200906899 九、發明說明： 【發明所屬之技術領域】 本發明是關於-種在常壓陽離子染料可染型共聚醋聚合物，其製備方 法，以及使用該常壓陽離子染料可染型共聚醋聚合物之在常壓陽離子染料 可染型共聚賴維。透過使用廉價對苯二曱酸之聚合法，可製備品質相同 且成本低之在«在1G(TC或町祕子染料可染型共聚㈣合物及共聚 酉旨纖維。 【先前技術】 先前已知之在常壓在丨⑽或以下陽離子染料可染型共聚i旨聚合物及 共聚醋纖維如下。日本專利公開第施_2_63號揭示—種在常壓陽離子 染料可染《«合物之持齡合綠m，該純含扣聚合物存 在之總酸成分計S2. 0至3. G莫耳%之金屬雜鹽、以聚合物重量計為4_ 〇 至6. 0重量％之分子量働至麵之聚烧基乙二醇、以聚合物重量計祀 至6.0莫耳%之二乙二醇’其中末端減濃度為2Q至3q當量/慨其具有 小的固有黏度變化。 ' 然而，由該發明製備之在常壓陽離子染料可染型聚黯纖維在維持纖维 結構上衫_，因為金屬俩鹽含量“造減量流域_間快速地 發生重量流失。再者，高含量的二乙二醇降低所製備之聚合物與纖_ 熱性。 陽離子染料可染型聚 1至10重量％之改善 曰本專利公開第2001-55626號揭示一種在常壓 酯纖維，其含有0· 1至10莫耳％的金屬石黃酸鹽以及〇· 5 200906899 耐熱性用具有式H0(CH2CH20)l(R0)m(CH2CH20)nH (此處R為C3-C25脂肪族 烴基，1及η為滿足1 匚]40之相同或不同的整數，以及m為整數2 至50)之化合物。然而，在常壓陽離子染料可染型聚酯纖維製備所需之具有 式H0(CH2C_) 1 (R0)m(CH2CH20)nH之化合物是昂貴的。如果如該專利例示 使用對苯二甲酸二曱酯聚合法，則製造成本更為增加。再者，該專利揭示 之具有陽離子染色位置之共聚合成分中，使用昂貴的異笨二甲酸衍生物， 以及工業可得之曱酯類難以直接應用於對苯二甲酸聚合法。 曰本專利特開平第5-331719號揭示經由共聚合績酸鱗系與聚氧院基 乙二醇所製備之常壓可染型纖維。然而磺酸鐫系太昂貴以至於無法應用於 工業。 曰本專利公開第2006-63215號揭示使用鎂或鋁化合物作為共聚合催 化劑之總酸成分計為〇. 5至8. 0莫耳％之金屬磺酸鹽與〇. 5至& 〇莫耳％之 C5-C10脂肪族二元酸之共聚合。然而共聚合催化劑太昂貴以至於無法應用 於工業。 因此’有需要具良好品質且低成本能產生在常壓陽離子染料可染型共 聚酯聚合物以及利用該共聚酯聚合物之纖維之製備方法。 【發明内容】 因此，本發明之一目的是提供一種聚合物及其製備方法，該聚合物用 於製備在常壓在1㈣或以下陽離子染料可染型共聚賴維，於τρΑ聚合法 能降低聚酯的製造成本。 本發明之另一目的是提供一種在常壓陽離子染料可染型共聚酯纖 200906899 維，使用趟備方法具有低綱轉移溫度以及優異的可染性。 a月之引述及其他目的與優點可由本發明日膽，且將詳細說明於以 下文中。 在觀點’本發明提供在常屋陽離子染料可染型共聚醋聚合物，以總 兀酉夂成刀。十3有1至20莫耳％的脂肪族二元酸以及U至2. 〇莫耳％包括 金屬磺酸鹽的異笨二甲酸雙經基乙酿。 在另觀點，本發明提供—種在健陽離子染料可染型共聚醋聚合物 之製備方法，其含有步驟： ()犯U對苯—曱酸與乙二醇以製備漿液(Slu㈣，然後添加脂肪族 二元酸至所得漿液； ⑹供應毁液至第—反應勒，紐進行S旨化作用； (C)將步驟⑹之產物轉移二反應槽内，供應式丨之異苯二甲酸雙 羥基乙酯到第二反應槽内，然後進行混合； 驟⑹之產物轉移到縮合反應槽内，然後縮合阻燃性聚醋；以 及 (e)從造粒機·步驟⑷之產物，並辦所得聚合物。 又另-觀點，本發明提供一種使用在常麵離子染料可染型共聚酿聚 合物之共聚酯纖維。 〜 【實施方式】 有關經由以下文中提供僅舉例說明用所附圖式舉例說明之某些示範 具體例’鶴詳細·本發明之以上及其他佩，且不因此_本發明， 7 200906899 以及其中： 第1圖為一流程圖 合反應器。200906899 IX. OBJECTS OF THE INVENTION: TECHNICAL FIELD The present invention relates to a cationic dyeable type copolymerized vinegar polymer, a preparation method thereof, and a copolymerizable vinegar polymer dyeable using the atmospheric pressure cationic dye In the atmospheric pressure cationic dye dyeable copolymerized copolymer. By using a low-cost terephthalic acid polymerization method, it is possible to prepare a fiber of the same quality and low cost in the 1G (TC or Machiko dye dyeable copolymer (tetra) compound and copolymerized fiber. [Prior Art] It is known that the cationic dye-dyeable copolymer of the cationic dye (10) or less is a polymer and a copolymerized vinegar fiber as follows. Japanese Patent Laid-Open No. _2-63 discloses that the cationic dye can be dyed in a normal pressure cationic dye. The weight of the polymer is from 4 to 3% by weight of the polymer, and the molecular weight of the polymer is from _ to 0.001% by weight of the polymer. The polyalkylene glycol, which is fluorinated to 6.0 mol% by weight of the polymer, wherein the terminal concentration is 2Q to 3q equivalents / has a small intrinsic viscosity change. 