TW200303880A - Reduction of the proportion of cyclic oligomeric ethers in polytetrahydrofuran or copolymers of tetrahydrofuran - Google Patents

Abstract

To reduce the proportion of cyclic oligomeric ethers in polytetrahydrofuran (PTHF) or copolymers of tetrahydrofuran (THF), the PTHF or THF copolymers are extracted at from 30 to 200 DEG C in one or more stages by means of an aliphatic, linear or branched or cycloaliphatic or olefinic hydrocarbon having from 4 to 15 carbon atoms, a mixture of such hydrocarbons or a mixture comprising at least 50% by weight of such hydrocarbons and the PTHF or THF copolymer phase and the hydrocarbon phase are separated from one another. The extraction is carried out in a column having a central stirrer which extends over a plurality of stirring zones located one above the other, with the ratio of the circumferential velocity of the stirrer to the power of three to the height of the stirrer being more than 0.5 m2/s3.

Description

200303880 (Ο 玫，發明說€ (發明說明應敘明：發明所屬之技術領域、先前技術、内容、實施方式及圖式簡單說明) 技術領域 聚四氫呋喃，下文中稱為PTHF，亦稱為聚環氧丁（烷）二 醇在塑膠和合成纖維工業中使用作為多方面適合之中間 物，其中，採用以製造聚胺甲酸酯彈性體、聚酯彈性體和 聚醯胺彈性體。另外，像其某些衍生物一樣，其係許多應 用中之一種有價值之輔助劑，例如作為分散劑，或用於廢 紙的脫除油墨。 PTHF通常工業上係由在適當觸媒上聚合四氫呋喃（下文 中稱為THF)予以製備。添加適當反應物使聚合物鏈的鏈 長能受控制而因此使平均分子量能被設定至所需要之數 值。將此等反應物稱為鏈終止劑或”調聚劑”。控制係由選 擇調聚劑的型式和數量予以實現。選擇適當調聚劑使附加 之官能基團能在聚合物鏈的一端或兩端被引入。 因此，舉例而言，使用羧酸或羧酸酐作為調聚劑能製備 PTHF的單酯或二酯，隨後必須將其經由皂化或轉酯化反 應轉化成為PTHF。因此將此等程序稱為兩級PTHF程序。 其他調聚劑不僅充作鏈終止劑而且亦經併合入PTHF的 生長之聚合物鏈中。彼等不僅具有調聚劑的功能而且同時 是共聚單體而因此可同等適當稱為調聚劑或共聚單體。此 等共聚單體的實例是具有兩個羥基基團之調聚劑，例如二 醇類（二醇）。舉例而言，此等可能是乙二醇、丙二醇、丁 二醇、1，3_丙二醇、1，4-丁 二醇、2-丁炔 _1，4_ 二醇、1，6·己二 醇或低分子量PTHF。另外適當之共聚單體是環狀醚例如 (2) 200303880200303880 (〇 Mei, invention) (The description of the invention should state: the technical field to which the invention belongs, the prior art, the content, the embodiments and the drawings are simply explained) Technical field Polytetrahydrofuran, hereinafter referred to as PTHF, also known as polycyclic Oxybutanediol is used in the plastics and synthetic fiber industries as a suitable intermediate in many ways. Among them, polyurethane elastomers, polyester elastomers, and polyamide elastomers are used. In addition, like Like some of its derivatives, it is a valuable adjuvant in many applications, such as as a dispersant, or for the removal of ink from waste paper. PTHF is generally industrially polymerized by the polymerization of tetrahydrofuran on a suitable catalyst (hereinafter (Called THF) to be prepared. The addition of appropriate reactants enables the chain length of the polymer chain to be controlled and thus allows the average molecular weight to be set to the desired value. These reactants are called chain terminators or "telomers" ". Control is achieved by selecting the type and amount of telogen. Choosing an appropriate telomer enables the additional functional groups to be introduced at one or both ends of the polymer chain. Therefore, For example, using carboxylic acids or carboxylic anhydrides as telomers can produce mono- or diesters of PTHF, which must then be converted to PTHF