利用總體聚合法製備超分枝高分子

Synthesis of Hyperbranched Polymers by Bulk Polymerization

藍明哲(Ming-Che Lan)

指導教授 ： 鄭國忠

國立臺北科技大學/工程學院/化學工程所/碩士(2006年)

摘要

本研究利用双官能基環氧樹脂（例如D.E.R.331，A2）與多官能基胺化合物（例如diethylene triamine，DETA，B5）利用總體聚合法製備超分枝高分子，分別探討單體進料組成，單體官能基數、官能基非等反應性（取代基效應）、單官能基罩蓋劑（例如PGE，phenyl glycidyl ether，AR）等對超分枝高分子聚合度及分子量分佈等之影響，並藉由上述結果設計相關製備單體組成及反應條件，調控超分枝狀高分子，並且鑑定分析其分子結構。
研究發現在雙官能基環氧樹脂（D.E.R.331）�diethylene triamine（DETA）五官能基（A2/B5）反應系統中添加單官能基稀釋劑PGE(AR)至一定量後反應系統無法凝膠化，均成可溶體(sol)，其原理係PGE只具單環氧基(A)，在聚合反應時與雙官能基（A2），爭相與胺基（B）結合，因此會在分子末端形成懸吊鏈，而無法形成有效網路而凝膠化，理論上這項實驗發現應可以延伸用於製備超分枝高分子，可將AR視為末端罩蓋體，在聚合反應時加入，避免其形成三維網狀結構。
將A2 +B5+AR依不同比例混和，加熱進行聚合反應，並且分段取出樣本，進行分析。利用熱差掃描熱卡計量測上述A2+ B5 +AR混和物，在升溫及恆溫下之反應放熱曲線，以及生成物之玻璃轉移溫度等性質；或選用適當溶劑，將上述混和物溶解，進行聚合反應，並且分段取樣進行分析；利用紅外線光譜儀測定環氧基之轉化率；以凝膠滲透色層分析儀測定聚合反應過程中，分子量之變化。
在本研究中，藉由雙官能基環氧樹脂(A2)與多官能基的胺化合物(Bƒ)和單官能基環氧樹脂(AR)的大量聚合作用所產生出的超分枝狀高分子。首先，參數結構的相依性，像是討論A2/Bf/AR比率之超分枝高分子的分子量和PDI分佈指數。加入單官能基環氧樹脂後可獲得重量平均分子量3500~27000及PDI分佈指數2.3~5.3。隨著單官能基環氧樹脂 (AR)添加量的增加，聚合物的重量平均分子量就會減少。由DSC測量超分枝狀高分子的玻璃轉溫移溫度隨分子量降低而減少。加入GMA合成多功能乙烯基群的超分枝狀高分子。

關鍵字

環氧樹脂 ； 超分枝高分子 ； 總體聚合反應 ； 分子量

並列摘要

In this research we use biheterofnctional epoxy resin（e.x.D.E.R.331，A2） and multifunctional gentisamides（e.x.diethylene triamine，DETA，B5） to produce hyperbranched polymer to explore monomer feed composition，monomer functionality number、functionality unequal reactivites（substituent effect）、single functional group capper（e.x.PGE，phenyl glycidy ether，AR）etc. individually in which way they effect hyperbranched polymer、polymerization and molecularweight distributiion.Aaccording to the result, we can design related fabricate monomer components and reaction condition to modulate and control hyperbranched polymer. Otherwise, we can authenticate and analyze the structure of molecules.
In the primary research, we have found that after adding single functional group diluents PGE（AR）up to a certain volume in double functional group epoxy resin(D.E.R.331)/ diethylene triamine（DETA）five functional group（A2/B5）system, the reaction system can’t act on gelatoin but come into sol. It is the rationale that PGE with only single epoxy group （A）competing against double functional group（A2） combine with polyamines（B） in the meanwhile of polymerization’s progress. Therefore, they would form suspended chain in the ends of molecules, and act on gelation due to forming effective networks in vain. Theoretically, the discovery of this experiment should extendedly apply it to produce hyperbranched polymer,which we regard AR as end-capping, and add PGE to avoid forming three dimensions net structure during polymerization.
According to different proportion, We mix A2+B5+AR, and heat them to carry polymerization out. Then, we can draw the samples in several stages to analyze. To use DSC measure the curve from the mentioned mixture of A2+B5+AR under the raising and unchanged temperature during releasing heat, and the chrematistics of Tg. In the other hand, we select suitable dissolvent to melt the mentioned compound to act on polymerization. We can draw the samples in several stages to analyze with FTIR to measure the conversion ratio of epoxy group. Otherwise, we can gauge the change of molecularweight with GPC during polymerization’s progress.
In this study, hyperbranched polymers were prepared by a bulk polymerization of diepoxides(A2), multi-function amine monomers (Bƒ), and monoepoxide (AR). First, the dependence of the structure parameters, such as molecular weight, and polydispersity, of the hyperbranched polymers on the ratio of A2/Bf/AR were discussed. By adding the monoepoxides, the number average molecular weight of the polymers of 3500~27000 with PDI of 2.3~5.3 can be obtained. The molecular weight of the polymers decreases with increasing of the monoepoxide (AR). The glass transition temperature of the hyperbranched polymers measured by a DSC decreased with the lower molecular weight. The hyperbranched polymers with multi-functional vinyl groups were synthesized by the addition of glycerol monomethacrylate.

並列關鍵字

epoxy ； hyperbranched polymers ； bulk polymerization ； molecular

參考文獻

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