OTPPTS對烯烴氫甲?；磻挠绊?/h1>

• 期刊名字：催化學(xué)報
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• 論文作者：徐斌，李敏，黃雪原，袁茂林，陳華，李賢均
• 作者單位：四川大學(xué)化學(xué)學(xué)院金屬有機絡(luò )合催化研究所,四川理工學(xué)院
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第25卷第5期催化學(xué)報2004年5月Vol. 25 No.5Chinese Journal of CatalysisMay 2004文章編號:0253-983X 2004 )05-034405研究論文:344-348OTPPTS對烯烴氫甲?；磻挠绊懶毂?2，李敏'，黃雪原'，袁茂林'，陳華，李賢均'( 1四川大學(xué)化學(xué)學(xué)院金屬有機絡(luò )合催化研究所,四川成都610064 ;2四川理工學(xué)院,四川自貢643000 )摘要:研究了水/有機兩相體系中TPPTS磺化三苯基膦氧化為OTPPTS氧化的TPPTS )對Rh/ TPPTS催化烯烴氫甲?；磻挠绊?結果表明在己烯-1、辛烯-1和十二烯-1氫甲?；磻挟攏( OTPPTSYn( TPPTS)<1時(shí)對催化劑體系性能的影響較小但當n(OTPPTSYn(TPPTS)>1時(shí)將引起催化劑體系的活性、選擇性和穩定性下降;如果保持體系中TPPTS的含量一定使m(TPPTSYn( Rh)≥18當n( OTPPTSYn( Rh)= 20時(shí)則對催化劑體系性能的影響不明顯.這說(shuō)明生成的OTPPTS不是銠催化劑的毒物. TPPTS 氧化為OTPPTS致使銠催化劑的活性和生成醛的選擇性下降, 是由于TPPTS濃度的降低導致n( TPPTISY n( Rh )值過(guò)低使催化循環(huán)中各活性物種的平衡發(fā)生變化及銠配合物的穩定性變差所造成的結果.關(guān)鍵詞:己烯,辛烯,十二烯,氫甲?；?庚醛,壬醛,十三醛,磺化三苯基膦,銠配合物,兩相催化體系中圖分類(lèi)號:0643文獻標識碼:A .Influence of OTPPTS on Olefin Hydroformylationin Biphase Catalytic SystemXU Bin'2 ,LI Min' , HUANG Xueyuan' , YUAN Maolin' , CHEN Hua' ,LI Xianjun'( 1 Institute of Homogeneous Catalysis , College of Chermistry , Sichuan University , Chengdu 610064 , Sichuan , China ;2 Sichuan Polytechnic College , Zigong 643000 , Sichuan , China )Abstract : The hydroformylation of hexene-1 ,octene-1 and dodecene-1 catalyzed by water/ soluble rhodium com-plex[ RhC[ COX TPPTS)I TPPTS- R( m-CH4SO;Na); ) in the presence of OTPPTS( oxidized TPPTS)and cationic surfactant CTAB( cetyltrimethyl ammonium bromide ) was studied. The results indicated that whenTPPTS was oxidized to OTPPTS , the catalyst activity and selectivity for aldehyde decreased because the TPPTScontent in aqueous solution decreased and thereby the TPPTS/Rh ratio was too low. If the TPPTS/Rh molarratio was kept being a constant and larger than 18 , moreover n( OTPPTSY n( TPPTS)<1 , the catalytic perfor-mance of rhodium complex did not obviously change with the increase of n( OTPPTSY n( Rh). It was confirmedthat although OTPPTS was not a poison for the rhodium catalyst , the increase of OTPPTS in the aqueous solu-tion made the total phosphine concentration increase , which caused the rhodium complex to become more stable ,thus the catalyst activity decreased. When the TPPTS/Rh ratio was larger ,for example n( TPPTS)n( Rh)= 30 ,and the molar ratio of total phosphine( TPPTS + OTPPTS) to Rh was higher than 60 , the selectivity for alde-hyde increased to about 98% , the content of dodecane and dodecene-2 in the products decreased to about 1.5%and zero , respectively.Key words : hexene , octene , dodecene , hydroformylation , heptanal , nonanal , tridecanal , trisodium salt of tri-( m-sulfonatophenyl ) phosphine( TPPTS ) , rhodium complex , biphase catalytic system自從以水溶性銠膦配合物為催化劑的兩相催有關(guān)水溶性銠膦配合物催化長(cháng)鏈烯烴氫甲?；椿w系在丙烯氫甲?；I(yè)上的成功應用1以來(lái),應的研究無(wú)論在工業(yè)界還是在學(xué)術(shù)界都受到廣泛收稿日期:2003-07-30.第一作者:徐 斌,女 ,1971年生, 碩士研究生.聯(lián)系人:李賢均. Tel ( 028 )85412904 E-mail : sculixj@ mail sc. cninfo. net.基金項目:國家重點(diǎn)基礎研究發(fā)展規劃項目( G2000048008 ).第5期徐斌等:OTPPTS對烯烴氫甲?；磻挠绊?45的重視2-7].水溶性膦配體的性質(zhì),不僅影響到催表1固定膦/銠比時(shí)OIPPIS/TPPIS比對己烯_1氫甲?；磻挠绊懟瘎┑拇呋阅?而且還決定了催化劑在水中的溶Table 1 Influence of OTPPTS/TPPTS ratio on hexene- 1 hydro-解度從而決定了催化劑能否被有效地固定在水相.formylation at m( TPPTS+ OTPPTSY m( Rh)= 18銠膦催化劑的失活其重要原因之-就是由于膦配.n(OTPPTS) x( CHn2-1)S/%體的氧化和降解所引起在催化劑的使用過(guò)程中，_川 PPTS)%Heptanal Hexane Hexene-2 i-093.291.95.52.73.4由于水和原料中不可避免地含有微量氧,它會(huì )將三91.696. 82.6價(jià)膦配體氧化為五價(jià)化合物導致磷原子的配位能1/892. 389.86.83.3力大為減弱，從而引起催化劑的活性降低.本文詳1/91.188.08.04.11/492.080.9 12. 27.0細研究了磺化三苯基膦(TPPTS,P( m-90.973.617.29.2C6H4SO;Na) )配體氧化為OTPPTS( O:P( m-1/285.960.2 25.6 14. 23.2C6H4SO;Na》時(shí)對烯烴氫甲?；磻挠绊?1/176.448.6 38.9 20. 33.1。38.617.162.7 20. 22.81實(shí)驗部分Reaction conditions: [ RhCl( CO )( TPPTS ) ]= 0.96mmol/L , n( C6H2-1 Vn( Rh)= 4193 ,[ CTAB]= 5 mmol/L.1.1主 要試劑和原料VH2OVV(oil)=2, Voil)=2 ml, p(Co)= p(H2)=1.0以磺化三苯基膦為配體參照文獻8報道的方MPa,θ= 100C ,t=2 h;CTAB - ctytrimethyl ammoum .法合成催化劑RhCK( COI TPPTS).己烯-1、辛烯_bromiden-/i--nm( n-RCHO)n( i-RCHO)1和十二烯_1為Fluka公司試劑純度均大于97% .合成氣按V(CO)V(H2)=1的比例配制H2和CO比對反應的影響.可以看出,隨著(zhù)n( OTPPTSY的純度分別為99.99%和99.95%.實(shí)驗中所用的n(TPPTS的增大,己烯_1轉化率呈逐漸下降的趨水均為去離子水.勢庚醛選擇性在n( OTPPTSY n( TPPTS)= 1/4時(shí)明1.2 OTPPTS 的制備顯降低,己烷和己烯-2的選擇性升高，但正構醛/異將10.41g的TPPTS裝入到圓底燒瓶( 100 ml )構醛比的變化很小維持在3.1~3.4間.當體系僅中再加入30%H2Q2水溶液,經(jīng)加熱，過(guò)濾和真空含OTPPTS時(shí),己烯_1轉化率和庚醛選擇性均急劇干燥即得白色OTPPTS固體9.89g收率為92.6%.下降,而己烷選擇性大幅度升高異構醛含量有所增經(jīng)}|P NMR表征( Bruker AVANCE型300 MHz，加.