by saponification or transesterification. These procedures are therefore referred to as two-stage PTHF procedures Other telomers not only act as chain terminators, but also incorporated into the growing polymer chain of PTHF. They not only have the function of telomers but are also comonomers, so they can be equally appropriately called telomers Or comonomers. Examples of such comonomers are telomers having two hydroxyl groups, such as glycols (diols). For example, these may be ethylene glycol, propylene glycol, butylene glycol , 1,3-propanediol, 1,4-butanediol, 2-butyne-1,4-diol, 1,6-hexanediol or low molecular weight PTHF. Also suitable comonomers are cyclic ethers such as ( 2) 200303880

如1，2-環氧烷，舉例而言，環氧乙烷或環氧丙烷， 四氫呋喃或3·甲基四氳呋喃。除去水、l : i夂甲基 子量PTHF外，使用此等共聚單體導致製備四氫呋=低分 物（下文中稱為THF共聚物）且以此方式能化學改質嗝共聚 工業上製備主要藉兩級程序來進行，其中舉例。 THF係在氟磺酸之存在下予以聚合而形成ρτΗρ酯而=， 將此酯水解成為PTHF。或者，舉例而言，THF :述隨後 媒疋存在下使用乙酸酐予以聚合而形成PTHF二 生觸 筠曰酸酉匕 隨後將此二酯，舉例而言，使用甲醇轉酯化而 曰， 生 PTjjp 舉例而言，如歐洲專利A 38 0〇9和德國專利a 28 〇1 ’ 述。 8中所 先前技術 PTHF的單級合成自世界專利w〇 96/〇39355中得知， ’係麵 由使用水、1，4-丁二醇或低分子量PTHF作為調聚劑將了^ 在酸性觸媒上聚合而進行。所熟知之觸媒包括兩種系統· 將其勻相溶入反應系統中以及不均勻系統（即：大半未溶 者），舉例而言，自歐洲專利B 126 471所知之異聚酸及自 美國專利A 4，120,903所知之過酸Nafion®離子交換樹脂。 德國專利A 44 33 606號中記述經由水、1，4- 丁二醇、具有 自200至700道爾頓（dalton)之分子量的PTHF等調聚劑之一 或此等調聚劑的混合物存在下將T H F在不勻相觸媒上聚 合來製備PTHF之方法，而該觸媒係一種受載觸媒其中包 括觸媒活性數量的含氧之鶏或鉬化合物或此等化合物之 200303880Such as 1,2-alkylene oxide, for example, ethylene oxide or propylene oxide, tetrahydrofuran or 3. methyltetrahydrofuran. Except for water, l: i 夂 methylon amount PTHF, the use of these comonomers leads to the preparation of tetrahydrofur = low fractions (hereinafter referred to as THF copolymers) and can be chemically modified in this way. Preparation is mainly carried out by a two-stage procedure, with examples. THF is polymerized in the presence of fluorosulfonic acid to form a ρτΗρ ester, and this ester is hydrolyzed to PTHF. Alternatively, for example, THF: described below is polymerized using acetic anhydride in the presence of a medium to form PTHF, which is a secondary acid, and then this diester, for example, is transesterified with methanol, and PTjjp For example, as described in European patent A 38 009 and German patent a 28 001 '. The single-stage synthesis of the prior art PTHF in 8 is known from the world patent WO96 / 〇39355, 'the surface is made by using water, 1,4-butanediol or low molecular weight PTHF as a telomerizing agent. Polymerization proceeds on the catalyst. The well-known catalysts include two systems: homogeneous dissolution into the reaction system and heterogeneous systems (ie, mostly undissolved), for example, the heteropolyacids known from European Patent B 126 471 and U.S. Patent No. 4,120,903 is known as a peracid Nafion® ion exchange resin. German patent A 44 33 606 describes the existence of one or a mixture of these telomers via water, 1,4-butanediol, PTHF and the like having a molecular weight from 200 to 700 daltons. A method for preparing PTHF by polymerizing THF on a heterogeneous catalyst, which is a supported catalyst that includes a catalytically active amount of an oxygen-containing hafnium or molybdenum compound or these compounds 200303880

