TW201323086A - 樹脂載持觸媒及樹脂載持觸媒之製造方法 - Google Patents
樹脂載持觸媒及樹脂載持觸媒之製造方法 Download PDFInfo
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- TW201323086A TW201323086A TW101131499A TW101131499A TW201323086A TW 201323086 A TW201323086 A TW 201323086A TW 101131499 A TW101131499 A TW 101131499A TW 101131499 A TW101131499 A TW 101131499A TW 201323086 A TW201323086 A TW 201323086A
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- resin
- catalyst
- thermosetting resin
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Abstract
本發明係一種樹脂載持觸媒,其含有熱硬化性樹脂之硬化體、及載持於上述硬化體表面之具有觸媒活性的微粒子,且上述熱硬化性樹脂具有酚性羥基。
Description
本發明係關於一種樹脂載持觸媒及樹脂載持觸媒之製造方法。
將觸媒載持於載體上而使用之情形時,可自反應後之複雜之系統容易地將觸媒與反應產物分離。因此,載持於載體上之觸媒(以下稱為載持觸媒)容易回收或再使用,尤其是於將昂貴之貴金屬用作觸媒之情形時成為有效之手段(例如參照專利文獻1及2)。
專利文獻1:日本特開2000-140643號公報
專利文獻2:日本特開2010-22980號公報
非專利文獻1:室井高城著,「工業貴金屬觸媒-實用金屬觸媒之實際與反應-」,JETI股份有限公司發行,2003年5月26日初版,P.6-7
非專利文獻2:觸媒學會編,「觸媒便覽」,講談社股份有限公司發行,2008年12月10日第1刷,P.309-311
然而,於載持觸媒中,觸媒與載體之結合力並不一定強。因此,存在使用時觸媒自載體脫離,脫離後之觸媒彼此凝聚的情形。於此情形時,由於重複使用載持觸媒而觸媒活性逐漸降低。
作為抑制由於重複使用而導致的載持觸媒之活性劣化的方法,例如有專利文獻1記載之方法。於專利文獻1中,
藉由將熱硬化性樹脂與由金屬或金屬化合物所構成之觸媒或其前驅物的混合物於非氧化性環境中加熱至500℃以上使熱硬化性樹脂碳化,而將該金屬或金屬化合物載持於碳化物。將熱硬化性樹脂之硬化體碳化之情形時,硬化體雖縮小但保持其形狀而碳化。另一方面,由金屬或金屬化合物所構成之觸媒在熱硬化性樹脂碳化之條件下大多較為穩定。因此,將觸媒等混合於熱硬化性樹脂中之後,使熱硬化性樹脂硬化且碳化,藉此獲得牢固地固定有觸媒物質之碳材料。
又,於專利文獻2中記載有如下技術:於球狀之樹脂粒子表面載持具有觸媒活性之微粒子,且以覆蓋該球狀之樹脂粒子之方式,形成由熱硬化性樹脂所構成之特定厚度的被覆層。藉由如此般設置由熱硬化性樹脂所構成之被覆層,可抑制使用時具有觸媒活性之微粒子脫離,且使得使用後容易自反應產物等分離、回收。
專利文獻1及2中記載之載持觸媒之載體彼此有可能凝聚。於載體彼此凝聚之情形時,反應物難以與觸媒接觸,故反應效率降低。即,單位載體之活性減少。
然而,如專利文獻1所述般,藉由對熱硬化性樹脂與觸媒或其前驅物的混合物加熱使熱硬化性樹脂碳化,而將觸媒載持於碳化物時,觸媒會滲入至碳化物之內部。一般而言,觸媒反應係於反應物可到達之觸媒表面進行。因此,滲入至碳化物之內部、尤其是反應物不易到達之部位的觸媒微粒子與反應物之接觸效率較低,因此難以用於觸媒反
應。關於此點,本案發明人等發現藉由提昇觸媒之反應效率,可提昇觸媒活性。
又,如專利文獻2所述般利用由熱硬化性樹脂所構成之被覆層覆蓋觸媒之情形時,被覆層會阻礙觸媒與反應物之接觸。因此,專利文獻2所記載之觸媒中存在難以與反應物接觸之部位,故而尚有提高與反應物之接觸效率的餘地。關於此點,本案發明人等發現藉由提昇觸媒之反應效率,可提昇觸媒活性。
本發明係鑒於上述情況而完成者,本發明提供一種重複特性及利用效率優異之樹脂載持觸媒。
