1286558 五、發明說明（1) 【發明所屬之技術領域】 ^ ^月係關於一種共聚酯聚合物，其係利用以對苯二 -文以下，稱為” Tp A ,,)為原料之對苯二甲酸製程製備， :::使用该共聚酯聚合物之纖維，及其製備方法。更特 S 2二本發明係關於一種共聚酯聚合物及利用TPA製程 2=二聚Ϊ聚合物之方法，其中，數平均分子量為 方 之聚烯烴二醇醚（以下，稱,丨PAG”）；l〜l〇wt%(以共 :酉曰聚δ物為基準）係利用TPA製程與對苯二甲酸進行共聚 :：：醇與對苯二甲酸之莫耳比被控制在h⑽〜1. 15 聚合物中之DEG含量。所得到之共聚酉旨聚合 之二i(T /τ\ Ϊι振動之玻璃轉移溫度（Tg)對溶融溫度（Tm) 故，相對j.55(以卡爾文絕對溫度為基準）。 :專、充的對苯二甲酸聚乙二醇酯（T H Ε ϊ Μ ^ 維欲確保固有、良好之 "九二曰(下# ΡΕΤ )纖 發明之共聚醋聚合物可於較:丄； 域融合熱（下稱"△Hf”），曰聚合物不定形區 【先前技術】 緣先PET纖維之67〜m。 PET纖維由於具有良好物理性質並且 你 境具有耐受性，因此為-種常被使用為衣料予貝或環 料、工業用纖維及薄膜之聚合物材 铁：用纖維原材 維具有良好物理及化學性f，但㈣其;=即使PET纖 染色用的官能基，因此，在使用分散染料料時缺乏 溫例如1 3 0 °c才能染色的問題。 、色日守有須以高 mi 彌 第8頁 5008-6327-PF(N2).Ptd 1286558 五、發明說明（2) 因此，PET纖維不能使用於在高溫高壓染色製程下易 損傷之紗線，例如，金屬紗或天然紗。1286558 V. INSTRUCTIONS OF THE INVENTION (1) [Technical field to which the invention pertains] ^ ^ is a pair of copolyester polymers which are based on a pair of benzene-based materials, referred to as "Tp A ," as a raw material. Process for the preparation of phthalic acid, ::: fibers using the copolyester polymer, and preparation methods thereof. Further S 2 2 The present invention relates to a copolyester polymer and a process using TPA 2 = dimeric ruthenium polymer A method in which a number average molecular weight is a polyolefin polyolefin ether (hereinafter, referred to as "丨PAG"); 1 to 10% by weight (based on a total of: 酉曰 polyδ), using a TPA process and a pair Copolymerization of phthalic acid::: The molar ratio of alcohol to terephthalic acid is controlled in the DEG content of the polymer of h(10)~1.15. The obtained copolymerization is the polymerization of the second i (T / τ \ Ϊι vibration of the glass transition temperature (Tg) versus the melting temperature (Tm), therefore relative to j.55 (based on Calvin absolute temperature). Polyethylene glycol terephthalate (TH Ε ϊ Μ ^ Wei want to ensure that the inherent, good " 九曰 (下# ΡΕΤ) fiber invention of the copolymerized vinegar polymer can be compared: 丄; domain fusion heat ( The following is called "△Hf"), the amorphous region of the ruthenium polymer [prior art] 67~m of the PET fiber. PET fiber is often used because it has good physical properties and is tolerant to you. It is a polymer material for clothing or shelling, industrial fiber and film. Iron: It has good physical and chemical properties with fiber material, but (4) it; = even functional groups for dyeing PET fibers, therefore, When dispersing the dye material, there is a lack of temperature, for example, 1 30 °c to dye. The color of the day is necessary to be high mi. Page 8 5008-6327-PF(N2).Ptd 1286558 V. Invention description (2) Therefore, PET fibers cannot be used in yarns that are susceptible to damage during high temperature and high pressure dyeing processes, such as metal yarn or Natural yarn.
