以EDA和TMPTA为原料树枝状大分子的合成、表征及应用
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摘要
树枝状大分子是一类结构高度支化、表面官能团密度大、单分散性的大分子。在光电传感、液晶、胶束、催化剂、药物制剂和光固化涂料等多方面有广阔的应用。其研究热点主要集中在新结构树枝状大分子的合成及现有树枝状大分子的功能化。本文分别在这两方面进行了研究。第一次以4官能团的EDA和3官能团的TMPTA为原料，省去保护——解保护和官能团活化步骤，采用发散法一步合成了一种新型树枝状大分子。具体工作如下：
1．以三羟甲基丙烷三丙烯酸酯(TMPTA)和乙二胺(EDA)为原料，甲醇为溶剂，通过Machael加成反应，分别合成以EDA或TMPTA为核，端基为丙烯酸酯双键或伯胺基的树枝状大分子(1.0—2.5代)，进行了分离并考察了原料配比、溶剂的量、反应温度和反应时间对产物的产率和纯度的影响。
2．用IR、NMR、HPLC、电喷雾质谱和元素分析等手段对树枝状大分子进行了表征。
3．将EDA为核，丙烯酸酯双键为端基的第1代树枝状大分子[G1(=)]，与其分子量相近，线型结构的紫外光固化齐聚物(601、602)进行固化速度比较，结果发现前者比后者快得多。
4．将TMPTA为核，伯胺基为端基的第1代树枝状大分子[G1(NH_2)]，EDA为核，伯胺基为端基的第1.5代树枝状大分子[G1.5(NH_2)]作为环氧树脂的固化剂。固化实验结果表明：固化时间缩短，适用期延长，而且具有无挥发性、黏度小、毒性低等优点。
Dendrimers have the more branching of structure, high density of peripheral functional group, single dispersion. They are applied in photoelectricity transducer, liquid crystal, micelle, catalyst, pharmaceutical preparation, light curing coat, etc. The study of dendrimers focuses on synthesizing the new dendrimers and the function of the existing dendrimers. In this paper, we study the two aspects. We omit protection - -undoing protection functional group activation and employ divergent strategy by one step way, synthesizing dendrimers and studying their application.
1. Dendrimers (1.0-2.5G) with an EDA or TMPTA core and peripheral acrylic ester double bond and amino are synthesized from ethylene diamine (EDA) and trimethylolpropane triacrylate (TMPTA), CH3OH as solvent, by Michael addition reaction. The effects of reaction temperature, reaction time, ratio of reactants and solvent content on the yield and purity of dendrimers are studied.
2. These dendrimers structures are identified by IP^ NMR, ESI-MS, HPLC and elementary analysis.
3. Comparing 1.0 generation dendrimer with an EDA core and peripheral acrylic ester double bond [G1(=)] and the same molecule weight, linear, normal oligomers, such as 601 , 602, we obtain the curing speed of the first higher than the later.
4. Because 1.0 generation dendrimer with a TMPTA core and peripheral amino [G1(NH2)] and 1.5 generation dendrimer with an EDA core and peripheral amino [G1.5(NH2)] have no volatilization, little viscosity and little toxicity, appling G1(NH2) and G1.5(NH2) regarding as curing agent of epoxy resin. It is found that curing speed becoming higher and application period prolonging.
1．以三羟甲基丙烷三丙烯酸酯(TMPTA)和乙二胺(EDA)为原料，甲醇为溶剂，通过Machael加成反应，分别合成以EDA或TMPTA为核，端基为丙烯酸酯双键或伯胺基的树枝状大分子(1.0—2.5代)，进行了分离并考察了原料配比、溶剂的量、反应温度和反应时间对产物的产率和纯度的影响。
2．用IR、NMR、HPLC、电喷雾质谱和元素分析等手段对树枝状大分子进行了表征。
3．将EDA为核，丙烯酸酯双键为端基的第1代树枝状大分子[G1(=)]，与其分子量相近，线型结构的紫外光固化齐聚物(601、602)进行固化速度比较，结果发现前者比后者快得多。
4．将TMPTA为核，伯胺基为端基的第1代树枝状大分子[G1(NH_2)]，EDA为核，伯胺基为端基的第1.5代树枝状大分子[G1.5(NH_2)]作为环氧树脂的固化剂。固化实验结果表明：固化时间缩短，适用期延长，而且具有无挥发性、黏度小、毒性低等优点。
Dendrimers have the more branching of structure, high density of peripheral functional group, single dispersion. They are applied in photoelectricity transducer, liquid crystal, micelle, catalyst, pharmaceutical preparation, light curing coat, etc. The study of dendrimers focuses on synthesizing the new dendrimers and the function of the existing dendrimers. In this paper, we study the two aspects. We omit protection - -undoing protection functional group activation and employ divergent strategy by one step way, synthesizing dendrimers and studying their application.
1. Dendrimers (1.0-2.5G) with an EDA or TMPTA core and peripheral acrylic ester double bond and amino are synthesized from ethylene diamine (EDA) and trimethylolpropane triacrylate (TMPTA), CH3OH as solvent, by Michael addition reaction. The effects of reaction temperature, reaction time, ratio of reactants and solvent content on the yield and purity of dendrimers are studied.
2. These dendrimers structures are identified by IP^ NMR, ESI-MS, HPLC and elementary analysis.
3. Comparing 1.0 generation dendrimer with an EDA core and peripheral acrylic ester double bond [G1(=)] and the same molecule weight, linear, normal oligomers, such as 601 , 602, we obtain the curing speed of the first higher than the later.
4. Because 1.0 generation dendrimer with a TMPTA core and peripheral amino [G1(NH2)] and 1.5 generation dendrimer with an EDA core and peripheral amino [G1.5(NH2)] have no volatilization, little viscosity and little toxicity, appling G1(NH2) and G1.5(NH2) regarding as curing agent of epoxy resin. It is found that curing speed becoming higher and application period prolonging.
引文
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