201204885 六、發明說明： 【發明所屬之技術領域】 本發明係相關於一種以電紡技術製備聚醯胺奈米纖維 之方法，尤其是相關於以電紡技術大量製備聚醯胺奈沭纖 維之方法，以及製備奈米纖維薄膜之方法。本發明亦相關 於一種奈米纖維薄膜結構，具有此類聚醯胺奈米纖維不織 布纖維網，以及由其製造之產品與用途。 c先前技術】 聚合性奈米纖維，亦稱之為微細聚合物纖維，可製備 為不織布纖維網形式’其可應詩許多料如過滤器。聚 合性奈米纖維亦可用於廣範圍之其他領域。這些領域包 括，尤其是，組織工程、特殊過濾器、強化物、保護布料、 催化劑支撐劑，以及各種塗覆物。 一般用於製備微細聚合物纖維之一方法為電紡法。奈 米纖維可由不同聚合物製備，取決於對於熱、濕度、反應 性材料、壓電性之穩定度要求，與其用途有關。用於製備 奈米纖維之聚合物’其中包括聚醯胺。 由聚醯胺製備之奈米纖維係描述於如 US2004/0_268。該專利中請案件中所使用之聚醢胺為对 隆6,66,610、耐隆66，以及耐隆46與耐隆66之共聚醯胺。雖 然US 2004/0060268中提及其所描述之聚醯胺奈米纖維是由 電紡法製造，但並未透露有關此方法之細節部分。 由聚醯胺11與聚醯胺i 2製備之電紡纖維係描述於 US20090042029。該聚醯胺係由含有甲酸與二氣甲烷之溶液 3 201204885 電纺而製備。電紡溶液之濃度相當低(3-5 wt%)，而該奈米 纖維通常為帶狀，且特徵為具有相對廣之纖維直徑分佈。 大規模電紡一般是經由多噴頭電紡技術，使用多喷頭 裝置，如W02005/073441中所描述的，在此併入本案以作 為參考資料，以及經由使用無喷頭裝置之無喷頭電紡法， 如使用Nanospider™裝置、氣泡電紡法或類似技術；或經由 電吹法(electroblowing)，如W003/080905中所描述的，在此 併入本案以作為參考資料。然而，許多研究都著重在單一 喷頭的設計，如使用針筒與針頭。 一般電紡法，尤其是聚醯胺奈米纖維使用者，面臨到 數個問題，尤其是要應用於多喷頭紡口之工業規模上時。 這些問題已發現於如WO-2005/033381-A2 、 WO-2005/073441-A1 與 US20090123591 中。 WO-2005/033381-A2中有電紡法的詳細描述。當外部 電場施加於一導電流體上時（如帶電荷之半稀釋聚合物溶 液，或帶電之聚合物熔融物）’會形成懸浮圓錐液滴，其中 該液滴之表面張力會與電場達到平衡。當電場夠強，足以 克服液體表面張力時，便會發生電紡現象。之後該液滴會 變得不穩定，且會有微細噴射流自紡口尖端孔中噴射出。 當達到標的後，该喷射流可以次微米尺寸纖維之互聯網形 式收集。由這些不織奈米級纖維(奈米纖維)所得之薄膜，具 有非常大之表面積對體積比。 如同WO-2005/033381-A2中所描述的，應瞭解到電紡 纖維製程中最主要的技術問題應該要被解決。主要技術影 201204885 響因素為製造速率。例如，若自紡口喷頭電紡出之聚合物 熔融物具有直徑700 μηι，最終形成的細絲直徨為25〇 nm , 則該拉伸比將為約3 X 106。由於單一紡口之典型擠壓生產 率為16 mg/min (或1 g/hr)，因此最終細絲生產速率將為約 136 m/s，與目前高速炼融紡絲製程之最高迷率相較(1〇 〇〇〇 m/min或167 m/s)。因此，傳統電紡技術之紡口生產率約低 於商業上高速熔融紡絲製程1000倍。 另一個大量製造電紡纖維之主要技術問題為，在電紡 過程中纺口之組裝問題。一般在高速溶融物紡絲技術中使 用的直線型多喷頭配置並無法使用，因為鄰近的電場通常 會互相干擾。 描述於WO-2005/073441-A1中的裝置包含一喷頭區 塊，其包含多個喷頭、一收集器，用於收集由噴頭區塊喷 出的纖維，以及一電壓產生器，用於施加電壓至喷頭區塊 與收集器上。W02005/073441中所使用之聚合物為耐隆6， 具相對黏度為3_2 (於96%硫酸溶液中測定），並具有Mw 48,000 g/mol。該聚合物用於製造紡絲液體，如具有黏度為 1050 cPs，於20 %固體含量下。依據W02005/073441，電紡 過程一般係於非常低之生產率下進行，約為1〇"2裏1〇~3 g/min每孔。因此，單孔電紡並不適用於商業用途之大量製 造需求。大量製造商業用途上所使用之大規模電紡裝置， 包含複數個喷頭，其應配置於一狹窄空間中。然而，在傳 統電纺裝置中’是無法在預定空間中安排有限數目個噴 頭，因此便造成商業化所需之量產困難。此外，傳統水平 201204885 電纺裝置會產生另-個問題’會有未由喷頭喷出之聚合物 液體聚集物（此後稱之為•液滴·)附著於收集板上，因而使產 品品質惡化。為了解決這個問題，w_5聰441便提出 了-種稱為由下而上之電纺裝置，其中該喷頭出口係以朝 上方式裝置於喷嘴區塊，而收集器則位於噴嘴區塊上方。 穴㈡兮〒睛累糸列號 10/936,568之分案，其以電紡技術製造奈米纖維之主要技術 瓶頸為製造速率低，以及聚合物溶液之加工限制。相關之 議題已摘錄於US20090123591，如下： 1.第一個瓶頸涉及鄰近電極（或喷射柱）間的電場干 擾’限制了電極間的最小空間距離，或可架構於多個喷射 電纺模具區塊上之紡口的最大密度。 2. 第二個瓶頸係相關於各紡口的低生產率。換言之， 由於纖維尺寸變得非常小，電紡製程產率便會變得相當低。 3. 第三個瓶頸為長時間連續操作性之限制，以及如何 使用最少人力進行多個紡口的自動清洗。 4. 電紡製程最後一個瓶頸為溶液加工的限制，其中需 使用溶劑，而嚴重限制了此技術在工業上的應用。 US20090123591提出了 一個特別的紡口形式，可克服傳 統電紡技術上的技術瓶頸（2)-(4)，並可以氣吹技袍^ (gas-blowing)影響（1)中的流體喷射流的流動狀況^然而， 並非所有的電紡製程都可經氣吹(gas blowing)修飾，而—般 的設計並不包含氣吹裝置（gas-blowing)。 US20090123591引用了另一份專利申請案 201204885 03/080905，其提出了相同的問題，並提出高生產率的製造 方法’部分以電紡技術為基礎：一種以電吹紡織 (electro-blown spinning)技術製備奈来纖維之製造裝置與 方法。依據US20090123591，此揭示之技術有下列數項缺 點：在電吹時並未完全利用電場達到足夠大的紡絲-拉伸比 例’無法製造出較小直徑的纖維（如直徑小於3〇〇 nm之纖 維）。無法支持長時間操作性(如>5天），由於無法避免聚合 物沈積（聚集）於紡口上，而產生長時間操作上的主要問題。 關於電紡纖維的文獻通常依據單細絲實驗，但卻忽略 了在大量製造中，多細絲電紡時會面臨的問題。 例如，S_S. Ojha et al, in J. Appl. Polymer Sc.，Vol. 108, 308-319 (2008) ’描述了電紡纖維的型態，為分子量與加工 參數的函數。該聚合物溶液係製備自具不同Mw，溶於曱酸 中之耐隆-6。該溶液係以一具有毛細管尖頭之針筒施加。 已顯示低Mw之耐隆6 (Mw 30,000)具有嚴重的小珠形成現 象。此小珠形成現象會隨著濃度增加而降低，以及當Mw增 加至50,000，甚至Mw增加至63,000時而降低。 專利申請案FR-2911151-A1亦描述了聚醯胺奈米纖維 之製造，使用裝配有針筒與針頭的裝置。係描述聚醯胺6與 聚醯胺6,6之溶液’具有Mw 10,000-50,000，於甲酸溶液中。 可得到直徑範圍為40-350 nm ’但具有廣範圍分佈之奈米纖 維。 C. Huang等人於Nanotechnology 17 (2006) 1558-+1563 中描述了具小直徑之電紡聚合物奈米纖維，製備自聚醯胺 201204885 4.6，於曱酸中。聚醯胺4.6為Aldrich的一種等級，經測定為 具有Mw 45.000。加入小量的吡啶至電紡溶液中，可防止在 低濃度電紡過程中，小珠化奈米纖維的產生。在此低濃度 下便可得到具小直徑的纖維。在較高濃度下，固體含量大 於12%時，其奈米纖維的直徑似乎會劇烈增加，幾乎是以 指數方使增加。 大規模商業電紡技術之另一項要求為聚合物溶液黏度 的長時間穩定性。一般而言，電紡技術所使用的聚合物可 溶解，溶液儲存於相對大的容器或槽中，並在電紡製程完 全消耗前保存數週。由於聚合物溶液的黏度會強烈影響所 得之奈米纖維直徑與分佈，具有穩定的聚合物-溶劑系統便 相當重要。 因此目前仍清楚需要一種增進之電紡製程，用於製備 奈米纖維，尤其是聚醯胺奈米纖維，可用於大量製造。 【發明内容】 本發明目的係提供一種電紡法，不會具有上述缺點， 至少可以降低某些程度，適用於製造具有小直徑、窄纖維 分佈以及有限之小珠形成之奈米纖維，同時可有高生產 率，並可於大規模上進行。 此目標可藉由使用本發明電紡法而達成，其中該方法 為使用多喷頭裝置之多喷頭電紡法，或使用無喷頭裝置之 無喷頭電紡法，包含下列步驟，其中： -施加高電壓； -將含有一聚合物與一溶劑之聚合物溶液進料至該多 201204885 喷碩裝置或無噴頭裝置中，並在高電壓作用下轉換 為帶電荷之噴射流； •將该喷射流沈積於基板上或以收集器收集；以及 _該喷射流中的聚合物固化，因而形成奈米纖維； 以及其中§亥聚合物包含半結晶之聚醯胺，具有c/N比至 多5‘5，以及童量平均分子量（Mw)至多35,000。 C/N比應瞭解為聚醯胺中碳原子(C)數目與聚醯胺中氮 原子(N)數目之比例。 本發明方法為-種電紡法，其中同時形成多條奈米纖 維’可於大規模下進行。 在此方法中，施加高電壓時，溶液或喷頭或自由懸浮 薄膜上會形成泰勒圓錐(τ咖s咖⑻。為了產生此泰勒圓 雜般電壓必須至少有2.5 kV。電壓可高達5〇 kV或60 或甚至更问，如65kV。適當之電壓為至少1〇kV，較 佳至少20 kV ’尤隹至少kv。 »玄方去可經用多噴頭電紡法，使用多喷頭裝置而達 成般而σ為具有—系列喷頭之紡口以及經由無喷頭 電纺法，個無喷頭裝置，如用於氣泡紡絲之ν咖啊頂 裝置。多喷頭電纺可選擇性地與喷頭加壓氣流結合，如電 吹法。201204885 VI. Description of the Invention: [Technical Field] The present invention relates to a method for preparing polyamidene nanofibers by electrospinning technology, in particular to the preparation of polyamidamine fibers by electrospinning A method, and a method of preparing a nanofiber film. The invention is also related to a nanofiber film structure having such a polyamide fiber nonwoven web, and products and uses made therefrom. c Prior Art] Polymeric nanofibers, also referred to as fine polymer fibers, can be prepared in the form of a nonwoven web which can be used as a filter. Polymeric nanofibers can also be used in a wide range of other fields. These areas include, inter alia, tissue engineering, special filters, reinforcements, protective cloths, catalyst proppants, and various coatings. One method generally used to prepare fine polymer fibers is electrospinning. Nanofibers can be made from different polymers, depending on the stability requirements for heat, humidity, reactive materials, and piezoelectricity, depending on their use. The polymer used to prepare the nanofibers' includes polyamine. Nanofibers prepared from polyamines are described, for example, in US 2004/0-268. The polyamines used in the patents in this patent are pylons 6, 66, 610, Nylon 66, and copolyamines of Nylon 46 and Nylon 66. Although the polyamido nanofibers described in US 2004/0060268 are made by electrospinning, no details are given regarding this method. An electrospun fiber system prepared from polyamido 11 and polyamidene i 2 is described in US20090042029. The polyamine is prepared by electrospinning a solution containing formic acid and dihalomethane 3 201204885. The concentration of the electrospinning solution is relatively low (3-5 wt%), and the nanofibers are generally ribbon-shaped and are characterized by a relatively broad fiber diameter distribution. Large-scale electrospinning is generally carried out via a multi-nozzle electrospinning technique using a multi-nozzle device, as described in WO2005/073441, which is incorporated herein by reference in its entirety, and by the use of a non-nozzle device. Spinning methods, such as the use of NanospiderTM devices, bubble electrospinning or the like; or via electroblowing, as described in W003/080905, incorporated herein by reference. However, many studies have focused on the design of a single nozzle, such as the use of syringes and needles. In general, electrospinning, especially for polyamidene fiber users, faces several problems, especially when applied to the industrial scale of multi-nozzle spinning. These problems have been found in, for example, WO-2005/033381-A2, WO-2005/073441-A1 and US20090123591. A detailed description of the electrospinning process is available in WO-2005/033381-A2. When an external electric field is applied to a conductive fluid (e.g., a charged semi-dilute polymer solution, or a charged polymer melt), a suspended cone droplet is formed, wherein the surface tension of the droplet is balanced with the electric field. When the electric field is strong enough to overcome the surface tension of the liquid, electrospinning occurs. The droplets then become unstable and a fine jet is ejected from the spin hole. When the target is reached, the jet can be collected in the form of an internet of sub-micron sized fibers. The film obtained from these non-woven nanofibers (nanofibers) has a very large surface area to volume ratio. As described in WO-2005/033381-A2, it should be understood that the most important technical problems in the electrospun fiber process should be addressed. The main technical shadow 201204885 The factor is the manufacturing rate. For example, if the polymer melt electrospun from the spout nozzle has a diameter of 700 μηι and the resulting filament is 25 〇 nm, the draw ratio will be about 3 X 106. Since the typical extrusion productivity of a single spun is 16 mg/min (or 1 g/hr), the final filament production rate will be about 136 m/s, which is comparable