(3) 混合在一種氧化物之支載物質上炎在施加含氧之鉬及/或 鎢化合物的前驅體化合物後，在自500°c至1000°c下換 燒。德國專利A 196 49 803號中揭示：藉促進劑來增加德國 專利A 44 33 606號中所述之觸媒的活性。 甚大比例的低分子量產物在上述和其他程序中四氫呋 喃的聚合或共聚時形成。此等非所欲副產物包括或包含低 聚之環狀醚。彼等可能以至高2 0重量％的比例而存在，而 在聚合或共聚之二級程序中較在單級程序中形成較小的 比例。因為許多原因此等低聚之環狀醚係非所欲。作為惰 性化合物，彼等干擾聚合物的更進一步處理，舉例而言， 其與異氰酸酯產生反應而形成聚胺甲酸酯。彼等充作塑化 劑且通常對於成品的機械性質具有不利影響。彼等亦可像 汗流出成品的表面上或經由溶劑予以瀝取，舉例而言，其 不利影響成品物件的尺寸穩定性。 為了補救此等缺陷，德國專利A-35 14 547中提議：藉水 和烴類的混合物自PTHF或THF共聚物中萃取環狀低聚 醚’而聚合物係自水相回收。 美國專利第A-3,478，109號中揭示自PTHF或THF共聚物中 移除低分子量餾份之方法，其中將聚合物的烴溶液使用f 醇/水混合物萃取。 歐洲專利A_153 794號中記述降低PTHF和THF共聚物中 低聚5幕狀醚的含量之方法，其中將環狀醚在自2 0 °C彡6 〇 C下藉煙類自原PTHF或THF共聚物中萃出。 先前技藝的各種程序之一個缺點是相當高殘餘數量的 200303880(3) It is mixed with an oxide-supporting substance. After applying a precursor compound containing molybdenum and / or tungsten compounds containing oxygen, it is burned at 500 ° c to 1000 ° c. German Patent A 196 49 803 discloses that the activity of a catalyst described in German Patent A 44 33 606 is increased by an accelerator. A very large proportion of low molecular weight products are formed during the polymerization or copolymerization of tetrahydrofuran in the above and other procedures. These undesirable by-products include or include oligomeric cyclic ethers. They may be present in a proportion of up to 20% by weight, while forming a smaller proportion in a secondary procedure of polymerization or copolymerization than in a single-stage procedure. These oligomeric cyclic ethers are undesirable for many reasons. As inert compounds, they interfere with further processing of polymers, for example, they react with isocyanates to form polyurethanes. They act as plasticizers and often have an adverse effect on the mechanical properties of the finished product. They can also leak out of the surface of the finished product like sweat or be leached by solvent, which, for example, adversely affects the dimensional stability of the finished object. To remedy these shortcomings, German Patent A-35 14 547 proposes to extract a cyclic oligoether 'from a PTHF or THF copolymer by using a mixture of water and hydrocarbons and the polymer is recovered from the aqueous phase. A method for removing low molecular weight fractions from a PTHF or THF copolymer is disclosed in U.S. Patent No. A-3,478,109, in which a hydrocarbon solution of a polymer is extracted with an alcohol / water mixture. European Patent No. A_153 794 describes a method for reducing the content of oligomeric 5 curtain ethers in PTHF and THF copolymers, in which cyclic ethers are copolymerized from original PTHF or THF by smoking at 20 ° C to 60 ° C. Extracted. One disadvantage of the various procedures of the prior art is the relatively high residual quantity of 200303880

