1364319 九、發明說明： [優先權] 本申凊案主張2003年5月6曰申請之美國臨時專利申請案 第60/468,226號以及2003年8月5曰申請之美國專利申請案 第10/634,687號之優先權，兩申請案均以弓丨用方式併入本文 中。 【發明所屬之技術領域】 本發明係關於採用固體吸附劑自聚三亞甲基醚二醇中移 除帶色體。 夕 【先前技術】 1，3·丙二醇（下文中也稱作” PD〇")係一種單體，其可用於 製備包括聚酯，聚胺基甲酸酯，聚醚和環狀化合物之多種 聚合物。聚三亞甲基醚二醇（下文中稱為”p〇3G")之均聚和 共聚醚係聚醚聚合物之實例。該聚合物最終用於各種用 途’包括纖維，薄膜等。 生產1，3-丙二醇之化學路徑係已知的。例如，可由下述路 役製備1,3 -丙二醇： 1. 在磷化氫，水，一氧化碳，氫氣及酸之存在下，環氧乙 烧經由催化劑製得（"加氫曱醯化路徑"）； 2. 丙烯醛之溶液相催化水合，然後還原（,，丙烯醛路徑”）。 此兩種1，3-丙二醇之合成路徑均包括3_羥基丙醛（下文中 也稱為"ΗΡΑ”）中間體之合成。在最終之催化加氫步驟中， 該ΗΡΑ還原為PD(^隨後之最終純化包含幾種方法包括真 空蒸餾。 〃 93143.doc 1364319 已描述了製備U-丙二醇之生化路徑，其使用之原料藉由 可再生生物資源如玉米原料生產。該pD〇在下文中稱為"生 ㈣0:或"生化衍生PD〇"。例如，在物種克雷氏桿菌，檸 檬酸#囷’梭狀芽孢桿菌和乳酸桿菌中發現菌株能將丙三 醇轉化為1，3·丙二醇。該技術公開於料專利中，包括美國 專利5,633,362，5,686,276及最近之5,821 ()92，它們均以引 用方式併入本文中。Nagarajan等在美國專利紗21々92中特別 揭示了 -種使用重組有機體由丙三醇製備丙二醇生物 產品之方法。該方法包括一種大腸桿菌，其藉由對U丙二 醇具有專-性之異種pdu二醇脫水酵素基因轉殖。該轉殖大 腸棒菌在作為碳源之丙三醇的存在下生長並將U•丙二醇 自生長媒質中分離出。由於細菌及酵母菌都可將葡萄糖(如 玉米糖）或其他碳水化合物轉化為丙三醇，因此本發明方法 :供了-種用於製備聚酯、聚醚及其他聚合物之快速、廉 4貝且環保的1，3 _丙二醇單體之來源。 十九世紀八十年代早期起一直使用沈澱法（例如用 1，2-丙二醇，以及羧酸酯或其他物質)從所需之產品(諸如酶) 中为離帶色及令人討厭（Qdife_s)之組分以得到純化製 品。從該發酵罐液體中沈澱出高分子量成分，然後藉由= 原劑漂白此等組分（德國專利3917645)，其係已知的。另一 方面，還發現微過滤之後進行奈米過渡以除去殘餘化合物 係有益的（歐洲專利657529) ’其中將大於分離尺寸之高分子 量物質截住。然而，奈米膜會很快淤塞並且可能十分昂貴。 先前技術中公開了多種處理方法以除去存在於該中 93I43.doc 1364319 昂貴並使該聚合物 之帶色如驅體’然而，該等方法費力、 之成本增加。例如，Kelsey在美國專利$527973中公開了 一 種提供純化之1，3-丙二醇的方法，其中該u•丙二醇可用作 製備低帶色聚酯之原料。該方法具有若干缺點，包括使用 大型設備以及需要蒸餾大量水分，其中此等水分難於從該 產品中除去。sunkara等在美國專利6,235,948中公開了一種 透過預熱’較佳地採用多相酸催化劑諸如全說化離子交換 聚合物自1，3·丙二醇t移除形成帶色雜質之方法。過遽掉該 催化劑，削i分離該m醇，較佳地透過真空蒸館進行 分離。從純化二醇製備之聚三亞曱基驗二醇具有之細A值 為30〜40，但未報導該聚合物之分子量。 該聚伸烧基趟二醇通常係透過從相應之伸院基二醇之酸 催化脫水或該環氧烷之酸催化開環製備。例如，可採用可 溶性酸催化劑藉由W丙二醇之脫水或環氧丙烧之開環聚 合製備聚三亞甲基驗二醇。在美國專利申請公開案 Nos. 2〇02/0007043Α1& 2〇〇2/〇〇1〇374αι 中詳細描述 了使用 硫酸作催化劑由該二醇製備p〇3G之方法，此等公開案之全 部以=用方式併人本文中。應指出，聚醇之合成條件大體 上決疋雜質、▼色前驅體及所形成之帶色體的量。可藉由 此項技術中已知之方法純化藉由該方法製備之聚醚二醇。 聚，亞f基越二醇之純化方法典型地包括⑴水解在該聚合 過程中形成之酸S旨之水解步驟，⑺移除該酸性催化劑、未 反應單體、低分子量線性寡聚物及環轉聚物之水萃取步 驟（3)驗處理’典型地採用氫氧化舞漿液中和並沈殿存在 93143.doc 1364319 之剩餘酸，及（4)乾燥並過濾該聚合物以除去殘餘之水和固 體。 眾所周知，由酸催化縮聚1>3_丙二醇所製備之聚三亞甲基 醚二醇有品質上之問題，尤其顏色係工業上所不可接受 的。該聚合物之品質一般地取決於該原料pD〇之品質。除 該原料外，其聚合條件及該聚合物之穩定性在一定程度上 也係造成脫色之原因。特別地就聚三亞甲基醚二醇而言， 該聚醚二醇易於帶淺色，其在許多最終用途中係不期望之 性質。該聚三亞甲基醚二醇易於透過與氧氣或空氣接觸， 尤其在高溫下接觸而脫色，因此在氮氣氣氛下實施該聚 合，並且在惰性氣體存在下貯存該聚醚二醇。更謹慎之做 法，可加入少量適宜之抗氧化劑。在每克聚醚中含有濃度 約100〜500微克之丁基化羥基甲苯（ΒΗΤ，2 6_二_第三丁基 -4 -甲基苯紛）係較佳的。 已嘗试透過常規方法減少聚三亞甲基趟二醇之顏色，但 並未取得很大成功。例如，Morris等在美國專利2,520,733 中指出了在酸催化劑存在下由PD〇聚合製備該聚三亞曱基 趟二醇之特殊的脫色趨勢。他們所嘗試之許多方法均未能 改善聚三亞曱基二醇之顏色，包括採用活性碳，活性氧化 紹’石夕膠，單獨滲透以及單獨加氫等方法。因此他們研製 出一種在酸催化劑存在下（重量比為2 5至6%)及溫度i75〇c 至200°C下純化由ι，3-丙二醇製備之聚醇的方法。此種純化 方法包括經由漂白土滲濾該聚合物，隨後加氫。此種粗放 式純化方法得到之最終產品的顏色係淺黃色，實際上，對 93143.doc 1364319 於此方法生產之聚三亞甲基醚二醇（其中之實例χι)，其顏 色僅減少至8加納爾色度，與品質相應之ΑρΗΑ值>3〇〇 ,總 體上不適合目前之需要。1364319 IX. INSTRUCTIONS: [Priority] This application claims US Provisional Patent Application No. 60/468,226, filed May 5, 2003, and U.S. Patent Application Serial No. 10/634,687, filed on August 5, 2003. The priority of both numbers, both applications are incorporated herein by reference. TECHNICAL FIELD OF THE INVENTION The present invention relates to the removal of color bodies from polytrimethylene ether glycol using a solid adsorbent. [Prior Art] 1,3·propanediol (hereinafter also referred to as "PD〇") is a monomer which can be used for preparing various kinds including polyesters, polyurethanes, polyethers and cyclic compounds. Polymer. An example of a homo- and copolyether-based polyether polymer of polytrimethylene ether glycol (hereinafter referred to as "p〇3G"). The polymer is ultimately used in a variety of applications including fibers, films and the like. The chemical pathways for the production of 1,3-propanediol are known. For example, 1,3-propanediol can be prepared by the following routes: 1. In the presence of phosphine, water, carbon monoxide, hydrogen and acid, epoxy bake is prepared via a catalyst ("hydrogenation path";); 2. The solution phase of acrolein catalyzes hydration and then reduces (, acrolein pathway). The synthetic routes of both 1,3-propanediols include 3-hydroxypropionaldehyde (hereinafter also referred to as " ΗΡΑ") Synthesis of intermediates. In the final catalytic hydrogenation step, the hydrazine is reduced to PD (the subsequent final purification comprises several methods including vacuum distillation. 