'However, by the invention The preparation of the cationic dyeable dyeable polyfluorene fiber in the maintenance of the fiber structure of the shirt _, because the metal salt content "to reduce the amount of water _ rapid loss of weight. In addition, the high content of diethylene glycol reduced The prepared polymer and fiber _ heat. Cationic dye can be dyed The present invention discloses a normal-pressure ester fiber containing 0. 1 to 10 mol% of metal rhein and 〇·5 200906899 for heat resistance. Formula H0(CH2CH20)l(R0)m(CH2CH20)nH (wherein R is a C3-C25 aliphatic hydrocarbon group, 1 and η are the same or different integers satisfying 1 匚]40, and m is an integer 2 to 50) However, it is expensive to prepare a compound of the formula H0(CH2C_) 1 (R0)m(CH2CH20)nH required for the preparation of a normal pressure cationic dye-dyeable polyester fiber. If the benzene is used as exemplified in the patent The diterpene formate polymerization method increases the manufacturing cost. Furthermore, in the copolymerized component having a cationic dyeing position disclosed in the patent, it is difficult to use an expensive isoparadicarboxylic acid derivative and an industrially obtainable oxime ester. It is directly applied to a terephthalic acid polymerization method. The atmospheric pressure dyeable fiber prepared by copolymerizing acid squama and polyoxyl ethylene glycol is disclosed in Japanese Patent Application Laid-Open No. Hei No. 5-331719. It is too expensive to be used in industry. 曰 Patent Publication No. 2006-63 No. 215 discloses that the total acid component using a magnesium or aluminum compound as a copolymerization catalyst is 〇. 5 to 8. 0 mol% of the metal sulfonate and 〇. 5 to & 〇 mol% of the C5-C10 aliphatic Copolymerization of a dibasic acid. However, the copolymerization catalyst is too expensive to be used in the industry. Therefore, there is a need for good quality and low cost to produce a cationic dyeable copolyester polymer at atmospheric pressure and to utilize the copolymer. SUMMARY OF THE INVENTION Accordingly, it is an object of the present invention to provide a polymer and a process for the preparation thereof for use in the preparation of a cationic dyeable copolymerized copolymer at normal pressure of 1 (four) or less. Dimensions, the τρΑ polymerization method can reduce the manufacturing cost of polyester. Another object of the present invention is to provide a low pressure transfer temperature and excellent dyeability in a conventional pressure cationic dye-dyeable copolyester fiber 200906899. References to a month and other objects and advantages may be made by the present invention and will be described in detail below. In the present invention, the present invention provides a cationic dye-type copolymerized vinegar polymer in a permanent house to form a knives. Thirty-three has 1 to 20 mol% of an aliphatic dibasic acid and U to 2. 