目前，聚酯生產之製程可依起始材料分類為2種。第j 種製程為以TPA為起始材料（TPA製程）。TPA製程係以TPA為 起始材料，且在聚酯領域被用得报廣，先將TPA以乙二醇 (下稱” E Gπ )酯化以產生雙（對苯二甲酸羥基乙酯）（下稱 π ΒΗΕΤ")及其低度聚合的募聚物，然後於高真空度下使 ΒΗΕΤ及募聚物進行縮聚反應。第2種生產聚酯之製程係使 用對苯二甲酸二甲酯（DMT)為起始材料（DMT製程）。其中， 雙（對笨二甲酸备基乙酯）及其低度聚合的寡聚物係利用於 觸媒存在下使DMT與EG進行轉酯反應而產生，然後將得到 之ΒΗΕΤ及寡聚物於高真空度下進行縮聚反應。這2種不同 的製程中’以ΤΡΑ為起始材料之ΤΡΑ製程在生產成本及生產 性上較具競爭力。相對的，以DMT為起始材料之DMT製程的 缺點為生產成本高及低生產性（對生產既定量之聚酯，須 使用的DM丁較TPA多1 7%)。於以DMT為起始材料之DMT製程 中，在DMT與EG之轉酯反應中係使用金屬鹽，例如，乙酸 ，:乙酸錳及乙酸鎂，作為觸媒。但，DMT製程會有的問 題是，上述觸媒會促進聚酯去聚合化，且觸媒會對陽光例 如紫外光有活性，故必須另外在DMT及EG中加入安定劑。 但對於TPA製程，並未使用該觸媒sTpA與“之酯化反應， =多半使用具有相對低的活性之三氧化銻作為縮聚反應觸 媒。故，在TPA製程中，不須要額外使用分開的安定劑。 本發明中，分子量為2〇〇〜2〇〇〇之共聚化pA(j係用於在At present, the process of polyester production can be classified into two types according to the starting materials. The jth process is based on TPA (TPA process). The TPA process is based on TPA and is widely used in the polyester field. TPA is first esterified with ethylene glycol (hereinafter referred to as "E Gπ" to produce bis(hydroxyethyl terephthalate) ( The following is called π ΒΗΕΤ ") and its low-polymerization of the polymer, and then the polycondensation reaction of the ruthenium and the polymer is carried out under high vacuum. The second process for producing polyester is to use dimethyl terephthalate ( DMT) is a starting material (DMT process), wherein bis (p-ethyl benzoate) and its oligomerized oligomer are used in the presence of a catalyst to transesterify DMT with EG. Then, the obtained oxime and oligomer are subjected to a polycondensation reaction under high vacuum. In the two different processes, the ΤΡΑ process starting from ruthenium is more competitive in production cost and productivity. The shortcomings of the DMT process based on DMT are high production cost and low productivity (for the production of a certain amount of polyester, DM butyl is required to be used more than 7% of TPA). Based on DMT. In the DMT process, a metal salt is used in the transesterification reaction between DMT and EG, for example, acetic acid. , manganese acetate and magnesium acetate, as a catalyst. However, the DMT process has the problem that the above catalyst will promote the depolymerization of the polyester, and the catalyst will be active to sunlight such as ultraviolet light, so it must be additionally in the DMT. And the stabilizer is added to the EG. However, for the TPA process, the catalyst sTpA is not used with the "esterification reaction, and most of the antimony trioxide having a relatively low activity is used as the polycondensation reaction catalyst. Therefore, in the TPA process, there is no need to use separate stabilizers. In the present invention, a copolymerized pA having a molecular weight of 2 〇〇 2 〇〇〇 (j is used in
第9頁 1286558Page 9 1286558
五、發明說明（3) 相當低溫下對聚酯進行深染色。本發明領域可使用某此 統，用PAG之技術。但，本發明與傳統技術在目的及、結^ ^是明顯不同的，例如，生產聚酯之方法以及聚酯的分子 量。曰本專利早期公開號平9 _ 1 3 2 2 9揭示了 一種製造聚酉t 的製程，其包括使分子量3 0 0 0〜25 0 0 0之聚乙二醇醚（^禾: nPEG)n0·3〜3wt%與分子量 5 0 0 〜 3 0 0 0 之PEG0·3〜3wt%混合Γ 在該製程中，PEG被萃取以於聚酯纖維表面形成縱溝。 故，該製程與欲省略萃取PEG步驟之本發明有所不同。再 者’日本專利早期公開號昭58-1 2 0 8 1 5揭示了一種製造聚 西旨的技術，其包括同時使用磺酸5一鈉二甲酯及PAG以容^ 地將聚酯染色。然而，該技術係關於陽離子染料之染色能 力’與本發明以提供容易以分散染料染色之聚酯纖維為S 標者有所不同。再者，該技術採用製程而非TPA製程。 此外’美國專利第6 2 1 8 0 0 7號專利建議一種生產纖維之方 法’該方法係利用含〇 · 5〜4wt%PEG之聚合物以生產單細絲 丹尼爾支數（denier)為1· 2〜2· 25dpf (每細絲之丹尼爾支 數）之纖維。