〃 93143.doc 1364319 has described the biochemical pathway for the preparation of U-propanediol, the raw materials used thereby Renewable biological resources such as corn raw material production. The pD〇 is hereinafter referred to as "raw(4)0: or "biochemically derived PD〇". For example, in the species Klebsiella, citric acid #囷' Clostridium and The strains found in Lactobacillus are capable of converting glycerol to 1,3-propanediol. The technique is disclosed in the patents, including U.S. Patent Nos. 5,633,362, 5, 686, 276, and 5, 821, each of which is incorporated herein by reference. Nagarajan et al., in U.S. Patent No. 21,92, specifically discloses a method for preparing a propylene glycol bioproduct from glycerol using a recombinant organism. The method comprises an Escherichia coli which has a specific heterogeneous pdu by U-propylene glycol. Alcohol dehydratase gene transfer. The transgenic E. coli grows in the presence of glycerol as a carbon source and separates U•propanediol from the growth medium. And yeast can convert glucose (such as corn sugar) or other carbohydrates into glycerol, so the method of the invention provides a fast and inexpensive method for preparing polyester, polyether and other polymers. Source of environmentally friendly 1,3 -propanediol monomer. Since the early 1980s, precipitation methods (such as 1,2-propanediol, and carboxylates or other substances) have been used from desired products (such as enzymes). Medium to color and nasty (Qdife_s) components to obtain a purified product. High molecular weight components are precipitated from the fermenter liquid, and then these components are bleached by the = original agent (German Patent 3917645), It is also known. On the other hand, it has also been found that it is beneficial to carry out a nano-transition to remove the residual compound after microfiltration (European Patent No. 657529), in which a high molecular weight substance larger than the separation size is intercepted. However, the nanofilm is very Quickly fouling and can be very expensive. Various treatment methods have been disclosed in the prior art to remove the presence of 93I43.doc 1364319 which is expensive and to color the polymer as a body. However, such methods are laborious, For example, Kelsey, U.S. Patent No. 5,527, 973, discloses a method of providing purified 1,3-propanediol which can be used as a starting material for the preparation of low color polyesters. This method has several disadvantages, including the use of large scales. The apparatus and the need to distill a large amount of water, wherein such water is difficult to remove from the product. A high-permeability acid catalyst such as a fully ionized polymer is preferably employed in the prior art by a preheating. 3. The method of removing propylene glycol t to form colored impurities. The catalyst is removed, and the m alcohol is separated, preferably by vacuum evaporation. The polytrimethylene diol prepared from the purified diol has a fine A value of 30 to 40, but the molecular weight of the polymer is not reported. The poly(alkylene terephthalate) is typically prepared by acid-catalyzed dehydration from the corresponding pendant diol or acid catalyzed ring opening of the alkylene oxide. For example, a polytrimethylene diol can be prepared by a dehydration of W propylene glycol or a ring opening polymerization of propylene propylene by a soluble acid catalyst. A method for preparing p〇3G from the diol using sulfuric acid as a catalyst is described in detail in U.S. Patent Application Publication No. 2, 02/0007, 043, 1 & 2, 2, 〇〇 1 〇 α 374, which is incorporated herein by reference. = Use the method in this article. It should be noted that the synthesis conditions of the polyalcohol are generally based on the amount of the impurity, the color precursor, and the formed color body. The polyether diol prepared by this method can be purified by a method known in the art. The purification method of poly, sub-f-based diol typically includes (1) hydrolysis to form an acid S formed during the polymerization, and (7) removal of the acidic catalyst, unreacted monomers, low molecular weight linear oligomers and rings Water extraction step of the polymer (3) The treatment typically neutralizes the remaining acid in the presence of the sulphate slurry and the presence of 93143.doc 1364319, and (4) dries and filters the polymer to remove residual water and solids. . It is well known that polytrimethylene ether glycol prepared by acid-catalyzed polycondensation of 1> 3-propylene glycol has problems in quality, especially in the color industry which is unacceptable. The quality of the polymer generally depends on the quality of the raw material pD. In addition to the raw materials, the polymerization conditions and the stability of the polymer are also responsible for the decolorization to some extent. Particularly in the case of polytrimethylene ether glycols, the polyether diols are susceptible to light color, which is an undesirable property in many end uses. The polytrimethylene ether glycol is easily detached by contact with oxygen or air, especially at a high temperature, so that the polymerization is carried out under a nitrogen atmosphere, and the polyether diol is stored in the presence of an inert gas. More cautiously, a small amount of a suitable antioxidant can be added. Butylated hydroxytoluene (ΒΗΤ, 2 6_di-t-butyl-4-methylbenzene) having a concentration of about 100 to 500 μg per gram of the polyether is preferred. Attempts have been made to reduce the color of polytrimethylene glycol by conventional methods, but have not been very successful. For example, Morris et al., in U.S. Patent 2,520,733, teach the special decolorization tendency of the polytrimethylene decanediol prepared by PD 〇 polymerization in the presence of an acid catalyst. Many of the methods they have tried have failed to improve the color of polytrimethylene glycol, including the use of activated carbon, reactive oxidization, and individual hydrogenation. Therefore, they developed a method for purifying a polyol prepared from iota, 3-propanediol in the presence of an acid catalyst (25 to 6% by weight) and at a temperature of i75 〇c to 200 °C. This purification method involves diafiltration of the polymer via bleaching earth followed by hydrogenation. The color of the final product obtained by this extensive purification method is light yellow. In fact, the polytrimethylene ether glycol produced by this method in 93143.doc 1364319 (in which example χι) is only reduced in color to 8 Ghana. The color chromaticity, corresponding to the quality of the ΗΑρΗΑ value > 3 〇〇, is generally not suitable for the current needs.
Mason在美國專利3,326,985中公開了 _種製備分子量在 U00〜剛範圍之聚三亞甲細二醇之方法，其在氮氣層下 藉由真空汽提較低分子量之聚三亞甲基趟二醇而具有改善 之顏色。然而，其顏色級別並未量化且無法達到上述要求。 【發明内容】 公開一種包括有色之!>03(}與吸附劑接觸並分離該p〇3G 與吸附劑方法，其中在與該吸附劑接觸之後，p〇3G具有約 250至約5000之分子量以及低於約5〇2ApHA色值。 【實施方式】 若非特別說明，所有百分比、份數、比率等均以重量計。 商標以大寫字母列出。 此外，當給出之數量，濃度，或其他值或參數為一範圍， 較佳之範圍或一較佳之上限值和較佳之下限值的列表時， 無論該範圍是否單獨公開，均應理解為明確地公開了由任 一上限值或較佳值與任一下限值或較佳值中之任意一對所 形成之全部範圍。 使用術語"吸附劑"中，所提及之物質係通常用於移除相 對少ϊ之令人不滿之成1分，而不管該移除係透過吸附法戈 吸收法進行，因為許多脫色方法同時包括兩種機理。 術語"顏色"及"帶色體"係指存在可見之顏色，其可採用分 光比色計’在可見光範圍内，使用約4〇〇〜8〇〇奈米之波長， 93143.doc -10· 1364319 亚藉由與純水比較來進行量化。PDO中之帶色前驅體在此 範圍内係不可見的，但在聚合之後帶來顏色。 由本發明之PDO製備之p〇3G可為p〇3G均聚物或共聚 物。例如’該PDO可與其他二醇（如下）聚合製備共聚物。本 發明中有用之PDO共聚物除丨，3_丙二醇及/或其募聚物外， 可含有重量比達50%(較佳地，重量比為20%或更少）之二醇 共聚單體。適合於本方法中採用之二醇共聚單體包括脂肪 族二醇’例如，乙二醇，1,6-己二醇，1，7-庚二醇，1，8-辛 一醇’ 1，9_壬二醇，ι，1〇_癸二醇，ι，12_十二烷二醇， 3,3,4,4,5,5-六氟-i，5_戊二醇，2,2,3,3,4,4,5,5_八氟-1，6_己二 醇 ’ 3,3’4,4,5,5,6,6,7,7,8,8,9,9，10，10-十六氟-1，12-十二烷二 醇’環脂肪族二醇，例如，丨，4_環己二醇，丨，4_環己烷二甲 醇和異山梨酯；多羥基化合物，例如，丙三醇，三羥甲基 丙烧’和異戊四醇。較佳之二酵共聚單體係選自由下列各 物組成之群：2-甲基-1，3-丙二醇，2,2-二甲基-1，3-丙二醇， 2,2-二乙基-L3·丙二醇，2_乙基_2_(羥曱基丙二醇，L6· 己二醇’ 1，8-辛二醇，ι，ι〇_癸二醇，異山梨酯，及其混合 物。若需要，可向該聚合混合物或最終聚合物中加入熱穩 定劑’抗氧化劑及著色物質。 根據本發明之一方面，一種包括使有色之P03G與吸附劑 接觸並將該P03G與吸附劑分離方法，其中在與該吸附劑接 觸之後，P03G具有約250至5000之分子量及低於約50之 APHA色值。较佳地該aphA色值為低於約40，更佳地為低 於30和最佳地為低於約2〇β APHA色值係ASTMD-1209(見下 93143.doc •11· 1364319 述測试方法1)中定義之測量顏色之標準。 該P03G之分子量係約25〇至約5〇〇〇。更佳地其分子量 係約500至約4〇〇〇。最佳地，其分子量係約1〇〇〇至約3〇〇〇。 根據本發明之另一方面，該吸附劑包括至少一種活性 碳，氧化銘’矽石，石夕藻土’蒙脫石黏土，漂白土，高嶺 土礦物及其衍生物。較佳地，該吸附劑包括活性碳。本文 中術語"活性碳”包括”木炭，，。 活性碳係一種非晶形固體，其具有很大内表面積和孔隙 度，並具有極低親水性。吸附劑用量取決於該吸附劑之性 質，該聚三亞曱基醚二醇中帶色體之濃度，與酶基之相互 作用及其製程條件諸如接觸時間和溫度。例如，在本發明 貫踐中，在惰性軋氛諸如氮氣下，藉由擾拌向有色之卩⑴〇 中加入以該聚醚二醇重量計之〇.卜5%，且較佳地為〇 25〜3〇/〇 的活性碳。 該P03G與吸附劑進行接觸之溫度應使得該聚合物為液 悲且具有足夠低之粘度以便混合和攪拌。其混合和攪拌可 在溫度約10〜15(TC，較佳地約25〜100°c下進行。