(4) 環狀低聚醚依然在聚合物中，甚至重複進行此等程序後亦 然。以其多分散性及色數為觀點，所獲得之pTHF或所獲 得之THF共聚物不能符合要求。 發明内容 本發明的一個目的在提供能以一種簡單且經濟上有利 之方式降低PTHF或具有自600至6000分子量之THF共聚物 中之環取低聚醚的比例至低於1重量％ (基於pTHF或T H F共 聚物）之方法。當降低環狀低聚醚的含量至所需要之數值 時’應萃取出基於萃取劑，不超過3重量％的線性聚THf 低聚物或共聚物。 余等發現：此目的經由申請專利範圍第i項中所特定之 措施而達到。 本發明的程序之有利具體實施例在申請專利範園第2至 7附屬項中予以界定。 欲予處理之PTHF或THF共聚物係以就其本身而論所熟 知之方式在強酸性觸媒之存在下以單級或經由PTHF之酯 類以二級隨後將其水解和轉酯化予以製備。舉例而言， PTHF可經由德國a料33 606號或世界專利w〇 96/%35中所 述之單級程序予以製備，因此通常含有至高1〇重量％的環 狀低聚醚。具有1，2 ·環氧烷，例如環氧乙烷之τ η F共聚物 亦可經由英國專利Β-854 958號和德國專利β-3 346 134號中 所述之方法可獲得但是通常含有自1至2〇重量❶之低聚之 環狀醚。 自PTHF或THF共聚物中選擇性移除環狀低聚物係由使 200303880 (5)(4) The cyclic oligoether is still in the polymer, even after repeating these procedures. From the viewpoint of its polydispersity and color number, the obtained pTHF or the obtained THF copolymer could not meet the requirements. SUMMARY OF THE INVENTION An object of the present invention is to provide a simple and economically advantageous way to reduce the proportion of cyclic oligoethers in PTHF or THF copolymers having a molecular weight from 600 to 6000 to less than 1% by weight (based on pTHF Or THF copolymer). When the content of the cyclic oligoether is reduced to the required value, a linear polyTHf oligomer or copolymer based on the extractant should not be more than 3% by weight. The others found that this objective was achieved through measures specified in item i of the patent application. Advantageous specific embodiments of the procedure of the present invention are defined in the sub-items 2 to 7 of the patent application park. The PTHF or THF copolymer to be treated is prepared in a manner known per se in the presence of a strongly acidic catalyst in a single stage or via the esters of PTHF in two stages followed by hydrolysis and transesterification. . For example, PTHF can be prepared via a single-stage procedure as described in German Patent No. 33 606 or World Patent WO 96 /% 35, and therefore usually contains up to 10% by weight of cyclic oligoethers. Τ η F copolymers with 1,2 · alkylene oxides, such as ethylene oxide, can also be obtained by methods described in British Patent B-854 958 and German Patent β-3 346 134 but usually contain from 1 to 20 weight percent oligomeric cyclic ether. The selective removal of cyclic oligomers from PTHF or THF copolymers is based on 200303880 (5)

用具有自4至15個碳原子（較佳自7至11個碳原子）之脂 族、環脂族或烯系烴類，或此等烴類的混合物或包括至少 5 0重量％的此等烴之混合物來萃取予以實現。 適合於該項萃取之烴類包括飽和和不飽和之脂族，與環 脂族化合物及亦包括烯屬烴類，每一者亦可帶有取代基例 如_素原子或烷氧基基團。優先權給予使用飽和和不飽 和’支鏈和直鏈脂族烴。亦可能使用烴類的任何混合物， 舉例而言’飽和脂族和環脂族烴類例如具有自4至丨5個碳 原子之fe例如丁烷、戊烷和癸烷；支鏈烷烴例如2 -甲基 己烷和異壬烷；具有自5至12個碳原子之環脂族烴例如環 戊、環己燒、環辛烷和環十二烷；不飽和脂族或環脂族 ^例如具有自4至1 2個碳原子之婦烴，例如異丁烯和環己 烯 〇 萃取中所使用之烴類或烴類混合物的數量可在廣大範 園内變更。就大體而論，烴類：pTHF或THF共聚物的重量 疋至少〇 ·5 ·1。特別，其係在自1:1至1 0:1之範圍内，較 二自1’5.1至5·1。碌項萃取通常係在自3〇至2⑼。c下進行， ^佳自/G°至1GG°C，特佳自，至8Gt。壓力係基於在所選 卒取溫度T溶劑蒸汽壓。優先權、給予在1氣壓下之 中 另 根據本發明，液體/液體萃取係以一或數級在具有一 3 ^攪拌态之塔中進行，該中央攪拌器延伸遍及—個位方 —個上面之兩或數個攪拌器，較佳自10至200，特佳I WO個攪拌區。