支化结构对脂肪族超支化聚酯玻璃化转变温度的影响.doc

摘 要：以1,1,1-三羟甲基丙烷为核、2,2-二羟甲基丙酸为支化单体、对甲苯磺酸为催化剂，通过“准一步法”熔融聚合得到第一至五代(G1~G5)端羟基超支化聚酯(HBP-OH)。用苯甲酰氯、乙酰氯、丙烯酸对其进行端基改性，分别得到端苯基超支化聚酯(HBP-Bz)、端乙酰基超支化聚酯(HBP-C2)以及端乙烯基超支化聚酯(HBP-C=C)。采用阳离子开环聚合的方法合成第一至第五代端羟基超支化聚醚(HBP-OHm)。通过红外表征表明得到了预期产物，用DSC测定了合成产物的玻璃化转变温度，从结构上分析了超支化聚合物玻璃化转变温度的各种影响因素。通过公式分析表明超支化聚合物的玻璃化转变温度与端基数和分子量之间存在线性关系。超支化聚合物的玻璃化转变温度随端基极性的增加而增大，当端基间形成氢键时，玻璃化转变温度增大。超支化聚合物的玻璃化转变温度随分子量的增加先增大，当分子量足够大时玻璃化转变温度不再受其影响。超支化聚合物的玻璃化转变温度随支化点间链段刚性的增大而增大。超支化聚合物的玻璃化转变温度随中心核可反应官能度的增加而增大。

关键词：超支化聚合物；玻璃化转变温度；端基；分子量；支化结构；中心核

Influence of branching architecture on glass transition temperature of aliphatic hyperbranched polyesters

Abstract: The first to the fifth generation of hyperbranched polyesters were synthesized by "quasi-one-step" melt polymerization with 1,1,1-trimethylolpropane as core, 2,2-dimethylol propionic acid as branched units and p-toluene sulfonic acid as catalyst.  Phenyl-terminated hyperbranched polyesters (HBP-Bz), acetyl-terminated hyperbranched polyesters (HBP-C2) and vinyl-terminated hyperbranched polyesters (HBP-C=C) were prepared with benzoyl chloride, acetyl chloride and acrylic acid as end-group modifier, respectively. The first to the fifth generation hydroxyl-terminated hyperbranched polyethers were synthesized by cationic ring-opening polymerization. The products were characterized by FTIR. The results showed that expected products were obtained. The glass transition temperature of products was studied by differential scanning calorimetry (DSC). Affecting factors of glass transition temperature of hyperbranched polymers were analyzed from anatomically. The relation of the glass transition temperature of hyperbranched polymers with properties of end groups and molecular weight were analyzed by free volume theory formula，which showed a linear relation between them. The glass transition temperature of hyperbranched polymers rises with the increase of the polarity of end groups, and the glass transition temperature of hyperbranched polymers rises when the hydrogen bonding was formed among end groups. The glass transition temperature of hyperbranched polymers rises with the increase of molecular weight. When the relative molecular mass was high enough it remained the same. The glass transition temperature of hyperbranched polymers rises with the increase of the rigidity of chain segments. The glass transition temperature of hyperbranched polymers rises with the increase of degree of functionality of central core.

Keywords: hyperbranched polymer; glass transition temperature; terminal groups; molecular weight; branched structure; central core

摘要·····································································································Ⅰ

目录·····································································································Ⅲ

术语表··································································································1

1 绪论···································································································2

1.1超支化聚合物的结构·············································································2

1.2超支化聚合物的性能············································································3

1.2.1溶解性能···························································································3

1.2.2粘度·····························································································3

1.2.3热性能··························································································3

1.2.4结晶性能·························································································4

1.3超支化聚合物的合成············································································4

1.3.1缩聚法·························································································4

1.3.2开环聚合························································································4

1.3.3加成反应·························································································5

1.4玻璃化转变温度·············································································5

1.5本课题的研究目的与意义·······································································6

2 实验部分··························································································8

2.1 实验原料·······················································································8

2.2 实验仪器及测试条件············································································9

2.2.1 红外(FTIR) ··········································································9

2.2.2 差示扫描量热分析(DSC) ······························································9

3 结果与讨论·························································································10

3.1 结构表征························································································10

3.2 玻璃化转变温度···································································13

3.3 玻璃化转变温度的影响因素分析·····················································15

3.3.1端基性质对玻璃化转变温度的影响··········································15

3.3.2分子量对玻璃化转变温度的影响···············································18

3.3.3 中心核对玻璃化转变温度的影响·····················································20

3.3.4 支化结构对玻璃化转变温度的影响·················································21

4 结论································································································23

参考文献·····························································································24

致谢······························································································26