經濟部中央梯準局負工消费合作社印掣 五、發明说明（1) 本發明係有機可溶性全芳香族聚醯胺纖維之製程，聚合物是在醯 胺類溶劑中，以低溫聚縮合方式聚合而成。聚合物溶液經中和後，將 聚合物溶液由紡嘴擠出，在专含金屬畫類之極性有機溶劑，重量百分 比低於40%之水溶液中，且於常溫(低於50°C，但高於冰點)條件下凝固 成形；隨即在另一個含有機溶劑之延伸槽，並在常溫(低於5(TC，但高 於冰點)下，進行總延伸率之60%以上延伸之，再將經水洗、乾燥之長 絲於接近聚合物之玻璃轉移溫度範固，加熱延伸。 一般而言，全芳香族聚醢胺高分子，在醢胺類溶劑中採低溫缩合 聚合方式進行反應❶聚合時亦可加入金屬鹽類例如氯化鈣(CaCl2)， 氣化鋰(LiCl)等促進溶劑之溶解度或中和聚合時所產生之氣化氫，藉以 提高聚合度❶ 傳碑的紡絲方法，可分為乾式紡絲法如美國專利3,287,324， 3,360,598所揭示，和濕式紡絲法如美國專利3,414,645，3,642,706， 3,751，546 ’ 3,869,429 ’ 4,073,837，4,342,715，4,842,796 等所揭示者。 紡絲所得之織維，需經水洗、濕延伸、乾燥、熱延伸等步驟，以達到 最後之織維性質’由於乾式紡絲法具有高成本的溶劑回收和環保問題 等缺點’因此近年來，濕式紡絲法較乾式紡絲法普遍。 漁式妨絲製程中，凝固液一般至少含40%之氣化朽，溫度則控制在 高於60°C(如對照例所示）。依此原則，凝固液中因含大量之氣化好’ 會降低溶劑之萃取速率；然而昇高溫度，除了可促進織維之延伸性 外，也同時加速了溶劑之萃取速率。換言之，凝固浴的高鹽類含量和 高溫’對於溶劑之萃取引起兩個互為矛盾的效應，實有減低效率之嫌。 —3 —(修正頁） 18412017 本纸張尺度逍用中國两家梯準（CNS ) A4規格（21〇χ297公釐> 83.3.10,〇〇〇 (請先閲讀背面之注$項再填寫本頁) - 訂 、ί>’ .1.匕 Α7 Β7 五、發明説明（2 ) • - 為了解決此高鹽類含量與高溫二者之間互為矛盾的現象，本發明 乃以常溫(低於5(TC ’高於冰點），且不含金屬里類之極性有機溶劑水 溶液為新的凝固液組份，（此有機溶劑與聚合反應過程中，所使用之溶 劑相同為佳），重量百分比低於40%之條件下，使紡絲原液凝固成形， 再將此已部份萃取之纖維，在濕延伸槽及常溫(低於50°C，高於冰點) 下延伸2〜2.5倍，而60%以上之延伸率在延伸槽中完成。於此條件下 紡絲’可得到有效率的凝固和延伸以及令人滿意之緘維物性。而在操 作上’適當的凝固槽舆延伸槽之有機溶劑含量，則須視紡絲原液之溶 劑/鹽含量與延伸倍率來決定。 下列實施例係用以闞明本發明之實施技術與功效，而非用以限制 本發明之適用性》 實施例、 本例為有機可溶全芳族聚醯胺，聚(間一苯基一異苯二醯胺），Poly (m-phenyleneisophthalamide)(MPD-I) ’ 之聚合物及織維備製方法。 經濟部中央揉準局貞工消费合作社印製 使用5L夹套式圓柱形玻璃反應器，裝配一支雙螺旋攪拌棒， 加入 409.0g (3.78 mole)的間一二胺苯（m-phenylene diamine, MPD) ’ 及3605g(35〇0ml)的無水氮一甲基一2—d比咯酮（N-methyl-2--pyrrolidone) _P)溶劑，並通入氮氣。將MPD/NMP之溶液冷卻至 0°C ’約在15分效後加入767.9g (3·78 mole)的間一苯二随氣 (isophthaloylchloride,IC1)的單體。並同時以循環水維持反應所需的低 溫’ 20分鐘後，將反應溫度昇高至60°C，持溫15分鐘後，中止反應。 此時聚合物之濃度為20wt%，而此聚合物經沈溉、水洗、乾燥等程序 後，取〇.5g樣品溶入l〇〇ml純度97%之硫酸在30°C之溫度下，所測得之 固有粘度値為l.ldL/g。 —4 _ (修正頁） 18412017 83. 3.10.000 (請先Η讀背面之注$項再填寫本頁) 本紙張尺度逋用中國«家樣率（CNS ) A4规格（210X297公釐） 五、發明説明（ A7 B7 經濟部中央榡準局負工消費合作社印製 為中和反應時所產生之氣化氫，需加入559.4g之氫氧化鈣 (Ca(OH)2)，並將聚合物之溶液在7〇°c下過濾並眞空下，脱泡4小 時，後準備抽絲。 將聚合物溶液以l〇.8ml/min的速率，由直徑0.08mm的1〇〇 孔紡口擠出，紡口與凝固浴保持2.5cm之空氣間隔（air gap)，將 聚合物擠入。 室溫狀態約20°C，内含15wt%之NMP水溶液中，擠出物出 凝固浴的速度為17m/min，接著將此半固化的長絲導入另—内含 20wt%之NMP水溶液槽中，經歷i〇〇cm長之延伸槽後以 40m/min速率離開該槽之後，續經兩道室溫之水洗槽，其速率分 別為 42m/min 及 46m/min。 延伸絲經水洗後，捲繞在筒上，經空氣乾燥後的長絲，在 330 C之咼溫延伸1_2倍，此製程條件，聚合物及纖維物性整理列 於表一所示。 實施例2 本實施例係改變MPD-I纖維製程條件而得。條件改變的部份 包括空氣間隔距離、凝固浴濃度、捲取速度、延伸比，其它之條 件則與實施例1相同。 ' 纺絲時’聚合物溶液之擠出速率，變更為，纺口 與凝固洛間之空氣間距縮短為1.5cm，而凝固浴中NMP之濃度提 高到20wt°/〇與濕延仲槽之NMP濃度相同，並同在室溫之情況下 分別以15m/min與31m/min之速率操作後，續經兩道室溫之水洗 槽’其速率則分別為36m/min及37m/min。捲取、乾燥後的長絲 在330°C之溫度下，做1_3倍之熱延伸，纖維之物性整理列於表一 所示。 (修正頁） 1850921a (請先w讀背面之注'項再填寫本頁) •裝 本纸張尺度逍用中國國家橾率（CNS ) A4現格（210X297公釐） 83. 3. 10,000 A7 B7 ^C(h 60 4 五、發明説明（ 、、谷及1t'辰度〈水溶液及相同溫度之凝固 /合及相冋延伸於的扭作條件下，仍可 實際操作上，細軸延伸槽，可依需要而 本例係依Shimada等所發表之美國專利第4,342,715號上所 揭不之條件，進行MPD-I纖維之紡絲。 本例中將聚合物毅轉溫度柳代後，〃 9 65ml/min之 速率擠出纺口，經0.7咖之空氣段間距後擠人呢之内今5加％ 之nmp、水5液凝固槽中，緊接著進入95。〇且内含4〇wt〇/；氣化鈣 (CaCl2)之第一綠固槽’接著將此半固化之纖維，分別通過Μ。。 及50 C之水洗槽水洗後，再進入水溫為8(rc之槽中延伸2 5倍 之後，再以90°C之水洗槽水洗。水洗完後的長絲在12(rc之溫度 下乾燥後，再以370°C之溫度延伸1.4倍。所得之纖維物性整理列 於表一所示。 (請先聞讀背面之注意事項再填寫本頁) -裝. 訂· 線 經濟部中央橾準局貝工消費合作社印装 1850921a 83. 3.10,000 本紙張適用中國國家揉準（CNS )入4祕（21〇><297公瘦〉 Α7 五、發明説明（5 ) 經濟部中央揉準局貝工消費合作社印製 表一本發明案技術與先前技術之製程條件及物性比較 實施例1 實施例2 對照例 擠出條件： 速率（ml/min) 10.8 11.1 9.65 溫度（°C) 20 20 100 空氣間隙（cm) '2.5 1.5 0.7 凝固條件： 第一槽：溶劑含量（wt%) 15 20 5 溫度（°C) 20 20 18 第二槽：鹽含量（wt%) 無 40 溫度（°C) ’ # »»» * *»> 95 水洗條件： 溫度（°C) «»»> * »»> 18/50 溶劑含量（wt%) 水 濕延伸條件： 溫度（°C) 20 20 80 溶劑含量（wt%) 20 (NMP) 20 (ΝΜΡ) 水 濕延伸倍率（X) 2.4 2.1 2.5 濕延伸/總延伸（％) 73 64 71 水洗條件： 溫度（°c) 20 20 90 溶劑含量（Wt%) 水 水 水 乾熱延伸條件： 溫度（°C) 330 330 370 倍率（X) 1.2 1.3 1.4 纖維物性： 細度（dgf). 2.2 3.5 3.0 強度（g/d) 4·1 ±0.6 4.0±0.5 3.1 ±0.3 伸張度（％) 37±7 33±7 29 土 4 一 7 —(修正頁） 1850921a (請先閲讀背面之注意事項再填寫本頁) •裝. 訂. 線· 本紙張尺度適用中國國家標準（CNS ) A4現格（210X297公釐） 83.3.10,000Printed by the Ministry of Economic Affairs, Central Bureau of Standards, and Consumer Cooperatives 5. Description of the invention (1) The present invention is a process of organic soluble fully aromatic polyamide fiber, the polymer is polymerized in a polyamide solvent by low-temperature polycondensation Made. After the polymer solution is neutralized, the polymer solution is extruded from the spinning nozzle, in a polar organic solvent containing metal paintings, in an aqueous solution of less than 40% by weight, and at normal temperature (less than 50 ° C, but Solidified under the condition of above freezing point; then in another extension tank containing organic solvent, and at room temperature (below 5 (TC, but above freezing point), extend more than 60% of the total elongation, and then The washed and dried filaments are solidified at a temperature close to the glass transition temperature of the polymer and heated to extend. Generally speaking, fully aromatic polyacetamide polymers are reacted in a low-temperature condensation polymerization method in acrylamide solvents ❶ during polymerization Metal salts such as calcium chloride (CaCl2), lithium vapor (LiCl), etc. can also be added to promote the solubility of the solvent or to neutralize the vaporized hydrogen generated during polymerization to increase the degree of polymerization ❶ The spinning method of Chuanbei can be Divided into dry spinning method as disclosed in US Patent 3,287,324, 3,360,598, and wet spinning method as disclosed in US Patent 3,414,645, 3,642,706, 3,751,546 '3,869,429' 4,073,837, 4,342,715, 4,842,796, etc. , Need to go through the steps of water washing, wet stretching, drying, hot stretching, etc., to achieve the final weaving properties. 