to the current highest rate of high-speed refining and spinning processes. (1〇〇〇〇m/min or 167 m/s). Therefore, the spinning yield of conventional electrospinning technology is about 1000 times lower than that of the commercial high-speed melt spinning process. Another major technical problem in the manufacture of electrospun fibers in large quantities is the assembly of the spun in the electrospinning process. Linear multi-nozzle configurations typically used in high speed melt spinning techniques are not available because adjacent electric fields typically interfere with each other. The device described in WO-2005/073441-A1 comprises a spray head block comprising a plurality of spray heads, a collector for collecting fibers ejected by the spray head block, and a voltage generator for Apply voltage to the showerhead block and collector. The polymer used in W02005/073441 is Nylon 6, having a relative viscosity of 3_2 (measured in 96% sulfuric acid solution) and having a Mw of 48,000 g/mol. The polymer is used to make a spinning liquid, such as having a viscosity of 1050 cPs at 20% solids. According to W02005/073441, the electrospinning process is generally carried out at very low productivity, about 1 〇"2 〇1〇3 g/min per hole. Therefore, single-hole electrospinning is not suitable for a large number of manufacturing needs for commercial use. A large-scale electrospinning device used in a large number of commercial applications, including a plurality of nozzles, which should be disposed in a narrow space. However, in the conventional electrospinning apparatus, it is impossible to arrange a limited number of nozzles in a predetermined space, thus causing mass production difficulties required for commercialization. In addition, the traditional level 201204885 electrospinning device will create another problem 'There will be a polymer liquid aggregate (hereinafter referred to as • droplets) that is not ejected from the nozzle to adhere to the collecting plate, thus deteriorating product quality. . In order to solve this problem, w_5 Satoshi 441 proposes an electrospinning device called bottom-up, in which the nozzle outlet is arranged in the nozzle block in an upward direction and the collector is located above the nozzle block. The hole (2) is divided into 10/936,568. The main technical bottleneck for the manufacture of nanofibers by electrospinning technology is the low manufacturing rate and the processing limitations of polymer solutions. Related topics have been extracted from US20090123591 as follows: 1. The first bottleneck involves electric field interference between adjacent electrodes (or jet columns) 'limits the minimum spatial distance between the electrodes, or can be constructed in multiple jet electrospinning mold blocks The maximum density of the spun on the top. 2. The second bottleneck is related to the low productivity of each spin. In other words, since the fiber size becomes very small, the electrospinning process yield becomes quite low. 3. The third bottleneck is the limitation of long-term continuous operation and how to automate multiple spinning ports with minimal manpower. 4. The final bottleneck in the electrospinning process is the limitation of solution processing, which requires the use of solvents, which severely limits the industrial application of this technology. US20090123591 proposes a special form of spinning that overcomes the technical bottlenecks of conventional electrospinning techniques (2)-(4) and can influence the fluid jets in (1) by gas-blowing Flow conditions ^ However, not all electrospinning processes can be modified by gas blowing, and the general design does not include gas-blowing. US 20090123591 cites another patent application 201204885 03/080905, which raises the same problem and proposes a high-productivity manufacturing process 'partially based on electrospinning technology: one prepared by electro-blown spinning technology Nielai fiber manufacturing apparatus and method. According to US20090123591, the disclosed technique has several disadvantages: it does not fully utilize the electric field to achieve a sufficiently large spinning-stretching ratio during electroblowing, and it is not possible to produce fibers of smaller diameter (e.g., having a diameter of less than 3 〇〇 nm). fiber). Long-term operability (e.g., > 5 days) cannot be supported, and since the deposition (aggregation) of the polymer cannot be avoided on the spun, a major problem in long-term operation is caused. The literature on electrospun fibers is generally based on single filament experiments, but ignores the problems that would be encountered in multi-filament electrospinning in high volume manufacturing. For example, S_S. Ojha et al, in J. Appl. Polymer Sc., Vol. 108, 308-319 (2008) 'describes the type of electrospun fiber as a function of molecular weight and processing parameters. The polymer solution was prepared from Nylon-6 in a different Mw and dissolved in citric acid. The solution is applied as a syringe with a capillary tip. Nylon 6 (Mw 30,000) with low Mw has been shown to have severe bead formation. This bead formation phenomenon decreases as the concentration increases, and decreases as Mw increases to 50,000, even when Mw increases to 63,000. Patent application FR-2911151-A1 also describes the manufacture of polyamide fibers using a device equipped with a syringe and a needle. It is described that the solution of polyamine 6 and polyamidamine 6,6 has a Mw of 10,000-50,000 in a formic acid solution. Nanofibers with a diameter range of 40-350 nm' but with a wide range of distribution are available. C. Huang et al., Nanotechnology 17 (2006) 1558-+1563, describe electrospun polymer nanofibers having a small diameter prepared from polydecylamine 201204885 4.6 in citric acid. Polyamine 4.6 is a grade of Aldrich which has been determined to have a Mw of 45.000. The addition of a small amount of pyridine to the electrospinning solution prevents the production of beaded nanofibers during low concentration electrospinning. At this low concentration, fibers having a small diameter can be obtained. At higher concentrations, at a solids content greater than 12%, the diameter of the nanofibers appears to increase dramatically, increasing almost exponentially. Another requirement for large-scale commercial electrospinning technology is the long-term stability of the viscosity of the polymer solution. In general, the polymers used in electrospinning are soluble, and the solution is stored in relatively large containers or tanks and stored for several weeks before the electrospinning process is completely consumed. Since the viscosity of the polymer solution strongly influences the diameter and distribution of the resulting nanofibers, it is important to have a stable polymer-solvent system. Therefore, it is still clear that there is a need for an improved electrospinning process for the preparation of nanofibers, especially polyamidamine fibers, which can be used in a large number of manufactures. SUMMARY OF THE INVENTION The object of the present invention is to provide an electrospinning method which does not have the above disadvantages, at least to some extent, and is suitable for producing nanofibers having a small diameter, a narrow fiber distribution and a limited bead formation, and may have High productivity and can be carried out on a large scale. This object can be attained by using the electrospinning method of the present invention, wherein the method is a multi-head electrospinning method using a multi-nozzle device, or a nozzleless electrospinning method using a nozzleless device, comprising the following steps, wherein: High voltage; - feeding a polymer solution containing a polymer and a solvent to the multi-201204885 spray device or the nozzleless device, and converting to a charged jet under high voltage; Deposited on a substrate or collected by a collector; and - the polymer in the jet solidifies, thereby forming a nanofiber; and wherein the polymer comprises a semicrystalline polyamine having a c/N ratio of at most 5'5 And the average molecular weight (Mw) of children is up to 35,000. The C/N ratio is understood to be the ratio of the number of carbon atoms (C) in the polyamine to the number of nitrogen atoms (N) in the polyamine. The method of the present invention is an electrospinning method in which a plurality of nanofibers simultaneously formed can be carried out on a large scale. In this method, when a high voltage is applied, a Taylor cone (8) is formed on the solution or the nozzle or the free-suspended film. In order to generate this Taylor, the voltage must be at least 2.5 kV. The voltage can be as high as 5 〇 kV. Or 60 or even more, such as 65kV. Appropriate voltage is at least 1〇kV, preferably at least 20kV 'especially at least kv.»Xuanfang can be achieved by multi-nozzle electrospinning method using multi-nozzle device And σ is a spinning nozzle with a series of nozzles and a nozzleless electrospinning method, such as a nozzleless device, such as a volt coffee spinning device for multi-nozzle electrospinning. The head is pressurized with a combined air flow, such as an electric blow.
