TWI752157B - 清潔樹脂之方法 - Google Patents
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- TWI752157B TWI752157B TW107102851A TW107102851A TWI752157B TW I752157 B TWI752157 B TW I752157B TW 107102851 A TW107102851 A TW 107102851A TW 107102851 A TW107102851 A TW 107102851A TW I752157 B TWI752157 B TW I752157B
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Abstract
提供一種清潔一批樹脂珠粒之方法,其中所述方法包括使所述批樹脂珠粒與水溶液接觸,其中所述水溶液包括一或多種溶解的胺化合物,其中所述批樹脂珠粒包括聚合物,所述聚合物包括所連接之羧酸基或磺酸基或其混合物。
Description
本發明之第一態樣係一種清潔一批樹脂珠粒之方法。
樹脂適用於多種多樣的用途。連接有酸性基團之樹脂可用作例如酸催化化學反應中之催化劑。在一種此類酸催化反應中,一個丙酮分子與兩個苯酚分子反應而產生一個雙酚A(「BPA」)分子及一個水分子。BPA通常用作製備透明聚合物之原材料,因此特別期望BPA不混雜有會賦予顏色之雜質。因而期望用作催化劑之樹脂具有極少有色或在BPA製備期間變得有色之雜質。
在一些情況下,有色或在BPA製備期間變得有色之雜質作為樹脂製造過程之副產物存在於樹脂中。此類雜質可能以極低量存在且可能對於大多數用途無影響,但其可能給BPA產物帶來不適宜量的顏色。舉例而言,若樹脂具有磺酸基,則在樹脂中可能存在有少量可能有色或可能變得有色之含硫化合物。因而期望提供一種在一批樹脂珠粒製造之後清潔樹脂珠粒以移除雜質之方法。
為評估催化劑樹脂對於特定化學反應之有效性,評判反應之轉化率及反應之選擇性。其中,選擇性尤其重要,因為高選擇性意味著幾乎無副產物生成且因此減小了對純化過程之需要。由此期望提供一種提供改善的對化學反應,例如產生BPA之反應,之選擇性的酸官能樹脂。
研究揭示案RD 369008教示一種再生離子交換樹脂,諸如磺化聚苯乙烯或苯乙烯-二乙烯基苯共聚物,之方法。RD 369008教示在使用樹脂作為製備BPA之催化劑之後之樹脂之再生。RD 369008教示,在BPA製備期間,有色體沈積在樹脂之微孔中且降低其效率。RD 369008教示藉由五步洗滌法再生。由RD 369008教示之洗滌溶液如下:第一水洗滌、視情況亦含有水之酮溶劑、強鹼(諸如氫氧化鉀或氫氧化鈉或碳酸鉀或碳酸鈉)之水溶液、強酸之水溶液及最終水洗滌。期望提供一種在一批樹脂珠粒之製造之後且在作為催化劑使用之前清潔樹脂珠粒之方法,其中所述方法具有一個或多個以下優勢:不需要用酮溶液洗滌;不需要用礦物鹼之水溶液洗滌;不需要用強酸之水溶液洗滌;移除有色雜質;提高樹脂之選擇性。
以下係本發明之陳述。
本發明之第一態樣係一種清潔一批樹脂珠粒之方法,其中所述方法包括使所述批樹脂珠粒與水溶液接觸,其中所述水溶液包括一或多種溶解的胺化合物,其中所述批樹脂珠粒包括聚合物,所述聚合物包括所連接之羧酸基或磺酸基或其混合物。
以下係本發明之詳細描述。
如本文所用,除非上下文另作明確指示,否則以下術語具有所指定之定義。