'Dry spinning method has high cost solvent recovery and environmental problems and other shortcomings.' In recent years, wet spinning method Dry spinning method is common. In the fish-like yarn production process, the coagulation liquid generally contains at least 40% of the gasification decay, and the temperature is controlled above 60 ° C (as shown in the comparative example). According to this principle, the Containing a lot of good gasification will reduce the extraction rate of the solvent; however, increasing the temperature will not only promote the extensibility of the weave, but also accelerate the extraction rate of the solvent. In other words, the high salt content and high temperature of the coagulation bath ' The extraction of the solvent caused two contradictory effects, which really reduced the efficiency. —3 — (revised page) 18412017 This paper standard is used in China ’s two standards (CNS) A4 specifications (21〇 × 297 mm > 83.3.10, 〇〇〇 (please read the $ item on the back and then fill in this page)-Order, ί > '.1. Dagger Α7 Β7 5. Description of the invention (2) •-In order to solve this high salt There is a contradiction between content and high temperature, The invention is based on normal temperature (lower than 5 (TC 'is higher than freezing point), and does not contain metal polar organic solvent aqueous solution as the new coagulation liquid component, (this organic solvent is the same as the solvent used in the polymerization process Preferably), under the condition that the weight percentage is less than 40%, the spinning stock solution is solidified and formed, and then the partially extracted fiber is extended in a wet extension tank and normal temperature (below 50 ° C, above freezing point) 2 ~ 2.5 times, and the elongation of more than 60% is completed in the extension groove. Spinning under this condition can obtain efficient coagulation and elongation and satisfactory physical properties. In operation, the appropriate organic solvent content of the coagulation tank and the extension tank depends on the solvent / salt content of the spinning dope and the extension ratio. The following examples are used to illustrate the implementation techniques and effects of the present invention, rather than to limit the applicability of the present invention. Examples, This example is an organic soluble fully aromatic polyamidoamine, poly (m-phenyl-isobenzene Diacrylamide), Poly (m-phenyleneisophthalamide) (MPD-I) 'polymer and weave preparation method. The Ministry of Economic Affairs, Central Engineering Bureau, Zhengong Consumer Cooperative printed a 5L jacketed cylindrical glass reactor, equipped with a double-screw stirring rod, and added 409.0g (3.78 mole) of m-phenylene diamine, MPD) 'and 3605g (350,000ml) of anhydrous nitrogen-methyl-2-dpyrrolidone (N-methyl-2--pyrrolidone) _P) solvent, and nitrogen gas was introduced. Cool the MPD / NMP solution to 0 ° C. After about 15 minutes, add 767.9g (3.78 mole) of isophthaloyl chloride (IC1) monomer. At the same time, the circulating water was used to maintain the low temperature required for the reaction. After 20 minutes, the reaction temperature was increased to 60 ° C. After the temperature was maintained for 15 minutes, the reaction was terminated. At this time, the concentration of the polymer was 20wt%. After the polymer was subjected to the procedures of irrigation, washing, drying, etc., 0.5g of the sample was dissolved in 100ml of 97% pure sulfuric acid at a temperature of 30 ° C. The measured intrinsic viscosity was l.ldL / g. —4 _ (Amendment page) 18412017 83. 