然而’該美國專利與本發明明顯不同，因其 並未敘述PEG之分子量範圍，且在該美國專利中揭示之實 施例係採用DMT製程。又，美國專利第5 〇 9 1 5 0 4號及 4 9 7 5 2 3 3號揭示一種製造聚酯纖維之製程，係使用分子量 20 0〜1 5 0 0之PEG1· 0〜4· Owt%。然而，因使用TPA製程所產生 之聚酯纖維其二乙二醇（下稱”DEG”）含量為lwt%或更低， 使的在TPA製程中產生之副產物之熱安定性降低。故，本 發明目標為抑制產生D E G含量為1 w t %或更低之聚自旨纖維。 1286558 五、發明說明（4)V. INSTRUCTIONS (3) Deep dyeing of polyester at a relatively low temperature. A certain system can be used in the field of the invention, using the technology of PAG. However, the present invention is significantly different from the conventional art in terms of purpose and structure, for example, a method of producing a polyester and a molecular weight of a polyester.曰本专利专利 Publication No. 9 _ 1 3 2 2 9 discloses a process for producing polyfluorene t, which comprises a polyethylene glycol ether having a molecular weight of 3 0 0 0 to 25 0 0 (^he: nPEG) n0 3 to 3 wt% of PEG0·3 to 3 wt% mixed with a molecular weight of 5 0 0 to 3 0 0 0 In this process, PEG is extracted to form a longitudinal groove on the surface of the polyester fiber. Therefore, the process differs from the invention in which the step of extracting PEG is omitted. Further, Japanese Patent Laid-Open Publication No. SHO 58-1 2 0 8 1 5 discloses a technique for producing a polyimide which comprises simultaneously using a sodium sulfonate sulfonate and a PAG to dye the polyester. However, this technique differs from the present invention in that the dyeing ability of a cationic dye is different from that of the present invention to provide a polyester fiber which is easily dyed with a disperse dye. Furthermore, the technology uses a process rather than a TPA process. In addition, the 'US Patent No. 6 2 1 0 0 7 7 patent proposes a method for producing fibers' which utilizes a polymer containing 〇·5 to 4 wt% PEG to produce a single filament denier of 1·. Fiber of 2~2·25dpf (denier count per filament). However, the U.S. patent is distinct from the present invention in that it does not describe the molecular weight range of PEG, and the embodiment disclosed in this U.S. patent uses a DMT process. Further, U.S. Patent Nos. 5,195,054 and 4,9,5,5, 3, 3, 3, disclose a process for producing a polyester fiber using a PEG1·0~4·Owt% having a molecular weight of 20 0 to 1 500. . However, since the polyester fiber produced by the TPA process has a diethylene glycol (hereinafter referred to as "DEG") content of 1 wt% or less, the thermal stability of by-products produced in the TPA process is lowered. Therefore, the object of the present invention is to suppress the production of a poly-fiber having a D E G content of 1 w % or less. 1286558 V. Description of invention (4)