該接觸進 行約5至約60分鐘，以及較佳地約1〇至約3〇分鐘。較佳地， 該P 〇 3 G與該吸附劑之接觸及隨後之過濾在惰性氮氣氣氛 下完成。 適合之真空過濾方法為熟習此項技術者所熟知。由於該 P03G之黏度，因此可方便地透過在高溫下之過濾加速過濾 過程。一般地，約50至約1〇〇。(：範圍之溫度係足夠的。對於 小規模製備’可將CELPURE C65過濾床緊壓在丄微米 93143.doc •12- 1364319A method for preparing a polytrimethylene glycol having a molecular weight in the U00 to a rigid range, which is obtained by vacuum stripping a lower molecular weight polytrimethylene glycol in a nitrogen blanket, is disclosed in U.S. Patent No. 3,326,985. Improve the color. However, its color level is not quantified and does not meet the above requirements. SUMMARY OF THE INVENTION A method comprising contacting and separating the p〇3G from an adsorbent with a sorbent is disclosed, wherein p〇3G has a molecular weight of from about 250 to about 5,000 after contact with the adsorbent. And a color value of less than about 5.2 ApHA. [Embodiment] Unless otherwise stated, all percentages, parts, ratios, etc. are by weight. Trademarks are listed in capital letters. In addition, when given the quantity, concentration, or other When the value or parameter is a list of ranges, preferred ranges or a preferred upper limit and preferred lower limit, whether or not the range is disclosed separately, it should be understood that the upper limit or the The best value formed by any pair of any lower limit or preferred value. In the term "sorbent", the substances mentioned are usually used to remove relatively unsatisfactory 1 point, regardless of the removal system by adsorption Fagor absorption method, because many decolorization methods include two mechanisms at the same time. The term "color" and "color body" means that there is visible color, It can be used The spectrophotometer 'is in the visible range, using a wavelength of about 4 〇〇 to 8 〇〇 nanometers, 93143.doc -10· 1364319 is quantified by comparison with pure water. The colored precursor in PDO is This range is not visible, but brings color after polymerization. p〇3G prepared from the PDO of the present invention may be a p〇3G homopolymer or copolymer. For example, 'The PDO can be polymerized with other diols (see below) The copolymer is prepared. The PDO copolymer useful in the present invention may contain, in addition to hydrazine, 3-propylene glycol and/or its polymer, a weight ratio of 50% (preferably, 20% by weight or less). Alcohol comonomers. The diol comonomers suitable for use in the process include aliphatic diols such as ethylene glycol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octane. Monool ' 1,9-decanediol, ι, 1 〇 癸 diol, ι, 12-dodecanediol, 3,3,4,4,5,5-hexafluoro-i,5-e Glycol, 2,2,3,3,4,4,5,5-octafluoro-1,6-hexanediol' 3,3'4,4,5,5,6,6,7,7, 8,8,9,9,10,10-hexadecafluoro-1,12-dodecanediol' cycloaliphatic diol, for example, hydrazine, 4_cyclohexanediol, hydrazine, 4_cyclohexane two Alcohol and isosorbide; polyhydroxy compound, for example, glycerol, trimethylolpropanol, and pentaerythritol. Preferably, the second comonomer system is selected from the group consisting of 2-methyl- 1,3-propanediol, 2,2-dimethyl-1,3-propanediol, 2,2-diethyl-L3.propanediol, 2-ethyl-2-(hydroxymercaptopropanediol, L6·hexanediol' 1,8-octanediol, iota, oxime diol, isosorbide, and mixtures thereof. If desired, a heat stabilizer 'antioxidant and coloring material can be added to the polymerization mixture or the final polymer. According to one aspect of the invention, a method comprising contacting colored P03G with an adsorbent and separating the P03G from an adsorbent, wherein after contact with the adsorbent, P03G has a molecular weight of from about 250 to 5000 and less than about 50 APHA color value. Preferably, the aphA color value is less than about 40, more preferably less than 30, and most preferably less than about 2 〇β APHA color value ASTM D-1209 (see next 93143.doc •11·1364319) Test the standard for measuring color as defined in Method 1). The molecular weight of the P03G is from about 25 Å to about 5 Å. More preferably, the molecular weight is from about 500 to about 4 Torr. Most preferably, the molecular weight is from about 1 Torr to about 3 Torr. According to another aspect of the invention, the adsorbent comprises at least one activated carbon, oxidized immortalite, shixiazao