這表明體系中大量TPPTS被氧化為OTPPTSD2O溶劑85%HPO4外標)其化學(xué)位移δ= 38.03 ,時(shí)銠催化劑逐漸失活生成正構醛的選擇性變差.證明TPPTS中的三價(jià)磷全被氧化為五價(jià)磷.表2為保持TPPTS/Rh比不變時(shí)OTPPTS/Rh1.3烯烴氫甲?；磻葘Ψ磻挠绊?可以看出,直至OTPPTS的量超在帶有電磁攪拌的不銹鋼高壓釜( 60 ml)中依過(guò)TPPTS的量時(shí)催化劑性能才稍變差.次加入配成-定濃度的RhCK( COX TPPTS)水溶表2固定TPPIS/Rh比時(shí)OIPPTS/Rh比對液TPPTS ,OTPPTS表面活性劑烯烴和水,加熱至反應溫度開(kāi)始攪拌并計時(shí).反應完畢后取出高Table 2 Infuence of OTPPTS/Rh ratio on hexene-1 hydro-壓釜用冷水迅速冷卻，反應產(chǎn)物用HP1890II型氣formylation at m( TPPTSYn( Rh)= 18相色譜儀分析氫火焰檢測器,SE 30毛細管色譜柱n( OTPPTS) X( G6H2-1)1-n( RhHeptanal Hexane Hexene2 i-( φ 0.25 mmX30 m).490.792.35.02.43.5為研究TPPTS被氧化為OTPPTS對催化劑性92.55.22.3能的影響我們采用加入不同量的OTPPTS ,以改變93.44.62.13.6291.8.5.5TPPTS/OTPPTS之比,模擬TPPTS被逐漸氧化The reaction conditions are the same as in Table 1.后測定催化劑性能的變化.表3為保持OTPPTS/ TPPTS比不變時(shí)壓力對2結果與討論反應的影響.可以看出隨著(zhù)壓力的升高,己烯-1 轉2.1己烯-1 氫甲?；磻Y果化率先升高后降低,庚醛選擇性略有降低,氫和異表1為保持膦/銠比不變時(shí)OTPPTS/TPPTS構化產(chǎn)物的選擇性則略有升高但正構醛/異構醛比346催化學(xué)報第25卷表3固定OIPPIS/TPPTIS比時(shí)壓力對表5固定膦/銠比時(shí) OTPPIS/IPTs比對己烯.1氫甲?；磻挠绊懶料?1氫甲?；磻挠绊慣able3 Infuance of prssure on hexene1 hydrormylationTable 5 Infuene of OTPPTSTPPTS ratio on octene1 hydro-at n(OIPPTSYn( TPTS)= 1/3formylation at m( TPPTS+ OTPPISYn( Rh)= 18μC+H) XCGH2-1)S/%OIPPTS) X(CsH6-1)%Heptanal Hexane Hexene-2 下以TPPTS)n-1.083.076.015.48.6 4.2091.6Nonanal Octane Otene-2 i1.584.375.217.67.23. 61/995.33.01.83.22.090.973.617.29.23.31/890.194.13.72.2 3. 22.590.0.74.216.69.2 3.11/689.494.03.82.53. 285.968.618.712.71/489.693.64.188.492.54.83. IThe reaction conditions are the same as in Table 1.1/388.73.62.31/290. 14.02.4 3. 1明顯減小。在水溶液中，無(wú)論銠以何種形式的前體87.591.35.6加入在氫甲?；磻獥l件下,都會(huì )很快形成HRh-67.8.47.936.415.6(CO),( TPPTS),型配合物9].當反應中合成氣的35.014.359.126.62. 8The reaction conditions are the same as in Table 1. excep總壓或CO分壓升高時(shí),有利于形成異構醛的活性川( CH46-1Vn( Rh)= 3308.中間體[ HRh( CO )( TPPTS)]的含量增加,從而導致正構醛/異構醛比下降.n( TPPTSYn( Rh)= 4.5導致銠催化劑的性能變差,表4為保持OTPPTS/TPPTS比不變時(shí)溫度對故辛烯1轉化率和壬醛選擇性均顯著(zhù)降低,而辛烷反應的影響.可以看出隨著(zhù)溫度的升高,己烯.1 轉和辛烯.2的選擇性顯著(zhù)升高.當體系中無(wú)TPPTS化率迅速上升當0> 100 C時(shí)己烯.1轉化率幾乎而僅有OTPPTS存在時(shí)辛烯-1轉化率和壬醛選擇不再變化;庚醛選擇性呈先上升后下降的趨勢.己性進(jìn)一步大幅度降低而辛烷和辛烯2的選擇性均烷和己烯2的選擇性呈先下降后上升的趨勢.正構超過(guò)壬醛的選擇性.醛/異構醛比逐漸增大不同于TPPTS末被氧化時(shí)由表6可以看出,固定膦/銠比時(shí)OTPPTS/的結果.TPPTS比對十二烯-1氫甲?；磻邢嗤挠绊懸幝?表4固定OTPPIS/TPPTIS比時(shí)溫度對己烯-1氫甲?