但美國專利第5〇915〇4號及4 9 7523 3號中，係進—步將D 加至♦ gg纖維中以改變聚g旨纖維之物理性質。若產^ DEG，聚酯纖維之結晶性及熔融溫度會下降，！ 了 k成不易味 產融溫度為510〜525K之聚酯。此外，美國專利第 王 42 1 1 678號揭示一種生產易染色共聚酯之製程，其勹 PEG2〜4wt%與二聚酸1〜3wt%反應。然而，該萝p ^ 將 衣柱之缺點 糸a過程複雜且因為使用二聚酸會使生產成本择 …’、、、 【發明内容】 9 有鑑於上述先前技術之缺點，本發明之目的為提供一 種以TPA製程生產聚酯纖維用共聚酯聚合物之方法，其/生 產成本具有競爭力，且該共聚酯聚合物可於較傳統染色溫 度為低之溫度染色，且仍能確保該聚酯纖維具有良好之2 理性質。 观 詳而言之，係將分子量2 〇 〇〜2 〇 〇 〇之聚烯烴二醇醚 1 Ηwt〆以共聚酯聚合物為基準）與對苯二曱酸以π'製程 進打共聚合，其中G值（乙二醇與對苯二甲酸之莫耳比）被 控制在1.05〜1.15以控制共聚酯聚合物中的DEG含量。當共 聚酯聚合物完成時，其玻璃轉移溫度（與熔融 之比值為1. 51〜1. 55。 m 、、本發明之另一目的為提供一種共聚酯聚合物，其係依 ^ ^方法生產，亚提供一種使用該共聚酯聚合物之纖維。 【貫施方式】 本^明者等為解決先前技術所遭遇之問題，對理&上 可於低溫染色之丘平舻八立从姐％ / 娜工 /、來S日分子結構進行了密集且完整的探 1286558 五、發明說明（6) 大會改變，此會阻止本發明目標之達成。 再者’共聚酯聚合物之PAG含量為1〜1 〇wt%。若共聚酯 聚合物之PAG含量低於iwt%，會太少以致於無法確保共聚 物之效率。相反的，若PAG含量超過1 〇wt%，則PET的結晶 區會溶解於PAG不定形區（無論PAG之分子量為多少），以致 顯著改變PET之物理性質。 於共I酯聚合物之TPA製程，未反應之TPA為不可溶且 不了炫融。故，未反應之TPA會阻塞聚合裝置之寡聚物過 濾，或聚合物過濾器，或者，當T p a進行精紡紗時，其擁 擠壓力會急速增加，使生產聚酯聚合物之作業性降低。因 此’須要有足夠長的酯化時間以及足夠高的酯化溫度以使 未反應TPA量減低。然而，若酯化時間長或酯化溫度高， 所產生之DEG副產物會增加使共聚酯聚合物之熱安定性下 降。故，較佳為儘可能使G值（乙二醇與對苯二甲酸之莫耳 比）下降以抑制DEG之產生。依本發明，較佳之G值為 1.05 1.15 Μ所生產之共聚酯聚合物其G值落於此1 2範圍， 聚醋聚合物之DEG含量為〇· 7〜1. 5wt%，可達到本發明的目 標，即生產出之共聚酯聚合物其玻璃轉移溫度（& )為 1 3 0〜3 5 0K，熔融温度（Tm)為510〜52 5K，1；與]^之』例 2 (Tm/Tg)為 1. 51 〜1· 55。 m、g 典型上用於生產聚酯之觸媒可使用於作為本發明之共 縮聚觸媒。共縮聚觸媒之例包括例如銻類觸媒，例如二二 化銻及乙酸銻、鍺類觸媒，例如二氧化鍺，及鈦類觸媒氧 例如四丁基欽酸及四異丙基鈦酸。用於生產共聚酯聚合物 1286558 五、發明說明（8) 2 · DEG含量··將聚合物樣本以單乙醇胺水解，再以氣相 層析法（GC)分析。 3.炫融溫度（Tm)及玻璃轉移溫度（Tg) ··聚合物樣本之熔 融>里度及玻璃轉移溫度係以Elmer Inc製）分 析聚合物樣本於10 ^/πιίη升溫速度時在熔融範圍之峰值。 4·染色能力··將灰紗線進行圓形編織製程並於丨〇〇艺以 倉敷編（kura 1 on )海軍藍染色。接著，以肉眼觀察得到 之灰紗線樣本。被染成所欲情形之灰紗線樣本評價為"〇 其他/染成不欲情形者則評為，，X，，。各染色灰紗線之色 彩密度係計算由分光光譜計得到之K/S最大值。 以上已對本發明加以一般性說明，進一步的闡明可參 照此處提供之實施例及比較例，其係用於解說，且除非特 別指明’並非意欲限制本發明。 實施例 實施例1〜5及比較例1〜3 將對苯二甲酸127〇kg及乙二醇62 0kg(G值1. 13)加入反 應容器並攪拌使成為漿狀物。此時，在對苯二甲酸及乙二 醇加入反應容器前反應容器内已含有酯化度96%之募聚物一 1 · 3噸，添加之乙二醇係使聚合物樣本中二氧化鈦含量為 表1所示實施例及比較例之量，且乙二醇内含有3〇%二氧化 鈦。該含募聚物之漿狀物於反應容器内 以使裝狀物充分排出理論量之流出物，接著，二;： 鐘直到酯化度達95. 5%〜97. 5%。將1. 3噸以外之一部分裳取 物移到聚縮聚反應器’再將PAG加入聚縮聚反應器。此時久 第15頁 5008-6327-PF(N2).ptd i I286558 五、發明說明（10) 袠2 麵例1 麵例2 麵例3 龍例4 SiS例 5 臓1 t\mi2 tt^j3 韌性 _lg/d) 4.8 4.7 4.6 4.6 4.4 4.5 4.3 4.7 延展性 ._⑴ 40 41 38 40 37 36 28 38 1 色能力 0 0 〇 0 0 X X χ *K/S j大値 19.3 18.2 18.0 17.5 19.0 8.3 6.5 3.0 由亡述报明顯地，本發明所提供之共聚酯聚合物，其係以 二甲酸為原料且可在較傳統pET纖維染色更低溫以分 ^ ^料加以深染色，且同時能確保所欲傳統”了纖維之物 '生質，本發明並提供製造該共聚酯聚合物之方法。故， 廉價的生產具有良好染色能力之聚1纖 敘述之用並非f i n;；亿η解所使用之用語係欲 之申請專利範圍別敘述者以外，本發明在所附 5008-6327-PF(N2).ptd 第17頁 1286558 圖式簡單說明 第18頁 5008-6327-PF(N2).ptdHowever, in U.S. Patent Nos. 5,915, 4 and 4,975,523, the addition of D to ♦ gg fibers is carried out to change the physical properties of the fibers. If the DEG is produced, the crystallinity and melting temperature of the polyester fiber will decrease, The k is not easy to taste. The melting temperature is 510~525K polyester. In addition, U.S. Pat. However, the present invention is complicated by the disadvantages of the clothes column and because the use of the dimer acid causes the production cost to be selected. [, the invention] In view of the above disadvantages of the prior art, the object of the present invention is to provide A method for producing a copolyester polymer for polyester fiber by a TPA process, which is competitive in production cost, and the copolyester polymer can be dyed at a temperature lower than a conventional dyeing temperature, and still ensures the aggregation. Ester fibers have good properties. In view of the above, the polyolefin glycol ether 1 Ηwt〆 with a molecular weight of 2 〇〇 2 〇〇〇 〆 is copolymerized with terephthalic acid in a π′ process, The G value (the molar ratio of ethylene glycol to terephthalic acid) was controlled at 1.05 to 1.15 to control the DEG content in the copolyester polymer. When the copolyester polymer is completed, the glass transition temperature (the ratio to the melting is 1.51~1. 