3.10.000 (please read the note item on the back first and then fill in this page) This paper uses Chinese «Home Sample Rate (CNS) A4 specification (210X297mm) V. Description of the invention (A7 B7 The Ministry of Economic Affairs Central Bureau of Preservation and Consumer Cooperatives prints the gasified hydrogen produced during the neutralization reaction. It is necessary to add 559.4g of calcium hydroxide (Ca (OH) 2) and the polymer The solution was filtered at 70 ° C and emptied, degassed for 4 hours, and then prepared for spinning. The polymer solution was extruded from a 100 ° orifice with a diameter of 0.08 mm at a rate of 10.8 ml / min. Maintain an air gap of 2.5cm between the spinning nozzle and the coagulation bath, and squeeze the polymer in. The room temperature is about 20 ° C, containing 15wt% NMP aqueous solution, and the speed of the extrudate out of the coagulation bath is 17m / min, and then introduce the semi-cured filament into another tank containing 20wt% NMP aqueous solution. After going through an extension tank with a length of 100cm and leaving the tank at a rate of 40m / min, it continues through two room temperature Water washing tank, the speed is 42m / min and 46m / min respectively. After the washed yarn is washed with water, it is wound on the drum and the filament after air drying is at 330 C The temperature can be extended 1_2 times. The process conditions, physical properties of polymers and fibers are listed in Table 1. Example 2 This example is obtained by changing the process conditions of the MPD-I fiber. The changed conditions include the air separation distance, The coagulation bath concentration, take-up speed, elongation ratio, and other conditions were the same as in Example 1. The extrusion rate of the polymer solution during 'spinning' was changed to shorten the air gap between the spinning nozzle and the coagulation roller to 1.5 cm , And the concentration of NMP in the coagulation bath is increased to 20wt ° / 〇, which is the same as the NMP concentration of the wet-stretched secondary tank, and after operating at a rate of 15m / min and 31m / min at room temperature, the two passes The speed of the water washing tank at room temperature is 36m / min and 37m / min respectively. The filament after winding and drying is heated 1 to 3 times at a temperature of 330 ° C. The physical properties of the fiber are listed in Table 1. (Revised page) 1850921a (please read the item on the back of the page before filling in this page) • Install this paper and use the Chinese National Standard Rate (CNS) A4 (210X297mm) 83. 