| 摘要: | 聚丙烯纖維(polypropylene fiber，簡稱P.P.)具有環保、質輕(密度0.91)、耐磨、強力佳、高透明性、尺寸安定性佳、優良電氣絕緣性及耐化學藥品性等諸多優異物性，且價格低廉，因此被譽為未來的〝夢中纖維〞；除了大量應用於紡織工業外，也是生醫材料及衛生用品上常用的基材，使得聚丙烯纖維成為目前及將來頗為重要的合成纖維之一。雖然聚丙烯纖維具有上述諸多優點，但因纖維本身不含任何反應官能基且結晶度相當高，所以親水性不佳，染色困難。目前最廣泛使用的染色方法為原液染色(Dope dyeing, Mass coloration)，但此上色方式不僅影響聚丙烯纖維的基本物性且需大量生產才符合經濟效益。然而，現今纖維製品需具少量多樣及快速反應的原則，因此原液染色恐無法達此優勢；另，此染法的色調過於單調亦是其缺點。目前有關聚丙烯纖維的各種改質染色法包括：表面接枝、共聚合反應、活性體混合擠壓抽絲、被覆加工、電漿加工、化學氯化改質… …等，雖然上述各種改質法各有其優缺點，但綜合其染色性能，經濟性及改質技術，其中表面接枝改質法係未來最具實用性及經濟效益的方法，同時國內外亦有許多專家學者致力於此方面之研究。事實上聚丙烯纖維的接枝改質於1963 年R.F.Stamm 等人，已曾利用γ 射線活化聚丙烯纖維並接枝氯甲基苯單體，以提高PP 纖維染色性。其後雖不斷地有研究者採用不同方法將乙烯基單體對聚丙烯纖維進行接枝改質之研究，但以往有關聚丙烯纖維接枝改質方面，大多採用γ 射線(γ-ray)誘導甲基丙烯酸，丙烯酸，苯乙烯等單體接枝於聚丙烯纖維，其中輻射誘導接枝不僅易引起纖維的降解且技術較複雜，費用較高，因此無法大量生產。目前許多的研究則朝電漿接枝進行探討，因纖維經電漿處理後不僅表面親水性明顯改善，且單體接枝效果良好。過去雖有人將乙烯基單體及馬來酸酐對聚丙烯進行接枝改質研究，且以分散染料及鹽基性染料進行染色，但在耐光及水洗染色牢度等方面仍存在某些問題尚未解決，因此尋求如何使聚丙烯纖維的染色效果及染色堅牢度更加提升乃目前相當被重視及頗為重要的課題。本研究之目的即是找尋更佳的接枝單體及接枝方式，並以適當的反應性染料對改質的聚丙烯纖維或織物進行染色，以期解決過去耐光及水洗染色堅牢度不佳之問題。因此本研究將利用甲基丙烯酸環氧丙酯與不同胺類(單元胺、二元胺、多元胺)行親核性開環加成聚合反應，利用控制共聚反應之條件製備出不同分子量丙烯酸環氧丙酯/胺類聚合物，隨後再以電漿表面處理技術及UV 光起始劑使不同分子量丙烯酸環氧丙酯/胺類共聚物接枝至聚丙烯纖維表面，使其表面同時帶有胺基與羥基，以利反應性染料之反應上色，此不同於過去為了增進鹽基性染料及分散性染料之上色效果，而採乙烯類單體或馬來酸酐單體的接枝改質方式。希望能發展出另一新的反應染料可染之改質聚丙烯纖維，同時可於低溫下(100℃以下)即能進行良好染色。此研究不僅使聚丙烯纖維獲致一個新的染色方式，同時又可達到低溫節能之效果，為頗新的創舉，至今尚未發現相關的探討。因此，本計畫將針對此一新的接枝改質程序與染色方法，分兩年依下列各階段進行深入的探討。第一年計畫之研究內容： 1. 電漿處理條件(電漿瓦數(W)、時間)及氣體種類(Ar,He:N2:O2 比例)對聚丙烯纖維接枝反應的影響 2. 以不同莫耳比例(如1：1、1：2、2：1 等…)甲基丙烯酸環氧丙酯/乙二胺行親核性開環加成聚合反應，並依不同聚合時間與不同聚合溫度制備不同分子量之甲基丙烯酸環氧丙酯/乙二胺共聚合物 3. 以 UV 光誘發不同光起始劑(諸如2-Hydroxy-methyl-propiophenone,安息香類(Benzoin), 二苯甲酮(Benzophenone)…等)對聚丙烯纖維光化學聚合(photo- chemical polymerization)接枝反應之影響 4. 不同接枝條件(起始劑濃度，不同分子量之甲基丙烯酸環氧丙酯/乙二胺共聚合物及 UV 光照時間)對光化學聚合接枝反應之影響 5. 聚丙烯纖維經 UV 光誘發接枝改質其物性(強力、吸濕性)變化之探討 6. 接枝改質聚丙烯纖維其染色性(染著率，染色堅牢度)及親水性之研究 7. 以不同反應性染料對接枝改質聚丙烯纖維染色性之探討第二年計畫之研究內容： 1. 以不同多元胺類與甲基丙烯酸環氧丙酯行親核性開環聚合反應，比較不同胺基含量的改變對共聚合反應後產物上的影響，同時探討不同胺基含量之理想聚合條件(單體間莫耳比例、反應溫度、反應時間) 2. 不同接枝條件(起始劑濃度，UV 光照時間，不同分子量之多元胺類共聚物)對聚丙烯纖維接枝的影響 3. 經不同分子量之多元胺類共聚物於 UV 光接枝後的改質聚丙烯纖維其物性(強力，吸濕性)之探討 4. 不同分子量之多元胺類共聚物之改質聚丙烯纖維其染色性及親水性之研究 5. 不同反應性染料對不同分子量之多元胺類共聚物之 PP 纖維其染色性之探討 6. 以 DSC 及DMA 測試經UV 光接枝後纖維熱性質(Tg,Tm)的變化 7. 利用 FTIR 紅外線吸收光譜偵測不同分子量之多元胺類共聚物接枝於聚丙烯纖維之表面官能基狀況 8. 以 SEM 電子顯微鏡觀察接枝改質纖維之外觀形態的變化 9. 利用 X-Ray 繞射儀偵測改質聚丙烯纖維之內部微細結構的變化以上各項完成後，聚丙烯纖維將可利用反應性染料進行低溫節能染色，同時亦可改善過去有關改質聚丙烯纖維染色堅牢度不佳的問題，此對聚丙烯纖維未來的應用將提供另一嶄新的技術，以提升國內紡織及相關產品的應用及加工層次，並增進產品的市場與附加價值，因此本計畫之執行不僅深具創新性及學術價值，且對國內業者在紡織產品開發及高級研究人才之培育上亦貢獻良多。