55. m, another object of the present invention is to provide a copolyester polymer, which is based on ^ ^ The method produces a fiber which uses the copolymer of the copolyester. [Comprehensive method] The present inventors have solved the problems encountered in the prior art, and the upper and lower sides can be dyed at low temperature. From the sister % / Nagong /, to S-day molecular structure carried out intensive and complete exploration 1286558 V. Description of the invention (6) General Assembly changes, this will prevent the achievement of the object of the present invention. In addition, 'copolyester polymer PAG The content is 1~1 〇wt%. If the PAG content of the copolyester polymer is less than iwt%, it will be too small to ensure the efficiency of the copolymer. Conversely, if the PAG content exceeds 1 〇wt%, PET The crystallization zone will dissolve in the amorphous region of the PAG (regardless of the molecular weight of the PAG), so that the physical properties of the PET are significantly changed. In the TPA process of the co-I ester polymer, the unreacted TPA is insoluble and does not melt. Unreacted TPA blocks the oligomer filtration of the polymerization unit. Or a polymer filter, or when T pa is subjected to worsted yarn, its squeezing force will increase rapidly, which will reduce the workability of producing polyester polymer. Therefore, it is necessary to have a sufficiently long esterification time and a sufficiently high ester. The temperature is lowered to reduce the amount of unreacted TPA. However, if the esterification time is long or the esterification temperature is high, the DEG by-product produced may increase to lower the thermal stability of the copolyester polymer. The G value (the molar ratio of ethylene glycol to terephthalic acid) is lowered to suppress the production of DEG. According to the present invention, a preferred G value of 1.05 1.15 Μ produces a copolyester polymer whose G value falls. The range of 1 2, the polyglycol polymer has a DEG content of 〇·7~1. 5wt%, which can achieve the object of the present invention, that is, the glass transition temperature (&) of the produced copolyester polymer is 1 3 0~ 3 5 0K, the melting temperature (Tm) is 510~52 5K,1; and the example 2 (Tm/Tg) is 1. 51 〜1· 55. m, g is typically used to produce polyester touch The medium can be used as the copolycondensation catalyst of the present invention. Examples of the copolycondensation catalyst include, for example, anthraquinone catalysts such as diterpenoids and Anthraquinone, anthraquinone-type catalysts such as cerium oxide, and titanium-based catalyst oxygen such as tetrabutyl-capric acid and tetraisopropyl titanic acid. For the production of copolyester polymers 1286558 V. Description of invention (8) 2 DEG content··The polymer sample was hydrolyzed with monoethanolamine and analyzed by gas chromatography (GC). 