〇mol% includes a metal sulfonate diiso-dicarboxylic acid di-based. In another aspect, the present invention provides a method for preparing a cationic cationic dye-dyeable copolymerized vinegar polymer, comprising the steps of: () making U-p-benzoic acid and ethylene glycol to prepare a slurry (Slu (four), and then adding fat a group of dibasic acids to the obtained slurry; (6) supplying a decomposing liquid to the first reaction column, and performing a reaction to the S; (C) transferring the product of the step (6) into the second reaction tank, supplying the dihydroxy group of isophthalic acid Ester to the second reaction tank, and then mixed; the product of step (6) is transferred to the condensation reaction tank, and then the flame-retardant polyester is condensed; and (e) the product from the granulator, step (4), and the obtained polymer Still another aspect, the present invention provides a copolyester fiber for use in a conventional surface ion dye-dyeable copolymerized polymer. ~ [Embodiment] The following is exemplified by the following description by way of example only. Some exemplary embodiments are described in detail in the above-mentioned and other aspects of the present invention, and are not, therefore, in the present invention, 7 200906899 and wherein: Figure 1 is a flow chart reactor.
，顯示驗製備本發«合物之示範性三管TPA 〇之’考，其貫施例舉例說明於附加的 現詳細地進行本發明較佳具體 圖式中。 本發明針料«合物·雜移溫度崎低祕溫度。當玻璃轉移 溫度低時，由於低溫時分子鏈可較自由移_«料分子能輕易穿過纖 維。就這-如言，脂肪族二猶比聚纽基乙二醇作為共聚合作用單體 有益。聚魏基乙二_效於降錄合物的玻補移溫度，但對改盖整體 分子鏈的可撓性無效果。較佳為所含脂肪族二元_量，㈣二猶成^ 計為1至20莫耳％。當脂肪族二元酸含量，以總二元酸成分計少於【莫耶 % ’則降低玻璃轉移溫度的效果減少。以及當其超過2〇莫耳％時，因為聚 合物的結晶度大大地減少而可就化可概(啦腿biHty)或其他加工特 (·生。以及仗TPA及EG(乙二醇）製備漿液其月間添加脂肪族二元酸。由於脂肪 族二元酸可溶於EG且比TPA更有反應性，添加至錄對改善反應效率是有 利的。 使用具有下式1之異苯二曱酸雙m基㈣(DES)作為金柄酸鹽成 分，以提供陽離子染料可染性： 200906899 H0CH2CH20C0The test shows the preparation of the exemplary three-tube TPA 本 of the present invention, and the examples thereof are exemplified in the following detailed description of the preferred embodiment of the present invention. The needle material of the invention has the low temperature of the compound. When the glass transition temperature is low, the molecular chain can move relatively freely due to the low molecular weight at low temperatures. In this case, it is believed that aliphatic two is more useful as a copolymerization monomer than polyglycolethane. Polyweiylethylene II acts as a glass-compensating temperature for the degradation of the complex, but has no effect on the flexibility of the entire molecular chain. Preferably, it is an aliphatic binary amount, and (4) is a ratio of 1 to 20 mol%. When the aliphatic dibasic acid content is less than [Moyer %' in terms of the total dibasic acid component, the effect of lowering the glass transition temperature is reduced. And when it exceeds 2 〇 mol%, because the crystallinity of the polymer is greatly reduced, it can be made (biHty) or other processing (and raw) and 仗TPA and EG (ethylene glycol) preparation The slurry is added with an aliphatic dibasic acid during the month. Since the aliphatic dibasic acid is soluble in EG and more reactive than TPA, it is advantageous to add it to the recording to improve the reaction efficiency. The isophthalic acid having the following formula 1 is used. Double m-based (tetra) (DES) as a gold salt component to provide cationic dye dyeability: 200906899 H0CH2CH20C0
COOCH2CH20H so3m 式1 其中M為驗金屬。 在式1中，舉例而言，驗金屬可為Na、Li、κ等等，但不限於此。 當使用異笨二甲酸雙經基乙則DES)以外之市售可得含金屬石黃酸鹽之 異苯二曱酸二烧酯時’纟TPA聚合法之後仍無反應性，因此造成紡絲過程 期間包捆壓力增加或惡化其他加工特性。 為防止田q反應，例如DES熱解(pyr〇lysis)產生之凝膠形成，使用如 第1圖所示三管聚合反應器進行聚合作用。使用兩管聚合反應器時（由醋化 作用槽及縮合反應槽驗成），難以決定何時加人添加劑。再者，當需要加 入各種添加劑時，該反應器並*適用，因為基本募聚物的品f可能已改變。 加入DES到DE-2槽以將其於反應器内部的滯留減至最小。 對於縮合反應催化劑，常麟聚㈣造之銻化合物具有優異的成本效 益及物理性質。 關於第1圖’將提供更詳細的說明。 ⑷在製備槽1内部製備反應物對苯二曱酸及乙二醇為激液。在此步 驟"』、、加月日肪知―元酸以製備漿液。脂肪族二元酸對對苯二甲酸之莫耳比為 20:80 至 1:99。 (b)將步驟(a)所製備之f液貯存在貯藏槽2。 200906899 (C)以半分批法(semi—batch prQcess)進行g旨化作用，經由持續供應 貯藏槽2之·至第—反應槽⑽-1)3，其中基本寡聚物健在定溫(通常 為250至260。〇。根據反應槽及已反應募聚物分劃（如如〇1〇排出的水量 決定酿化作_終止。最初量的基本絲物留在职反應槽，並透過遽器 經由氮氣加壓將其餘的轉移到第二反應槽(DE_2)5。 ⑷透過轉移線濾n (k式濾II )4將已自旨化寡聚物從DE—丨反應槽轉移 到DE-2反應槽，以及進一步進行反應後添加式丨之DEs。 (e)透過轉矛夕線濾為（監式濾器⑽將所得阻燃性寡聚物從见一2反應槽 轉移至縮合反賴7 ’並反應崎到阻祕如旨。紐騎得崎&聚醋進 行縮合反應。 (0從造粒機8排出反應槽7所製備之聚合物並進行切碎。 TPA聚合法期間，二乙二醇⑽）是從τρΑ的酸成分所產生之副產物。 在本發明中’聚合物的DEG含量以聚合物總重計為丨· 5至3. 5重量％。根據 本發明之聚合法，DEG含量不能低於h 5重量％。當DEG含量為h 5重量％ 或以上日杨達到降低聚合物之玻璃轉移溫度的效果。但當含量超過3· 5 重量％時，聚合物的可紡性因熱穩定性差而惡化。 未反應TPA及熱解所產生者之末端絲的濃度，以聚合物總重計維持 在30至50當量/嘴。當末端羧基的濃度低於3〇當量/噸時，可能降低反應 溫度或增加EG含量。但任-情形，反麟間是增加的，@此導致聚合物降 解及增加副產物DEG之無用效果。且當末端缓基濃度超過5()當量/β頓時， 聚合物的降解可引起凝膠化或其他問題，因為大部分的末输基是熱解所 200906899 致。 聚合物中未反應TPA之含量維持在不超過2〇 _。由於未反應砰八 既不充姐化也不充分溶解於溶射，當含量超過2Q _時其可惡化聚合 物的可紡性。 聚合物的炫化溫度以215至240〇C為佳。當溶化溫度低於215。〇時， 由於财熱性低而使可紡性惡化，域得纖維的耐熱性差。#聚鮮二甲酸 乙二醋經充分共聚合時，舰降低。因此，難以得雜化溫度高於2赃之 聚合物。再者，當溶化溫度高於2批時，未反應之共聚合單體可存在於聚 合物中，因而惡化聚合物與纖維的品質。 貫施例 以下列非限制實施例進一步詳細說明本發明。 在實施例及比較實施例中，如下分析物理性質： 1 對苯二甲sm旨化侧程度1由滴定法測定已酯化絲物之叛酸 濃度。 2. 固有黏度（IV):將聚合物溶解於6:4 (w/w)之紛及j，^ 2, 2一四氯乙 烧溶液。在30 C恆溫槽中使用Ubbelohde黏度計測量IV。 3. 熔化溫度及玻璃轉移溫度：使用DSC 7熱示差掃瞄分析儀 (PerkinElmer)以 l〇°C/min 加熱速率測量。 4·二元酸及DES含量：以棚腿z NMR分析。 5· DEG含將聚合物溶解於乙醇胺，並以氣相色層分析法進行分析。 實施例1 200906899 使用己工酸⑽)作為脂肪族二元酸。混合τρΑ、AA及EG(TpA:AA:EG = 600:315:50 ’以體積計）以製備槳液。制供應所得漿液朗含^ 3嘲熔化 之包括8. 7莫耳％己二酸（以總二元酸計)之基本寡聚物的DE—丨反應槽（參照 第1圖），並雜在255°C。供賴駐職合物量達丨· 5健輯3〇分鐘 酯化作用後，定量泵浦將1_ 5鱗聚物轉移到DE_2反應槽。對寡聚物 添加以總二元酸(TPA、AA及DES)計為1. 3莫耳％具有式1之DES，以及M為 Na(分子量=356，以35重量％濃度溶解於EG)。充分攪拌後，轉移到縮合反 應槽（爹照第1圖），添加2 %三氧化二銻EG溶液(三氧化二銻濃度=25〇鹏， 以聚合物重料）’並在娜。(：在1 torr或以下進行反應。所得聚合物之 物理性質提供於下面表1。 實施例2 以如實施例1之相同方法製備聚合物，但添加以總二元酸計為8. 5莫 耳°/。的壬ΚΑΖΑ)储AA除外。所得聚合物之物雜f提供於表卜 實施例3 除添加DES之外，以如實施例i之相同方法製備聚合物，其中M = u。 所得聚合物之物理性質提供於表1。 比較實施例1 除不添加AA之外，以如實施例丨之相同方法製備聚合物。所得聚合 物之物理性質提供於表】。 比較實施例2 除不添加DES之外，以如實施例1之相同方法製備聚合物。所得聚合 200906899 物之物理性質提供於表1。 表1 — ---- 實施例1 Γ—--- 實施例2 實施例3 比較實施例1 比較實施例2 脂肪族二元酸含量 (莫耳％) 8. 32 8.23 8.35 0 8.2 鹼金屬（Μ) Na Na Li _一·-Na 一 DES含量（莫耳。/0) 1.31 ------ 1.24 卜— 1.32 1.35 0 DEG含量（莫耳%) —-— 2.19 2.40 2.32 1.56 1.21 CEG(當量Λ頓） 35 33 36 31 27 熔化溫度(°c) — 232 ---- 231 234 243 241 玻璃轉移溫度(。〇 65 -~~---J 63 66 76 64 實施例4 於塑膠真空乾燥皿(濕氣含量=15酬)在丨犹乾躁實酬丨製備之 聚合物’並在295 C旋轉’首先在8〇〇c滾速為l m/min，然後在12(rc 滾速為3,700 m/min。編織所得纖維並在耶它以Kayacryl染料(Nipp〇n Kayaku)染色。達到優異的可染性。 比較實施例3 除使用比較實施例1製備之哿人榀+从 馆之來σ物之外’以如實施例4之相同方法進 行乾燥、紡絲及染色。得到差的可染性。 13 200906899 根據本發明，在loot：或以下以陽離子染料染色時可提供優異可染性 之在常壓陽離子染料可㈣共聚S旨纖維’能以低成本製備之。關於寡聚物 濾器接替及?Tm特性而言，根據本發明之韻方法較佳且因此能降低生 產成本。 本叙明之不範具體例已說明於本文中，雖然使用特定用詞，但使用他 們/、用方、般!·生及敘述的概念解釋而無限制之意。因此，所屬技術領域具 有通常知識者應明白，犯a , ^ — 形式上及細郎的各種變化可被做出，但不背離本笋 明以下中請專利範_出之精神及範圍。 ^ 【圖式簡單說明】 頌不用於製備本發明聚合物之示範性三管ΤΡΑCOOCH2CH20H so3m Formula 1 where M is the metal. In Formula 1, for example, the metal may be Na, Li, κ, or the like, but is not limited thereto. When a commercially available rhein-containing isodecyl phthalate diester is used other than the use of a dipyridyl diisoacetate (DES), 'the TPA polymerization method remains unreactive, thus causing spinning The baling pressure increases or worsens other processing characteristics during the process. In order to prevent the formation of a gel, such as gel formation by DES pyrolysis, polymerization is carried out using a three-tube polymerization reactor as shown in Fig. 1. When a two-tube polymerization reactor is used (tested by a hydration tank and a condensation reaction tank), it is difficult to determine when to add an additive. Further, when various additives are required to be added, the reactor and * are suitable because the product f of the basic polymer may have changed. DES was added to the DE-2 tank to minimize its retention inside the reactor. For the condensation reaction catalyst, the ruthenium compound produced by Changlin Poly (IV) has excellent cost-effectiveness and physical properties. A more detailed description will be provided regarding Fig. 1'. (4) The reactants, p-benzoic acid and ethylene glycol, were prepared in the preparation tank 1 as a liquid. In this step, "』, add the moon and know the acid to prepare the slurry. The molar ratio of aliphatic dibasic acid to terephthalic acid is from 20:80 to 1:99. (b) The liquid f prepared in the step (a) is stored in the storage tank 2. 200906899 (C) The semi-batch method (semi-batch prQcess) is carried out by continuously supplying the storage tank 2 to the first reaction tank (10)-1)3, wherein the basic oligomer is at a constant temperature (usually 250 to 260. 〇. According to the reaction tank and the reaction of the polymerized component (such as the amount of water discharged as 〇1〇 determines the brewing _ termination. The initial amount of the basic silk remains in the working tank, and through the sputum through the nitrogen Pressurize and transfer the rest to the second reaction tank (DE_2) 5. (4) Transfer the solidified oligomer from the DE-丨 reaction tank to the DE-2 reaction tank through the transfer line filter n (k type filter II)4 And further reacting the DEs after adding the hydrazine. (e) Filtering by rotating the spear ray (the monitoring filter (10) transfers the obtained flame-retardant oligomer from the reaction tank to the condensation reaction 7' and reacts Sakisaki obstructs the secret. New cyclist & poly vinegar carries out the condensation reaction. (0) The polymer prepared in the reaction tank 7 is discharged from the granulator 8 and chopped. During the TPA polymerization, diethylene glycol (10) Is a by-product produced from the acid component of τρΑ. In the present invention, the DEG content of the polymer is based on the total weight of the polymer. 