；磻挠绊懕?固定膦/銠比時(shí)OIPPIS/TPPTS比對Table4 Inluence of temprature on hexene1 hyromylation十二烯.1氫甲?；磻挠绊慳t M(OTPPISYr( TPPTS)= 1/3Table 6 Infuene of OTPPTSTPPTS ratio on doeene hydro-X(CH2-1)formylation at以( TPPTS+ OTPPTSYn( Rh)= 18θ/nHeptanal_ Hexane Hexene2 in(OIPPTS) X(C2H2+1)1-8036.628.751.620. 1n( TPPTS)Tridecanal Ddecane Ddecene-2 i9055.630.447.721.9)89.895.21.4 3.310080.11.9 3.311089.577.414.97. 63.478.494.51.8 3.012093.876.39.43.584.794.61.8 3.0 .3058.623.918.081.694.4The reaction condions are the same as in Table 1.79.72.0 3.082.93.92.22.92.2辛烯-1 和十二烯_1的氫甲?；磻Y果a42.589.95. !31.34.0 3.014.72.8表5為固定膦/銠比時(shí)OTPPTS/IPPTS比對The reaction conditious are the same as in Table 1.exept辛烯-1氫甲?；磻挠绊?可以看出,直到m(C2H24-1Vm( Rh)= 2343.n( OTPPTSYn( TPPTS)=1時(shí),辛烯_1轉化率下降幅表7為固定TPPTS/Rh比時(shí)OTPPTS/Rh比度很小壬醛的選擇性稍有降低.這主要是由于辛對辛烯.1氫甲?；磻挠绊?可以看出,隨著(zhù)烷和辛烯: 2有所增加的緣故.正構醛/異構醛比基OTPPTS/Rh比的增大催化劑的性能幾乎不變,僅本保持不變,維持在3.1左右.當mTPpTSY當OTPPTS含量很高時(shí)辛烯1轉化率才略有下降，n"(TPPTS)=3時(shí),由于TPPTS的濃度很低,而壬醛的選擇性及正構醛/異構醛比都保持在一定第5期徐斌等:OTPPTS對烯烴氫甲?；磻挠绊?47表7固定 TPPIS/Rh比時(shí)OTPPIS/Rh比對表9固定 TPPIS/ Rh比時(shí)OIPPIS/ Rh比對辛烯.1氫甲?；磻挠绊懯1氫甲?；磻挠绊慣able 7 Influence of OTPPTS/Rh ratio on octene-1 hydro-Table 9 Influence of OTPPTS/ Rh ratio on dodecene-1 hydro-formylationat m( TPPTSVn( Rh)= 18forrmylationat n( TPPTSYn( Rh)= 30n(OTPPTS) XCsH6-1)S/%1-n(OTPPTS) X( C2H2-1)n-n( Rh)%NonanalOctane Octene2 i-n(Rh)Tridecanal Dodecane Dodecene-2 i289.894.53.21.83.1049.396.42.21.63.586.795.23.02.11044.996.93.787.196.01.537.098.43.9890.094. 93035.697.83.81(89.795.133.697.9.3.81289.54.82.6 3. 0501.198.71.31490.494.62.0The reaction conditions are the same as in Table 1 , except16.3.51.9n( TPPTSYn( Rh)= 30 and n( Cr2H2-1 )Vn( Rh)= 2343.1885.993.14.52. 52(88.3.90.56.5.03結論n( CH6-1Vn( Rh)= 3308.通過(guò)向反應溶液中加入一定量的OTPPTS模的水平辛烷和辛烯-2也沒(méi)有明顯的增加.這進(jìn)一擬烯烴氫甲?；磻^(guò)程中TPPTS被氧化,考察步表明,只要體系中 TPPTS/Rh比保持 穩定,了對催化劑性能的影響得到以下--些實(shí)驗結果.(1 )只要保持n( TPPTSVn( Rh)> 18 ,溶液中OTPPTS含量對催化劑性能的影響很小.由表8可以看出,固定TPPTS/Rh比時(shí).十二OTPPTS的含量即使與TPPTS的含量相當,對銠烯_1氫甲?；磻c辛烯_1氫甲?；磻薪醮呋瘎┑男阅芤矡o(wú)明顯影響.(2)TPPTS被氧化引起OTPPTS的濃度升高,相同的規律.致使銠催化劑的活性和生成醛的選擇性降低.