超支化聚(酯-胺)分子结构及固化涂层性能研究

近年来,颜德岳等基于A2型单体二丙烯酸酯及BB2′型单体二胺化合物合成了多种端胺基超支化聚(酯-胺),并对反应机理及聚合物结构进行了系统研究[1,2],结果表明,由于B与B′活性差异,反应首先生成AB2′型和B4′型中间体,进一步聚合得到可溶性产物.我们基于A3型单体三丙烯酸酯与B2型单体二胺化合物合成了端丙烯酸酯基超支化聚(酯-胺)[3,4].在这些体系中,由于官能团反应活性高,难以控制反应程度.另外,由于超支化聚合物不能直接用作结构材料,其在涂料、粘合剂等领域的应用多基于末端官能团的固化反应[5].但通常由于官能团在分子表面密集分布,部…     

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(酰胺-酯)的端基光致变色改性研究

采用丁二酸酐、三羟甲基氨基甲烷为主要原料,先在冰水浴条件下合成AB3型单体,然后进行熔融缩聚制得超支化聚(酰胺-酯)(HBP),最后用4-(4′-二甲氨基苯基偶氮)苯甲酸对HBP的末端羟基进行功能化改性,得到了一种具有光致变色和酸碱变色性的HBP;用紫外光谱对改性超支化聚(酰胺-酯)的变色性进行了研究。结果表明：随紫外光照时间延长紫外吸收强度增加;随pH值增大紫外吸收波长向短波方向移动。     

两亲性超支化聚(酯-胺)在染料相转移中的应用

具有树枝状结构的大分子由于其独特的结构、大量的分子内空穴、可修饰的表面端基及良好的溶解性，已被用作主体分子与客体分子进行复合，并在药物释放、纤维染色、印刷、传感器等方面显示良好的应用前景。通过长烷基链或氟碳链改性的两亲性树枝状分子可以将水溶性酸性染料     

含乙烯基超支化聚(酯-酰胺)大单体的合成

以顺丁烯二酸酐、二乙醇胺、邻苯二甲酸酐等为原料,利用官能团活性的差异,通过逐步展开的方法合成了含有双键和端羟基的聚（酯-酰胺）型分子结构的超支化大单体（3）。IR分析表明：3的分子末端为大量伯羟基,具有较高的反应活性;3含有可供聚合的乙烯基,将3与其它乙烯基单体共聚可以获得含超支化结构的共合物。     

十八烷基三氯硅烷改性超支化聚(胺-酯)吸附亚硝胺的研究

以十八烷基三氯硅烷对超支化聚(胺-酯)进行改性,合成了改性的超支化聚(胺-酯)。将改性前后的超支化聚合物用于吸附二甲基亚硝胺和二苯基亚硝胺。吸附结果表明,聚合物对二甲基亚硝胺和二苯基亚硝胺的吸附率分别为51.3%和11.9%,而改性后的超支化聚合物对二甲基亚硝胺和二苯基亚硝胺的吸附率分别为67.3%和37.2%。     

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].     

超支化聚(酯-酰胺)的合成与流变改性研究

近十几年来 ,超支化聚合物因具有独特的结构和特殊的性能而受到普遍关注[1] .超支化聚合物具有低的熔体粘度 ,与线性聚合物共混可显著改善其加工流变性 ,具有商业应用潜力 .关于超支化聚合物在流变改性方面的应用已有文献报道[2～ 6] ,但目前文献中的大多数单体合成较繁琐且收率不高 ,这已成为制约超支化聚合物应用的瓶颈 ,如何以简便的途径合成超支化聚合物已成为当前研究的重点 .本文设计一条新的合成路线 ,即以 1 ,2 ,4 苯三酸酐、乙醇胺及乙酸酐为原料 ,以高的收率得到了单体N ( 2 乙酰氧基乙基 ) N ( 2′ ,4′ 二羧基苯甲酰基 )胺 (…     

AB_3型超支化聚(酰胺-酯)的合成及缩聚动力学研究

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AB3型单体 ,然后进行熔融缩聚制得超支化聚 (酰胺 酯 ) ,没有出现凝胶现象 .采用Fourier变换红外谱仪 (FTIR)、粘度测试、端基分析等方法对其结构、特性粘数进行了表征 .同时对AB3型超支化聚 (酰胺 酯 )的缩聚反应动力学进行了研究 ,得出了130℃、14 0℃和 15 0℃时的缩聚反应速率常数 ,并进一步得出了缩聚反应活化能 .实验结果证明缩聚过程为自催化过程 ,且为三级反应     

超支化聚(胺酯)的合成及其光固化性能研究

采用甲基丙烯酸酐直接改性和先以丁二酸酐或邻苯二甲酸酐酯化再以甲基丙烯酸缩水甘油酯改性所得到的甲基丙烯酸酯化超支化聚 (胺 酯 )齐聚物在光引发剂存在时紫外光辐照下发生快速聚合反应 ;反应速率和双键转化率随超支化分子的结构不同而变化 ;高度交联的涂膜具有较好的热学性能     

NOVEL HYPERBRANCHED POLY（PHENYLENE OXIDE）S WITH PHENOLIC TERMINAL GROUPS： EFFECTS OF REACTION TIME AND CORE MOLECULES ON THE MOLECULAR WEIGHT AND POLYDISPERSITY

A novel hyperbranched poly（phenylene oxide） （HPPO） with phenolic terminal groups was prepared from 4-bromo-4＇,4＂-dihydroxytriphenylmethane as AB2 monomer in dimethylsulfoxide （DMSO） via a modified Ullmann reaction. The molecular weight and polydispersity （PD） of the resulting polymers increased with increasing reaction time. In the presence of core molecules （bisphenol A and 1,3,5-trihydroxybenzene）, which have the similar molecular backbones to the reactive monomer, the molecular weight could be controlled by varying the core-to-monomer ratio. Incorporation of a very small amount of core molecules could lead to a higher molecular weight as compared with that without the addition of core molecules. However, when the core content reached certain extent, the molecular weight would decrease with the further increase in the core content. A new similar behavior of control over the PD was also obtained. The resulting polymers were characterized by ^1H-NMR, ^13C-NMR, FT-IR, and GPC.     