5 to 3.5 wt%. According to the polymerization method of the present invention, the DEG content cannot be lower than h 5% by weight. When the DEG content is h 5% by weight or more, the yang reaches the effect of lowering the glass transition temperature of the polymer. When the content exceeds 3.5% by weight, the spinnability of the polymer is deteriorated due to poor thermal stability. The concentration of the end filament of the unreacted TPA and pyrolysis is maintained at 30 to 50 equivalents based on the total weight of the polymer / Mouth. When the concentration of the terminal carboxyl group is less than 3〇 equivalent/ton, the reaction temperature may be lowered or the EG content may be increased. However, in any case, the reverse reaction is increased, which leads to the degradation of the polymer and the uselessness of the by-product DEG. The effect of polymer degradation in the polymer can cause gelation or other problems when the terminal retardation concentration exceeds 5 () equivalent / β ton, because most of the final input is pyrolysis 200906899. Unreacted TPA in the polymer The content is maintained at no more than 2 〇. Since the unreacted 砰8 is neither fully charged nor fully soluble in the spray, it can deteriorate the spinnability of the polymer when the content exceeds 2Q _. 215 to 240 〇 C is preferred. When the melting temperature At 215 〇, the spinnability is deteriorated due to low finernicity, and the heat resistance of the domain fiber is poor. # When the polyethylene diacetate is sufficiently copolymerized, the ship is lowered. Therefore, it is difficult to obtain a hybridization temperature higher than Further, when the melting temperature is higher than 2 batches, the unreacted copolymerized monomer may be present in the polymer, thereby deteriorating the quality of the polymer and the fiber. The following non-limiting examples are given by way of example. The present invention will be further described in detail. In the examples and comparative examples, the physical properties were analyzed as follows: 1 The degree of tethering of the esterified silk was determined by titration with respect to the degree of the side of the phthalic acid sm. 2. Intrinsic viscosity ( IV): Dissolve the polymer in 6:4 (w/w) and j,^ 2, 2 -tetrachloroethane solution. The IV was measured using a Ubbelohde viscometer in a 30 C thermostat. 3. Melting temperature and glass transition temperature: measured using a DSC 7 Thermal Differential Scanning Analyzer (PerkinElmer) at a heating rate of 10 °C/min. 4. Dibasic acid and DES content: analyzed by scaffolding z NMR. 5. DEG contains the polymer dissolved in ethanolamine and analyzed by gas chromatography. Example 1 200906899 The activated acid (10) was used as an aliphatic dibasic acid. The τρΑ, AA and EG (TpA:AA:EG = 600:315:50 Å by volume) were mixed to prepare a slurry. The resulting slurry contains a DE-丨 reaction tank containing a basic oligomer of 8.7 mol% adipic acid (based on total dibasic acid) (see Figure 1), and is mixed with 255 ° C.