soil, montmorillonite clay, fuller's earth, kaolin minerals and derivatives thereof. Preferably, the adsorbent comprises activated carbon. The term "activated carbon" in this context includes "charcoal,". Activated carbon is an amorphous solid which has a large internal surface area and porosity and has extremely low hydrophilicity. The amount of adsorbent depends on the nature of the adsorbent, the concentration of the color bodies in the polytrimethylene ether glycol, the interaction with the enzyme groups, and the process conditions such as contact time and temperature. For example, in the practice of the present invention, 5%, and preferably 〇, of the weight of the polyether diol is added to the colored ruthenium (1) oxime by inerting under an inert rolling atmosphere such as nitrogen. 25~3〇/〇 of activated carbon. The temperature at which the P03G is contacted with the adsorbent is such that the polymer is liquid and has a sufficiently low viscosity for mixing and agitation. The mixing and stirring can be carried out at a temperature of about 10 to 15 (TC, preferably about 25 to 100 ° C. The contact is carried out for about 5 to about 60 minutes, and preferably about 1 to about 3 minutes. Preferably, the contact of the P 〇 3 G with the adsorbent and subsequent filtration is carried out under an inert nitrogen atmosphere. Suitable vacuum filtration methods are well known to those skilled in the art. Due to the viscosity of the P03G, it is convenient to pass through. Filtration at elevated temperatures accelerates the filtration process. Typically, from about 50 to about 1 Torr. (The temperature in the range is sufficient. For small scale preparations, the CELPURE C65 filter bed can be pressed at 丄 microns 93143.doc • 12 - 1364319
Whatman濾紙上，由250 mL之玻璃過濾漏斗支撐，安裝有 用於加熱該職器之裝置。可使用其他過據介質並且:為 熟習此項技術者所熟知’要求過濾器之； 性碳且對該乙二醇無活性。 活 根據本發明之另一方面，在與吸附劑接觸之前，該聚三 亞甲基醚二醇具有之APHA色值至少為5GApHA。在與該= 附劑接觸之前’其色值可為約7G至約在與該吸附劑接 觸之前，該APHA色值也可為約85〜25〇 ApHA，或約 100〜200 APHA。 可採用批式法，其中該吸附劑可透過混合有效地與該聚 醇接觸’ -段時間之後，藉由適合之方式如過濾、離心過 濾等將該聚醇從吸附劑中分離出。本發明之方法也可採用 連續或半連續之方式實施。例如，可將該聚醇從儲存槽泵 送通過該吸附劑之固定床。其進料速率可由固定床中吸附 劑之種類、數量和先前使用之吸附劑以及該原料之顏色含 量進行調整，使得該聚醇與該吸附劑之接觸時間足夠長， 以製得所期望之脫色流出物。該流出物可在儲存槽中停留 短暫時間，或立即使用或航運。其他變化也將為熟習此項 技術者認識到。 根據本發明之另一方面，該聚三亞甲基醚二醇之APHA 色值減少至少約5〇%。較佳地，該聚三亞曱基醚二醇之 APHA色值減少至少約60%，更佳地’減少至少約70%。 本發明之方法可用於藉由PD〇之聚合所製備之聚三亞甲 基峻二醇的脫色，其中PDO係透過石化原料，諸如該方法 93143.doc 13- 1364319 中採用之丙烯醛製備，也可用於透過聚合由生化路徑製備 之PDO而製備之聚醇的脫色。 該活性碳處理可對其最終聚合物實施或僅在純化製程之 過濾步驟之前實施。較佳之方式為僅在最終過濾之前向 P03G聚合物中加入該活性碳並在抗氧化劑諸如BHT存在 下儲存所過濾之聚合物。 使用多種來源及形式之碳似乎係有效的。可自多種來源 得到不同形式之活性碳，諸如粉末狀，顆粒狀，以及成形 之產品。其較佳之形式係粉末狀活性碳。 可使用各種品牌之碳，包括，但並不侷限於Norit America G60，NORIT R0 0·8，Calgon PWA，BL和 WPH，及 Ceca ACTICARONE ENO。其他形式將為熟習此項技術者所熟 知。 根據本發明之另一方面，一種方法包括： (a) 提供包括1,3-丙二醇及縮聚催化劑之反應物； (b) 使該反應物縮聚為有色之P03G ; (c) 使該P03G與吸附劑接觸；及 (d) 將該P03G與吸附劑分離。 '其中在與該吸附劑接觸之後，該P03G之顏色具有低於約50 之APHA色值。其APHA色值較佳地為低於約40，更佳地為 低於30且最佳地為低於約20。較佳地，該吸附劑包含活性 碳，該P03G與以該聚三亞曱基醚二醇之重量計為約0.1至約 5重量％之活性碳接觸，且該接觸在溫度約10至約150°C下 進行。 93143.doc •14- 1364319 根據本發明之另一方面，產物包括⑴有色之p〇3G和（Η) 吸附劑（其已在本文中描述），其中該P03G具有之ΑΡΗΑ色值 低於約50。較佳地，該ΑΡΗΑ色值為約40，更佳地為約30， 最佳地為約20。此外較佳地，該產物含有約0.25%至約5% 之吸附劑，更佳地為約1%至約3°/。之吸附劑。 [材料，褒置及測試方法] 由得自DuPont或市售之1，3-丙二醇製備該P03G聚合物。 活性碳（DARCO，CALG0N，及 CECA)和 BHT係得自 Aldrich 鲁 Chemicals(Milwaukee WI)。CELPURE產品係得自 Advanced Minerals(Santa Barbara，CA)。此等產品不僅用於除去該聚 合物中之帶色體，還可用作助濾劑。 測試方法1，顏色測量和ΑΡΗΑ值。 在固體吸附劑處理之前及之後，使用Hunterlab ColorQuest分光比色計[Reston，VA]測量該聚合物之顏色。 根據ASTM D-1209測量該聚合物之色數作為ΑΡΗΑ值（鉑-鈷 體系）。該聚合物分子量由滴定法得到之羥基數計算。 · [實例] 下列所顯示之實例係用於說明本發明，但不希望為限制。The Whatman filter paper is supported by a 250 mL glass filter funnel and is equipped with a device for heating the unit. Other media may be used and are known to those skilled in the art to require a filter; carbon and inactive to the glycol. In accordance with another aspect of the invention, the polytrimethylene ether glycol has an APHA color value of at least 5 GApHA prior to contact with the adsorbent. The APHA color value may also be about 85 to 25 Å ApHA, or about 100 to 200 APHA, before the contact with the auxiliaries can have a color value of from about 7 G to about about contact with the sorbent. A batch process may be employed in which the adsorbent is permeable to the polyol after it has been effectively