bis(4-acetooxyphenyl)]ethylphenyl}-4-carboxy phthalimides were prepared starting from condensation of nitrobenzaldehydes or nitroacetophenones with phenol and used for synthesis of hyperbranched poly(ester-imide)s containing terminal acetyl groups by transesterification reaction. These hyperbranched poly(ester-imide)s were produced with weight-average molecular weight of up to 6.87 g/mol. Analysis of ¹H NMR and ¹³C NMR spectroscopy revealed the structure of the four hyperbranched poly(ester-imide)s. These hyperbranched poly(ester-imide)s exhibited excellent solubility in a variety of solvents such as N,N-dimethylacetamide, dimethyl sulfoxide, and tetrahydrofuran and showed glass-transition temperatures between 217 and 255 °C. The thermogravimetric analytic measurement revealed the decomposition temperature at 10% weight-loss temperature (T_d¹⁰) ranging from 365 to 416 °C in nitrogen.