3. Thawing temperature (Tm) and glass transition temperature (Tg) ··Solution of polymer sample> The degree of the glass transition temperature was measured by Elmer Inc.) and the peak of the melting range of the polymer sample at a heating rate of 10 ^/πιη. 4. Dyeing ability · The gray yarn was subjected to a circular weaving process and dyed in kura 1 on navy blue. Next, the obtained gray yarn sample was visually observed. The sample of the gray yarn dyed to the desired condition is evaluated as "〇 Others/dyed as undesired cases are rated as, X,,. The color density of each of the dyed ash yarns was calculated from the K/S maximum value obtained by the spectroscopic spectrometer. The invention has been described in detail with reference to the accompanying claims, Examples Examples 1 to 5 and Comparative Examples 1 to 3 127 〇 kg of terephthalic acid and 62 0 kg of ethylene glycol (G value 1.13) were placed in a reaction vessel and stirred to obtain a slurry. At this time, before the addition of terephthalic acid and ethylene glycol to the reaction vessel, the reaction vessel already contains 96% of the polymerized ester having a degree of esterification of 1.3 tons, and the added ethylene glycol system makes the content of titanium dioxide in the polymer sample The amounts of the examples and comparative examples shown in Table 1 were such that ethylene glycol contained 3% by weight of titanium dioxide. 5%〜97. 5%。 The propylene-containing granules in the reaction vessel to allow the slag to be discharged in a sufficient amount of the effluent. One part of the litter other than 1.3 tons was transferred to the polycondensation reactor' and the PAG was added to the polycondensation reactor. At this time, the 15th page 5008-6327-PF(N2).ptd i I286558 V. Invention description (10) 袠2 Face 1 Case 2 Face 3 Dragon case 4 SiS case 5 臓1 t\mi2 tt^j3 Toughness _lg/d) 4.8 4.7 4.6 4.6 4.4 4.5 4.3 4.7 Ductility._(1) 40 41 38 40 37 36 28 38 1 Color capability 0 0 〇0 0 XX χ *K/S j greater than 19.3 18.2 18.0 17.5 19.0 8.3 6.5 3.0 It is apparent from the death report that the copolyester polymer provided by the present invention is based on dicarboxylic acid and can be dyed at a lower temperature than the conventional pET fiber to be deeply dyed, and at the same time, can ensure The present invention also provides a method for producing the copolyester polymer. Therefore, the inexpensive production of a polystyrene having a good dyeing ability is not a fin; In addition to the stipulations of the patent application scope, the present invention is attached to the accompanying 5008-6327-PF (N2).ptd page 17 1286558 Schematic description of the 18th page 5008-6327-PF (N2).ptd