適當之塔是適合萃取之就其本身而論冷 -10- 25 200303880Use of aliphatic, cycloaliphatic or olefinic hydrocarbons having from 4 to 15 carbon atoms, preferably from 7 to 11 carbon atoms, or a mixture of these hydrocarbons or including at least 50% by weight of these Extraction of mixtures of hydrocarbons is achieved. Suitable hydrocarbons for this extraction include saturated and unsaturated aliphatic, and cycloaliphatic compounds, and also olefinic hydrocarbons, each of which may also have a substituent such as a prime atom or an alkoxy group. Priority is given to the use of saturated and unsaturated ' branched and straight chain aliphatic hydrocarbons. It is also possible to use any mixture of hydrocarbons, for example 'saturated aliphatic and cycloaliphatic hydrocarbons such as fe having from 4 to 5 carbon atoms such as butane, pentane and decane; branched alkanes such as 2- Methylhexane and isononane; cycloaliphatic hydrocarbons having from 5 to 12 carbon atoms such as cyclopentane, cyclohexane, cyclooctane, and cyclododecane; unsaturated aliphatic or cycloaliphatic ^ such as having The number of feminine hydrocarbons from 4 to 12 carbon atoms, such as isobutene and cyclohexene. The amount of hydrocarbons or hydrocarbon mixtures used in the extraction can be changed within a wide range of fields. In general, the weight of hydrocarbons: pTHF or THF copolymers is at least 0 · 5 · 1. In particular, it is in the range from 1: 1 to 10: 1, more than 2 from 1'5.1 to 5.1. Crude extraction is usually from 30 to 2⑼. It is performed under c, preferably from / G ° to 1GG ° C, particularly preferably from 8Gt. The pressure is based on the solvent vapor pressure at the selected stroke temperature T. Priority, given under 1 atmosphere. In addition, according to the present invention, the liquid / liquid extraction is carried out in one or several stages in a tower with a 3 ^ agitated state. The central agitator extends all the way up to the top. Two or more stirrers, preferably from 10 to 200, particularly preferably I WO stirring zones. The proper tower is suitable for extraction as it is cold -10- 25 200303880

(6) 熟知之禮捽塔其中一相具有相當高黏度（Wagner，Ι· ; 2000 ; 在 TU 慕尼黑之論文 ’’Der Einfluss der Viskositat auf den Stofftibergang in Fliissig-Fltissig-Extraktionskolonnen”）。實例是 ”Die Chemische Produktion”（1979，12月）中所述之”SCHEIBEL，， 塔，QVF ENGINEERING攪拌槽攪拌器及ΚϋΗΝΙ攪拌塔（’’ΚϋΗΝΙ 塔’’）。攪捽系統中之一個重要參數是能量散逸ε (epsilon)。 攪拌元件上之最大能量散逸的量度是攪拌器的圓周速度u 之三次方：攪拌器的高度h之比： ε 〜u3/h 當恆定時，關於許多攪拌器，使用0.1數值： ε = 0.1 u3/h 為了實現最適宜萃取，將PTHF或THF共聚物與烴類的 混合物在高於0.5 m2/s3的u3/h比率時處理（ε = 0.05 W/kg)。 由於此項量度之結果，顯著加速自黏性PTHF相之質量 傳送。再者，抑制經由黏性分散相潤溼塔内部，如在實例 中所示。優先權給予在攪拌塔中進行萃取，此等攪捽塔具 有在0.1-l*d的攪拌器高度及高於0.15 m/s的圓周速度時 0.2-0.8*D (D =塔的内直徑）的通常攪拌器直徑（d)。因此， 舉例而言，在具有40毫米的外直徑和8毫米的攪拌器高度 之葉片攪拌器的情況中成功地所採用之圓周速度是0.31 m/s。此數值示出在3.9 m2/s3的攪拌器時u3/h比率（ε = 0.39 W/kg) ° 根據本發明的另外特徵，萃取的有效性可由在經直接安 裝在塔的上游之混合裝置中使用烴類完全或部份飽和 200303880 ⑺ PTHF或THF共聚物予以改良。可能之混合裝置是攪拌容器 、靜態或動態管道混合器或一具栗。 根據本發明所進行之萃取能降低環狀低聚醚的含量至 低於1重量％(基於PTHF)。萃取後，經由相分離將PTHF或 THF共聚物與包括環狀低聚醚和基於總數量小部份，以質 量計低於2%的PTHF之烴類相分離。 隨後經由蒸餾，PTHF或THF共聚物相主要無仍存留在其 中之烴類，即：低至自0.01至i重量％(基於PTHF)的烴類含 量，較佳低至0.05至0.5重量％。蒸餾可分批或連續進行。 優先權給予單級或多級蒸發其中，將經純化之pTHF或殘 邊；自每級中作為塔底館份取出，如適當通至接著的下一級 將來自各蒸發級之蒸氣分開或在一起冷凝。將來自第一級 之冷凝液循環至萃取並可將來自隨後各級之冷凝液同樣 循環至萃取或循環至先前各蒸發級之一中。可將每一個的 個別蒸發級借助於蒸餾塔補足。 煙類相經由蒸餾予以處理。可將蒸餾分批或連續進行。 優先椎給予單級或多級蒸發。將經蒸餾之烴循環至萃取。 將殘}查（其包括環狀和線性低聚醚）拋棄或餵供至再解離 處成為THF及共聚物，如可應用，可將其再使用於該 程序中。 實例 將具有〇.5重量％的環狀低聚醚（SFC)含量和825的莫耳 質量（Mn)之112仟克/小時的PTHF在50°C下，在攪拌”Ktihni，’ 塔中用19.1仟克/小時之正庚烷萃取。