此類大規模之多喷頭電紡法包含數個步驟，其中 .在紡口與收集器之間，或在單—電極與收集器之 施加高電壓，該紡口包含-系列之喷頭，B -含有-聚合物與—溶劑之聚合物溶液流係進料至該 201204885 紡口，以及 -該聚合物溶液經由電紡喷頭自該紡口離開，並在高 電壓作用下轉換為帶電荷之喷射流， -該喷射流係沈積於收集器或基板上，或由其收集； 在沈積於收集器或基板上，或由其收集之前或同時， 該喷射流中的聚合物會固化，因而形成奈米纖維。 在無喷頭製程中，並無具喷頭之紡口，而是使用另一 項使溶液進料之裝置，其中並無喷射流形成。例如，該溶 液係由一旋轉電極吸收，如同nanospider裝置，或藉由將氣 體打至該溶液中而產生氣泡（如氣泡紡絲法）。在無喷頭製 程中，溶液係以此類裝置進料，而在高電壓作用下產生泰 勒圓錐。由這些泰勒圓錐，便可在高於臨界電壓下形成帶 電喷射流，最終產生奈米纖維，如同上述多喷頭製程中所 述。 I：實施方式】 在本發明之第一實施例中，聚合溶液中的聚合物包含 半結晶聚醯胺，具有C/N比至多5.5，以及重量平均分子量 (Mw)至多 35,000。 本發明方法使用該具有C/N比至多5.5，以及重量平均 分子量（Mw)至多35,000之半結晶聚醯胺，有多項作用。所 製造之複數纖維組合物中之纖維厚度差異值會降低（或藉 由加入高Mw分支聚醯胺而達成）。具較高聚醯胺濃度之聚 合物溶液，如大於15 wt%，或甚至大於20 wt.%，可用於得 到較高之生產率。加工條件可依據薄或厚纖維之目的而選 10 201204885 擇，同時可使製造速率最大化，且可控制平均纖維厚度或 纖維直徑。由本發明方法製造之奈米纖維之纖維厚度，可 於廣範圍中變化，即，可選用不同之製程、製程條件，而 製造出相對薄之纖維(如藉由降低溶液黏度、降低聚合物分 子量）’以及相對厚之纖維（如藉由增加溶液黏度、增加甲酸 /乙醇混合物中之乙醇含量）。 5亥方法可在相對應及其他具有較高MW之聚醯胺之可 比較/谷劑組成物與浪度下，產生較低之喷頭阻塞。該方法 可使用較環保之溶劑組成物，尤其是高含水量之溶劑組成 物。相對於該具有C/N比大於6之標準半結晶聚醯胺，本發 明製％中所使用之聚酿胺可於較高水含量之甲酸/水混合 液中加工。 §亥製程會得到具高熔融溫度之聚醯胺聚合物，否則會 在炼融製程中無法加工或降解過快，這些聚合物可加工成 為奈米纖維β 故些結果相當令人驚訝，因為與其他聚醯胺相較，濃 度呵於2〇%之耐隆6與10%之耐隆6,66,610並無法用 於大規 _之多噴頭紡σ ’且這些聚合物的溶液黏度變化並無法使 、裁維厚度呈廣範圍變化。可得直徑為約100 nm之耐隆6纖 維以及直彳空範圍約為200-300 nm之耐隆6,66,610纖維。降 低耐隆6的]Viw並不會產生較平順的電紡製程，且無法產生 適用之奈米纖維。 在第—實施例中，該聚合物包含第一聚醯胺，具C/N 比至夕6，且1^至多35,000，以及第二聚醯胺，為高Mw之 11 201204885 直線型聚醯胺。 該第一聚醯胺可為咼Mw之直線型聚酿胺，選擇性地經 陰離子性聚合，或高Mw分支聚醯胺，較佳存在量為〇_1〇 wt·%，更佳0-5 wt·% ’相對於聚合物之總重量。此外，第 一聚醯胺之Mw範圍較佳為5,000-25,000。 第二實施例之方法可產生穩定之製程及具有良好品 質、小纖維直徑分佈’與非常低量之小珠形成之纖維產物。 此與相對應之製程相反’包括其使用僅含較低Mw聚醯胺之 溶液。早期使用具有此較低Mw之聚醯胺，是為了得到較低 黏度及/或較南濃度之溶液，但一般會產生小珠，或與小珠 混合之纖維，尤其是使用高電壓之多喷頭（用於高生產 率），並為薄纖維及/或低機械特性。 術語半結晶聚酿胺之半結晶，於此係指一種固體形式 之聚醯胺，包含不是非晶形之結晶相。結晶相存在之證據 可以多種技術證明，如Rontgen繞射，以及掃瞄式熱差分析 儀(DSC)。此部分結晶聚醯胺之熔融溫度亦可以DSC測定。 術語溶融溫度，如下列所使用，於此係指該溫度，依 據ASTM D3418-97 ’於氮氣環境下以DSC測量，加熱速率 為10°C/min，為最高熔融速率。 更值得注意的是’範圍的標記為χ-y範圍格式，其中χ 與y為下限與上限，這些界限亦包括於該範圍中。 可用於本發明方法之聚醯胺為由直線型二胺 H2N-(CH2)x-NH2 ’ 其中 X=2、3、4、5，及/或6，與二叛酸 H02C(CH2)YC02H ’其中Y=0、卜2、3，及/或4，製備之聚 12 201204885 醯胺。就C6二胺而言，即具有6個碳之二胺，係與C6二羧 酸，即具有6個碳之二羧酸結合，顯然其必須與較短之二胺 及/或較短之二羧酸結合，以達到C/N比為5 5或更低。其他 可使用之聚醯胺為得自胺基酸只21^-((：112)2-(：02[1，或内醯胺 [NH(CH2)-zCO]，其中Z=1、2、3、4及/或5。 此外’可使用結合上述單體與含有6個或更多個碳原子 之單體單元之共聚醯胺，其中總C/N比至多為5 5。較佳該 共聚物為PA46/6，具有大於70 wt·%之PA46與至多30 wt.% 之PA6-單元，以及PA46/66，具有大於7〇 wt.%之PA46與至 多30 mol %之PA66單元。 可使用作為具有C/N比至多5.5，重量平均分子量(Mw) 至多35,000之半結晶聚醯胺適當範例包括，聚酿胺46、聚 醯胺26、聚醯胺24、聚醢胺4、聚醯胺36與聚醯胺56之同元 聚合物與其共聚物。 較佳該C/N比範圍為4-5.5，更佳為4.5-5.25。 此外’ §亥半結晶聚酿胺較佳包含一同元聚合物，更佳 為具C/N比為5之耐隆46，以及具C/N比為4之耐隆26。 具低C/N比之聚醯胺，如聚醯胺26與24，與其共聚物， 尤其是其同元聚合物，之一般特徵為具有非常高之熔點， 且這些聚合物一般會在高溫加工下降解。此降解作用使得 這些聚合物無法於高溫下加工，尤其是熔融加工，且在許 多情況下亦無法製造高Mw之產物。使用此類方法並無法製 造出具良好特性之奈米纖維。 具C/N比至多5.5之半結晶聚酿胺之存在量可於廣範圍 13 201204885 中變化，與聚合物總量相較。較佳為，該半結晶聚醯胺之 量為至少50 wt.%，更佳為75-100 wt.%，最佳為90-100 wt·%，相對於奈米纖維中之聚合物總量。 半結晶聚醯胺之重量平均Mw可於廣範圍中變化，至多 為35,0〇〇。此述之重量平均分子量（]VIw)係以凝膠通透層析 & (GPC)測定其分子量分佈’更佳使用尺寸排除層析法 (SEC)與三重偵測法結合。於此，GPC裝置係與一黏度、折 射率與光散射偵測儀結合(90度）^該測量係使用六氟異丙 醇進行，含有01 wt%三氟醋酸鉀，相對於作為溶劑之六氟 異1^醇重量’並使用尺寸排除層析法，裝配有3 PFG直線型 XLi夕膠管柱。重量平均分子量係使用Viscotek公司之Such a large-scale multi-head electrospinning process comprises several steps, wherein a high voltage is applied between the spun and the collector, or between the single electrode and the collector, the spun containing a series of nozzles, B - a polymer solution stream containing - polymer and solvent - is fed to the 201204885 spun, and - the polymer solution exits the spun via an electrospinning nozzle and is converted to a charged charge under high voltage Jet stream, - the jet stream is deposited on or collected from the collector or substrate; the polymer in the jet will solidify before or at the same time as it is deposited on or collected from the collector or substrate, thus forming Nanofiber. In the no-nozzle process, there is no spout with a sprinkler, but another device for feeding the solution, in which no jet is formed. For example, the solution is absorbed by a rotating electrode, like a nanospider device, or bubbles are generated by hitting the gas into the solution (e.g., bubble spinning). In a nozzleless process, the solution is fed with such a device and a Taylor cone is produced under high voltage. From these Taylor cones, a charged jet can be formed above the threshold voltage to ultimately produce nanofibers as described in the multi-nozzle process described above. I: Embodiments In the first embodiment of the present invention, the polymer in the polymerization solution contains a semi-crystalline polyamine having a C/N ratio of at most 5.5 and a weight average molecular weight (Mw) of at most 35,000. The process of the present invention employs a plurality of semi-crystalline polyamines having a C/N ratio of at most 5.5 and a weight average molecular weight (Mw) of up to 35,000. The difference in fiber thickness in the plurality of fiber compositions produced is reduced (or achieved by the addition of a high Mw branched polyamine). Polymer solutions having a higher polyamine concentration, such as greater than 15 wt%, or even greater than 20 wt.%, can be used to achieve higher productivity. The processing conditions can be selected according to the purpose of thin or thick fibers, while maximizing the manufacturing rate and controlling the average fiber thickness or fiber diameter. The fiber thickness of the nanofibers produced by the method of the present invention can be varied in a wide range, that is, different processes and process conditions can be used to produce relatively thin fibers (for example, by reducing the viscosity of the solution and lowering the molecular weight of the polymer). 'And relatively thick fibers (eg by increasing the viscosity of the solution, increasing the ethanol content of the formic acid/ethanol mixture). The 5H method produces lower nozzle blockage at comparable/valve compositions and levels of corresponding and other higher MW polyamides. This method allows the use of more environmentally friendly solvent compositions, especially high water content solvent compositions. The polyamine used in the % of the invention can be processed in a higher water content formic acid/water mixture relative to the standard semicrystalline polyamine having a C/N ratio of greater than 6. §Hai process will get polyamide polymer with high melting temperature, otherwise it will not be processed or degraded too fast in the refining process. These polymers can be processed into nanofiber β. The results are quite surprising because Compared with other polyamines, the concentration of 2% of Nylon 6 and 10% of Nylon 6,66,610 can not be used for the large-scale spun σ ' and the viscosity of these polymers does not change, The thickness of the cutting dimension varies widely. Nylon 6 fibers with a diameter of about 100 nm and Nylon 6,66,610 fibers with a straight hollow range of about 200-300 nm are available. The reduction of the Nylon 6] Viw does not result in a smoother electrospinning process and does not produce suitable nanofibers. In a first embodiment, the polymer comprises a first polyamine, having a C/N ratio of -6, and 1^ up to 35,000, and a second polyamine, which is a high Mw of 11 201204885 linear polyamine . The first polyamine can be a linear polyamine of 咼Mw, optionally an anionic polymerization, or a high Mw branched polyamine, preferably present in an amount of 〇_1〇wt·%, more preferably 0- 5 wt·% 'relative to the total weight of the polymer. Further, the Mw of the first polyamine is preferably in the range of 5,000 to 