mixed with the polyol for a period of time, and the polyalcohol is separated from the adsorbent by a suitable means such as filtration, centrifugation, or the like. The process of the invention can also be carried out in a continuous or semi-continuous manner. For example, the polyol can be pumped from a storage tank through a fixed bed of the adsorbent. The feed rate can be adjusted by the type and amount of the adsorbent in the fixed bed and the previously used adsorbent and the color content of the raw material, so that the contact time of the polyalcohol with the adsorbent is sufficiently long to obtain the desired discoloration. Effluent. The effluent can stay in the storage tank for a short period of time or be used or shipped immediately. Other changes will also be recognized by those skilled in the art. According to another aspect of the invention, the polytrimethylene ether glycol has a reduced APHA color value of at least about 5%. Preferably, the polytrimethylene ether glycol has a reduced APHA color value of at least about 60%, more preferably ' at least about 70%. The process of the present invention can be used for the decolorization of polytrimethylene sulphate prepared by polymerization of PD oxime, wherein the PDO is passed through a petrochemical feedstock such as acrolein used in the process 93143.doc 13-1364319, also available Decolorization of a polyol prepared by polymerizing PDO prepared from a biochemical pathway. The activated carbon treatment can be carried out on its final polymer or only prior to the filtration step of the purification process. Preferably, the activated carbon is added to the P03G polymer only prior to final filtration and the filtered polymer is stored in the presence of an antioxidant such as BHT. The use of multiple sources and forms of carbon seems to be effective. Different forms of activated carbon, such as powdered, granulated, and shaped products, can be obtained from a variety of sources. A preferred form thereof is powdered activated carbon. Various brands of carbon can be used, including, but not limited to, Norit America G60, NORIT R0 0·8, Calgon PWA, BL and WPH, and Ceca ACTICARONE ENO. Other forms will be familiar to those skilled in the art. According to another aspect of the invention, a method comprises: (a) providing a reactant comprising a 1,3-propanediol and a polycondensation catalyst; (b) polycondensing the reactant to a colored P03G; (c) rendering the P03G and adsorbing Contacting the agent; and (d) separating the P03G from the adsorbent. 'The color of the P03G has an APHA color value of less than about 50 after contact with the adsorbent. Preferably, the APHA color value is less than about 40, more preferably less than 30 and most preferably less than about 20. Preferably, the adsorbent comprises activated carbon, and the P03G is contacted with from about 0.1 to about 5% by weight of activated carbon based on the weight of the polytrimethylene ether glycol, and the contact is at a temperature of from about 10 to about 150°. Under C. 93143.doc • 14-1364319 According to another aspect of the invention, the product comprises (1) a colored p〇3G and a (Η) sorbent (which has been described herein), wherein the P03G has a ΑΡΗΑ color value of less than about 50 . Preferably, the color value is about 40, more preferably about 30, and most preferably about 20. Further preferably, the product contains from about 0.25% to about 5% of the adsorbent, more preferably from about 1% to about 3%. Adsorbent. [Materials, Disposal and Test Methods] The P03G polymer was prepared from DuPont or commercially available 1,3-propanediol. Activated carbon (DARCO, CALG0N, and CECA) and BHT were obtained from Aldrich Lu Chemicals (Milwaukee WI). CELPURE products are available from Advanced Minerals (Santa Barbara, CA). These products are not only used to remove the color bodies in the polymer, but also as filter aids. Test Method 1, color measurement and enthalpy. The color of the polymer was measured before and after solid adsorbent treatment using a Hunterlab ColorQuest spectrophotometer [Reston, VA]. The color number of the polymer was measured as a enthalpy value (platinum-cobalt system) according to ASTM D-1209. The molecular weight of the polymer is calculated from the number of hydroxyl groups obtained by titration. [Examples] The following examples are shown to illustrate the invention, but are not intended to be limiting.
