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  • 學位論文

功能性尼龍六與不飽和聚酯高分子/黏土 奈米複材的開發與放大製程之研究

Studies on the Application and Pilot Process of functional Nylon 6 and UP /Clay Nanocomposites

指導教授 : 蔡宗燕
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摘要


本論文主要分為兩個部分,分別探討蒙脫土(montmorillonite)在熱塑性高分子尼龍六(Nylon 6)及熱固性高分子不飽和聚酯(Unsaturated polyester resins,UP)的奈米複材製程開發與性質研究。尼龍六/蒙脫土奈米複材的製備主要是使用純化級黏土,藉由聚合時的爆破力而達到奈米級分散,並進行工廠級300L批次放大製程與開發;不飽和聚酯樹脂/蒙脫土奈米複材的製備主要是利用黏土的層狀結構添加在基材中,減少不飽和聚酯樹脂的體積收縮,並進行工廠級FRP模板試驗以確認螺紋印現象的減少。 尼龍六/蒙脫土奈米級複材的製備有別於傳統方法,天然黏土沒有使用任何四級銨鹽先行改質就能提升有機相和無機層材之間的相容性,而達到奈米混成的效應。先將尼龍六單體己內醯胺(caprolactam, CPL)在酸性條件下插層於黏土層間,再利用原位聚合法來合成尼龍六/黏土奈米級複合材料。並以廣角X光繞射儀(WXRD)與穿透式電子顯微鏡(TEM)來評估奈米級複合材料的分散型態。再使用熱重分析儀(TGA)與圓錐熱量儀(Cone Calorimeter)檢測其熱穩定性與熱釋放速率;根據美國ASTM,動態機械分析儀(DMA) 是用於測量複合材料之機械強度,結果顯示儲存模數、拉伸強度、彎曲強度與衝擊強度皆提升20 %以上,黏土添加量為4 phr的奈米複材其熱變形溫度(HDT)由69℃提升至160℃;另外,從氣體穿透分析儀(GPA)的量測顯示良好的氣體阻隔性質。 以實驗室最佳聚合條件,委託紡研中心進行300L放大試驗製備尼龍六/黏土奈米複材及至尼洛奈米複材公司吹膜製成薄膜,並檢測及探討其分散型態、熱性質、機械性質及阻氣性質。結果顯示尼龍六/黏土奈米級複合材料及其薄膜較純尼龍六薄膜具有較佳的光學性質、機械性質及氣體阻隔性質。 不飽和聚酯/蒙脫土奈米複材的製備有別於一般傳統樹脂藉由添加抗收縮劑(Low Profile Additives, LPA)於UP/ST 系統中,以減少不飽和聚酯樹脂的體積收縮,本成果僅添加奈米黏土達到尺寸控制而具較小的體積收縮率。 目前製作遊艇之船體最好的辦法被認為是真空灌注法。然而,當船用樹脂採用不飽和聚酯樹脂(UP)/玻璃纖維和乙烯基樹脂(VE)/玻璃纖維複合材料時,其遊艇表面則會出現螺紋印現象(PTP)。其原因在於不飽和聚酯樹脂或乙烯基樹脂的固化程度不同,而導致複合材料的表面產生不同熱收縮的現象。當不飽和聚酯樹脂(UP)/苯乙烯(ST)以自由基聚合反應形成共聚物時,自文獻報導,可知其體積收縮率約7~10%1,2,從而在表面上造成曲折和皺紋,稱之為螺紋印現象。為了降低螺紋印的現象,利用有機蒙脫土充當填料添加,以改善的不飽和聚酯樹脂(UP)/苯乙烯(ST)基材的尺寸穩定性。在本研究中,天然黏土及其他有機分子進行改質後,並利用廣角X光繞射儀(WXRD)及熱重分析儀(TGA)確認改質前後黏土的層間距變化與改質劑進入黏土層間所佔的比例。將不飽和聚酯單體膨潤於黏土層間,再利用原位聚合法合成不飽和聚酯/黏土奈米級複合材料。廣角X光繞射儀(WXRD)與穿透式電子顯微鏡(TEM)來評估奈米級複合材料的分散型態。樹脂的體積收縮率則以阿基米的密度測量來表示。纖维增强塑料(FRP)的螺紋印現象(PTP)則用光學照片與表面粗糙度量測儀來表示。分別使用熱重分析儀(TGA)與圓錐熱量儀(Cone Calorimeter)檢測其熱穩定性與熱釋放速率;根據ISO 527-4:1997(E),射出標準試片是用於測量複合材料之機械強度。

並列摘要


This study is divided into two parts, one is for the thermoplastic polymer (Nylon 6)/ montmorillonite nanocomposites and the other is for thermosetting polymer (unsaturated polyester resins)/ montmorillonite nanocomposites. Nylon 6/ montmorillonite nanocomposites were prepared by mainly using the purified clay, and via in situ polymerization process to achieve the nanoscale dispersion, and then applied to the pilot process of 300L. The unsaturated polyester resin/ montmorillonite nanocomposites were mainly made by using the modified clay to decrease the volume shrinkage. To confirm the reduction of the print-through phenomenon (PTP) for fiber-reinforced plastic (FRP) Nylon 6/montmorillonite nanocomposites were prepared without any modification of clay compared with the traditional methods which used alkylammonium salt as the modified agent to improve the accessibility and compatibility between the organic and inorganic materials. Nylon 6/clay nanocomposites were prepared by intercalating the monomer, caprolactam, into the gallery of clay via in situ polymerization process. Wide angle X-ray diffraction (WAXD) and transmission electron microscopy (TEM) techniques were employed to assess the dispersion morphology of the nanocomposites. The thermal stability and heat release rate are measured by thermo gravimetric analysis (TGA) and cone calorimeter, respectively. According to ASTM, the dynamic mechanical analyzer (DMA) is applied to measure the reinforcing mechanical properties of the nanocomposites that show over 20% enhancement of storage modulus, tensile strength, flexural strength and impact strength. The heat distorted temperature (HDT) increases from 69C to 160C with 3 wt% clay content. Finally, Gas permeability analyzer (GPA) shows the excellent gas barrier property. The best polymerization conditions in laboratory were applied to the 300L pilot process of the Nylon 6/ montmorillonite nanocomposite, which was blew to the membrane for the application of packaging materials. This membrane was detected and investigated the dispersion morphology, thermal properties, mechanical properties and gas barrier properties. Membranes prepared from Nylon 6/clay nanocomposites has better optical and gas barrier than pure Nylon 6. Preparation of unsaturated polyester resin/ montmorillonite nanocomposites was different from the conventional resin by adding anti-shrinkage agents (Low Profile Additives, LPA) in the UP / ST system, reducing the volume shrinkage of unsaturated polyester resin. Recently, the vacuum-injection method was considered the best approach for making the hulls of yachts. However, the resins cause a print-through phenomenon (PTP) on the yacht surface when using unsaturated polyester resins (UP)/glass fiber and vinyl ester (VE)/glass fiber composites. One of the reason is from the different curing degree within the UP or VE resin which induces the different thermal contractions of the composites. When the UP/ST or VE/ST copolymers were prepared by the free-radical polymerization reactions, the variation in volume shrinkage are about 7–10%, thereby inducing twist and wrinkle on the surface. To reduce these problems, organomontmorillonite was added as the filler to improve the dimension stability of the UP/ST matrix. In this study, clays were modified by organic compounds. The modified clays were characterized by wide-angle X-ray diffraction (WAXD) and thermogravimetric analysis (TGA) to confirm the change of d-spacings and the amount of modified agent within the clay layers. UP/clay nanocomposites by intercalating the monomer into the gallery of clay via in situ polymerization process. Wide angle X-ray diffraction (WAXD) and transmission electron microscopy (TEM) techniques were employed to assess the dispersion morphology of nanocomposites. The volume shrinkage of the resin was determined by density measurements. The print-through phenomenon (PTP) of fiber-reinforced plastic (FRP) was determined by optical photo picture. The thermal stability and heat release rate are measured by thermo gravimetric analysis (TGA) and cone calorimeter, respectively. Standard testing specimens according ISO 527-4:1997(E) is applied to measure the reinforcing mechanical properties of the nanocomposites.

並列關鍵字

Nylon 6 UP clay nanocomposities

參考文獻


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