25,000. The method of the second embodiment produces a stable process and a fiber product having a good quality, small fiber diameter distribution' formed with very low amounts of beads. This is in contrast to the corresponding process' including its use of a solution containing only a lower Mw polyamine. Early use of polyamines with this lower Mw is to obtain lower viscosity and / or more southerly concentrations of the solution, but generally produce beads, or fibers mixed with beads, especially with high voltage spray Head (for high productivity) and is thin fiber and / or low mechanical properties. The term semi-crystalline polyamine can be referred to herein as a solid form of polyamine which comprises a crystalline phase which is not amorphous. Evidence for the presence of crystalline phases can be demonstrated by a variety of techniques, such as Rontgen diffraction, and Scanning Thermal Differential Analyzer (DSC). The melting temperature of this partially crystalline polyamine can also be determined by DSC. The term melting temperature, as used herein, refers to the temperature, which is measured by DSC under a nitrogen atmosphere according to ASTM D3418-97, at a heating rate of 10 ° C/min, which is the highest melting rate. More notably, the range of marks is in the χ-y range format, where χ and y are the lower and upper limits, and these limits are also included in the range. Polyamines which can be used in the process of the invention are linear diamines H2N-(CH2)x-NH2' wherein X = 2, 3, 4, 5, and / or 6, with di-hectoric acid H02C(CH2)YC02H' Wherein Y = 0, Bu 2, 3, and / or 4, prepared poly 12 201204885 indoleamine. In the case of a C6 diamine, a diamine having 6 carbons, which is combined with a C6 dicarboxylic acid, ie a dicarboxylic acid having 6 carbons, obviously it must be combined with a shorter diamine and/or a shorter one. The carboxylic acid is combined to achieve a C/N ratio of 5 5 or less. Other polyamines that can be used are those obtained from amino acids only 21^-((:112)2-(:02[1, or indoleamine [NH(CH2)-zCO], where Z=1, 2 3, 4 and/or 5. Further, a copolymerized guanamine in combination with the above monomer and a monomer unit having 6 or more carbon atoms may be used, wherein the total C/N ratio is at most 55. Preferably, the copolymerization The material is PA46/6, having more than 70 wt.% of PA46 and up to 30 wt.% of PA6-unit, and PA46/66, having more than 7 wt.% of PA46 and up to 30 mol% of PA66 unit. Suitable examples of semi-crystalline polydecylamines having a C/N ratio of at most 5.5 and a weight average molecular weight (Mw) of up to 35,000 include polystyrene 46, polyamine 26, polyamidamide 24, polyamidamine 4, polydecylamine. 36. The homopolymer of the polyamine 56 and its copolymer. Preferably, the C/N ratio ranges from 4 to 5.5, more preferably from 4.5 to 5.25. Further, the semi-crystalline polyamine comprises a homopolymer. More preferably, it is an Nylon 46 having a C/N ratio of 5, and an endurance 26 having a C/N ratio of 4. Polyamines having a low C/N ratio, such as polyamines 26 and 24, Copolymers, especially their homopolymers, are generally characterized by very high The melting point, and these polymers are generally degraded under high temperature processing. This degradation makes these polymers incapable of processing at high temperatures, especially in melt processing, and in many cases cannot produce high Mw products. It is not possible to produce nanofibers with good properties. The presence of semi-crystalline polyamines having a C/N ratio of up to 5.5 can vary over a wide range of 13 201204885, compared to the total amount of polymer. Preferably, the half The amount of crystalline polyamine is at least 50 wt.%, more preferably 75-100 wt.%, most preferably 90-100 wt.%, relative to the total amount of polymer in the nanofiber. Semi-crystalline polyamine The weight average Mw can vary over a wide range, up to 35,0. The weight average molecular weight (] VIw) described herein is better by using gel permeation chromatography & (GPC) to determine its molecular weight distribution. Size exclusion chromatography (SEC) is combined with triple detection. Here, the GPC device is combined with a viscosity, refractive index and light scattering detector (90 degrees). The measurement is performed using hexafluoroisopropanol. Contains 01 wt% potassium trifluoroacetate relative to hexafluoroisopropanol as solvent The amount of 'using size exclusion chromatography, equipped with a 3 PFG linear XLi Xi gel column. Weight average molecular weight based Company using Viscotek
TnSEC 3.0軟體計算所測的之分子量分佈。Mw單位為 g/m〇N二重摘測法之優點為該方法可提供絕對值，而不需 外部參考值。The molecular weight distribution measured by the TnSEC 3.0 software was calculated. The advantage of the Mw unit g/m〇N double-pig method is that the method provides absolute values without an external reference value.
Mw較佳為至少1，〇〇〇，更佳為至少2,000 ’尤佳為範圍 5’〇〇0-3G’GGG，特佳為範圍1G，__25,議。較低編之優點 為製程中可使用較高濃度，及/或溶射可包含較高之水或 醇類含量。 非常低之聚醯胺Mw，即Mw範圍為1，000_5,〇〇〇，適用 於與具有咼Mw之第二聚醯胺結合。該第二聚醯胺可為具高 Mw之直線型聚醯胺，選擇性地經陰離子性聚合，或具高 MW之分支聚酿胺，較佳其量為0-10 wt.%，更佳為〇-5 wt.%， 相對於聚合物總量。使用此低Mw聚醯胺聚合物之優點為， 所製備之奈米纖維網中各奈米纖維的附著性增加，且生產 201204885 力增加。 具C/Ν比至多5·5，且Mw至多35,000之聚醯胺亦可由不 同聚醯胺混合物組成。例如，該混合物可由具非常低Mw， 如範圍為1,000-5,000之聚酸胺，與具Mw範圍為5,〇〇〇至 35,000或等於35,000之聚醯胺組成。 該溶液之聚合物可包含非半結晶聚醯胺之另一或其他 聚合物。可使用之其他聚合物為可溶於或可分散於溶液中 之溶劑者。此類聚合物較佳量為至多50 wt.°/D，更佳範圍為 0-25% wt，尤佳為0-5 wt%，相對於聚合物總重量。 該其他聚合物可為另一聚醯胺，於此稱之為第二聚醯 胺。因此該聚合物可包含聚醯胺之混合物，包含具C/Ν比至 多5.5且Mw至多35,000之聚醯胺，於此稱之為第一聚醯胺， 以及第二聚醯胺。該第二聚醯胺可與第一聚醯胺位於相同 化學組成物，或不同化學組成物中。較佳為，該第二聚醯 胺為具高Mw之直線型聚醯胺，或具高Mw之分支聚酿胺。 該高Mw聚醯胺可為經良好陰離子性聚合之聚醯胺。該第二 聚醯胺亦可為具C/Ν比大於5.5，及/或Mw至多50,000，較佳 大於70,000，更佳大於100,000 g/mole，且至多為200,000 g/mol或更高之聚醯胺。 較佳§亥第一聚酿胺之存在置範圍為〇_1〇 wt.%，較佳為 0.5-5 wt·%，相對於聚合物總重量。該第二聚合物量受限之 優點為’尤其是iijMw聚醯胺’具Mw大於50,000，或其分 支修飾物’ s亥溶液之剪切黏度可維持於低值，而能製造相 對高厚度之奈米纖維。 15 201204885 使用於聚合物溶液之溶劑較佳係由一溶劑混合物組 成。更佳為，該溶劑混合物包含不同極性溶劑之組合。這 些極性溶劑可選自於酸類、醇類、水，選擇性地與較低極 性溶劑如酯類及/或溶解度增強劑如鹽類組合。 適當之溶劑混合物包括含有（I)水、水溶性鹽類，以及 曱醇、乙醇、乙二醇，及/或甘油，並選擇性地包含NH3、 脂肪胺，及/或二胺，或含有（II)曱酸及/或醋酸，以及至少 一液體，選自於由水、甲醇、乙醇、乙二醇、甘油與甲酸 甲酯組成之混合物。亦可使用純曱酸，或甲酸與酸類之混 合物。 本發明所使用之聚醯胺之親水性，可用於與其低Mw之 特性結合，而使得具相對高水及/或醇含量之溶劑混合物可 使用。 在含有水與甲酸組合之溶劑混合物中，較佳水量為至 少15 wt.%，更佳範圍為20-30 wt.%，相對於溶劑混合物之 總重量。 在含有水與甲醇與鹽類組合之溶劑混合物中，較佳之 水量為至少30 wt.%，更佳的範圍為40-60 wt·%，相對於溶 劑混合物之總重量。 高水含量之優點為該方法較環保，且溶劑價格較低， 較快的相分離，以及喷射流中聚合物固化得較早。 使用高水含量之可能性亦可用於增加該製程之彈性。 水含量可藉由將水加至進料流中而增加，即在進料步驟 時，在進入紡口之前加至溶液中。藉由此動作，便可使用 16 201204885 含有高聚合物濃度、不同濃度與纖維直徑之溶液之單一儲 存槽。藉由加入水，可控制溶液中聚合物之濃度，及/或溶 液黏度，及/或離開紡口後之相分離速度，因而影響所得纖 維直徑。水矸依此加入，或較佳先以一部份之共溶劑稀釋° 此步驟可預防溶劑組成物内部有太大的局部差異’而導致 聚合物預先沈澱。 除了上述溶劑與聚合物之外，含水溶液中之聚合物亦 可包含一水溶性聚合物。該水溶性聚合物可自所製造之奈 米纖維中，以水萃取出，因而得到微孔狀奈米纖維。較佳 該水溶性聚合物為聚乙烯。比B各院酮(PVP)。 該溶液可更包含一或多種添加物。 適當之添加物包括表面張力試劑或界面活性劑（如過 氟化吖啶）、交聯劑、黏度修飾劑（如高度分支聚合物，如 HYBRANE)、電解質、抗生素添加物、附著增進劑，如順 丁烯二酸酐接枝橡膠’或其他可增進與ρρ或PET基板之附 著性之添加物、奈米顆粒如奈米管或奈米黏土，以及類似 物。適當之電解質包括水溶性金屬鹽類，如鹼金屬鹽類、 鹼土金屬鹽類，與鋅鹽。適當之電解質範例為Lic卜 (曱酸鉀）、CaCh、ZnCl2、Kb、Nab。較佳該電解質之量範 圍為〇-2wt.%，相對於溶液之總重量。水溶性鹽類可自所製 造之奈米_中’以水萃取出’因而制微孔狀奈米纖維。 將奈米顆粒加至聚合性奈米纖維中，可維持額外之要 求，由於奈米顆粒可改變甚至可增強纖維之機械、 熱學、磁學、光學與化學特性。 17 201204885 在電紡法中’喷射流中之聚合物會固化，因而形成奈 米纖維，而由此製造之噴射流及/或奈米纖維會沈積於收集 器或基板上，或由其收集。 較佳為，該奈米纖維由滾筒或軸心以半連續式捲繞法 收集。這些奈米纖維之後亦可進行後拉伸步驟，以進一步 增進其特性。此外’該奈米纖維可於基板或收集板上收集， 因而形成奈米纖維之不織布網。 由本發明方法製備之奈米纖維，不論是否為連續纏繞 纖維或不織布網或任何形狀，皆可進行一或多個其他加工 步驟。該奈米纖維可經如清洗、乾燥、固化、退火及/或後 縮合步驟。 一旦噴射流中之聚合物固化，且奈米纖維形成，該奈 米纖維便可經水適當地清洗，由於聚合物為水不溶性，之 後進行乾燥。乾燥步驟較佳係於大於loot：之溫度下進行。 此溫度可高至2〇〇°C或更高。 較佳進行固化步驟，若聚合物溶液與由其製造之奈米 纖維包含一交聯劑或附著增進劑。 本發明亦相關一種由本發明方法製備之奈米纖維，其 特定與較佳實施例’尤其是由含有C/N比至多5.5，MW至多 35,000之聚醯胺之聚合物組成物組成之奈米纖維。 該組成物中包含之聚醯胺可為任一聚醯胺，具有C/N 比至多5.5 ’ Mw至多35,〇〇〇,如上所述，亦稱之為第—聚蟪 胺。同樣情況可應用於選擇性使用的第二聚醯胺、其他聚 醯胺與添加物，可包含於溶液中，以製備奈米纖維，且可 18 201204885 與第一聚醯胺一同沈澱出。這些聚合物之種類、含量等範 例與實施例，亦可用於聚合物組成物上。 較佳為，該奈米纖維由聚合物組成物組成，該組成物由： a) 75-100 wt%之聚醯胺，具C/Ν比至多5.5，Mw至多 35,000 ； b) 0-25 wt·%之第二聚合物，可為具C/Ν比大於5.5及/ 或Mw大於35,000之聚醢胺，及/或另一聚合物； 其中a)與b)項中之wt.%係指相對於a)與b)之總重量；以及 c) 0-25 wt·%之至少一添加物，組成 其中c)之wt·%為相對於a)、b)與c)之總重量。 更佳為，該第一聚醯胺(a)具C/Ν比小於5。 該奈米纖維中之聚醯胺較佳具有炼點(Tm)至少250 °C，更佳至少27(TC，尤佳至少29〇t，以及最佳之範圍為 300-350。(：。 本發明亦相關於一種由聚合物組成物組成之奈米纖 維，該組成物係由： ⑴75-10〇 wt%之聚醯胺，具有C/N比小於5，河以大 於35,000 ; (ii) 〇-25wt.%之第二聚合物，可為具C/N比至少5之 聚醯胺，及/或另一聚合物； 其中（1)與(11)之Wt·%係相對於⑴與⑼之總重量，以及 ⑽0-25Wt.%之至少一添加物，其中該⑽之机％ 係相對於⑴、⑴)與(iii)之總重量。 此類不米纖維可由本發明方法製造，使用具c/n比小於 19 201204885 5，Mw小於35,000之聚醯胺，之後進行後縮合步驟或退火 步驟。此方法之優點為所得之奈米纖維具有非常良好之機 械與高溫特性，否則此類奈米纖維無法被製造出。 較佳本發明奈米纖維中之聚醯胺具有熔融溫度至少 290°C，更佳範圍為300-350°C。