摘 要：以1,1,1-三羥甲基丙烷為核、2,2-二羥甲基丙酸為支化單體、對(duì)甲苯磺酸為催化劑，通過(guò)“準(zhǔn)一步法”熔融聚合得到第一至五代(G1~G5)端羥基超支化聚酯(HBP-OH)。用苯甲酰氯、乙酰氯、丙烯酸對(duì)其進(jìn)行端基改性，分別得到端苯基超支化聚酯(HBP-Bz)、端乙?；Щ埘?HBP-C2)以及端乙烯基超支化聚酯(HBP-C=C)。采用陽(yáng)離子開(kāi)環(huán)聚合的方法合成第一至第五代端羥基超支化聚醚(HBP-OHm)。通過(guò)紅外表征表明得到了預(yù)期產(chǎn)物，用DSC測(cè)定了合成產(chǎn)物的玻璃化轉(zhuǎn)變溫度，從結(jié)構(gòu)上分析了超支化聚合物玻璃化轉(zhuǎn)變溫度的各種影響因素。通過(guò)公式分析表明超支化聚合物的玻璃化轉(zhuǎn)變溫度與端基數(shù)和分子量之間存在線性關(guān)系。超支化聚合物的玻璃化轉(zhuǎn)變溫度隨端基極性的增加而增大，當(dāng)端基間形成氫鍵時(shí)，玻璃化轉(zhuǎn)變溫度增大。超支化聚合物的玻璃化轉(zhuǎn)變溫度隨分子量的增加先增大，當(dāng)分子量足夠大時(shí)玻璃化轉(zhuǎn)變溫度不再受其影響。超支化聚合物的玻璃化轉(zhuǎn)變溫度隨支化點(diǎn)間鏈段剛性的增大而增大。超支化聚合物的玻璃化轉(zhuǎn)變溫度隨中心核可反應(yīng)官能度的增加而增大。

關(guān)鍵詞：超支化聚合物；玻璃化轉(zhuǎn)變溫度；端基；分子量；支化結(jié)構(gòu)；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

目錄·····································································································Ⅲ

術(shù)語(yǔ)表··································································································1

1 緒論···································································································2

1.1超支化聚合物的結(jié)構(gòu)·············································································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熱性能··························································································3

1.2.4結(jié)晶性能·························································································4

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

1.3.1縮聚法·························································································4

1.3.2開(kāi)環(huán)聚合························································································4

1.3.3加成反應(yīng)·························································································5

1.4玻璃化轉(zhuǎn)變溫度·············································································5

1.5本課題的研究目的與意義·······································································6

2 實(shí)驗(yàn)部分··························································································8

2.1 實(shí)驗(yàn)原料·······················································································8

2.2 實(shí)驗(yàn)儀器及測(cè)試條件············································································9

2.2.1 紅外(FTIR) ··········································································9

2.2.2 差示掃描量熱分析(DSC) ······························································9

3 結(jié)果與討論·························································································10

3.1 結(jié)構(gòu)表征························································································10

3.2 玻璃化轉(zhuǎn)變溫度···································································13

3.3 玻璃化轉(zhuǎn)變溫度的影響因素分析·····················································15

3.3.1端基性質(zhì)對(duì)玻璃化轉(zhuǎn)變溫度的影響··········································15

3.3.2分子量對(duì)玻璃化轉(zhuǎn)變溫度的影響···············································18

3.3.3 中心核對(duì)玻璃化轉(zhuǎn)變溫度的影響·····················································20

3.3.4 支化結(jié)構(gòu)對(duì)玻璃化轉(zhuǎn)變溫度的影響·················································21

4 結(jié)論································································································23

參考文獻(xiàn)·····························································································24

致謝······························································································26