實例1，製備P〇3G 將13.9 kg之1,3-丙二醇和139 g濃硫酸加入22 L玻璃反應 器中，並且其在160°C及氮氣下聚合，直至達到所期望之數 量平均分子量。一般地，反應時間越長得到之聚合物的分 子量越高。將一部分粗製聚合物（5 kg)與等體積之蒸餾水轉 移至另一個22 L玻璃反應器中，並在氮氣層下緩慢攪拌該 93143.doc -15- 1364319 反應混合物，同時加熱至100°C保持4小時。4小時之後，將 該混合物冷卻並藉由重力作用將其分離為兩相。取出並丟 棄該水相。再次用水清洗該聚合物。藉由過量氫氧化約中 和該聚合物中剩餘之硫酸°將該聚合物在9〇°C下減壓乾燥 3小時，然後透過預先塗覆CELPURE助滤劑之Whatman過遽 紙進行過瀘、。分析得到之純化P03G聚合物之分子量和顏 色。 實例2，活性破處理至較低之聚合物色值 牢固地安裝一 250 ml燒結玻璃漏斗。將CELPURE C65 (4.4 g，1.2 kg/m2)緊壓在放置於該燒結玻璃上之1微米尺寸 的Whatman過滤紙上。在該漏斗周圍纏繞加熱帶以便在過 濾過程中給該聚合物提供熱量。將P03G(80 g，MW=24〇〇) 放置在250 ml圓底燒瓶中。向該聚合物中加入活性木炭 (0.008 g，0.01重量％ ’ DARCO G60)。向該聚合物增加磁授 拌，然後在室溫下和氮氣環境中，在攪拌器上攪拌該聚合 物10分鐘。然後在氮氣層下借助於家用真空裝置使該聚合 物透過該燒結玻璃漏斗進行過濾。透過調節其溫度控製器 (VARIAC)將溫度設定在60°C ~7〇°C之間。採用Hunterlab ColorQuest分光比色計測量該最終聚合物之顏色。一旦測量 完成就向該聚合物中加入BHT(200微克/克聚合物）。對省略 該木炭之試樣做對照測量。其結果列於表1中。 實例3〜5 採用用各種數量之DARCO G60活性木炭重複實例2中之 步驟。該P03G分子量為2170 »結果也列於表1中。 93I43.doc -16· 1364319 表1 .P03 G色值對活性碳重量百分比 實例 重量％活性碳 聚合物色值APHA 對照試樣 0 126 2 0.01 121 3 0.05 104 4 0.15 96 5 0.25 88 表1中之數據顯示活性木炭可除去P03G聚合物中之帶色雜 質且隨著活性木炭量以聚合物計從0.01增加至0.25重量 %，其色值減少。 實例6〜11 重複實例5之步驟測定該方法之再現性。此等實例中使用 之P03G聚合物具有之分子量為2449，色值為145 APHA，且 包含200微克BHT/克聚合物。其結果列於表2中。 表2.P03G色值再現性 實例 重量％活性碳 色值APHA 對照試樣 0 145 6 0.25 106 7 0.25 104 8 0.25 106 9 0.25 109 10 0.25 107 11 0.25 109 表2中之數據顯示用木炭脫色之再現性約為±3 APHA單 位，與單個試樣之測量結果的重複再現性相當。 實例12 在3-L過濾單元中使用2.5千克PO3G(MW = 2170，色值 = 126 APHA)和62.5克Darco G-60活性木炭重複實例5之步 驟。在過濾過程中，於不同時間採集聚合物，測量每一份 93143.doc -17- 1364319 之色值，其結果列於表3中。 表3.較大規模之P03G脫色 P03G 色值APHA 活性碳處理之前 126 第一份 87 第二份 88 第三份 87 第四份 89 實例13〜17 使用較高量之活性碳，以及使用具有2 2 1 2分子量和 70 APHA色值之P03G聚合物重複實例5。 表4.活性碳量對P03G色值之影響 實例 重量％活性碳 色值APHA %改變量 對照試樣 0 70 — 13 0.25 52 25.7 14 1.0 42 40.0 15 2.0 39 44.3 16 3.0 35 50.0 17 5.0 34 51.4 在70°C下過濾該聚合物以分離碳。 表4中之數據顯示在較高含量活性碳（3重量％)時，該聚合物 顏色可極大地提高約50%。 實例1 8 用該粗製聚合物代替純化之聚合物重複實例5。該粗製聚 合物具有134 APHA之色值。將該聚合物水解，藉由過量氫 氧化鈣中和並乾燥。向所乾燥之包含剩餘鹼和鹽的P03G聚 合物中加入0.25重量％活性碳並採用上述方法過濾。測量過 濾後之P03G色值，發現為80 APHA，其表明可在純化方法 93143.doc -18· 1364319 之最終過濾步驟之前加入該活性碳。 實例19〜24 使用固定量（2重量％)之幾種不同等級和形式的活性碳處 理P03G聚合物（MW，2070和色值，92 APHA)，其結果報告 於表5中。 表5 實例 19 20 21 22 23 24 製造商 Norit American Norit American CALGON CALGON CALGON CECA 等級 DARCO- G60 NORIT ROO.8 PWA BL WPH ACTICARBONE ENO 碳形式 粉末狀 小球狀 粉末狀 粉末狀 粉末狀 粉末狀 块數，mg/g ΝΑ 1050 900 1000 800 ΝΑ P03G色值 52 77 56 61 53 48 表5中之數據顯示所有粉末狀活性碳試樣均有效地將該 P03G聚合物色值從92 APHA減少至48〜61 APHA。 93143.doc 19-Example 1, Preparation of P〇3G 13.9 kg of 1,3-propanediol and 139 g of concentrated sulfuric acid were placed in a 22 L glass reactor and polymerized at 160 ° C under nitrogen until the desired average molecular weight was achieved. Generally, the longer the reaction time, the higher the molecular weight of the polymer obtained. Transfer a portion of the crude polymer (5 kg) to an equal volume of distilled water to another 22 L glass reactor and slowly stir the 93143.doc -15-1364319 reaction mixture under a blanket of nitrogen while heating to 100 ° C to maintain 4 hours. After 4 hours, the mixture was cooled and separated into two phases by gravity. Remove and discard the water phase. The polymer was washed again with water. The polymer was dried under reduced pressure at 9 ° C for 3 hours by excessive hydrogenation to neutralize the remaining sulfuric acid in the polymer, and then passed through a Whatman paper which was previously coated with CELPURE filter aid. . The molecular weight and color of the purified P03G polymer were analyzed. Example 2, Active Breaking to a Lower Polymer Color Value A 250 ml sintered glass funnel was securely installed. CELPURE C65 (4.4 g, 1.2 kg/m2) was pressed onto a 1 micron size Whatman filter paper placed on the sintered glass. A heating belt is wound around the funnel to provide heat to the polymer during the filtration process. P03G (80 g, MW = 24 Torr) was placed in a 250 ml round bottom flask. Activated charcoal (0.008 g, 0.01% by weight of 'DARCO G60) was added to the polymer. Magnetic polymerization was added to the polymer, and the polymer was stirred on a stirrer for 10 minutes at room