這是由于TPPTS濃度的降低造成TPPTS/Rh比過(guò)低,表8固定TPPIS/ Rh比時(shí)OIPPIS/Rh比對使催化活性物種向生成多羰基銠配合物的方向移Table 8 Influence of OTPPTS/ Rh ratio on dodecene-1 hydro-動(dòng):formylation at m( TPPISYm( Rh)= 18RhC[ COl TPPTS) F+H2,+ TPPTS、n( OTPPTS) X( Cz2H24-1)，-H2,- TPPTSTridecanal Dodecane Dodecene-2 i-178.194.83.3HRK(COXTPPTS) + HCI470.394.92.368.595.02.6HRH( COX TPPTS) =TPPTS、68.42.9t TPPTS71.894.466.0HRH( COX TPPTS)67.395.32.7366.895.52062. 795.7HRI( COXTPPTS)2 +005 TP-CO,+ TPPTSn( C2H+-1)n( Rh)= 2343.HRH( CO)( TPPTS)我們進(jìn)-步將n(TPPTSYn(Rh提高到30考察HRH CO )( TPPTS)+C0,- TPPTS、= co.t Pr HRK(CO)了m( OTPPTSY n( Rh )此對十二烯-1氫甲?；磻挠绊?與表8中的數據相比表9中的數據說(shuō)明提形成的催化活性物種4和5 ,對烯烴氫甲?；磻遪(TPPTSYn(Rh)此到30時(shí),催化的活性明顯降的催化活性較低,而對氫和異構化反應的催化活性低并且隨著(zhù)m( OTPPTSYn( Rh的升高十二烯1轉較高.由于OTPPTS的配位能力較弱,因此有利于化率逐漸降低,但十三醛選擇性升高而十二烷選擇4和5的形成;直到TPPTS完全被氧化后,只能形性降低異構化為十二烯2的反應則完全被抑制.成催化活性物種5 ,TPPTS 對銠配合物的穩定能力348催化學(xué)報第25卷也即喪失導致催化劑活性急劇下降乃至還原分解?陳華,黎耀忠,李東文，程溥明，李賢均.化學(xué)進(jìn)展形成金屬銠.這可由實(shí)驗后催化劑溶液變?yōu)榛疑?ChenH,Li Y Zh,LiD W ,ChengPM,Li XJ. Progr到證實(shí).Chem ), 1998 , 10(2):146(3)生成的OTPPTS不是銠催化劑的毒物而3 ChenH,Li Y Zh,ChenJ R ,ChengPM,He Y E,Li X是與銠有較弱的配位能力,因此在n( TPPTSYn( Rh)J. J Mol CatalA , 1999 , 149 1/2):1=18時(shí),只有當OTPPTS的含量大于TPPTS的含4 Riisager A , HansonBE. J Mol Catal A ,2002 , 189 2):量時(shí)烯烴轉化率才有所下降.然而,當 n( TPPTSY195n(Rh)= 30時(shí),由于溶液中膦配體的濃度很高,5 Bahrmann H , Bogdanovic. In : Cornils B , Herrmann W AOTPPTS的濃度增加膦/銠比大幅度升高,此時(shí)引eds. Aqueous Phase Organometallic Catalysis. Weinheim : .起催化劑的活性下降.這是由于膦濃度很高時(shí)使銠Wiley-VCH , 1998.306配合物穩定化同時(shí)也造成銠周?chē)目臻g位阻增大,6 ChenH,Li Y Zh ,ChenJR ,ChengP M,LiXJ. Catal使烯烴配位困難所致.這與文獻10 ,11 ]報道的反Today ,2002 ,74( 1/2):131應機理研究結果相一致.在保持較高的TPPTS/Rh7 Haumann M , Koch H, Hugo P , Schomicker R. ApplCatal A ,2002 ,225( 1/2):239比時(shí)OTPPTS的大量存在提高了銠催化劑對生成8陳華,劉海超，黎耀忠,程溥明，李賢均.分子催化醛的選擇性,但降低了對氫和異構化反應的催化活(ChenH,LiuHCh,Li Y Zh ,ChengPM,LiXJ. J Mol性.這一方面說(shuō)明OTPPTS仍具有較弱的配位能Catal( China )),1994 ,82):124力另-方面也說(shuō)明它對銠催化劑無(wú)毒害作用.(4)銠催化劑在長(cháng)期循環(huán)使用中難免發(fā)生膦配9吳己丑,袁剛,周啟召.石油化工( WuJ Ch, YuanG,Zhou Q Zh. Petrochem Technol ), 1991 ,20(2):79體被氧化,但只要盡量減緩這-氧化反應過(guò)程,同時(shí)10 Cormils B , Herrmann W A. Applied Homogeneous Cataly-適當補充膦配體TPPTS以保持TPPTS/Rh比在sis with Organomealic Compounds( Vol. 1 ). Weinheim :一定的水平,即可保證催化劑的性能穩定.這對銠Wiley-VCH , 1996. 44催化劑的工業(yè)應用有重要的指導意義.11 Torrent M , Sola M , Frenking G. Chem Rev ,2000 , 100參考文獻(2):4391 Kuntz EG. CHEMTECH , 1987 ,179):570( Ed WGZh)