供 驻 驻 驻 5 5 5 5 健 健 健 健 健 健 健 健 健 健 5 5 5 5 5 5 酯 酯 酯 酯 酯 酯 酯 酯 酯 酯 酯 酯 酯The oligo was added with a total of dibasic acid (TPA, AA and DES) of 1.3 mol% having the DES of formula 1, and M being Na (molecular weight = 356, dissolved in EG at a concentration of 35 wt%). After thorough stirring, transfer to a condensation reaction tank (see Fig. 1), and add 2% antimony trioxide EG solution (concentration of antimony trioxide = 25 〇 ,, to the polymer heavy material) ‘and in Na. The singularity of the total amount of the dibasic acid is 8. 5 mo Ears / / 壬ΚΑΖΑ) except for storage AA. The material f of the obtained polymer was provided in the table. Example 3 A polymer was prepared in the same manner as in Example i except that DES was added, wherein M = u. The physical properties of the obtained polymer are provided in Table 1. Comparative Example 1 A polymer was prepared in the same manner as in Example except that AA was not added. The physical properties of the resulting polymer are provided in the table. Comparative Example 2 A polymer was prepared in the same manner as in Example 1 except that DES was not added. The resulting polymer 200906899 physical properties of the material are provided in Table 1. Table 1 - ---- Example 1 Γ---- Example 2 Example 3 Comparative Example 1 Comparative Example 2 Aliphatic dibasic acid content (% by mole) 8. 32 8.23 8.35 0 8.2 Alkali metal ( Μ) Na Na Li _一·-Na-DES content (mole./0) 1.31 ------ 1.24 卜 - 1.32 1.35 0 DEG content (mole%) —-— 2.19 2.40 2.32 1.56 1.21 CEG ( Equivalent )) 35 33 36 31 27 Melting temperature (°c) — 232 ---- 231 234 243 241 Glass transfer temperature (.〇65 -~~---J 63 66 76 64 Example 4 Vacuum drying in plastic The dish (moisture content = 15%) is prepared in the ' 躁 躁 丨 丨 丨 丨 丨 丨 丨 并 295 295 295 295 295 295 295 295 295 295 295 295 295 295 295 295 295 295 295 295 295 295 295 295 295 295 295 295 295 295 295 295 295 m/min. The obtained fiber was woven and dyed with Kayacryl dye (Nipp〇n Kayaku) in Yaya to achieve excellent dyeability. Comparative Example 3 In addition to the use of Comparative Example 1, the 哿人榀+ from the library σ Drying, spinning and dyeing were carried out in the same manner as in Example 4. A poor dyeability was obtained. 13 200906899 According to the present invention, it can be provided when dyeing with a cationic dye at a loot: or below The excellent dyeability can be produced at a low cost in a normal pressure cationic dye. The genomic method according to the present invention is better and thus can reduce production. Costs. The specific examples of the descriptions have been described in this article. Although specific terms are used, they are interpreted without limitation by the concepts of their /, user, general, and narrative. Therefore, the technical field has Generally, the knowledge person should understand that the various changes in the form of a, ^ - form and slang can be made, but do not deviate from the spirit and scope of the patent in the following. ^ [Simple description] 颂Exemplary three-tube hydrazine not used in the preparation of the polymers of the present invention
第1圖為一流程圖， 合反應器。 14Figure 1 is a flow chart of a reactor. 14