3. 10,000 A7 B7 ^ C (h 60 4 V. Description of the invention (,, valley and 1t '℃ <aqueous solution and phase Under the conditions of temperature solidification / combination and twisting, the thin shaft extension groove can still be actually operated. The example is based on the US Patent No. 4,342,715 published by Shimada et al. Conditions, spinning of MPD-I fiber. In this example, after the polymer was turned to temperature, it will be extruded at a rate of 9 65ml / min, and it will be squeezed after the air gap of 0.7 coffee. 5% of NMP and 5 liquids of water solidify tank, and then enter 95. 〇And contains 40wt〇 /; vaporized calcium (CaCl2) of the first green solid tank 'then the semi-cured fibers, respectively, through Μ. . After washing with a 50 C water washing tank, enter the water temperature of 8 (rc tank extended 25 times, and then wash with 90 ° C water washing tank. The filament after drying is dried at 12 (rc temperature After that, it is extended by 1.4 times at a temperature of 370 ° C. The resulting physical properties of the fibers are listed in Table 1. (Please read the precautions on the back and then fill out this page) -Installation. Order · Central Ministry of Thread Economy Printed 1850921a 83. 3.10,000 This paper is suitable for China National Crushing (CNS) into the 4th secret (21〇 < 297 public thinning) Α7 V. Invention description (5) The Central Ministry of Economic Affairs Printed Table 1 by the Bureau Cooperative Consumer Cooperative. Comparison of process conditions and physical properties between the technology of the present invention and the prior art Example 1 Example 2 Comparative example Extrusion conditions: Rate (ml / min) 10.8 11.1 9.65 Temperature (° C) 20 20 100 Air gap (cm) '2.5 1.5 0.7 Solidification conditions: First tank: Solvent content (wt%) 15 20 5 Temperature (° C) 20 20 18 Second tank: Salt content (wt%) None 40 Temperature (° C ) '# »» »* *» ≫ 95 Washing conditions: temperature (° C) «» »> *» »> 18/50 Content (wt%) Water-wet stretch condition: Temperature (° C) 20 20 80 Solvent content (wt%) 20 (NMP) 20 (NMP) Water-wet stretch ratio (X) 2.4 2.1 2.5 Wet stretch / total stretch (%) 73 64 71 Washing conditions: temperature (° c) 20 20 90 Solvent content (Wt%) Water water dry heat extension conditions: temperature (° C) 330 330 370 magnification (X) 1.2 1.3 1.4 Fiber properties: fineness (dgf ). 2.2 3.5 3.0 Strength (g / d) 4 · 1 ± 0.6 4.0 ± 0.5 3.1 ± 0.3 Elongation (%) 37 ± 7 33 ± 7 29 soil 4 1 7 — (correction page) 1850921a (please read the back side first (Notes to fill out this page) • Packing. Ordering. Threads • This paper scale is applicable to the Chinese National Standard (CNS) A4 (210X297mm) 83.3.10,000