temperature under a nitrogen atmosphere. The polymer was then filtered through a sintered glass funnel under a nitrogen blanket by means of a domestic vacuum apparatus. Set the temperature between 60 ° C and 7 ° ° C by adjusting its temperature controller (VARIAC). The color of the final polymer was measured using a Hunterlab ColorQuest spectrophotometer. Once the measurement is complete, BHT (200 micrograms per gram of polymer) is added to the polymer. A comparative measurement was made on the sample in which the charcoal was omitted. The results are shown in Table 1. Examples 3 to 5 The procedure of Example 2 was repeated using various amounts of DARCO G60 activated charcoal. The P03G molecular weight was 2170 » The results are also listed in Table 1. 93I43.doc -16· 1364319 Table 1. P03 G color value versus activated carbon weight percentage Example weight % Activated carbon polymer color value APHA Control sample 0 126 2 0.01 121 3 0.05 104 4 0.15 96 5 0.25 88 Data in Table 1 It is shown that activated charcoal can remove colored impurities in the P03G polymer and its color value decreases as the amount of activated charcoal increases from 0.01 to 0.25 wt% in terms of polymer. Examples 6 to 11 The procedure of Example 5 was repeated to determine the reproducibility of the method. The P03G polymer used in these examples had a molecular weight of 2,449, a color value of 145 APHA, and contained 200 micrograms of BHT per gram of polymer. The results are shown in Table 2. Table 2. P03G color value reproducibility example weight % active carbon color value APHA control sample 0 145 6 0.25 106 7 0.25 104 8 0.25 106 9 0.25 109 10 0.25 107 11 0.25 109 The data in Table 2 shows the reproduction of charcoal decolorization The performance is about ±3 APHA units, which is comparable to the repeatability of the measurement results of a single sample. Example 12 The procedure of Example 5 was repeated using a 2.5 kg PO3G (MW = 2170, color value = 126 APHA) and 62.5 g of Darco G-60 activated charcoal in a 3-L filtration unit. During the filtration process, the polymers were collected at different times and the color values of each of 93143.doc -17-1364319 were measured. The results are shown in Table 3. Table 3. Larger scale P03G decolorized P03G color value APHA before activated carbon treatment 126 first 87 second copy 88 third 87 fourth 89 examples 13 to 17 using a higher amount of activated carbon, and using with 2 Example 2 was repeated for a P 1 2 polymer of 2 1 2 molecular weight and 70 APHA color value. Table 4. Effect of activated carbon amount on P03G color value Example weight % Active carbon color value APHA % Change amount Control sample 0 70 — 13 0.25 52 25.7 14 1.0 42 40.0 15 2.0 39 44.3 16 3.0 35 50.0 17 5.0 34 51.4 The polymer was filtered at 70 ° C to separate the carbon. The data in Table 4 shows that at higher levels of activated carbon (3% by weight), the polymer color can be greatly increased by about 50%. Example 1 8 Example 5 was repeated using the crude polymer instead of the purified polymer. The crude polymer had a color value of 134 APHA. The polymer was hydrolyzed, neutralized by excess calcium hydroxide and dried. To the dried P03G polymer containing the remaining base and salt, 0.25 wt% of activated carbon was added and filtered by the above method. The filtered P03G color value was measured and found to be 80 APHA, which indicated that the activated carbon could be added prior to the final filtration step of purification method 93143.doc -18·1364319. Examples 19 to 24 P03G polymer (MW, 2070 and color value, 92 APHA) was treated with a fixed amount (2% by weight) of several different grades and forms of activated carbon, and the results are reported in Table 5. Table 5 Example 19 20 21 22 23 24 Manufacturer Norit American Norit American CALGON CALGON CALGON CECA Grade DARCO- G60 NORIT ROO.8 PWA BL WPH ACTICARBONE ENO Carbon form powdery small spherical powdery powdery powdery powder, Mg/g ΝΑ 1050 900 1000 800 ΝΑ P03G color value 52 77 56 61 53 48 The data in Table 5 shows that all powdered activated carbon samples effectively reduced the color value of the P03G polymer from 92 APHA to 48 to 61 APHA. 93143.doc 19-