本發明人等針對將熱硬化性樹脂之硬化體用作觸媒載體的樹脂載持觸媒,對於提昇觸媒之重複特性及利用效率反覆努力研究,結果發現,將具有酚性羥基之熱硬化性樹脂的硬化體用作觸媒載持用之載體之情形時,可抑制觸媒微粒子自載體脫離,因此可獲得觸媒之利用效率優異之載持觸媒,從而完成本發明。
根據本發明,可提供一種樹脂載持觸媒,其含有:熱硬化性樹脂之硬化體、及載持於上述硬化體表面之具有觸媒活性的微粒子;且上述熱硬化性樹脂具有酚性羥基。
進而,根據本發明,可提供一種樹脂載持觸媒之製造方法,其包括:硬化步驟:使具有酚性羥基的熱硬化性樹脂硬化;及載持步驟:於上述硬化步驟中所獲得之硬化體的表面
載持具有觸媒活性之微粒子。
根據本發明,可提供一種觸媒之重複特性及利用效率優異之樹脂載持觸媒。
以下,列舉具體例對本發明之樹脂載持觸媒及其製造方法之實施形態進行說明。
本實施形態之樹脂載持觸媒含有:具有酚性羥基之熱硬化性樹脂之硬化體、及載持於該熱硬化性樹脂之硬化體之表面且具有觸媒活性的微粒子(以下亦稱為「觸媒微粒子」)。
(第1實施形態)
本實施形態之樹脂載持觸媒中,觸媒微粒子載持於熱硬化性樹脂之硬化體的表面,故而反應物容易到達觸媒微粒子。因此,觸媒之利用效率優異。
又,本實施形態之樹脂載持觸媒之觸媒的重複特性優異。其理由尚不明確,但可認為如下。本實施形態之樹脂載持觸媒中,載體係使用表面具有酚性羥基的熱硬化性樹脂之硬化體。而且,可認為係藉由觸媒載體中存在的酚性羥基進行載持。藉此,與先前之載持觸媒相比,觸媒微粒子得以更牢固地載持。因此,觸媒微粒子變得不易自作為觸媒載體的熱硬化性樹脂之硬化體脫離,觸媒之重複特性及利用效率提昇。
又,於本實施形態之樹脂載持觸媒中,如上所述,觸媒微粒子係由分散存在於作為觸媒載體的熱硬化性樹脂之
硬化體中的酚性羥基所載持。如此,可認為本實施形態之樹脂載持觸媒中,觸媒微粒子由於係由酚性羥基所載持,故而與先前之載持觸媒相比更均勻地分散於觸媒載體上。因此,利用時觸媒微粒子不易產生凝聚,觸媒之重複特性及利用效率提昇。
<熱硬化性樹脂之硬化體>
熱硬化性樹脂之硬化體於本實施形態中係作為觸媒載體而使用。熱硬化性樹脂之硬化體例如可形成為粒子狀、膜狀、均勻之層狀。作為硬化處理前之熱硬化性樹脂,只要為具有酚性羥基之熱硬化性樹脂則無特別限定,較佳為含有酚樹脂或其衍生物。
本實施形態中之熱硬化性樹脂之硬化體中,較佳為熱硬化性樹脂之酚性羥基當量為30 g/eq以上,更佳為35 g/eq以上。若熱硬化性樹脂之酚性羥基當量為上述下限值以上,則可獲得表面具有羥基之硬化體,可抑制利用時觸媒脫離。
又,本實施形態之熱硬化性樹脂之硬化體中,熱硬化性樹脂的酚性羥基當量為500 g/eq以下,較佳為400 g/eq以下,更佳為350 g/eq以下。藉由使熱硬化性樹脂之酚性羥基當量在該範圍內,可提供具有優異之觸媒活性的樹脂載持觸媒。又,於熱硬化性樹脂之酚性羥基當量為上述上限值以下之情形時,硬化體表面之酚性羥基增多,觸媒之保持力可得以維持而不會減弱。又,酚性羥基當量可藉由乙醯化法等眾所周知的方法而定量。
本實施形態中之酚樹脂係使酚類與醛類於鹼性或酸性觸媒之存在下進行反應而得者,其分子中具有至少1個以上之酚性羥基。
例如,可列舉:苯酚樹脂、甲酚樹脂、間苯二酚樹脂、二甲苯酚樹脂、萘酚樹脂、雙酚A樹脂、芳烷基苯酚樹脂、聯苯基芳烷基苯酚樹脂、及利用具有酚性羥基之腰果油等所得的改質酚樹脂等。又,亦可使用含有具有酚性羥基之物質的二甲苯改質酚樹脂,以及以酚類與松香、萜烯油等改質之油改質酚樹脂,以橡膠改質之橡膠改質酚樹脂等各種改質酚樹脂。
作為用以獲得上述酚樹脂之酚類,較佳為分子中具有酚性羥基者,亦可進而具有酚性羥基以外之取代基。例如可列舉:苯酚,鄰甲酚、間甲酚、對甲酚等甲酚,混合有該等之混合甲酚;2,3-二甲苯酚、2,4-二甲苯酚、2,5-二甲苯酚、2,6-二甲苯酚、3,4-二甲苯酚、3,5-二甲苯酚等二甲苯酚;鄰乙基苯酚、間乙基苯酚、對乙基苯酚等乙基苯酚,異丙基苯酚,丁基苯酚、對三級丁基苯酚等丁基苯酚,對三級戊基苯酚、對辛基苯酚、對壬基苯酚、對異丙苯基苯酚等烷基苯酚;氟苯酚、氯苯酚、溴苯酚、碘苯酚等鹵化苯酚;對苯基苯酚、胺基苯酚、硝基苯酚、二硝基苯酚、三硝基苯酚等一元苯酚取代體,及1-萘酚、2-萘酚等一元萘酚;間苯二酚、烷基間苯二酚、鄰苯三酚、鄰苯二酚、烷基鄰苯二酚、對苯二酚、烷基對苯二酚、間苯三酚、雙酚A、雙酚F、雙酚E、雙酚S、二羥基萘等多元