INFLUENCE OF MOLECULAR STRUCTURES OF SECONDARY AMINE TERMINATED POLY（ESTER-AMINE）S ON THE CURING PERFORMANCE WITH EPOXY RESIN

Five secondary amine terminated poly(ester-amine)s(defined as PEA)with controlled molecular structures were synthesized through reacting excessive piperazine with phthalicdiglycol diacrylate(PDDA)and 1,1,1-trimethylolpropane triacrylate(TMPTA)at a constant secondary amine/acrylate group ratio of 1.5/1 and at different PDDA/TMPTA molar ratios. Both IR and ~(?)H-NMR spectra indicated that all acrylate groups were consumed in the reaction,based on which the structural parameters were calculated from the ~(?)H-NMR spectra.With decreasing PDDA/TMPTA ratio,the content of secondary amine,degree of branching,molecular weight,T_g and T_d increased accordingly.These polymers were further used as both crosslinkers and flexibilizers for a linear epoxy resin E51 to form cured films under ambient condition.The gel content, relative hardness and T_g of the resulting films increased as PEA molecules changed from linear to highly branching structures.Due to the flexibility of PEA molecules,all the films possessed excellent mechanical performance.     

聚氧硫杂蒽树脂固化特性及其动力学的研究

以DSC、TG等技术手段研究了聚氧硫杂蒽树脂 (POSPF)的固化特性及其动力学 .结果表明 ,用六次甲基四胺 间二氯苄作固化剂 ,加热至 10 5～ 2 2 5℃能使POSPF树脂固化 ,在固化过程树脂中的活性羟甲基和固化剂参与反应生成亚甲基桥从而形成网状体型结构 ;动态DSC曲线上出现宽的固化放热峰 ,用T β外推法确定其凝胶温度Ti=10 0 0℃、固化温度Tp=181 5℃、后固化温度Tf=2 2 5 7℃ .固化后树脂具有优良的耐热性 ,失重 5 %时热分解温度高达 4 0 3℃ .     

SYNTHESIS AND CHARACTERIZATION OF HYPERBRANCHED POLYURETHANE-BENZYLTETRAZOLE

A series of hyperbranched polyurethane-benzyltetrazoles(H-PBTZs) with different linkage structures were synthesized via the polycondensation of hexamethylenediisocyanate as an A_2 type monomer with(4-(1H-tetrazol-5- yl)benzyl)-diethanolamine(TBDEA) as a BB'_2 type monomer in the absence of catalyst at different temperatures.The FTIR, and ~(13)C and ~1H-NMR spectroscopy were used to characterize the molecular structures of TBDEA and H-PBTZs as well as the counterpart linear polyurethane-benzyltetrazole(L-...     

STUDY OF NANOSIZED SILICA GRAFIED WITH HYPERBRANCHED POLY（AMINE-ESTER）

A new method to chemically modify the surface of nanosized-SiO2 was studied in this paper. Nanosized-SiO2 was grafted with hyperbranched poly(amin ester) through one-spot polycondensation between AB2 monomer and active hydroxyl on silica surface in present of catalyst.Compared with the results of FTIR and TEM, it is found hyperbranched poly(amin ester) is successfully grafted on the surface of nanosized-SiO2 and the surface properties have been changed with an expected way. The results indicate that nanosized-SiO2 grafted with hyperbranched poly(amin ester) has better dispersion in the ethanol or chloroform than that unmodified.     

STUDY OF NANOSIZED SILICA GRAFIED WITH HYPERBRANCHED POLY(AMINE-ESTER)

1. INTRODUCTIONIn order to solve the agglomeration of nano-SiO2 and improve its dispersion stability in polymer matrix, the study on surface modification of nano-SiO2 has been always attended. At present, surface modification of nano-SiO2 is mostly carrie…     

PREPARATION AND CHARACTERIZATION OF INCLUSION COMPLEXES OF TWO-ARM LINEAR AND FOUR-ARM STAR-SHAPED POLY（ε-CAPROLACTONE）S WITH α-CYCLODEXTRIN

Both four-ann star-shaped poly（ε-caprolactone） （4sPCL） and two-ann linear PCL （2LPCL） were synthesized and their inclusion complexation with α-cyclodextrin （α-CD） were studied. The inclusion complexes （ICs） formed between the PCL polymers and α-CD were characterized by ^1H-NMR, DSC, TGA, WAXD, and FT-1R, respectively. Both branch ann number and molecular weight of the PCL polymers have apparent effect on the stoichiometry （CL：CD, mol：mol） of these ICs. All these analytical results indicate that the branch arms of the PCL polymers are incorporated into the hydrophobic α-CD cavities and their original crystalline properties are completely suppressed. Moreover, the inclusion complexation between two-ann linear or four-ann star-shaped PCL polymers and α-CD not only enhances the thermal stability of the guest PCL polymers but also improves that of α-CD.