如本文中所使用,「樹脂」與「聚合物」同義。如本文中所使用,「聚合物」指由較小化學重複單元之反應產物組成之相對大的分子。聚合物可具有線性、支化、星形、環形、超支化、交聯或其組合之結構;聚合物可具有單個類型之重複單元(「均聚物」)或其可具有多於一種類型之重複單元(「共聚物」)。共聚物可具有隨機配置、依序配置、嵌段配置、其他配置或其任何混合或組合之各種類型之重複單元。聚合物具有2,000或更高之重量平均分子量。將在所有溶劑中均不可溶之充分交聯之聚合物視為具有無限分子量。
乙烯基單體具有結構(II)(II) 其中各R11
、R12
、R13
及R14
獨立地係氫、鹵素、脂族基(諸如烷基)、經取代之脂族基、芳基、經取代之芳基、另一經取代或未經取代之有機基團,或其任何組合。乙烯基單體能夠自由基聚合形成聚合物。一些乙烯基單體具有併入至R11
、R12
、R13
及R14
中之一或多者中的一個或多個可聚合碳-碳雙鍵,且此類乙烯基單體在本文中稱作多官能乙烯基單體。具有恰好一個可聚合碳-碳雙鍵之乙烯基單體在本文中稱為單官能乙烯基單體。
苯乙烯類單體係其中各R11
、R12
及R13
係氫或未經取代之烷基且R14
含有一個或多個經取代或未經取代之芳環的乙烯基單體。
單體間形成一或多種聚合物之反應在本文中被稱作聚合過程。在發生聚合過程之後單體之殘餘物在本文中稱為所述單體之聚合單元。
聚合物珠粒係個別粒子,各含有按聚合物重量計之50%或更大。珠粒在23℃下呈固體狀態。珠粒之體積平均直徑係10 µm或更大。若粒子不為球形,在本文中則認為粒子之直徑係與粒子具有相同體積之假想球體之直徑。
如本文中所使用,有機化合物係含有一個或多個碳原子之任何化合物,除了以下之外:具有恰好一個除氫之外之其他元素之碳之二元化合物;金屬氰化物;金屬羰基;光氣;硫化羰;金屬碳酸鹽。無機化合物係不為有機之化合物。有機基團係含有一個或多個碳原子之化學基團,其中有機基團中之一個或多個碳原子共價鍵結於有機基團之外之一個或多個原子。
如本文中所使用,酸係能夠對另一化合物供給氫離子之化合物。強酸之pKa為6或更低。鹼係在水中能夠接受氫離子或能夠為溶液供給氫氧根離子之化合物。強鹼之共軛酸之pKa為8或更高。
如本文中所使用,烷基及烯基可以係線性、支化、環狀或其組合。
如本文中所使用,在本文中若化學基團連接於取代基(亦即,原子或化學基團)則說化學基團係「經取代之」。適合取代基包含,例如烷基、烯基、芳基、鹵原子、包含胺基(包含單及二烷基胺基)之含氮基團、含氧基團(包含羧基及烷氧基)、含硫基團(包含磺酸基)、腈基,及其組合。
如本文中所使用,雜原子係除碳及氫之外之原子。
一批粒子係由直徑之基於體積的分佈表徵。參數D60表示直徑之值,其具有按體積計恰好60%之所述批粒子具有小於或等於D60之直徑的特性。參數D10表示直徑之值,其具有按體積計恰好10%之所述批粒子具有小於或等於D10之直徑的特性。參數「均勻係數」(縮寫「UC」)係UC=D60/D10。
在本文中,若磺酸基鍵結於聚合物之碳原子,則說樹脂珠粒具有磺酸基。磺酸基可以呈氫形式或呈具有關聯陽離子之陰離子形式。
樹脂珠粒亦可根據珠粒之孔隙度分類,所述孔隙度係使用布厄特(Brunauer-Emmett-Teller,BET)方法使用氮氣在乾燥樹脂上量測。大網狀(「MR」)樹脂珠粒之數均微孔直徑係50 nm至500 nm。凝膠樹脂珠粒之微孔比MR樹脂珠粒小得多。凝膠樹脂珠粒之數均微孔直徑通常太小而無法使用BET方法正確量測。認為凝膠樹脂珠粒之數均微孔直徑小於20 nm。