酚類;由具有酚性羥基之物質所構成之腰果油等。可將該等單獨使用或組合兩種以上而使用。又,亦可使用該等具有酚性羥基之酚類與其他不含酚性羥基之物質的共聚物。藉此,可獲得分子中含有至少1個以上酚性羥基的酚樹脂。
又,作為用以獲得上述酚樹脂之醛類,例如可列舉:甲醛、三聚甲醛、三烷、乙醛、丙醛、聚甲醛、三氯乙醛、六亞甲四胺、糠醛、乙二醛、正丁醛、己醛、丙烯醛(allyl aldehyde)、苯甲醛、巴豆醛、丙烯醛(acrolein)、四甲醛、苯乙醛、鄰甲苯甲醛、柳醛、對苯二甲基二甲醚等。可將該等單獨使用或組合兩種以上而使用。
作為使上述酚類與醛類反應之方法,並無特別之限定,可採用眾所周知的方法。
作為獲得上述酚樹脂時之觸媒,並無特別之限定,可列舉酸觸媒、鹼觸媒、過渡金屬鹽觸媒等。作為酸觸媒,例如可使用鹽酸、硫酸、磷酸類等無機酸,草酸、對甲苯磺酸、有機膦酸等有機酸。又,作為鹼觸媒,例如可使用氫氧化鈉、氫氧化鉀、氫氧化鋰等鹼金屬氫氧化物,氫氧化鈣、氫氧化鋇等鹼土金屬氫氧化物,氨、烷基胺等胺類。進而作為過渡金屬鹽觸媒,可列舉草酸鋅、乙酸鋅等。
本實施形態之樹脂載持觸媒利用BET法所得之比表面積較佳為300 m2/g以下,特佳為200 m2/g以下。若比表面積為上述上限值以下,則可抑制滲入至熱硬化性樹脂之硬化體內部的觸媒微粒子之量。因此,可使觸媒之利用效率更進一步提昇。
又,本實施形態中之熱硬化性樹脂之硬化體的形狀並無特別之限定。可列舉固形、粉末狀、球狀,可以任一種形態而使用。或者,亦可於將熱硬化性樹脂與有機物或無機物之填料混合且成形後進行硬化處理,亦可於將其含浸於其他基材中後進行硬化處理。
<觸媒微粒子>
作為本實施形態中之熱硬化性樹脂之硬化體表面所載持的觸媒微粒子,只要為具有觸媒活性者,則可為金屬、金屬氧化物及金屬化合物中之任一種,並無特別之限定。例如可列舉由選自下述者中之至少一種所構成者:鈦、鉻、鈷、鎳、銅、釕、銠、鈀、錸、鋨、鉑、鐵、鋅、錳、鎂、鈣、銀、釩、錫等金屬及其氧化物,其他有機鈦等金屬化合物及錯合物等。又,亦可使用含有該等中之至少兩種以上的複合體。該等之中,尤其適合使用鈀或鉑。
觸媒微粒子之平均粒徑較佳為1μm以下。藉此,可提供具有更優異之觸媒活性的樹脂載持觸媒。又,亦可使用平均粒徑為1 nm以上100 nm以下之奈米級之金屬微粒子等。基材及熱硬化性樹脂之硬化體與觸媒微粒子之質量比可適當決定,例如熱硬化性樹脂之硬化體:觸媒微粒子=1:1~10000:1左右。
以下,對本實施形態之樹脂載持觸媒之製造方法進行說明。
本實施形態之製造方法包括:使具有酚性羥基之熱硬化性樹脂硬化,藉此製造作為觸媒載體之硬化體的步驟;
及於作為觸媒載體之硬化體之表面載持觸媒微粒子的步驟。於本實施形態之製造方法中,較佳為於獲得作為觸媒載體的熱硬化性樹脂之硬化體之後載持觸媒微粒子。藉此,可防止將觸媒微粒子埋入於作為觸媒載體的熱硬化性樹脂之硬化體之內部。因此,可使樹脂載持觸媒之重複特性及利用效率提昇。
首先,就對熱硬化性樹脂進行硬化處理之方法進行說明。
本實施形態中之熱硬化性樹脂之硬化處理方法並無特別之限定,可採用眾所周知的方法。
於使用可溶酚醛樹脂型酚樹脂作為熱硬化性樹脂之情形時,可藉由加熱而使其硬化。或者,可列舉下述方法:混合對甲苯磺酸、苯酚磺酸等酸類,藉由常溫或加熱而使其硬化。
又,於使用酚醛清漆型酚樹脂作為酚樹脂之情形時,可列舉以下等方法:將六亞甲四胺等硬化劑與添加化合物一起混合,加熱而進行硬化;將環氧樹脂、聚異氰酸酯、三聚氰胺樹脂等熱硬化性樹脂與添加化合物一起混合,藉由加熱而進行硬化。
本實施形態中之熱硬化性樹脂之硬化處理溫度並無特別之限定,較佳為250℃以下。若硬化溫度為上述上限值以下,則可獲得經濟之硬化速度,且可抑制酚樹脂之主鏈分解。
<觸媒微粒子之載持方法>
對向本實施形態中之熱硬化性樹脂之硬化體上載持上述觸媒微粒子之方法進行詳細說明。於本實施形態中,較佳為於製作熱硬化性樹脂之硬化體之後,於該硬化體之表面載持觸媒微粒子。藉此,可抑制觸媒微粒子滲入至硬化體之內部。
對於本實施形態而言,熱硬化性樹脂之硬化體上之觸媒微粒子之載持並無特別之限定,可採用眾所周知的方法。例如有如下方法:將熱硬化性樹脂之硬化體與成為觸媒的金屬化合物之膠體溶液混合,將金屬化合物還原後,進行固液分離且乾燥。
再者,亦可將藉由本實施形態而獲得之樹脂載持觸媒形成於基材表面。以下,將於基材表面形成樹脂載持觸媒之觸媒稱為「基材載持觸媒」而進行說明。
