高分子材料應用在功能化塗裝之研究開發

Functionalization of Polymeric Materials for Coating Applications

陳威宏(Wei-Hung Chen)

指導教授 ： 陳幹男

淡江大學/理學院/化學學系博士班/博士(2009年)

https://doi.org/10.6846/TKU.2009.00971

摘要

本論文是利用紫外光交聯技術、溼氣交聯技術及電子束照射技術，開發一系列高分子材料應用於功能化塗裝技術。鑒於傳統高分子塗裝材料在合成與加工過程上，往往需要消耗大量的能源，且在加工紡織品等較細緻的材料時，也常會破壞織物原有的特性與手感，同時易受洗滌等外力剝離而效果不彰；本論文針對這些需求，開發出多種有別傳統的塗裝用高分子材料。

論文第一部分為紡織品的撥水與吸濕加工，將含氟化合物改質成氟化甲基丙烯酸化合物後，再與甲基丙烯酸甲酯進行自由基聚合反應，合成含氟之疏水性高分子，此高分子可與紫外光交聯型環氧樹脂混合作為織物之撥水加工塗料，或搭配電子束照射後處理，將超吸濕織物樣品表面加工成為撥水特性，對水接觸角超過130°，且經過50次洗滌後仍能維持效果。吸濕部分，製備兩種不同型式的紫外光交聯型PU，分別為離子型和非離子型，藉由PU懸掛的強親水基團以及主鏈段上的聚乙二醇具有親水的性質，對於織品的表面能達到快速的吸濕處理，加工後的織物表面。對水接觸角低於35°，具有耐洗滌能力。織物加工前後之手感數據比較，能證明加工對織物手感的維持，有良好的成效。

第二部分為含聚矽氧烷PU的合成與應用，首先製備各種紫外光交聯型PU塗料，塗料中含有不同類型的聚矽氧烷鏈段，藉由PDMS材料低表面能的特性，能在織物纖維表面形成長效性的撥水塗層，加工後的紡織品不論是聚酯纖維、尼龍纖維或棉質布料，表面對水接觸角皆能超過130°，且經過50次洗滌後仍能維持效果。論文中亦合成出溼氣交聯型的撥水高分子塗料，在最適條件加工下，可讓吸濕織物的表面轉變成超撥水性質，對水接觸角超過150°，並且具備快速、長效性、及節能的優點。

論文第三部分為電磁波吸收型水性PU奈米複合材料之製備與應用，將水性PU與碳包奈米鐵粉，奈米碳管與奈米鐵加工製成導電型複合材料，利用TGA，DMA等技術測試其物理性質，並利用網路分析儀量測其電磁特性，研究中製備的水性PU奈米複合材料，其介電係數獲得大幅提升，同時材料的柔軟度及熱穩定性也獲得提升，有效增加材料的應用性。

關鍵字

撥水 ； 塗佈加工 ； 紫外光交聯 ； 電子束輻照 ； 聚胺基甲酸酯

並列摘要

In the first part of this discourse, a fluorinated acrylate monomer, octafluoropentylmethacrylate (OFPMA) was synthesized from a reaction between methacrylol chloride and fluorine containing alcohol. The fluorine containing acrylate co-polymer (OFPMA-MA) was prepared by a solution copolymerization of OFPMA and methyl acrylate (MA). An inter-penetrating polymeric network (IPN) system was formulated by mixing fluorine containing co-polymer OFPMA-MA and UV curable epoxy acrylate oligomer. The UV-curable IPN system was coated on fabric surface and cured by UV radiation process. Upon UV curing, the highly cross-linked polymer anchored into fabric fibers that enhance the washing durability of treated fabric. The water repellency of the treated fabric surface was exhibited that related to its fluorine content of UV-cured IPN system. Their surface properties were proved by the contact angle measurements and Kawabata fabric evolution system (KES-FB). With the optimum coating treatment, the contact angle of textile could reach over 130° and remain the efficiency after 50 washing cycles.
In the second part of this discourse, a UV-curable PDMS-containing polyurethane (PU) oligomer (UV-PDMS-PU), having a PDMS moiety is designed for textile (PET, Nylon and Cotton) surface treatment with a long lasting hydrophobic property. Polydimethylsiloxane (PDMS) is a super-hydrophobic material with low surface energy. UV-PDMS-PU was prepared by an addition of 2-hydroxyethyl methacrylate (2-HEMA) to NCO-terminated PDMS-containing PU pre-polymer (NCO-PDMS-PU). NCO-PDMS-PU was obtained from an addition reaction of alkyl hydroxyl-terminated PDMS with an excess amount of isophorone diisocyanate (IPDI). The UV-cured PDMS-containing PU films were evaluated by the measurements of thermal and physical properties. The hydrophobic characters and silicone content were remained on textile surface after water washing cycles, which indicating that UV-curing process can help the PDMS moiety to anchor onto textile fibers. With the optimum coating treatment, the contact angle of textile could reach over 150° and remain the efficiency after 50 washing cycles.

In the third part of this discourse, a polymeric composite materials with highly conductivity are prepared by the blending of aqueous-based polyurethane (PU) as a matrix and with three different types nano-size materials. These three nano-materials are carbon-coated nano-iron particles, nano-iron metal particles, and carbon-nanotubes. The thin films of composite materials are obtained from the drying of these PU dispersion blends at ambient temperature. The conductivity (ε) and permeability (μ) of these composite films are measured by a network analyzer. The thermal and mechanical properties are measured by TGA and DMA, respectively. Among these measurements and find out the PU film with carbon-nanotube behaving the highest dielectric constant on the broad-band (3~18GHz) range. It also proves that the iron metal particles reach to nano size, the magnetic properties of its composite material shifts from ferromagnetic to paramagnetic characters.

並列關鍵字

water repellency ； coating treatment ； UV-Curing ； electron beam radiation ； Polyurethane

參考文獻

[2] Sharfrin, E. (1960). "Constitutive relations in the wetting of low energy surfaces and the theory of the retraction method of preparing monolayers". The Journal of Physical Chemistry 64 (5): 519-524

[4] Schrader, M.E (1992). Modern Approaches to Wettability Theory and Applications'. New York: Plenum Press

[5] de Gennes, P.G. (1985). "Wetting: statics and dynamics". Reviews of Modern Physics 57 (3): 827-863.

[7] Robert J. Good (1992). "Contact angle, wetting, and adhesion: a critical review". J. Adhesion Sci. Technol. 6 (12): 1269-1302.

[8] 葉錫宜 林睿哲 記憶金屬表面之血栓調節束固定化，及其生活物性及血液相容性之研究 國立成功大學 化學與工程學系 2002