新穎聚合法製備功能性高分子材料之探討研究

New Polymerization Methods for Functional Polymeric Materials

陳博正(Po-Cheng Chen)

指導教授 ： 陳幹男

淡江大學/理學院/化學學系博士班/博士(2007年)

https://doi.org/10.6846/TKU.2007.00482

摘要

本論文所探討之主題，主要分為兩個部份；第一部份為常溫快速聚合反應之應用研究，第二部份為含聚二甲基矽氧烷之自由基硬化型聚胺基甲酸酯之製備與應用。
本論文第一部份是以含多元次乙亞胺或單元次乙亞胺官能基之化合物與含雙鍵之有機酸，如丙烯酸(又稱壓克力酸，Acrylic acid)等單體進行配方調整，並利用pH值之控制進行反應，可快速自行聚合成一種新型共聚物。本論文利用反應單體配方，結合了三階段且連續性的反應，進行快速聚合反應：1. 首先含雙鍵之有機酸與多元次乙亞胺或單元次乙亞胺在常溫下，進行酸鹼中和(Acid-base neutralization reaction)的放熱(Exothermic)反應；2. 前段放熱反應加速(Accelerated)進行次乙亞胺與羧酸根之間的開環反應；而其開環反應後形成含二級胺官能基之β-胺基酯 (β-amino-ester)化合物；3. 此二級胺基再與含雙鍵之有機酸之雙鍵進行分子間或分子內麥可加成(Inter or intra molecular Michael Addition reaction)反應。此配方以液態單體存在，再經由pH值之調整，控管此自發且連續性反應的反應速率，自行聚合成為具有高度分支及架橋密度之固態或直線型之高分子材料。藉由含多元次乙亞胺化合物等單體配方之選擇，則可選擇性製備出具備高度分支及網狀交聯結構之高分子材料；此網狀交聯結構之高分子材料，不溶於任何溶劑，可應用於快速接著劑或複合材料之基材。此快速聚合所形成的高度分支及網狀交聯聚合物之高分子鏈段中含有大量之酯基，故可在酸性或鹼性條件下進行酯基的水解(Hydrolysis)反應；水解後之主產物為水溶性的β-胺基酸(β-amino acid)，成為水溶性物質，使原來不溶的網狀交聯結構之高分子材料，成為可溶性物質。本論文的快速自行聚合合成方法，選用單元次乙亞胺化合物單體配方與丙烯酸，在常溫聚合製備直線型聚β-胺基酯[Poly(β-amino ester)]，可應用於基因轉植(Gene Transfer)或藥物釋放(Controlled Drug Release)等生技用途。本論文的快速聚合成法，提供一種製備直線型聚β-胺基酯[Poly(β-amino ester)]的方便捷徑。
本論文第二部份是以末端官能基為羥烷基(Alkylhydroxyl groups)之聚二甲基矽氧烷，取代傳統所使用之聚乙二醇(Polyethylene glycol, PEG)、聚丙二醇(Polypropylene glycol, PPG)等，引入到自由基硬化型聚胺基甲酸酯(UV-curable polyurethane, UV-PU)的製程中；所得到之含聚二甲基矽氧烷結構之自由基硬化型聚胺基甲酸酯，藉由聚二甲基矽氧烷結構之疏水性質(Water repellency)，可以應用於織物表面之批覆改質，使原先具吸水性之織物表面，呈現高度撥水的性質。

關鍵字

自身聚合 ； 次乙亞胺 ； 共聚物 ； 紫外光硬化

並列摘要

There are two main discussions in this report. One of them is rapid self-polymerization to obtain the β-Amino-ester alternative copolymers and the other is the application of UV-curable PDMS-structured polyurethanes.
In the first part of this report, the multi-aziridinyl containing compound, trimethylolpropane tris(1-aziridinyl) propionate (TMPTA-AZ), was prepared via the Michael Addition reaction of aziridine (AZ) and trimethylolpropane triacrylate (TMPTA). A rapid self-polymerization of acrylic acid (AA) and TMPTA-AZ occurred at ambient temperature without any catalyst. The rapid self-polymerization reaction mechanism was identified by a designed model reaction of methyl 3-(aziridin-1-yl) propanoate (MAP), trimethylacetic acid (TMAA) and ethyl acrylate (EA). According to the modeling reaction, it was illustrated that the proposed process involved three subsequent reactions: (1) a highly exothermic acid-base neutralization reaction took place between TMPTA-AZ and AA; (2) the neutralization heat triggered AZ ring-opening reaction and that carboxyl group (of AA) served as the nucleophile and resulted in an amino-ester bond formation; (3) a final hyper branched and cross-linked copolymers were obtained from that amino group reacted with acrylic double bond via the inter or intra-molecular Michael Addition reaction. These new hyper branched and cross-linked copolymers with various performance properties were obtained from a mixture of AA and TMPTA-AZ in different ratios and post heating.
During the new rapid self-polymerization process, the linear poly(β-amino-ester) was obtained when MAP instead of TMPTA-AZ as the starting material. The rapid self-polymerization reaction mechanism of MAP and AA was also identified via the model reaction. The average molecular weight and polydispersity index (PDI) of resulting poly(β-amino-esters) that obtained from rapid self-polymerization of AA and MAP under various conditions were determined by an aqueous gel permeation chromatography (GPC). This rapid self-assembly process was a new route for synthesizing the poly(β-amino-esters).
In the second part of this report, alkylhydroxyl-terminated PDMS was introduced into the conventional process instead of polyethylene glycol (PEG), polypropylene glycol (PPG) and etc., to prepare the NCO-terminated polyurethane and further modified by 2-hydroxyethyl methacrylate (2-HEMA) to obtain the UV-curable PDMS-structured polyurethane. The UV-curing reaction was simply took place via the UV irradiation and without any organic solvent emissions. It was a convenient and environmental friendly process. The UV-curable PDMS-structured polyurethane was applied in textile surface water repellency treatment which was due to the low surface energy and low water affinity of PDMS structures.

並列關鍵字

Self-polymerization ； β-Amino-ester ； Aziridine ； Copolymer ； PDMS ； UV-curable ； Water repellency

參考文獻

1. B. L. Rivas, G. del C. Pizarro, L. H. Tagle, D. Radie, Makromol. Chem. 1995, 231, 199

2. T. Saegusa, S. Kobayashi, Y. Kimura, Pure & Appl. Chem. 1976, 48, 307

3. T. Saegusa, Y. Kimura, S. Sawada, S. Kobayashi, Macromolecules 1974, 7, 956

6. Chen, G.-N.; K.-N. Chen J Appl Polym Sci 1997, 63, 1609.

8. Chen, G.-N.; Chen, K.-N. J Appl Polym Sci 1998, 67, 1661.