<基材載持觸媒>
本實施形態之基材載持觸媒為片狀或板狀,因此可配合反應裝置之形狀而變形為各種形狀。觸媒片材之形狀例如可配合反應裝置中之反應管的形狀而變形為摺疊之狀態、卷團之狀態等各種形狀。於片狀之樹脂載持觸媒中設置有連通孔之情形時,亦可作為觸媒過濾器而使用。
<基材>
其次,基材之形狀並無特別之限定,例如可使用粒子狀、片狀或板狀。於該等之中,較佳為片狀或板狀。
又,基材較佳為多孔體或形成有網目結構者,尤其是形成有網目結構者更佳。藉此,可增大表面積,可使更多
之熱硬化性樹脂之硬化體形成於基材表面上作為觸媒載體。因此,可載持更多觸媒微粒子。故而,可使基材載持觸媒中之反應場增大,可提昇反應活性。此處,所謂多孔體,可為具有複數個凸凹者,亦可為設置有複數個自表面至背面連通之孔(以下表示為連通孔)者。
進而,本實施形態之基材更佳為具有網目結構之板狀。藉此,可使觸媒微粒子與反應物之接觸效率明顯提昇。即,可提昇反應活性,可提供具有更優異之觸媒活性的基材載持觸媒。
又,藉由使用具有網目結構之板狀之基材,亦可對形成反應場之觸媒微粒子始終供給未反應之反應物。於反應裝置利用使用液體或氧體反應物的流通式反應槽之情形時,此點對於反應效率之提昇非常有效。如此,由於可對觸媒微粒子始終供給未反應之反應物,因此可提昇觸媒微粒子之活性。
再者,於基材為設置有連通孔者之情形時,該連通孔亦可形成蜂窩結構。於此情形時,可提昇基材本身之機械強度。又,亦可使觸媒微粒子均勻且高密度地分散。
本實施形態之基材可為化學結構中包含羰基、醯亞胺基及羥基等極性官能基之化合物或高分子,亦可為不含極性官能基之化合物或高分子。作為包含極性官能基之化合物或高分子,例如可使用:纖維素、聚胺甲酸酯、聚醯胺、及聚酯等。作為不含極性官能基之化合物或高分子,例如可使用:聚乙烯、聚丙烯、聚甲基戊烯、聚丁烯、聚丁二
烯、聚苯乙烯、聚異丁烯、聚四氟乙烯等氟樹脂、天然橡膠、苯乙烯丁二烯橡膠及丁基橡膠等。
<於基材之表面形成熱硬化性樹脂之硬化體的方法>
於本實施形態中,於基材之表面形成熱硬化性樹脂之硬化體的方法可根據基材之形狀而選擇適當方法。例如,於基材為網狀之情形時,可使用將固形或粉末樹脂之溶液或液狀樹脂含浸於基材中且硬化之方法,將固形或粉末樹脂加熱熔融後含浸於基材中且硬化之方法等。相對於此,於基材為粒子狀之情形時,可使用塗佈熱硬化性樹脂之硬化體的方法等。藉此,可於基材上均勻地形成熱硬化性樹脂之硬化體。
(第2實施形態)
本實施形態係關於第1實施形態中所使用之觸媒微粒子之具體製造方法。
要使微粒子表現觸媒活性之情形時,需要在載持於觸媒載體上之前預先還原。先前,於獲得具有觸媒活性之觸媒微粒子之情形時,一直採用使用還原劑預先將觸媒微粒子還原之方法(非專利文獻1及2)。作為此時所使用之還原劑,例如可列舉選自由氫、一氧化碳、醛類、羧酸類、胺類、金屬氫化物、及肼所組成之群中的還原劑。
然而,使用還原劑預先將觸媒微粒子還原之方法就觸媒微粒子凝聚之觀點而言並不充分。
另一方面,於本實施形態中,並非藉由還原劑而是藉由酚性羥基將觸媒微粒子還原,可製造重複特性及利用效
率優異之樹脂載持觸媒。如此,藉由利用酚性羥基將觸媒微粒子還原,可防止觸媒微粒子凝聚。即,於藉由酚性羥基將觸媒微粒子還原之情形時,可對作為觸媒載體的熱硬化性樹脂之硬化體表面均勻地載持觸媒微粒子。因此,可使反應效率提昇,可製造重複特性及利用效率優異之樹脂載持觸媒。
再者,藉由酚性羥基將觸媒微粒子還原時,只要對形成觸媒微粒子之材料不顯示還原作用,且為不阻礙由酚性羥基所引起的觸媒微粒子之還原反應的程度,則亦可將上述還原劑含於觸媒載持反應溶液中。具體而言,於觸媒載持反應溶液中,可相對於形成觸媒微粒子之材料1 mol含有上述還原劑0 mol以上10 mol以下,更佳為0 mol以上5 mol以下。藉此,可於具有酚性羥基之熱硬化性樹脂之表面將觸媒微粒子還原。因此,可將觸媒微粒子均勻且微細地載持於熱硬化性樹脂之硬化體之表面。因此,可獲得重複特性及利用效率優異之樹脂載持觸媒。
又,最佳為於觸媒載持反應溶液中不含上述還原劑。藉此,與藉由先前之方法而獲得之樹脂載持觸媒相比,所載持之觸媒微粒子不易產生凝聚。因此,與藉由先前之方法而獲得之樹脂載持觸媒相比,藉由本實施形態之方法而獲得之樹脂載持觸媒之重複特性及利用效率顯著優異。其理由尚不明確,但可認為如下:根據本實施形態之製造方法,由於還原觸媒微粒子時的觸媒載持反應溶液中不含阻礙觸媒微粒子分散的上述還原劑分子,故而得以將觸媒微
粒子均勻且微細地分散於熱硬化性樹脂之硬化體之表面。因此,可認為本實施形態之樹脂載持觸媒與先前之樹脂載持觸媒相比,觸媒微粒子更牢固地載持於熱硬化性樹脂之硬化體之表面。
以下,對本實施形態與先前之樹脂載持觸媒之製造方法的差異更詳細地進行說明。
如上所述,於先前之樹脂載持觸媒之製造方法中,係使用還原劑預先將觸媒微粒子還原。作為此處所用之還原劑,例如可列舉:氫、一氧化碳、甲醛等醛類、甲酸或草酸等羧酸類、三乙胺等胺類、硼氫化鈉或氫化鋁鋰等金屬氫化物、及肼。
如先前之樹脂載持觸媒之製造方法般使用還原劑將觸媒微粒子還原之情形時,可以下述所說明之順序將觸媒微粒子載持於觸媒載體上。首先,使用還原劑預先將觸媒微粒子還原。其次,對觸媒載體載持藉由還原劑而還原且析出之觸媒微粒子。即,於先前之樹脂載持觸媒之製造方法中,係使將觸媒微粒子還原而析出之觸媒微粒子分散於溶液中之後,對觸媒載體載持觸媒微粒子。
另一方面,於本實施形態之樹脂載持觸媒之製造方法中,係藉由酚性羥基將觸媒微粒子還原。具體而言,係於具有酚性羥基之熱硬化性樹脂表面進行觸媒微粒子之還原。即,於本實施形態之樹脂載持觸媒之製造方法中,係使觸媒微粒子與作為觸媒載體的熱硬化性樹脂之硬化體接觸之後,將觸媒微粒子還原而使其析出。根據該樹脂載持
觸媒之製造方法,可對觸媒載體均勻且微細地載持觸媒微粒子。藉此,可製造重複特性及利用效率優異之樹脂載持觸媒。其理由尚不明確,但可認為係由於經還原之觸媒微粒子之析出、與析出之觸媒微粒子於觸媒載體上之載持大致同時發生之緣故。即,可認為與先前之樹脂載持觸媒之製造方法相比,可無須使所析出之觸媒微粒子分散於溶劑中而將觸媒微粒子載持於觸媒載體上,因此可高度抑制觸媒微粒子之凝聚。
本實施形態之觸媒微粒子之載持方法中,係於液相中藉由酚性羥基將觸媒微粒子還原,且載持於具有酚性羥基之觸媒載體上。於藉由酚性羥基將觸媒微粒子還原時,較佳為不添加上述還原劑。藉此,可於具有酚性羥基之熱硬化性樹脂之表面將觸媒微粒子還原。因此,可將觸媒微粒子均勻且微細地載持於熱硬化性樹脂之硬化體的表面。
又,於本實施形態中,作為熱硬化性樹脂之硬化體、觸媒微粒子、基材載持觸媒、基材及於基材之表面形成熱硬化性樹脂之硬化體的方法,亦可使用與第1實施形態中之記載相同者。
以上對本發明之實施形態進行了敍述,但該等係本發明之示例,本發明亦可採用上述以外之各種構成。
[實施例]
以下,藉由實施例及比較例而說明本發明,但本發明並不僅限定於該等。
<實施例A>
(實施例A1)
(酚樹脂之硬化體的製作)
於包含攪拌裝置、回流冷卻器及溫度計之5 L之圓筒形可分離式燒瓶中,加入苯酚1300份、43%甲醛水溶液1600份、水800份、三乙胺30份及作為懸浮劑之聚乙烯醇(Kuraray Poval PVA117,皂化度98%,聚合度1700)30份,於100℃下加熱3小時而合成球狀酚樹脂硬化體。再者,於反應經過1小時之時採集反應物,進行冷凍乾燥,藉由乙醯化法測定酚性羥基當量,結果酚性羥基當量為115 g/eq。對所合成之球狀酚樹脂硬化體進行固液分離,於150℃下進行乾燥,獲得平均粒徑為100μm的球狀酚樹脂硬化體。
(樹脂載持觸媒之製備)
摻合乙酸鈀(和光純藥工業公司製造)5 mg、作為觸媒載體之上述球狀酚樹脂硬化體500 mg、三乙胺(和光純藥工業公司製造)0.15 mL、乙腈(和光純藥工業公司製造)5 mL,於封管中在100℃下加熱12小時。繼而,將分散液過濾之後,洗淨過濾物並進行乾燥,藉此獲得表面載持有鈀粒子之樹脂載持觸媒。樹脂載持觸媒中之鈀觸媒的載持量為1 wt%。又,該樹脂載持觸媒之比表面積為10 m2/g以下。再者,鈀觸媒之載持量係利用市售的原子吸收分光光度計而測定,比表面積係藉由氮氣、BET3點法而測定。
(實施例A2)
於市售之可溶酚醛樹脂型酚樹脂(Sumitomo Bakelite公司製造,Sumiliteresin(r)PR-50087,酚性羥基當量為130
g/eq)50份中混合甲基乙基酮50份,將其含浸於濾紙(ADVANTEC(r)No.590)中,於180℃下乾燥1小時,獲得酚樹脂硬化體(酚樹脂成分為50 wt%)。進而,利用與實施例A1相同之方法而獲得樹脂載持觸媒。該樹脂載持觸媒之鈀觸媒的載持量為1 wt%,比表面積為20 m2/g。
(實施例A3)
除將市售之酚醛清漆型酚樹脂(Sumitomo Bakelite公司製造,Sumiliteresin(r)PR-310,酚性羥基當量為105 g/eq)30份作為酚樹脂而溶解於甲基乙基酮70份中之外,利用與實施例A2相同之方法獲得樹脂載持觸媒(觸媒載體中之酚樹脂成分為50 wt%)。該樹脂載持觸媒之鈀觸媒的載持量為1 wt%,比表面積為25 m2/g。
(比較例A1)
將實施例A1中所獲得之球狀酚樹脂硬化體於市售之碳化活化爐中、氮氣氣流下及空氣氣流下,於900℃下進行碳化活化。進而,利用與實施例A1相同之方法而獲得樹脂活性碳載持觸媒。該樹脂活性碳載持觸媒之鈀觸媒的載持量為1 wt%、比表面積為950 m2/g。
(比較例A2)
將以不具有酚性羥基的熱硬化性樹脂之硬化體作為觸媒載體的市售之鈀-脲樹脂(和光純藥工業公司製造,Pd EnCat 30)作為比較例A2。該鈀-脲樹脂之鈀觸媒的載持量為4.2 wt%,比表面積為10 m2/g以下。
(比較例A3)
將市售之鈀-活性碳(和光純藥工業公司製造,鈀-活性碳)作為比較例A3。該鈀-活性碳之鈀觸媒的載持量為5 wt%,比表面積為650 m2/g。
(評價試驗)
根據與碘苯、丙烯酸甲酯進行赫克反應(Heck reaction)所獲得的反式肉桂酸甲酯之反應產率而評價載持觸媒之觸媒活性。
將碘苯23μL(0.20 mmol)、丙烯酸甲酯23μL(0.25 mmol)、三乙胺35μL(0.25 mmol)溶解於乙腈(2 mL)中。於所得之溶液中添加載持觸媒50 mg。使用油浴對混合物加熱,於120℃下攪拌12小時。反應結束後,過濾載持觸媒。
將濾液減壓濃縮,利用矽膠層析法(正己烷:乙酸乙酯=5:1)純化殘渣,獲得反式肉桂酸甲酯。
再者,視需要可無須取出反式肉桂酸甲酯,而取出一定量之反應液,利用液相層析法進行分析。以下,只要無特別說明,則係由反應前後之層析圖之面積比算出反應產率。此處,反應產率係由(Co-Cf)/Co×100(%)而定義,Co為反應前之碘苯之莫耳數,Cf為反應後之碘苯之莫耳數。
(重複試驗)
反應結束後,暫時自反應液中取出載持觸媒,並將其洗淨。之後,再次作為載持觸媒而進行上述之赫克反應。將該等之赫克反應之一系列操作重複4次。
將赫克反應之反應產率的結果示於表1中。與先前之
載持觸媒相比,本實施形態之樹脂載持觸媒具有較高之反應產率。即,所載持之觸媒的利用效率優異。並且,即便重複使用,亦可維持其較高之反應產率。
<實施例B>
(實施例B1)
(酚樹脂之硬化體的製作)
於以重量比1:1混合有液態酚樹脂(Sumitomo Bakelite公司製造,Sumiliteresin PR-50087)與甲醇之酚樹脂溶液中,將片狀之聚丙烯不織布(Japan Vilene公司製造)於室溫下浸漬1分鐘,於常溫下自然乾燥30分鐘。乾燥後,於90℃下加熱30分鐘,進而於150℃下加熱30分鐘,獲得含有30重量%之酚樹脂的片狀之酚樹脂載體。
(樹脂載持觸媒之製備)
摻合乙酸鈀(和光純藥工業公司製造)10 mg、作為觸媒載體之上述酚樹脂觸媒載體1 g、及乙腈(和光純藥工業公司製造)10 mL,於封管中在100℃下加熱12小時。繼而,用鑷子將酚樹脂載體取出之後,進行洗浄並乾燥,藉此獲
得載持有鈀粒子之酚樹脂載持觸媒。酚樹脂載持觸媒中之鈀觸媒的載持量為1重量%。鈀觸媒之載持量係使用市售之原子吸收分光光度計而測定。
(實施例B2)
摻合乙酸鈀(和光純藥工業公司製造)10 mg、與實施例B1同樣製作之酚樹脂載體1 g、三乙胺(和光純藥工業公司製造,相對於乙酸鈀為5 mol)0.03 mL、乙腈(和光純藥工業公司製造)10 mL,於封管中在100℃下加熱12小時。繼而,用鑷子取出酚樹脂載體之後,進行洗淨並乾燥,藉此獲得載持有鈀粒子之酚樹脂載持觸媒。酚樹脂載持觸媒中之鈀觸媒的載持量為1重量%。
(實施例B3)
摻合乙酸鈀(和光純藥工業公司製造)10 mg、與實施例B1同樣製作之酚樹脂載體1 g、三乙胺(和光純藥工業公司製造,相對於乙酸鈀為50 mol)0.3 mL、及乙腈(和光純藥工業公司製造)10 mL,於封管中在100℃下加熱12小時。繼而,用鑷子取出酚樹脂載體之後,進行洗淨並乾燥,藉此獲得載持有鈀粒子之酚樹脂載持觸媒。酚樹脂載持觸媒中之鈀觸媒的載持量為1重量%。
(評價試驗)
根據與碘苯、丙烯酸甲酯進行赫克反應而獲得的反式肉桂酸甲酯之反應產率而評價載持觸媒之觸媒活性。
將碘苯230μL(2.0 mmol)、丙烯酸甲酯230μL(2.5 mmol)、三乙胺350μL(2.5 mmol)溶解於乙腈(20 mL)
中。於所得之溶液中添加載持觸媒500 mg。使用油浴加熱混合物,於120℃下攪拌12小時。反應結束後,用鑷子將載持觸媒取出,或藉由過濾而進行回收。
對過濾所獲得之反應液進行減壓濃縮,利用矽膠層析法(正己烷:乙酸乙酯=5:1)純化殘渣,獲得反式肉桂酸甲酯。再者,視需要可無須取出反式肉桂酸甲酯而取出一定量的反應液,利用液相層析法進行分析。以下,只要無特別之說明,則反應產率係由反應前後之層析圖的面積比而算出。此處,反應產率係由(Co-Cf)/Co×100(%)定義,Co係反應前之碘苯的莫耳數,Cf係反應後之碘苯的莫耳數。
(重複試驗)
反應結束後,自反應液回收載持觸媒並進行洗淨。之後,利用所回收之載持觸媒進行上述之赫克反應。重複該等之赫克反應之一系列操作直至反式肉桂酸甲酯的反應產率低於80%為止。將其結果示於下述表2中。
根據表2,實施例之酚樹脂載持觸媒隨著製造過程中所使用之還原劑的摻合量減少,於觸媒之重複使用方面變得優異。即,若使用實施例中記載之樹脂載持觸媒,則可無須更換觸媒而使優異之觸媒活性長時間地持續。
本發明包括以下之態樣。
[1-1]一種樹脂載持觸媒,其含有:
具有酚性羥基之熱硬化性樹脂的硬化物、及載持於上述熱硬化性樹脂之硬化物表面之具有觸媒活性的微粒子。
[1-2]如[1-1]中記載之樹脂載持觸媒,其中上述熱硬化性樹脂之酚性羥基當量為30 g/eq以上500 g/eq以下。
[1-3]如[1-1]或[1-2]記載之樹脂載持觸媒,其中上述熱硬化性樹脂含有酚樹脂。
[1-4]如[1-1]至[1-3]中任一項記載之樹脂載持觸媒,其中藉由BET法所得之比表面積為300 m2/g以下。
[1-5]如[1-1]至[1-4]中任一項記載之樹脂載持觸媒,其中上述熱硬化性樹脂之硬化物係藉由將上述熱硬化性樹脂於250℃以下硬化而獲得。
[1-6]如[1-1]至[1-5]中任一項記載之樹脂載持觸媒,其中於上述熱硬化性樹脂之硬化後,使上述具有觸媒活性的微粒子載持於上述硬化物之表面。
[1-7]如[1-1]至[1-6]中任一項記載之樹脂載持觸媒,其中上述具有觸媒活性的微粒子含有金屬、金屬氧化物及金屬化合物中之任意一種以上。
[1-8]一種樹脂載持觸媒之製造方法,其包括:
硬化步驟:對具有酚性羥基之熱硬化性樹脂進行硬化處理;及載持步驟:於上述熱硬化性樹脂之硬化物的表面載持具有觸媒活性之微粒子。
[1-9]如[1-8]中記載之樹脂載持觸媒之製造方法,其中上述熱硬化性樹脂的羥基當量為30 g/eq以上500 g/eq以下。
[1-10]如[1-8]或[1-9]中記載之樹脂載持觸媒之製造方法,其中上述熱硬化性樹脂含有酚樹脂。
[1-11]如[1-8]至[1-10]中任一項記載之樹脂載持觸媒之製造方法,其中上述硬化步驟包含使上述熱硬化性樹脂於250℃以下硬化之步驟。
[2-1]一種樹脂載持觸媒之製造方法,其包括:硬化步驟:使具有酚性羥基的熱硬化性樹脂硬化;載持步驟:於上述硬化步驟中所獲得之硬化體的表面載持具有觸媒活性的微粒子;且上述微粒子係由以金屬、金屬氧化物及金屬化合物中之任意一種以上構成之材料所形成者,上述載持步驟包含藉由上述酚性羥基將上述微粒子還原的還原步驟。
[2-2]如[2-1]中記載之樹脂載持觸媒之製造方法,其
中,上述還原步驟中,相對於上述材料1 mol,含有選自由氫、一氧化碳、醛類、羧酸類、胺類、金屬氫化物及肼所組成之群中的還原劑0 mol以上10 mol以下。
[2-3]如[2-1]中記載之樹脂載持觸媒之製造方法,其中,於上述還原步驟中,不添加選自由氫、一氧化碳、醛類、羧酸類、胺類、金屬氫化物及肼所組成之群中之還原劑的任一種。
[2-4]如[2-1]至[2-3]中任一項記載之樹脂載持觸媒之製造方法,其中,上述微粒子係由含有下述中任意一種以上之材料所形成者:由鈦、鉻、鈷、鎳、銅、釕、銠、鈀、錸、鋨、鉑、鐵、鋅、錳、鎂、鈣、銀、釩、錫構成之金屬及其氧化物,其他由有機鈦構成之金屬化合物及錯合物。
[2-5]如[2-1]至[2-4]中任一項記載之樹脂載持觸媒之製造方法,其中,上述熱硬化性樹脂為酚樹脂。
[2-6]如[2-1]至[2-5]中任一項記載之樹脂載持觸媒之製造方法,其中,上述硬化步驟係使上述熱硬化性樹脂於250℃以下硬化之步驟。
[2-7]如[2-1]至[2-6]中任一項記載之樹脂載持觸媒之製造方法,其進而包括準備基材之步驟,且
上述載持步驟係於上述基材之表面形成熱硬化性樹脂之上述硬化體,且於上述熱硬化性樹脂之表面載持具有觸媒活性之微粒子的步驟。
[2-8]如[2-1]至[2-7]中任一項記載之樹脂載持觸媒
之製造方法,其中,上述熱硬化性樹脂中之酚性羥基當量為500 g/eq以下。
本申請案係主張以2011年9月6日提出申請之日本申請案特願2011-193647號、及2012年8月6日申請之日本申請案特願2012-174359號為基礎的優先權,且將其揭示之全部內容併入本文中。
Claims (16)
- 一種樹脂載持觸媒,其含有:熱硬化性樹脂之硬化體、及載持於該硬化體表面之具有觸媒活性的微粒子;該熱硬化性樹脂具有酚性羥基。
- 如申請專利範圍第1項之樹脂載持觸媒,其中,該熱硬化性樹脂為酚樹脂。
- 如申請專利範圍第1項之樹脂載持觸媒,其中,該熱硬化性樹脂中之酚性羥基當量為500 g/eq以下。
- 如申請專利範圍第1項之樹脂載持觸媒,其藉由BET法測得之比表面積為300 m2/g以下。
- 如申請專利範圍第1項之樹脂載持觸媒,其中,該微粒子係由以金屬、金屬氧化物及金屬化合物中之任意一種以上構成之材料形成者。
- 如申請專利範圍第1項之樹脂載持觸媒,其中,該微粒子係由含有下述中任意一種以上之材料形成者:由鈦、鉻、鈷、鎳、銅、釕、銠、鈀、錸、鋨、鉑、鐵、鋅、錳、鎂、鈣、銀、釩、錫構成之金屬及其氧化物,其他由有機鈦構成之金屬化合物及錯合物。
- 一種樹脂載持觸媒之製造方法,其包括:硬化步驟:使具有酚性羥基之熱硬化性樹脂硬化;及載持步驟:於該硬化步驟中獲得之硬化體的表面載持具有觸媒活性的微粒子。
- 如申請專利範圍第7項之樹脂載持觸媒之製造方 法,其中,該微粒子係由以金屬、金屬氧化物及金屬化合物中之任意一種以上構成之材料形成者。
- 如申請專利範圍第8項之樹脂載持觸媒之製造方法,其中,該載持步驟包含藉由該酚性羥基將該微粒子還原的還原步驟。
- 如申請專利範圍第9項之樹脂載持觸媒之製造方法,其中,該還原步驟中,相對於該材料1 mol,含有選自由氫、一氧化碳、醛類、羧酸類、胺類、金屬氫化物及肼組成之群中的還原劑0 mol以上10 mol以下。
- 如申請專利範圍第10項之樹脂載持觸媒之製造方法,其中,該還原步驟係不使用該還原劑之步驟。
- 如申請專利範圍第7項之樹脂載持觸媒之製造方法,其中,該微粒子係由含有下述中任意一種以上之材料形成者:由鈦、鉻、鈷、鎳、銅、釕、銠、鈀、錸、鋨、鉑、鐵、鋅、錳、鎂、鈣、銀、釩、錫構成之金屬及其氧化物,其他由有機鈦構成之金屬化合物及錯合物。
- 如申請專利範圍第7項之樹脂載持觸媒之製造方法,其中,該熱硬化性樹脂為酚樹脂。
- 如申請專利範圍第7項之樹脂載持觸媒之製造方法,其中,該硬化步驟係使該熱硬化性樹脂於250℃以下硬化之步驟。
- 如申請專利範圍第7項之樹脂載持觸媒之製造方法,其中,該熱硬化性樹脂中之酚性羥基當量為500 g/eq以下。
- 如申請專利範圍第7項之樹脂載持觸媒之製造方法,其中,該微粒子係於使該熱硬化性樹脂硬化後載持於該硬化體之表面。
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WO2013035270A1 (ja) | 2013-03-14 |
RU2014113353A (ru) | 2015-10-20 |
US9314783B2 (en) | 2016-04-19 |
CN103764283A (zh) | 2014-04-30 |
EP2754490A4 (en) | 2014-12-10 |
IN2014DN01623A (zh) | 2015-05-15 |
CA2848167A1 (en) | 2013-03-14 |
KR20140059277A (ko) | 2014-05-15 |
US20140213434A1 (en) | 2014-07-31 |
EP2754490A1 (en) | 2014-07-16 |
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