Polypropylene(PP) is a versatile and widely used polymer, enjoying applications as diverse as textiles, biomedical materials, packaging, pipes, household appliances, films and automotive factors. The success of the polymer can be attributed to several intrinsic, advantageous properties, namely low specific weight, good processability, almost zero water adsorption, good chemical resistance, good antistatic character as well as wide availability and low coat. The mechanical properties of standard PP fibers are described as sufficient, in the case of high-tenacity fibers as very good. The light and weather stability are sufficient only with the corresponding stabilization. PP is available in manifold applications, as exemplified by medical fabrics, industrial sewing threads, cordage, artificial turf, carpeting and geotextiles; little is used in apparel. However, polypropylene fiber is undyeable because of its non-polar, aliphatic structure as well as its high crystallinity and high stereo-regularity, so that the exhaust dyeability of PP fibers is insufficient with the former modification. Therefore, new methods such as pigmenting in mass had to be developed for colored fibers, that was named by “Dope dyeing or Mass coloration”, but the methods must be mass production for economic factor. The disadvantageous problems were that the manufacture could not be diverse products and not be quick response. In addition, the colored tone of dope dyeing were only simples appearance. Nowadays, many attempts have been made over many decades to overcome this problem including: (1) modification of the polymer by attaching dye-receptive monomer or functional groups to the polymer molecules via grafting or copolymerization. (2) incorporating dye-receptive additives within the polymer prior to fiber spinning. (3) plasma treatment for PP fibers. (4) chemical modification of PP fibers used chloride compounds…and so on. Although above methods had advantageous and disadvantageous points, but considered the dyeing and economic properties and modified techniques, among other methods of modified PP, the alternative way of introducing dyeing sites to the fiber is graft copolymerization, because the method possesses practical and economic effects. In the past, surface modification of polypropylene fibers vis surface polymerization had been widely studied in many field, most research tend to use radiation (γ-ray) initiated dyeable monomers grafting onto P.P fibers (1963 R.F. Stamm et al).Though the method of γ-ray radiation initiated graft can obtain good grafted results, but they are clearly disadvantageous results for physical properties of PP fibers, and their techniques are complex and difficult and high cost, so can’t be mass production for commercialization. Another, they had been recently researched for modification of PP fibers tended to graft polymerization by plasma methods. The surface modification of PP fibers then were grafted with vinyl monomer or maleic anhydride, and were dyed by disperse or basic dyestuff. But the dyed PP fibers still existed low washing and lighting colorfastness. Up to now, the problems have been not solved yet. The purpose of the present project