此特性是由於奈米纖維進 行後縮合步驟或退火步驟而得，該奈米纖維可包含具C/N 比小於5之聚醯胺、同元聚醯胺，如pA26、PA4或PA44，或 PA26、PA4或包含有限量共單體之pa44之共聚醯胺。 本發明亦相關於由本發明第二實施例所得之奈米纖 維，尤其是由聚醯胺組成物組成之奈米纖維，其中該聚醯 胺組成物包含具C/N比大於5.5 ’以及Mw至多35,000之聚醯 胺，以及直線型或分支型聚醯胺，具Mw大於35,〇〇〇。 本發明之奈米纖維，或由本發明之一實施例製備之奈 米纖維’可具有廣範_化之纖維直徑。該纖維直徑範圍 可為5-500nm，甚至超過，且較佳範圍為5〇 3〇〇 ，更佳 為100-25G nme此述之平均直#為這些直徑之數目平均 數’由知9¾錢子賴鏡(s E M )測量統計學上夠大數量之測 量點。 .截、准直從測定如下。每一奈米纖維樣本或網層皆取得 + #] αΰπΜΐ像’ 5Q()()x放大。每—張圖像皆測量十個⑽） 可/月晰刀辨之奈米纖維直徑，並紀錄，得總共—百個⑽） 獨立'則里值。並不包括缺陷(即奈米纖維團塊、聚合物液 滴不米、截維橫斷物）。由該一百個（100)獨立測量值計算每 一奈米纖維樣本的數目平均纖維直徑。 20 201204885 本發明之奈米纖維，以及其各種範例與實施例，可為 連續多細絲纖維形式，或不織布網形式。由本發明方法製 造之奈米纖維製成的不織布纖維網，非常適合用於作為薄 膜。此類薄膜稱之為奈米纖維薄膜或微孔狀薄膜。 本發明亦相關於本發明奈米纖維之用途，及其各種範 例與實施例，或由本發明方法之實施例獲得之微孔狀薄 膜，而該微孔狀薄膜可應用於下列任一用途：分子之分離 與過滤^如氣體/氣體過滤、熱氣體過渡、顆粒過渡、液體 過滤如微過渡、超過渡、奈米過遽、逆渗透；廢水純化、 油與燃料過濾之電化學應用，包括電透析、電去離子化、 電池（如電池分隔器）與燃料電池；經控制釋放之應用，包 括醫藥與保健食品成分；薄膜萃取、滲透蒸發與接觸濾材 之應用；酵素之固定，以及加濕器、藥物傳送；（工業用） 濕紙巾、手術衣與覆蓋巾、傷口敷料、組織工程、保護布、 催化劑支撐物與各種塗覆物。該薄膜亦可如與薄層結合， 如透明薄層，而使用作為強化物。 本發明之奈米纖維與其製造之產品為親水性，因此非 常適合醫療用途；因為親水性聚合物具有非常低或甚至無 蛋白質堆附作用。該薄膜具有非常高之過濾效率，且較佳 與極性溶劑及水組合使用。用於傷口敷料用途，該薄膜較 佳包含抗生素添加物。該抗生素添加物可於電紡製程開始 前加至溶液中，或可施加至如由本發明方法製備之孔狀奈 米纖維薄膜中。 本發明可以下列各範例與比較範例進行更詳細之說 21 201204885 明。 方法 以凝膠通透層析法(G P C)測定分子量 GPC之測量係於Viscotek GPCmax裝置（Malvern)上進 行’裝配有Viscotek三重偵測器分析儀（tda 302)以及 Viscotek PDA。使用三個PFG直線型XL 7μ管柱(PSS)。動相 為含有0.1 wt%三氟醋酸鉀修飾劑之六氟異丙醇。流速為〇 8 ml/rmn。該SEC裝置、管柱與偵測器皆於35Y下操作。收 集數據’並使用〇mnisec 4.6.1軟體(Viscotek)分析，以三重 偵測器（折射率、黏度與光散射)校正值為基礎。樣本於真空 下乾燥16小時，之後溶解於溶劑中（與動相溶劑相同）。溶液 經過濾，之後經由〇·45μηι過濾器（Schleicher&ScM11)注射 至GPC裝置上。 溶液黏度 t合物溶液之溶液黏度係於Anton Paar Physica MCR 501流變儀上偵測，裝配有 c_PTD2〇〇_SN8〇4255〇2(peltier) 溫度控制裝置，適用於圓筒測量裝置。用於同心圓筒系統 CC27(系列編號177〇，直徑26.64 mm ,以及同心度ό μηι)。 使用拋棄式圓筒，每—單獨溶液都使用新的圓筒。圓筒中 的洛液係蓋上含有些許水之溶劑捕捉器（s〇lvent “叩），其連 接在圓筒上方’以預防/最小化測量過程中的蒸散作用。-般而5，該溶液溫度係維持於25。(：，倒入拋棄式圓筒中， 之後該樣本在5分鐘内達到2yc。以穩定剪切速率，自1〇掃 至1000 s 1 ’於25 c進行測量。剪切速率為1〇〇 8_丨時之黏度 22 201204885 值被報導為溶液黏度，單位為mPa.s。值得注意的是，在剪 切速率約為100 s-1時，不同溶液中所有黏度測量值皆與剪 切速率無關。 製造速率 連續奈米纖維電紡法之製造速率[g/hr]係定義為每小 時所製造之薄膜或奈米網之量。就製造速率的測量而言， 直徑為47 mm之圓形樣本(稱之為圓盤），係自連續紡織之奈 米纖維薄膜單層上打孔出。測量五個（5)小圓盤的重量，並 計算數目平均值。 由此平均值可知，該製造速率可使用下列公式計算： P = —.S.W (式 1) Ο 其中 P=製造速率[g/hr] Μ =每圓盤上沈積材料之平均重量[g] Ο =圓盤表面積[m2] S =線速度[m/hr] W=電極寬度[m] 奈米纖維之鑑定：纖維直徑、數目平均與分佈，及標準差 為了決定纖維直徑之數目平均值，自奈米纖維網層上 取下十個（10)樣本，每一個樣本皆經掃瞄式電子顯微鏡 (SEM)，5,000x影像成像。每一張圖像皆測量十個（10)可清 晰分辨之奈米纖維直徑，並紀錄，得總共一百個（100)獨立 測量值。並不包括缺陷（即奈米纖維團塊、聚合物液滴、奈 23 201204885 米纖維橫斷物）。纖維直徑分佈係由此一百個獨立測量值組 成。由該一百個（100)獨立測量值，可計算出每一奈米纖維 樣本的數目平均直徑(d)與標準差（S)。 材料 PA46 -1/7 聚醯胺46聚合物，所有皆為直線型，MW自13, 000 g/Mol變化至65,000 g/Mol，所有皆使用標 準聚合法製備内部DSM。 PA46-X PA46樣本係得自Aldrich (產品編號44,299-2) PA6-1/2 聚醯胺6聚合物，二者皆為直線型，Mw 30,000 resp. 41,000 g/Mol，二者皆使用標準聚合法製 備内部DSM。 曱酸 工業級，95%曱酸，5%水。 所有聚合性材料皆以上述GPC法鑑定。PA46-X為得自 Aldrich之PA46樣本，可以GPC進行更詳細的分析，此結果 與PA46-1之結果列於表1。 表 1. PA46-X與PA46-1 之GPC數據 PA46-X PA-46-1 Mn [kg/mol] 23 14 Mw [kg/mol] 44 28 Mz [kg/mol] 78 45 Mw/Mn [-] 1.9 1.95 Mz/Mw [-] 1.7 1.6 24 201204885 可看出Aldrich產物具有相當高之Mw，與PA 46-1相較， 洛於本發日賊圍之外。另外值得注意的是此二產物皆在 Mark_Houwink圖上顯示出為直線型聚合物。 電紡聚合溶液之製備 fe圍在10-30 g之聚合物粉末或顆粒係經秤重，並加至 2〇Oml之95%甲酸中（Merck之準分析等級）。溶液使用磁性撥 拌子，在密閉錐形瓶中，於室溫下（25。〇攪拌12小時。之後 係使用上述方法，於25t，f切速率為·，之條件下測量 溶液黏度。 不同濃度之溶液係使用不同量之聚合物製備。所得之 黏度數據示於濃度/黏度圖中，驗指出製備具特^黏度之 溶液所需之材料量。減約_ mPas之驗，相對於用於 其他實驗之;f同聚合物之麵⑽。，係個上述相同方式 ，備，起始於由該圖中衍生之特定量y容液製備後，係測 量其黏度。這些溶液之相對數據包括於表2與3中。 無喷頭電紡裝置之奈米纖維電紡法 奈米纖維係使用Elmarco s.r.〇_公司’位於捷克，之NsMw is preferably at least 1, 〇〇〇, more preferably at least 2,000 Å, particularly preferably in the range of 5' 〇〇 0-3G' GGG, particularly preferably in the range of 1 G, __25. Advantages of lower compilations Higher concentrations can be used in the process, and/or the spray can contain higher water or alcohol content. Very low polyamine Mw, i.e. Mw in the range of 1,000 Å, is suitable for combination with a second polyamine having 咼Mw. The second polyamine can be a linear polyamine having a high Mw, optionally anionic polymerization, or a branched melamine having a high MW, preferably in an amount of 0-10 wt.%, more preferably It is 〇-5 wt.%, relative to the total amount of the polymer. The advantage of using this low Mw polyamine polymer is that the adhesion of each nanofiber in the prepared nanofiber web is increased, and the production of 201204885 is increased. Polyamines having a C/Ν ratio of up to 5.6 and a Mw of up to 35,000 may also consist of a mixture of different polyamines. For example, the mixture may be composed of a polyamine having a very low Mw, such as a range of 1,000 to 5,000, and a polyamine having a Mw range of 5, 〇〇〇 to 35,000 or 35,000. The polymer of the solution may comprise another or other polymer other than a semi-crystalline polyamine. Other polymers which can be used are those which are soluble or dispersible in the solution. The preferred amount of such a polymer is at most 50 wt. ° / D, more preferably from 0 to 25% by weight, particularly preferably from 0 to 5% by weight, based on the total weight of the polymer. The other polymer may be another polyamine, referred to herein as a second polyamine. Thus the polymer may comprise a mixture of polyamines comprising a polyamidamine having a C/Ν ratio of at most 5.5 and a Mw of up to 35,000, referred to herein as a first polyamine, and a second polyamine. The second polyamine can be in the same chemical composition as the first polyamine or in a different chemical composition. Preferably, the second polyamine is a linear polyamine having a high Mw or a branched polyamine having a high Mw. The high Mw polyamine can be a well anionically polymerized polyamine. The second polyamine may also be a polyfluorene having a C/Ν ratio of greater than 5.5, and/or a Mw of up to 50,000, preferably greater than 70,000, more preferably greater than 100,000 g/mole, and up to 200,000 g/mol or greater. amine. Preferably, the first polyamine is present in the range of 〇_1〇 wt.%, preferably 0.5-5 wt.%, based on the total weight of the polymer. The advantage of the second amount of polymer limitation is that 'especially iijMw polyamide' has a Mw greater than 50,000, or the shear viscosity of the branched modification 's solution can be maintained at a low value, and a relatively high thickness can be produced. Rice fiber. 15 201204885 The solvent used in the polymer solution is preferably composed of a solvent mixture. More preferably, the solvent mixture comprises a combination of solvents of different polarities. These polar solvents may be selected from the group consisting of acids, alcohols, water, and optionally in combination with lower polar solvents such as esters and/or solubility enhancers such as salts. Suitable solvent mixtures include (I) water, water soluble salts, and sterols, ethanol, ethylene glycol, and/or glycerin, and optionally NH3, fatty amines, and/or diamines, or II) Capric acid and/or acetic acid, and at least one liquid selected from the group consisting of water, methanol, ethanol, ethylene glycol, glycerol and methyl formate. Pure citric acid or a mixture of formic acid and acid can also be used. The hydrophilicity of the polyamine used in the present invention can be used in combination with its low Mw characteristics, so that a solvent mixture having a relatively high water and/or alcohol content can be used. In a solvent mixture comprising a combination of water and formic acid, preferably the amount of water is at least 15 wt.%, more preferably in the range of 20-30 wt.%, relative to the total weight of the solvent mixture. In a solvent mixture comprising water in combination with a mixture of methanol and a salt, preferably, the amount of water is at least 30 wt.%, more preferably in the range of 40 to 60 wt.