在本文中比率表徵如下。舉例而言,當稱比率為3:1或更大時,所述比率可以為3:1或5:1或100:1但不可以為2:1。將此以通用方式來敍述便是,在本文中,當稱比率為X:1或更大時,意指所述比率係Y:1,其中Y大於或等於X。類似地,例如,當稱比率為15:1或更少時,比率可以為15:1或10:1或0.1:1但不可以為20:1。將此以通用方式來敍述便是,在本文中當稱比率為W:1或更小時,意指所述比率係Z:1,其中Z小於或等於W。
本發明係含有一批樹脂珠粒之組合物。較佳樹脂含有一個或多個乙烯基單體之聚合單元。較佳,樹脂中乙烯基單體之聚合單元之量係,基於樹脂之重量按重量計95%或更大;更佳99%或更大。
較佳樹脂含有一個或多個苯乙烯類單體之聚合單元。較佳苯乙烯類單體係苯乙烯、經烷基取代之苯乙烯、二乙烯基苯以及其混合物;更佳係苯乙烯、二乙烯基苯以及其混合物。較佳,樹脂中苯乙烯類單體之聚合單元之量係,基於樹脂之重量按重量計,50%或更大;更佳75%或更大;更佳85%或更大;更佳95%或更大;更佳99%或更大。
較佳樹脂珠粒係凝膠樹脂珠粒。
較佳,所述批樹脂珠粒之調和平均直徑係100 µm或更大;更佳200 µm或更大;更佳400 µm或更大;更佳600 µm或更大。較佳,所述批樹脂珠粒之調和平均直徑係2,000 µm或更小,更佳1,500 µm或更小。較佳,所述批樹脂珠粒之均勻係數係1.8或更小;更佳1.5或更小;1.3或更小;更佳1.2或更小;更佳1.15或更小。
較佳,多官能乙烯基單體之聚合單元之量係,基於樹脂之重量按重量計,0.5%或更大;更佳1%或更大;更佳1.5%或更大。較佳,多官能乙烯基單體之聚合單元之量係,基於樹脂之重量按重量計,15%或更小;更佳10%或更小;更佳8%或更小;更佳6%或更小。較佳多官能乙烯基單體係二乙烯基苯。
樹脂可以由連接於樹脂之磺酸基之量表徵。在本文中,若磺酸基連接於樹脂且若SO3
基係完整的則認為磺酸基貢獻於此「量」。因此,只要磺酸基連接於樹脂且SO3
基係完整的,磺酸基便貢獻於此「量」,無論其係呈氫化形式、呈離子形式、酯形式、呈與另一化學基團之複合物或某其他形式。
較佳,連接於樹脂之磺酸基與所有單體之聚合單元之莫耳比係0.1:1或更大;更佳0.2:1或更大;更佳0.5:1或更大;更佳0.75:1或更大。較佳,連接於樹脂之磺酸基與所有單體之聚合單元之莫耳比係2:1或更低;更佳1.5:1或更低;更佳1.3:1或更低。
較佳,磺酸基在樹脂中以0.3莫耳每公升樹脂(mol/L)或更大;更佳0.4 mol/L或更大;更佳0.5 mol/L或更大;更佳0.6 mol/L或更大存在。較佳,磺酸基在樹脂中以4 mol/L或更小;更佳3 mol/L或更小;更佳2 mol/L或更小存在。
本發明之方法涉及使用包括一或多種胺化合物之水溶液(本文中「溶液A」)。較佳胺化合物具有結構(I):(I) 其中各R1
、R2
及R3
獨立地係氫或有機基團。較佳,各R1
、R2
及R3
獨立地係氫或具有1至30個碳原子之有機基團;更佳氫或具有1至15個碳原子之有機基團;更佳氫或具有1至8個碳原子之有機基團;更佳氫或具有1至4個碳原子之有機基團。R1
、R2
及R3
可為獨立基團,或R1
、R2
及R3
中之兩者或更多者可鍵結在一起形成環結構。
較佳,R1
係具有1至30個碳原子之有機基團;更佳R1
及R2
皆係具有1至30個碳原子之有機基團;更佳R1
、R2
及R3
均係具有1至30個碳原子之有機基團。
較佳,R1
、R2
及R3