具有27個攪拌槽之該 -12- 200303880(6) One phase of the well-known ritual tower has a relatively high viscosity (Wagner, Ι; 2000; TU Munich paper "Der Einfluss der Viskositat auf den Stofftibergang in Fliissig-Fltissig-Extraktionskolonnen"). An example is "Die "Chemische Produktion" (1979, December) as described in "SCHEIBEL," tower, QVF ENGINEERING stirred tank agitator and ΚϋΗΝΙ stirring tower ("Κ''ΝΙ tower"). An important parameter in agitated systems is epsilon. The measure of the maximum energy dissipation on the stirring element is the cube of the peripheral speed u of the agitator: the ratio of the height h of the agitator: ε ~ u3 / h When constant, for many agitators, use a value of 0.1: ε = 0.1 u3 / h For optimal extraction, a mixture of PTHF or THF copolymer with hydrocarbons is processed at a u3 / h ratio higher than 0.5 m2 / s3 (ε = 0.05 W / kg). As a result of this measurement, the mass transfer of the self-adhesive PTHF phase is significantly accelerated. Furthermore, wetting of the inside of the tower via the viscous dispersed phase is suppressed, as shown in the examples. Priority is given to extraction in stirred towers which have a stirrer height of 0.1-l * d and a peripheral speed above 0.15 m / s of 0.2-0.8 * D (D = inner diameter of the tower) The usual stirrer diameter (d). Therefore, for example, in the case of a blade agitator having an outer diameter of 40 mm and an agitator height of 8 mm, the peripheral speed successfully employed is 0.31 m / s. This value shows the u3 / h ratio (ε = 0.39 W / kg) at a stirrer of 3.9 m2 / s3. According to a further feature of the invention, the effectiveness of the extraction can be obtained in a mixing device installed directly upstream of the tower. Use hydrocarbons fully or partially saturated 200303880 880 PTHF or THF copolymers to improve. Possible mixing devices are agitating vessels, static or dynamic pipe mixers or a chestnut. The extraction according to the invention can reduce the content of cyclic oligoethers to less than 1% by weight (based on PTHF). After extraction, the PTHF or THF copolymer is separated from the hydrocarbon phase including cyclic oligoether and PTHF based on a small amount of the total amount by less than 2% by mass based on phase separation. Subsequent to distillation, the PTHF or THF copolymer phase is predominantly free of hydrocarbons remaining therein, i.e., hydrocarbon contents as low as 0.01 to i% by weight (based on PTHF), preferably as low as 0.05 to 0.5% by weight. Distillation can be carried out batchwise or continuously. Priority is given to single-stage or multi-stage evaporation, among which purified pTHF or stubs will be removed; from each stage, it will be taken out as the bottom of the tower, and the steam from each evaporation stage will be separated or together if appropriate to the next stage. Condensation. The condensate from the first stage is recycled to the extraction and the condensate from the subsequent stages is also recycled to the extraction or to one of the previous evaporation stages. Each individual