%, based on the total weight of the solvent mixture. The advantage of high water content is that the process is environmentally friendly, the solvent price is lower, the phase separation is faster, and the polymer in the jet solidifies earlier. The possibility of using a high water content can also be used to increase the flexibility of the process. The water content can be increased by adding water to the feed stream, i.e., during the feed step, to the solution prior to entering the spin. With this action, you can use 16 201204885 a single storage tank containing a solution of high polymer concentration, different concentrations and fiber diameter. By adding water, the concentration of the polymer in the solution, and/or the viscosity of the solution, and/or the rate of phase separation after exiting the spinning port can be controlled, thereby affecting the resulting fiber diameter. The leeches are added as such, or preferably diluted with a portion of the co-solvent. This step prevents too much local variation within the solvent composition and causes the polymer to pre-precipitate. In addition to the above solvents and polymers, the polymer in the aqueous solution may also comprise a water soluble polymer. The water-soluble polymer can be extracted from water from the manufactured nanofibers, thereby obtaining microporous nanofibers. Preferably, the water soluble polymer is polyethylene. More than B hospital ketone (PVP). The solution may further comprise one or more additives. Suitable additives include surface tension agents or surfactants (such as acridine peroxide), crosslinkers, viscosity modifiers (such as highly branched polymers such as HYBRANE), electrolytes, antibiotic additives, adhesion promoters, such as Maleic anhydride grafted rubber' or other additives that enhance adhesion to ρρ or PET substrates, nanoparticles such as nanotubes or nanoclay, and the like. Suitable electrolytes include water soluble metal salts such as alkali metal salts, alkaline earth metal salts, and zinc salts. Examples of suitable electrolytes are Lic (potassium citrate), CaCh, ZnCl2, Kb, Nab. Preferably, the amount of the electrolyte is in the range of 〇-2 wt.%, relative to the total weight of the solution. The water-soluble salts can be extracted from the prepared nano-"water" to form microporous nanofibers. The addition of nanoparticle to the polymeric nanofibers maintains additional requirements as the nanoparticle can modify or even enhance the mechanical, thermal, magnetic, optical and chemical properties of the fiber. 17 201204885 In electrospinning, the polymer in the jet will solidify, thus forming nanofibers, and the jets and/or nanofibers thus produced will be deposited on or collected from the collector or substrate. Preferably, the nanofibers are collected by a roller or a shaft in a semi-continuous winding process. These nanofibers can also be subjected to a post-stretching step to further enhance their properties. Further, the nanofibers can be collected on a substrate or a collecting plate, thereby forming a nonwoven fabric of nanofibers. The nanofibers prepared by the process of the present invention, whether continuous wound fibers or nonwoven webs or any shape, may be subjected to one or more other processing steps. The nanofibers can be subjected to, for example, washing, drying, curing, annealing, and/or post-condensation steps. Once the polymer in the jet solidifies and the nanofibers are formed, the nanofibers can be suitably washed with water, since the polymer is water insoluble and then dried. The drying step is preferably carried out at a temperature greater than the loot:. This temperature can be as high as 2 〇〇 ° C or higher. Preferably, the curing step is carried out if the polymer solution and the nanofibers produced therefrom comprise a crosslinking agent or adhesion promoter. The invention also relates to a nanofiber prepared by the process of the invention, which is specifically and preferably in the form of a nanofiber comprising a polymer composition comprising a polyamine having a C/N ratio of at most 5.5 and a MW of up to 35,000. . The polyamine contained in the composition may be any polyamine having a C/N ratio of at most 5.5 Å Mw and at most 35 Å, as described above, also referred to as a poly-polyamine. The same can be applied to the selectively used second polyamine, other polyamines and additives, which can be included in the solution to prepare nanofibers, and can be precipitated together with the first polyamine at 18 201204885. Examples and examples of the types and contents of these polymers can also be used for the polymer composition. Preferably, the nanofiber is composed of a polymer composition consisting of: a) 75-100 wt% polydecylamine having a C/Ν ratio of at most 5.5 and a Mw of at most 35,000; b) 0-25 wt % of the second polymer, which may be a polyamine having a C/Ν ratio greater than 5.5 and/or a Mw greater than 35,000, and/or another polymer; wherein wt.% in items a) and b) With respect to the total weight of a) and b); and c) at least one additive of 0-25 wt.%, the wt% of composition c) is the total weight relative to a), b) and c). More preferably, the first polyamine (a) has a C/Ν ratio of less than 5. The polyamine in the nanofiber preferably has a refining point (Tm) of at least 250 ° C, more preferably at least 27 (TC, particularly preferably at least 29 〇t, and an optimum range of 300-350. (:. The invention is also related to a nanofiber composed of a polymer composition consisting of: (1) 75-10% by weight of polyamidamine having a C/N ratio of less than 5 and a river of greater than 35,000; (ii) 〇 -25 wt.% of the second polymer, which may be a polyamine having a C/N ratio of at least 5, and/or another polymer; wherein W1·% of (1) and (11) are relative to (1) and (9) The total weight, and at least one additive of (10) 0-25 Wt.%, wherein the % of the machine (10) is relative to the total weight of (1), (1), and (iii). Such non-rice fibers can be made by the method of the present invention, using The c/n ratio is less than 19 201204885 5, the polyamine of Mw is less than 35,000, and then the post-condensation step or the annealing step is carried out. The advantage of this method is that the obtained nanofiber has very good mechanical and high-temperature characteristics, otherwise such nano-nano The fiber cannot be produced. Preferably, the polyamine in the nanofiber of the present invention has a melting temperature of at least 290 ° C, more preferably in the range of 300 - 350 ° C. The nanofiber is obtained by performing a post-condensation step or an annealing step, and the nanofiber may comprise a polydecylamine having a C/N ratio of less than 5, a homo-polyamine, such as pA26, PA4 or PA44, or PA26, PA4. Or a copolymerized guanamine containing a limited amount of a co-monomer. The invention also relates to a nanofiber obtained from the second embodiment of the invention, in particular a nanofiber composed of a polyamine composition, wherein the polyamine The composition comprises a polyamine having a C/N ratio greater than 5.5' and a Mw of up to 35,000, and a linear or branched polyamine having a Mw greater than 35, 〇〇〇. The nanofiber of the invention, or by the invention The nanofibers prepared in one embodiment may have a broad fiber diameter. The fiber diameter may range from 5 to 500 nm, or even exceed, and preferably ranges from 5 to 3 Å, more preferably from 100 to 25 G nme. The average straightness of the description is the number average of these diameters. A statistically large number of measurement points are measured by the s EM. The cut and collimation are determined as follows. Both the sample or the mesh layer get + #] αΰπΜΐ' 5Q()()x to enlarge. Each - Zhang Like all measured ten ⑽) can / March resolution of clarity knife nanofiber diameter, and recorded to give a total of - one hundred ⑽) independent 'in the value. It does not include defects (ie, nanofiber briquettes, polymer droplets, and cross-cutting cross-cuts). The number average fiber diameter of each nanofiber sample is calculated from the one hundred (100) independent measurements. 20 201204885 The nanofibers of the present invention, as well as various examples and embodiments thereof, may be in the form of continuous multifilament fibers, or in the form of a nonwoven web. A nonwoven web made of nanofibers produced by the method of the present invention is very suitable for use as a film. Such films are referred to as nanofiber films or microporous films. The invention is also related to the use of the nanofibers of the invention, and various examples and embodiments thereof, or microporous films obtained by embodiments of the method of the invention, which microporous film can be used for any of the following purposes: Separation and filtration ^ such as gas / gas filtration, hot gas transition, particle transition, liquid filtration such as micro-transition, ultra-transition, nano-perfluorene, reverse osmosis; wastewater purification, oil and fuel filtration electrochemical applications, including electrodialysis , deionization, batteries (such as battery separators) and fuel cells; controlled release applications, including pharmaceutical and health food ingredients; application of membrane extraction, pervaporation and contact media; immobilization of enzymes, and humidifiers, Drug delivery; (industrial) Wet wipes, surgical gowns and cover towels, wound dressings, tissue engineering, protective cloths, catalyst supports and various coatings. The film can also be used as a reinforcement if it is combined with a thin layer, such as a transparent thin layer. The nanofibers of the present invention and the products from which they are made are hydrophilic and therefore are very suitable for medical use; because hydrophilic polymers have very low or even no protein accumulation. The film has very high filtration efficiency and is preferably used in combination with a polar solvent and water. For wound dressing applications, the film preferably comprises an antibiotic additive. The antibiotic additive can be added to the solution prior to the start of the electrospinning process or can be applied to the apertured nanofiber film as prepared by the process of the present invention. The present invention can be described in more detail by the following examples and comparative examples. Method Determination of molecular weight by gel permeation chromatography (G P C) The measurement of GPC was performed on a Viscotek GPCmax device (Malvern) equipped with a Viscotek triple detector analyzer (tda 302) and a Viscotek PDA. Three PFG linear XL 7μ columns (PSS) were used. The mobile phase is hexafluoroisopropanol containing 0.1 wt% potassium trifluoroacetate modifier. The flow rate is 〇 8 ml/rmn. The SEC device, the column and the detector are all operated at 35Y. Collect data' and use 〇mnisec 4.6.1 software (Viscotek) analysis based on the triple detector (refractive index, viscosity and light scattering) correction values. The sample was dried under vacuum for 16 hours and then dissolved in a solvent (same as the mobile solvent). The solution was filtered and then injected onto a GPC apparatus via a 〇·45 μηι filter (Schleicher & ScM11). Solution Viscosity The solution viscosity of the T solution was detected on an Anton Paar Physica MCR 501 rheometer equipped with a c_PTD2〇〇_SN8〇4255〇2 (peltier) temperature control device for cylindrical measuring devices. For concentric cylinder system CC27 (series number 177〇, diameter 26.64 mm, and concentricity ό μηι). Using a disposable cylinder, a new cylinder is used for each individual solution. The liquid in the cylinder is covered with a solvent trap containing a little water (s〇lvent “叩”, which is attached above the cylinder to prevent/minimize the evapotranspiration during the measurement. -5, the temperature of the solution The system was maintained at 25. (:, poured into a disposable cylinder, after which the sample reached 2 yc in 5 minutes. The shear rate was measured at a steady shear rate from 1 Torr to 1000 s 1 ' at 25 c. Viscosity at 1〇〇8_丨22 201204885 Value is reported as solution viscosity in mPa.s. It is worth noting that at a shear rate of approximately 100 s-1, all viscosity measurements in different solutions are The shear rate is independent. The manufacturing rate of the continuous rate nanofiber electrospinning process [g/hr] is defined as the amount of film or nanowire produced per hour. For the measurement of the manufacturing rate, the diameter is 47 mm. A circular sample (referred to as a disc) is perforated from a single layer of continuous-woven nanofiber film. The weight of five (5) small discs is measured and the number average is calculated. The manufacturing rate can be calculated using the following formula: P = —.SW (form 1) Ο where P = manufacturing rate [g/hr] Μ = average weight of deposited material per disc [g] Ο = disc surface area [m2] S = linear velocity [m/hr] W = electrode width [m Identification of nanofibers: fiber diameter, number average and distribution, and standard deviation To determine the average number of fiber diameters, ten (10) samples were taken from the nanofiber mesh layer, and each sample was scanned. Electron microscopy (SEM), 5,000x image imaging. Each image is measured for ten (10) clearly distinguishable nanofiber diameters and recorded for a total of one hundred (100) independent measurements. Including defects (ie, nanofiber briquettes, polymer droplets, Nai 23 201204885 rice fiber cross-section). The fiber diameter distribution is composed of one hundred independent measurements. From the one hundred (100) independent measurements The average diameter (d) and standard deviation (S) of each nanofiber sample can be calculated. Material PA46 -1/7 Polyamide 46 polymer, all linear, MW from 13,000 g/ The Mol was changed to 65,000 g/Mol, all using standard polymerization to prepare the internal DSM. The PA46-X PA46 sample was obtained from Aldrich ( Product No. 44,299-2) PA6-1/2 Polyamide 6 polymer, both linear, Mw 30,000 resp. 41,000 g/Mol, both of which are prepared by standard polymerization to prepare internal DSM. 95% citric acid, 5% water. All polymerizable materials were identified by the above GPC method. PA46-X is a PA46 sample from Aldrich, which can be analyzed in more detail by GPC. The results of this result and PA46-1 are listed in the table. 1. Table 1. GPC data for PA46-X and PA46-1 PA46-X PA-46-1 Mn [kg/mol] 23 14 Mw [kg/mol] 44 28 Mz [kg/mol] 78 45 Mw/Mn [- ] 1.9 1.95 Mz/Mw [-] 1.7 1.6 24 201204885 It can be seen that the Aldrich product has a relatively high Mw, compared with PA 46-1, which is outside the thief of this day. It is also worth noting that both products are shown as linear polymers on the Mark_Houwink diagram. Preparation of electrospun polymerization solution Polymer powder or granules of 10-30 g were weighed and added to 2% Oml of 95% formic acid (Merck's quasi-analytical grade). The solution was magnetically mixed, and the mixture was stirred at room temperature (25 ° 12 for 12 hours) in a closed conical flask. After that, the solution viscosity was measured at 25 t, f cutting rate was used. The solution is prepared using different amounts of polymer. The obtained viscosity data is shown in the concentration/viscosity diagram, indicating the amount of material required to prepare a solution with a specific viscosity. The test is reduced by about _ mPas, relative to other Experimental; f-polymer side (10), in the same manner as above, prepared, starting from the specific amount of y solution derived from the figure, the viscosity is measured. The relative data of these solutions are included in the table. 2 and 3. The nanofiber electrospinning nanofiber fabric without nozzle electrospinning device uses Elmarco sr〇_company's located in the Czech Republic, Ns
Lab 500 ’包含一裝置室、溶液儲存槽、18cm之旋轉4-線圓 筒電極，頂部f極，以及空氣循環系統。當於溶液儲存槽 中旋轉時，該電極會搭載部分溶液於線上。 係使用約0.01 m m厚之家用鋁箔作為基板。就所有實驗 而口係使用4_線18 cm寬之電極。電紡間距與施加電壓在 所有貫驗中都固定，分別為1〇 (：111與6〇 kv。裝置室之相對 濕度係經設定並控制於預設值（分別為45、38與27% RH)， 25 201204885 在每次電紡實驗中皆使用標準相對濕度裝置連續測量。為 了獲得乾燥空氣條件，係於裝置下方之空氣吸入區放置矽 膠顆粒。當需要較濕的條件時，則可將飽和鹽類溶液或熱 水儲存槽置入裝置室内部。 聚合物溶液係以25°C或29°C之溫度供應，並使用裝置 室之空調系統維持該溫度。在實驗過程中，溫度係經監測 並回報。基板速度為0.13 m/min，較低圓筒電極之旋轉頻率 為50Hz。每一實驗係進行至少3分鐘，收集塗覆有奈米纖維 沈積層之基板。 係研究奈米纖維沈積層之製造速率、奈米網之基礎重 量、纖維群之數目平均直徑，以及纖維直徑之分佈。 不同相對濕度下之不同聚合物溶液結果，列於下表中。 表2.範例I-V之無喷頭電紡法與比較實驗A-D之數據與測 試結果The Lab 500' contains a device chamber, a solution storage tank, an 18 cm rotating 4-wire cylindrical electrode, a top f-pole, and an air circulation system. When rotated in the solution storage tank, the electrode carries a portion of the solution on the wire. A household aluminum foil having a thickness of about 0.01 m is used as a substrate. A 4-line 18 cm wide electrode was used for all experiments. The electrospinning spacing and applied voltage were fixed in all tests, 1 〇 (: 111 and 6 〇 kv. The relative humidity of the device chamber was set and controlled to preset values (45, 38 and 27% RH, respectively). ), 25 201204885 Continuous measurement using a standard relative humidity device in each electrospinning experiment. In order to obtain dry air conditions, silicone particles are placed in the air suction zone below the device. When wet conditions are required, saturation can be achieved. A salt solution or a hot water storage tank is placed inside the device. The polymer solution is supplied at a temperature of 25 ° C or 29 ° C and maintained by the air conditioning system of the equipment room. During the experiment, the temperature is monitored. And return. The substrate speed is 0.13 m/min, and the rotation frequency of the lower cylindrical electrode is 50 Hz. Each experiment is carried out for at least 3 minutes to collect the substrate coated with the nanofiber deposition layer. The manufacturing rate, the basis weight of the nanoweb, the average diameter of the fiber population, and the distribution of fiber diameters. The results of the different polymer solutions at different relative humidity are listed in the table below. Table 2. Examples No-head electrospinning method of I-V and comparative experiment A-D data and test results