中之一或多者係含有一個或多個雜原子之有機基團。較佳雜原子係一個或多個氧原子、一個或多個氮原子及其組合;更佳係一個或多個氧原子。較佳,R1
、R2
及R3
均不含有任何硫原子。當存在氧原子時,較佳各氧原子鍵結於兩個碳原子或鍵結於一個碳原子及一個氫原子。
更佳係結構(III)至(XI);更佳係三乙醇胺(結構(VI))。
較佳一或多種胺化合物係共軛酸之pKa為6或更高;更佳7或更高之鹼。較佳一或多種胺化合物係共軛酸之pKa為14或更低;更佳12或更低;更佳10或更低之鹼。
較佳一或多種胺化合物在20℃下在水中之溶解性為1 g/L或更高;更佳3 g/L或更高;更佳10 g/L或更高;更佳30 g/L或更高;更佳100 g/L或更高。
胺化合物在水溶液(「溶液A」)中作為溶質存在。較佳在溶液A中胺化合物之總量係,基於溶液A之重量按重量計,0.01%或更大;更佳0.03%或更大;更佳0.1%或更大;更佳0.2%或更大;更佳0.5%或更大;更佳1%或更大。較佳在溶液A中胺化合物之總量係,基於溶液A之重量按重量計,20%或更小;更佳10%或更小;更佳5%或更小;更佳3%或更小;更佳2%或更小。
較佳所有胺化合物之量加上水溶液A中之水之量之總和係,基於溶液A之重量按重量計,80%或更大;更佳90%或更大;更佳95%或更大;更佳98%或更大;更佳99%或更大。
在本發明之方法中,使溶液A與所述批樹脂珠粒接觸。可使用使溶液A與樹脂珠粒接觸之任何方法。舉例而言,可將樹脂珠粒及溶液A放入內部體積大於溶液A與所述批樹脂珠粒之混合物之體積的容器中。在此實例中,可對溶液A與樹脂珠粒之混合物,例如藉由攪拌,進行機械攪動歷時接觸時間。
在一較佳實施例中,使用具有入口、出口及能容納所述批樹脂珠粒之體積之容器(本文中「管柱」)。管柱經組態以將樹脂珠粒截留在管柱內,而液體經由入口進入管柱穿過含有樹脂珠粒之體積且經由出口離開管柱。可使用溶液A作為所述液體,且設想當溶液A穿過含有樹脂珠粒之體積時溶液A將與樹脂珠粒接觸。
在使溶液A與所述批樹脂珠粒接觸之後,較佳溶液A隨後與所述批樹脂珠粒分離。在涉及攪拌較大體積之樹脂珠粒與溶液A之混合物之實施例中,分離可藉由過濾或離心完成。在涉及管柱之實施例中,較佳進行以下循環:將溶液A引入管柱,隨後停止向管柱引入新鮮溶液A且保持溶液A在管柱中與所述批樹脂珠粒接觸歷時接觸時間,且隨後允許其餘溶液A中之一些或全部例如藉由重力離開管柱。此循環較佳進行兩次或更多次,每一次均使用新鮮溶液A。
較佳接觸時間係10分鐘或更多;更佳20分鐘或更多;更佳30分鐘或更多。較佳,當溶液A與所述批樹脂珠粒接觸時,溫度係20℃至95℃。
與所述批樹脂珠粒接觸之溶液A之總體積比所述批樹脂珠粒之體積(本文中「床體積」或「BV」)之比率係1:1或更高;更佳2:1或更高。與所述批樹脂珠粒接觸之溶液A之總體積比所述批樹脂珠粒之床體積之比率係10:1或更低;更佳7:1或更低;更佳4:1或更低。
較佳,在所述批樹脂珠粒已與溶液A接觸且隨後與溶液A分離之後,使所述批樹脂珠粒隨後與溶液B接觸。較佳,溶液B中之水之量,基於溶液B之重量按重量計,係98%或更大;更佳99%或更大;更佳99.5%或更大。較佳溶液B係去離子水。較佳,溶液B在25℃下之電導率係20微西門子/公分或更小。較佳,溶液B之pH係6至8;更佳6.5至7.5。
較佳,所述批樹脂珠粒不與任何含有基於溶液之重量按重量計0.1%或更大之濃度之溶解的無機鹼的溶液接觸。較佳,所述批樹脂珠粒不與任何含有基於溶液之重量按重量計0.1%或更大之濃度之溶解的強酸的溶液接觸。
設想本發明之清潔過程在製造樹脂珠粒之過程完成之後進行。舉例而言,具有所連接之磺酸基之樹脂珠粒可藉由包含製備苯乙烯/二乙烯基苯共聚物之珠粒之製程來製造。可使彼等共聚物珠粒與硫酸溶液接觸以引起使磺酸基連接至共聚物之化學反應。如此與硫酸溶液之接觸在本文中被認為係製造過程之一部分而非本發明之清潔過程中之步驟。類似地,用於製造所述批樹脂珠粒之其他製程及溶液在本文中被認為係製造過程中之步驟而非本發明之清潔過程中之步驟。
在已經本發明之方法清潔之後所述批樹脂珠粒之一個適合用途係作為用於製備BPA之催化劑。有時,在樹脂珠粒已經洗滌之後,在樹脂珠粒上沈積促進劑以提高其作為催化劑之效力。典型促進劑具有巰基,且除了巰基之外許多促進劑還具有諸如胺基之活性團以結合於催化劑樹脂。常用促進劑係2,2-二甲基噻唑啶(「DMT」),其可在使用期間轉化為半胱胺。促進劑典型地藉由以下沈積於樹脂珠粒上:在溶劑中溶解促進劑以形成溶液,使所述溶液與樹脂珠粒接觸一段時間,且隨後移除溶液,留下促進劑中之一些沈積在樹脂上。如此在一批樹脂珠粒上沈積促進劑之過程被認為係獨立於本發明之洗滌過程之外之操作。
在製備BPA期間,將使樹脂珠粒與含有丙酮比酚之莫耳比為1:1至1:15之丙酮及酚的反應物溶液接觸。較佳地,在與此類反應物溶液接觸之前,所述批樹脂珠粒不與任何含有基於溶液之重量按重量計20%至100%之有機化合物之總量的溶液接觸。
以下係本發明之實例。
材料及縮寫如下使用: 樹脂1 = AMBERLYSTTM
131樹脂(陶氏化學公司(The Dow Chemical Company)),磺酸官能樹脂珠粒,氫型,1.35 eq/L酸位點,調和平均尺寸700至800 µm,均勻係數≤1.15。 TEA =三乙醇胺 DIW =去離子水,電導率≤1微西門子/公分 RT =室溫,大約23℃ TOC =總有機碳 µs =微西門子
如下對樹脂樣品進行「振盪測試」。將一個重量份之樹脂與3個重量份之DIW混合且振盪20分鐘。自所得混合物中濾出樹脂,且在室溫下測試剩餘溶液之TOC、pH及電導率。使用pH計量測pH。使用量程擴大的電導率儀(Expanded Range Conductivity Meter)#23226-523(VWR International)量測電導率。使用Sievers 900攜帶型總有機碳分析儀(GE Water & Process Technologies Analytical Instruments)量測TOC。
實例1:胺化合物之濃度
如下完成樹脂之洗滌。垂直安裝配備循環水加熱夾套之有玻璃層析管柱。夾套中之水循環且升溫至75℃。隨後將100 mL樹脂裝載入管柱中(亦即,床體積「BV」=100 mL)。隨後5 BV之測試洗滌溶液以1.2 BV/小時穿過管柱。隨後加熱夾套降至室溫,且1.4 BV之DIW以4 BV/小時穿過管柱。將樹脂虹吸乾燥且於玻璃瓶中儲存7天,且隨後藉由振盪測試來測試。
製備五份於去離子水中之TEA的測試洗滌溶液。濃度,按重量計,係0.2%、1%、2%、3%及5%。結果如下: 表1-胺化合物之濃度
電導率及pH結果顯示,TEA之濃度愈高結果愈好。TOC結果顯示,1%至2%TEA最佳。
實例2:較長期儲存
如下完成樹脂之洗滌。垂直安裝配備循環水加熱夾套之有玻璃層析管柱。夾套中之水循環且升溫至測試溫度(「溫度」)(室溫或90℃)。隨後將100 mL樹脂裝載入管柱中(亦即,床體積「BV」=100 mL)。隨後在管柱上裝載1.2 BV之「測試洗滌」溶液(DIW或溶解於DIW中之按重量計1.5%之TEA)且保持30分鐘。隨後自管柱排出測試洗滌溶液。隨後將加熱夾套設置為室溫,且1.4 BV之DIW以4 BV/小時穿過管柱。將樹脂虹吸乾燥且於玻璃瓶中儲存13天或60天,且隨後藉由振盪測試來測試。結果如下: 表2:儲存13天後之結果
表3:儲存60天後之結果
針對給定儲存持續時間及測試溫度,在每一情況中經TEA洗滌之樣品比對應的經DIW洗滌之樣品具有更好的電導率、更好的pH及更好的TOC。
另外,藉由眼睛觀察表3中之樣品。兩個經TEA洗滌之樣品相比於經DIW洗滌之樣品顏色明顯較淺。
實例3:用於BPA製備之催化劑
如下完成樹脂之洗滌。垂直安裝配備循環水加熱夾套之有玻璃層析管柱。夾套中之水循環且升溫至測試溫度(室溫或90℃)。隨後將100 mL樹脂裝載入管柱中(亦即,床體積「BV」=100 mL)。隨後在管柱上裝載1.2 BV之「測試洗滌」溶液(DIW或溶解於DIW中之按重量計1.5%之TEA)且保持40分鐘,且自管柱排出測試洗滌溶液。隨後將新鮮的相同類型之1.2 BV之測試洗滌溶液裝載在管柱上且保持40分鐘,且自管柱排出測試洗滌溶液。隨後自加熱夾套排出經加熱之水,使管柱降至室溫,且1.4 BV之DIW以4 BV/小時穿過管柱。
為提高作為催化劑之效能,將樹脂如下裝載「促進劑」2,2-二甲基噻唑啶(「DMT」)。經洗滌樹脂置於具有充足DIW之圓底燒瓶中形成漿液。將1.71 g DMT溶解於10 mL DIW中形成溶液,且在攪拌下將溶液逐滴加入漿液中。攪拌持續1小時。藉由過濾移除液體,且將樹脂返回至管柱。隨後將樹脂用5 BV之DIW以2 BV/小時洗滌。將樹脂轉移至管柱之外,藉由真空移除表面水,且將樹脂封裝於塑膠瓶中。
如下進行製備BPA之反應。在90℃下將樹脂乾燥隔夜。在於70℃水浴中之圓底燒瓶中,將3 g乾燥樹脂以及28.8 g酚置於燒瓶中。在攪拌1小時之後,向燒瓶中迅速添加1.2 g丙酮。在0.5小時、1小時、2小時、3小時及4小時之後取樣液體反應混合物且藉由氣相層析針對丙酮含量及BPA含量進行分析。
如下評估轉化率及選擇性: 轉化率= 100 X (PI - PF) / PI 選擇性= 100 X B / (PI - PF) 其中PI=丙酮之初始莫耳數,PF=丙酮之最終莫耳數,且B=所產生之對,對-BPA(para-,para-BPA)之莫耳數。
另外,在反應結束時藉由眼睛檢查燒瓶中之溶液。DIW樣品最暗;在90℃下之TEA溶液中洗滌之樣品明顯較淺,且在室溫下之TEA溶液洗滌之樣品更淺。
Claims (7)
- 一種清潔一批樹脂珠粒之方法,其中所述方法包括使所述批樹脂珠粒與水溶液接觸,其中所述水溶液包括一或多種溶解的胺化合物,其中所述批樹脂珠粒包括聚合物,所述聚合物包括所連接之羧酸基或磺酸基或其混合物。
- 如申請專利範圍第2項所述的方法,其中R1 另外包括一個或多個氧原子、一個或多個氮原子或其組合。
- 如申請專利範圍第1項所述的方法,其中所述胺化合物存在於所述水溶液中之濃度以所述水溶液之重量計為0.1重量%至6重量%。
- 如申請專利範圍第1項所述的方法,其中所述胺化合物之共軛酸之pKa為6至10。
- 如申請專利範圍第1項所述的方法,其中所述聚合物包括所連接之磺酸基。
- 如申請專利範圍第1項所述的方法,其中所述批樹脂珠粒包括凝膠樹脂珠粒。
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