evaporation stage can be made up by means of a distillation column. The smoke phase is processed via distillation. The distillation can be carried out batchwise or continuously. Priority vertebrae are given single or multiple levels of evaporation. The distilled hydrocarbons are recycled to extraction. Residues (which include cyclic and linear oligoethers) are discarded or fed to the re-dissociation place to become THF and copolymers, which can be reused in this procedure if applicable. Example PTHF having a cyclic oligoether (SFC) content of 0.5% by weight and a molar mass (Mn) of 825 g / h at 112 ° g / h at 50 ° C was used in a stirred "Ktihni," tower 19.1 g / h of n-heptane extraction. The -12-200303880 with 27 stirred tanks

⑻ 塔的標稱直徑是6 0毫央&八^ w 笔木而分離-活性高度是1·1米。攪拌器 直徑d是40亳米而播牲哭合 視件器同度h是8亳米。分隔板的敞口部 份是20%在上部^ 一刀 < 一處及30%在塔的其餘部份中。攪 拌以150 Ι/min之速率進行。圓周速度^是〇 31瓜“而u3/h比是 3·9 m /s (所計算之最大能量散逸ε = 〇 39 w/kg)。 來自萃取之萃餘物，即：PTHF相，含有約41重量％的已 溶之庚燒並具有0.08重量％的環狀低聚物（SFC)之殘餘含 量，相當於無庚烷之PTHF中0.14重量0/〇。 出人意料以外，頃發現：在液體/液體系統聚THF/正、 庚烷中，烷烴中聚THF的小滴以及亦聚THF中烷烴的小滴 大體上潤溼金屬、玻璃/陶瓷和塑膠的固體表面。潤溼角 係在自0°至40°之範圍内。高程度的潤溼通常減少塔中之 質量傳送面積並降低分離性能。 三個理論上之萃取級在所述之攪拌塔中實現；一個理論 上分離級的高度是3 7厘米。分離性能相當於具有黏性分散 相之非潤溼系統中之數值。此顯示：用以自PTHF或THF 共聚物中萃取環狀低聚醚，攪捽塔的特別適合性。 環狀低聚物的分析： SFC 方法 n = 3-7 : 該測定係由内部標準之方法予以進行。定量係基於具有 所熟知比例的環狀低聚物n==3-7之參考物質。使用癸酸甲 酯作為内部標準。 "13 -⑻ The tower's nominal diameter is 60 milliyangs & eight ^ w penwood and the separation-active height is 1.1 meters. The diameter d of the agitator is 40 亳 m and the same degree h of the visualizer is 8 亳 m. The open part of the partition is 20% in the upper part ^ one knife & 30% in the rest of the tower. Stirring was performed at a rate of 150 l / min. Circumferential speed ^ is 〇31, and the u3 / h ratio is 3.9 m / s (the calculated maximum energy dissipation ε = 〇39 w / kg). The raffinate from the extraction, namely: the PTHF phase, contains approximately 41% by weight of dissolved heptane and 0.08% by weight of cyclic oligomer (SFC) residual content, equivalent to 0.14% by weight of 0 / 〇 in heptane-free PTHF. Unexpectedly, it was found that Liquid system polyTHF / n-heptane, droplets of polyTHF in alkanes and droplets of alkanes in polyTHF generally wet solid surfaces of metals, glass / ceramics and plastics. Wetting angles range from 0 ° Within the range of 40 °. A high degree of wetting usually reduces the mass transfer area in the tower and reduces the separation performance. Three theoretical extraction stages are achieved in the agitated tower; one theoretical separation stage is 3 in height 7 cm. Separation performance is equivalent to the value in a non-wetting system with a viscous dispersed phase. This shows that it is particularly suitable for agitating towers to extract cyclic oligoethers from PTHF or THF copolymers. Analysis of oligomers: SFC method n = 3-7: The determination is based on the internal standard method . In quantified based on == n cyclic oligomers having known proportions of the used reference materials 3-7 decanoic acid methyl ester as the internal standard " 13 -..