Mw [kg/mol] 濃度 [wt.%] 黏度 [mPa.s] T (°C) 製造速率 [g/hr] 標準差 平均纖維 直徑 [nm] 標準差 A 部分,25°C,45%RH EX-I PA46-1 25 18.3 596 24.8 0.564 0.008 87 28 CE-A PA46-3 52 12.7 595 24.6 0.352 0.054 130 53 CE-B PA6-1 30 16.5 549 24.6 0.362 0.006 110 39 B部分，25°C,27%RH EX-II PA46-2 34 14.8 606 24.6 0.741 0.008 155 29 CE-C PA46-3 52 12.7 595 24.3 0.647 0.010 156 30 CE-D PA6-1 30 16.5 549 24.9 0.537 0.025 93 52 C 部分,29°C,27%RH EX-III PA46-2 34 14.8 606 29,3 0,89 0,010 156 30 EX-IV PA46-4 19 22 618 29,0 1,18 0,008 127,8 38,2 EX-V PA46-5 13 27 730 29,0 1.697 0,009 190 42 26 201204885 第一部份之數據組(A部分）顯示出範例I中具較低Mw 之PA46具有明顯較高之製造速率。而比較範例八中具較高 Mw之PA46之製造速率則低許多，比較範例B中較低Mw之 PA 6亦是如此。此較低之製造速率無法簡單地以濃度較低來 解釋，如同比較範例B中之PA6之數據所示，其濃度僅稍低 於範例I中之濃度，但卻較比較範例A中之濃度高出許多。 此外，高Mw之PA46之纖維直徑明顯較高，儘管濃度非常低。 第二部分數據組(B部分)顯示，在低相對濕度下，製造 速率會明顯增加。由比較實驗C至範例II，製造速率增加， 即降低聚醯胺46之Mw可增加製造速率。最低製造速率係得 自比較實驗D，即在三實驗中具最低Mw與最高濃度之 PA-6。 最後一部分數據組(C部分)顯示，若加工時溫度增高， 則製造速率會增高更多，如同範例III與範例II相較所得，而 幾乎不會對於纖維直徑與其分佈有影響。此外，該製造速 率可藉由降低PA46之Mw而增加，且不會導致明顯小珠形 成》此與比較實驗B與D二結果相較，二者皆顯示出有小珠 形成。 更值得注意的是，所有PA46之實驗僅顯示出非常有限 之製造速率差異，以及相對窄之纖維分佈，可由低標準差 看出，除了範例IV與具最低mw之pa46範例之外，其纖維 分佈稱寬。這些聚合物可提㈣_與最高製造速率，而 不會有小珠形成。這些結果可以高濃度之溶液達成，而不 需使用其他方法’如加入U比。定。 27 201204885 多喷頭電紡法 多喷頭電紡法之設計係類似於W02005/073441 A1中 所述者。電紡間距與施加電壓在所有實驗中都固定，分別 為12 cm與32kV。基板速率為〇.7 m/min。空氣溫度與濕度 控制於25°C與40 % RH。實驗溶液係製備自具不同數目平均 分子量之PA46聚合物，於曱酸/水比為85/15 w/w之溶劑中。 就電紡法製程而言’係使用具黏度約1〇〇〇 mPa.s之聚合物溶 液。數據與結果收集於表3。 表3_範例¥1-¥11與比較實驗£-?，於25。(：與40%1111之 條件下之多噴頭電紡法之數據與結果 聚合物 Mw [kg/mol] 濃度 [wt.%] 黏度 [mPa.s] Αν. FD [nm] EX-VI PA46-1 25 22.5 1000 137 EX-VII PA46-6 31 20 995 150 CE-E PA46-7 46 16 1041 167 CE-F PA46-3 52 15 975 168 本發明範例VI與VII之聚合物可具有高濃度，同時保有 低黏度，以及較高之生產率，而電紡製程可運作地更順利， 與比較範例E與F相較。結果亦顯示出可使用高濃度之溶 液，而仍能獲得具小直徑之奈米纖維。 溶液穩定性 特定量之聚合物粉末或顆粒係加至2〇〇ml之不同溶劑 混合物與系統中。三種不同之純溶劑成分係❹於此試驗 中，分別為99.9%之曱酸、乙醇與水。含不同溶劑換合物之 組成物列於表3。溶液係使用磁性攪拌子，在密閉錐形瓶 28 201204885 中，於室溫下攪拌12小時。經12小時後，溶液黏度係使用 上述方法，於Anton Paar Physica MCR501流變儀上測量。 忒錐形瓶儲存於室溫條件下，溶液黏度係於8週内的數個時 間點上測i。4週與8週後之測試結果，係與初始黏度比較， 以初始黏度百分比表示之降低值列於表4。 甲醅/7匕中） wt.%，於85/15Mw [kg/mol] Concentration [wt.%] Viscosity [mPa.s] T (°C) Manufacturing rate [g/hr] Standard deviation Average fiber diameter [nm] Standard deviation Part A, 25 ° C, 45% RH EX-I PA46-1 25 18.3 596 24.8 0.564 0.008 87 28 CE-A PA46-3 52 12.7 595 24.6 0.352 0.054 130 53 CE-B PA6-1 30 16.5 549 24.6 0.362 0.006 110 39 Part B, 25°C, 27 %RH EX-II PA46-2 34 14.8 606 24.6 0.741 0.008 155 29 CE-C PA46-3 52 12.7 595 24.3 0.647 0.010 156 30 CE-D PA6-1 30 16.5 549 24.9 0.537 0.025 93 52 Part C, 29°C ,27%RH EX-III PA46-2 34 14.8 606 29,3 0,89 0,010 156 30 EX-IV PA46-4 19 22 618 29,0 1,18 0,008 127,8 38,2 EX-V PA46-5 13 27 730 29,0 1.697 0,009 190 42 26 201204885 The first part of the data set (Part A) shows that the PA46 with lower Mw in Example I has a significantly higher manufacturing rate. The manufacturing rate of PA46 with higher Mw in Comparative Example 8 is much lower, as is the lower Mw PA 6 in Comparative Example B. This lower manufacturing rate cannot be explained simply by the lower concentration, as shown by the data for PA6 in Comparative Example B, which is only slightly lower than the concentration in Example I, but higher than the concentration in Comparative Example A. A lot. In addition, the fiber diameter of the high Mw PA46 is significantly higher, although the concentration is very low. The second part of the data set (Part B) shows that at low relative humidity, the manufacturing rate increases significantly. From Comparative Experiment C to Example II, the manufacturing rate was increased, i.e., lowering the Mw of the polyamide 46 increased the manufacturing rate. The minimum manufacturing rate was obtained from Comparative Experiment D, which is the lowest Mw and highest concentration of PA-6 in the three experiments. The last part of the data set (Part C) shows that if the temperature increases during processing, the manufacturing rate will increase more, as compared to Example III and Example II, with little impact on fiber diameter and its distribution. In addition, the manufacturing rate can be increased by lowering the Mw of PA46 without causing significant bead formation. This compares with the results of Comparative Experiments B and D, both of which show bead formation. More notably, all PA46 experiments showed only very limited manufacturing rate differences, as well as a relatively narrow fiber distribution, as can be seen from the low standard deviation, except for the example IV and the pa46 example with the lowest mw. Weighing. These polymers provide (4) _ with the highest manufacturing rate without the formation of beads. These results can be achieved with a high concentration of solution without the use of other methods such as the addition of a U ratio. set. 27 201204885 Multi-nozzle electrospinning The design of the multi-nozzle electrospinning method is similar to that described in WO2005/073441 A1. The electrospinning spacing and applied voltage were fixed in all experiments, 12 cm and 32 kV, respectively. The substrate rate was 〇.7 m/min. Air temperature and humidity are controlled at 25 ° C and 40 % RH. The experimental solutions were prepared from PA46 polymers having different numbers of average molecular weights in a solvent having a citric acid/water ratio of 85/15 w/w. For the electrospinning process, a polymer solution having a viscosity of about 1 mPa.s is used. Data and results are collected in Table 3. Table 3_Examples ¥1-¥11 and comparison experiments £-?, at 25. (: Data and results of multi-spray electrospinning method under conditions of 40% and 1111 Polymer Mw [kg/mol] Concentration [wt.%] Viscosity [mPa.s] Αν. FD [nm] EX-VI PA46-1 25 22.5 1000 137 EX-VII PA46-6 31 20 995 150 CE-E PA46-7 46 16 1041 167 CE-F PA46-3 52 15 975 168 The polymers of the inventive examples VI and VII can have a high concentration while retaining Low viscosity and high productivity, while the electrospinning process works more smoothly, compared to Comparative Examples E and F. The results also show that high concentration solutions can be used while still obtaining small diameter nanofibers. Solution stability A specific amount of polymer powder or granules is added to a different solvent mixture and system of 2 〇〇ml. Three different pure solvent components are used in this test, 99.9% of citric acid, ethanol and Water. Compositions containing different solvent exchanges are listed in Table 3. The solution was stirred at room temperature for 12 hours in a closed conical flask 28 201204885 using a magnetic stir bar. After 12 hours, the solution viscosity was used. Method, measured on an Anton Paar Physica MCR501 rheometer. At room temperature, the solution viscosity was measured at several time points within 8 weeks. The test results after 4 weeks and 8 weeks were compared with the initial viscosity, and the reduction values expressed as a percentage of initial viscosity are listed in Table 4. A/7匕) wt.%, at 85/15
表4.數據-聚合物溶液之黏度降低值(2〇 表中所列數據顯示出，具較_w聚合物之溶 以較其他聚合物長 合IS1與I具有較佳之黏_ 物之各液相較，說明本發明方法可 儲存時間來運作 【圖式簡單説明】 (無） 【主要元件符號說明】 (無） 29Table 4. Viscosity reduction values for data-polymer solutions (2) The data listed in the table shows that solutions with a longer viscosity than the other polymers IS1 and I have better viscosity. In comparison, the method of the present invention can be stored for a long time to operate [Simple description of the drawing] (None) [Key element symbol description] (None) 29