will be to determine whether the dyeability and colorfastness of PP fabrics could be improved through the grafting copolymer both of glycidyl methacrylate(GMA) and various amines(such as amine diamine triamine),via additional polymerization of nucleophilic opening of ring. The surface of PP fibers after treating of plasma and then grafted with copolymer will be modified and possess the amine(~NH2) and hydroxy(~OH) groups. The two type of dyeing sites, ~NH2 and ~OH, will effectively improve the dyeability of modified PP fibers dyed by reative dyestuffs. On addition, the dyeing temperature would drop at 30~60℃, the energy savings that can be obtained by following low-temperature procedure for dyeing modified PP fibers. The All project will be carried out for two years. The contents of project in the first and second year are described as follow, respectively. The contents of project in the first year are listed as follow: (1) The effect of conditions of plasma treatment on grafting ratio of PP fibers. (2) The copolymers both glycidyl methacrylate and ethylenediamine are preparated at different mole ratio(such as 1:1, 1:2, 2:1…etc.) and conditions of polymerization(such as time and temperature) (3) The effect of conditions of grafting (e.g. con. of initiator and monomer of amides or amines, time of UV irradiation) on grafting results of PP fibers. (4) The effect of concentration of initiator and various MW of copolymer and irradiation time of UV on grafting ratio of PP fibers are researched. (5) The dyeability and colorfastness of modified PP fibers and dyed by reactive dyes will be investigated. (6) Various reactive dyes influence on dyeability and colorfastness of modified PP fibers. The contents of project in second year are listed as follow: (1) The effect of different amines(single amine, diamine,…ect.) of nucleophilic opening of ring of glycidyl methacrylate(GMA) will be studied. In addition, the number of amine groups should be researched. (2) The relationships between grafting conditions(such as con. of initiator, irradiation time of UV and MW of copolymer) and grafting ratio of PP fibers are investigated. (3) The study on physical properties of modified PP fibers after treating of plasma and then grafted with various copolymers. (4) The dyeability and hydrophilic property of PP fibers modified by different amine copolymers. (5) Various reactive dyes influence on dyeability and colorfastness of modified PP fibers grafted with acrylic acid and amines will be investigated. (6) The thermal properties (e.g. Tg, Tm) of modified PP fibers will be tested by DSC and DMA. (7) The functional groups on modified PP fibers could be identified by FTIR. (8) The morphology and microstructure of modified PP fibers will be examined by SEM and X-Ray. |