Claims (1)

200303880 拾、申請專利範園200303880 Patent Park 1. 一種用以降低聚四氫呋喃（PTHF)或四氫呋喃（THF)之共 聚物中環狀低聚醚比例之方法，其中將PTHF或THF共 聚物在自30至20CTC下在一級或多級中藉具有自4至15 個碳原子之脂族、線性或支鏈或環脂族或烯系烴類、 此等烴類之混合物或包括至少5 0重量％的此等烴類混 合物萃取，並將PTHF或THF共聚物相和烴類相相互分 離，其中該萃取係在具有一支中央攪拌器（其延伸遍及 一個位於另一個上面之許多攪拌區）之塔中進行，而攪 拌器的圓周速度之三次方：攪拌器高度的比係超過0.5 m2/s3。 2. 如申請專利範圍第1項之方法，其中直接安裝在塔 的上游之混合裝置中之PTHF或THF共聚物之烴類係 為完全或部份飽和。1. A method for reducing the proportion of cyclic oligoethers in a copolymer of polytetrahydrofuran (PTHF) or tetrahydrofuran (THF), wherein the PTHF or THF copolymer is borrowed in one or more stages from 30 to 20 CTC Extraction from aliphatic, linear or branched or cycloaliphatic or olefinic hydrocarbons of 4 to 15 carbon atoms, mixtures of these hydrocarbons or mixtures of these hydrocarbons comprising at least 50% by weight, and PTHF or The THF copolymer phase and the hydrocarbon phase are separated from each other, in which the extraction is performed in a tower having a central agitator which extends through a plurality of agitating zones located one above the other, and the agitator has a cubic speed of three : The ratio of the height of the agitator exceeds 0.5 m2 / s3. 2. The method according to item 1 of the patent application, wherein the hydrocarbons of the PTHF or THF copolymer installed in the mixing device directly upstream of the column are fully or partially saturated. 3. 如申請專利範圍第2項之方法，其中該混合裝置是 一個攪捽容器。 4. 如申請專利範圍第2項之方法，其中該混合裝置是 一個管道混合器。 5. 如申請專利範圍第4項之方法，其中該管道混合器 是靜態混合器。 6. 如申請專利範圍第4項之方法，其中該管道混合器 是動態混合器。 7. 如申請專利範圍第6項之方法，其中該動態管道混 合器是一具泵。 200303880 陸、（一) (二) 本案指定代表圖為：第 麗 本代表圖之元件代表符號簡單說明： 柒、本案若有化學式時，請揭示最能顯示發明特徵的化學式：3. The method of claim 2 in which the mixing device is a stirring vessel. 4. The method according to item 2 of the patent application, wherein the mixing device is a pipe mixer. 5. The method according to item 4 of the patent application, wherein the pipe mixer is a static mixer. 6. The method according to item 4 of the patent application, wherein the pipe mixer is a dynamic mixer. 7. The method according to item 6 of the patent application, wherein the dynamic pipeline mixer is a pump. 200303880 Lu, (a) (b) The designated representative of this case is: Di Li Brief description of the element representative symbols of this representative: 柒 If there is a chemical formula in this case, please disclose the chemical formula that can best show the characteristics of the invention: