CN106588619B - 一种烯烃氢甲酰化制备醛的方法 - Google Patents
一种烯烃氢甲酰化制备醛的方法 Download PDFInfo
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- 238000000034 method Methods 0.000 title claims abstract description 30
- 238000007037 hydroformylation reaction Methods 0.000 title claims abstract description 28
- 150000001336 alkenes Chemical class 0.000 title claims abstract description 16
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 title claims abstract description 13
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 claims abstract description 73
- 239000003446 ligand Substances 0.000 claims abstract description 46
- 239000003054 catalyst Substances 0.000 claims abstract description 42
- 229910000073 phosphorus hydride Inorganic materials 0.000 claims abstract description 37
- 239000010948 rhodium Substances 0.000 claims abstract description 26
- 229910052703 rhodium Inorganic materials 0.000 claims abstract description 13
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims abstract description 13
- 238000002360 preparation method Methods 0.000 claims abstract description 4
- 238000006243 chemical reaction Methods 0.000 claims description 30
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 claims description 15
- 239000004711 α-olefin Substances 0.000 claims description 13
- 238000003786 synthesis reaction Methods 0.000 claims description 11
- CUJRVFIICFDLGR-UHFFFAOYSA-N acetylacetonate Chemical compound CC(=O)[CH-]C(C)=O CUJRVFIICFDLGR-UHFFFAOYSA-N 0.000 claims description 10
- 230000015572 biosynthetic process Effects 0.000 claims description 9
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 claims description 8
- ZGEGCLOFRBLKSE-UHFFFAOYSA-N 1-Heptene Chemical compound CCCCCC=C ZGEGCLOFRBLKSE-UHFFFAOYSA-N 0.000 claims description 6
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 claims description 6
- 229940125904 compound 1 Drugs 0.000 claims description 6
- 229940125782 compound 2 Drugs 0.000 claims description 6
- WAVGXIXQMBSEMK-UHFFFAOYSA-N lithium;phenol Chemical compound [Li].OC1=CC=CC=C1 WAVGXIXQMBSEMK-UHFFFAOYSA-N 0.000 claims description 4
- MZRVEZGGRBJDDB-UHFFFAOYSA-N n-Butyllithium Substances [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 claims description 4
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 claims description 4
- GGRQQHADVSXBQN-FGSKAQBVSA-N carbon monoxide;(z)-4-hydroxypent-3-en-2-one;rhodium Chemical group [Rh].[O+]#[C-].[O+]#[C-].C\C(O)=C\C(C)=O GGRQQHADVSXBQN-FGSKAQBVSA-N 0.000 claims description 3
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical group CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 claims description 3
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims description 3
- VYXHVRARDIDEHS-UHFFFAOYSA-N 1,5-cyclooctadiene Chemical compound C1CC=CCCC=C1 VYXHVRARDIDEHS-UHFFFAOYSA-N 0.000 claims description 2
- 239000004912 1,5-cyclooctadiene Substances 0.000 claims description 2
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- 238000011065 in-situ storage Methods 0.000 claims description 2
- DLEDOFVPSDKWEF-UHFFFAOYSA-N lithium butane Chemical compound [Li+].CCC[CH2-] DLEDOFVPSDKWEF-UHFFFAOYSA-N 0.000 claims description 2
- 239000004215 Carbon black (E152) Substances 0.000 claims 1
- 229930195733 hydrocarbon Natural products 0.000 claims 1
- 150000002430 hydrocarbons Chemical class 0.000 claims 1
- 230000000694 effects Effects 0.000 description 10
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 7
- 239000007789 gas Substances 0.000 description 6
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 5
- 238000002474 experimental method Methods 0.000 description 5
- 229910052698 phosphorus Inorganic materials 0.000 description 5
- 239000011574 phosphorus Substances 0.000 description 5
- 238000011160 research Methods 0.000 description 5
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 4
- 238000006555 catalytic reaction Methods 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 229910052723 transition metal Inorganic materials 0.000 description 3
- 150000003624 transition metals Chemical class 0.000 description 3
- 150000001335 aliphatic alkanes Chemical group 0.000 description 2
- -1 aryl phosphine Chemical compound 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000002390 rotary evaporation Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 1
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- 238000004679 31P NMR spectroscopy Methods 0.000 description 1
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- LFZAGIJXANFPFN-UHFFFAOYSA-N N-[3-[4-(3-methyl-5-propan-2-yl-1,2,4-triazol-4-yl)piperidin-1-yl]-1-thiophen-2-ylpropyl]acetamide Chemical compound C(C)(C)C1=NN=C(N1C1CCN(CC1)CCC(C=1SC=CC=1)NC(C)=O)C LFZAGIJXANFPFN-UHFFFAOYSA-N 0.000 description 1
- LYEDGKPMDYUPDP-UHFFFAOYSA-N [Li].C=1(C(=CC(=CC1)C)C)O Chemical compound [Li].C=1(C(=CC(=CC1)C)C)O LYEDGKPMDYUPDP-UHFFFAOYSA-N 0.000 description 1
- YRXLEVCVWKECOD-UHFFFAOYSA-N [Li].Cc1ccccc1O Chemical compound [Li].Cc1ccccc1O YRXLEVCVWKECOD-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000012937 correction Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000007172 homogeneous catalysis Methods 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- BAZQYVYVKYOAGO-UHFFFAOYSA-M loxoprofen sodium hydrate Chemical compound O.O.[Na+].C1=CC(C(C([O-])=O)C)=CC=C1CC1C(=O)CCC1 BAZQYVYVKYOAGO-UHFFFAOYSA-M 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000010606 normalization Methods 0.000 description 1
- 230000005311 nuclear magnetism Effects 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- WJIBZZVTNMAURL-UHFFFAOYSA-N phosphane;rhodium Chemical compound P.[Rh] WJIBZZVTNMAURL-UHFFFAOYSA-N 0.000 description 1
- 150000008301 phosphite esters Chemical class 0.000 description 1
- 125000004437 phosphorous atom Chemical group 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 238000004451 qualitative analysis Methods 0.000 description 1
- 238000004445 quantitative analysis Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 150000003283 rhodium Chemical class 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/49—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reaction with carbon monoxide
- C07C45/50—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reaction with carbon monoxide by oxo-reactions
- C07C45/505—Asymmetric hydroformylation
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/22—Organic complexes
- B01J31/2204—Organic complexes the ligands containing oxygen or sulfur as complexing atoms
- B01J31/2208—Oxygen, e.g. acetylacetonates
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- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/28—Phosphorus compounds with one or more P—C bonds
- C07F9/48—Phosphonous acids [RP(OH)2] including [RHP(=O)(OH)]; Thiophosphonous acids including [RP(SH)2], [RHP(=S)(SH)]; Derivatives thereof
- C07F9/4866—Phosphonous acids [RP(OH)2] including [RHP(=O)(OH)]; Thiophosphonous acids including [RP(SH)2], [RHP(=S)(SH)]; Derivatives thereof the ester moiety containing a substituent or structure which is considered as characteristic
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Abstract
本发明涉及一种烯烃氢甲酰化制备醛的方法,采用的催化剂为新型膦配体和铑络合催化剂,能够解决现有技术制备的产品中正异比较低、选择性差的问题。
Description
技术领域
本发明涉及一种烯烃氢甲酰化制备醛的方法,属于有机合成领域。
背景技术
烯烃氢甲酰化反应是重要的有机合成反应,在现代工业中起着举足轻重的作用。烯烃氢甲酰化的产物醛是很有用的化学中间体,能够合成出多种重要的化学化工产品,是迄今为止生产规模最大的均相催化过程。
自上世纪七十年代以来,含磷配体所修饰的铑催化剂以其高活性、优秀的选择性和温和的反应条件等突出的优点主导了烯烃的氢甲酰化反应研究,成为工业氢甲酰化工艺过程的催化剂,国际上常见的氢甲酰化工艺供应商如BASF、Evonik、OXENO、Perstorp、DOW等均采用含磷配体所修饰的铑催化剂。其中,含磷配体的成分和结构是磷/铑催化体系反应效能的关键性因素,它直接决定了催化剂的活性、选择性和使用寿命等重要指标。
从上个世纪50年代Slaugh等人发现了叔膦配体PR3,为催化系统的优化开辟了一条新的道路,极大地推动了烯烃氢甲酰化反应工业化的发展。1965年,Wilkinson发现的磷改性的铑催化剂RhCl(PPh3)3更是催化领域的又一大重要发现,自此以后,铑膦体系催化剂引起了科学家们更为广泛的研究兴趣,各种结构的配体及催化剂及其烯烃氢甲酰化的成果见诸报道,至今已经取得了很大的发展。
在过渡金属络合催化研究中,膦配体的结构和性质对络合物催化剂的性能具有重要的影响,是改变催化剂的活性和选择性的重要方法手段。各种结构膦配体的合成,为调节过渡金属络合物催化剂性能,实现适应各种不同反应需要的多样性催化剂的合成,提供了良好的基础。因此,膦配体的设计和合成一直是过渡金属络合物研究中重要的研究内容之一。
在各种膦配体中,芳基膦(Ar3P)由于P原子具有适当的配位能力,并能通过对芳基(Ar)的修饰对其电子效应和空间效应进行调节而得到广泛的研究和应用。早在1958年S.Ahrland等人对三苯基膦进行改性,在苯环上增加了甲基。1977年C.A.Tolman用甲基取代了三苯基膦两个苯环上的氢。1994年Hanson等合成了新型带有链状烷烃基团的表面活性膦配体P[C6H4(CH2)mC6H4-p-SO3-Na]3(m=3,6),不仅提高了烯烃氢甲酰化的反应速率,也提高了催化剂的选择性,但是现有技术中产品正异比较低(不高于60:1)。
2001年四川大学陈华课题组提出了正丁基和正辛基取代三苯基膦一个苯环的膦配体,考察其催化活性和选择性都有较好的效果,但是其配体稳定性下降。
因此,需要寻找一种配体结构简单、催化活性高、选择性好等的新型膦配体催化剂,实现α-烯烃氢甲酰化催化剂性能的提高。
发明内容
本发明所要解决的技术问题是提供一种烯烃氢甲酰化制备醛的方法,将一种新型膦配体结构引入到催化剂中,解决现有技术中产品中正异比较低、选择性差的问题,该方法具有产品中正异比较高、选择性好的优点。
为实现以上发明目的,本发明采用的技术方案如下:
一种烯烃氢甲酰化制备醛的方法,α-烯烃、合成气进入氢甲酰化反应器,在反应温度为50~200℃,优选100~150℃、反应压力(表压)为2~10MPa,优选4.0~6.0Mpa、反应时间为2~3h下,与催化剂接触,生成包括醛的产物;
所述催化剂为络合催化剂,所述络合催化剂包括铑络合物、膦配体,所述膦配体结构如式L所示:
其中,R1-R8分别独立地代表C1-C10的烷基、C5-C12的环烷基,优选R1-R8相同。
本发明中,所述膦配体优选为L1、L2、L3、L4、L5和L6中的一种或多种,更优选为L3和/或L4,所述L1-L6的结构式如下所示:
本发明中,所述催化剂通过络合物和膦配体在合成气氛围下原位配位使用。
本发明中,所述的铑络合物选自乙酰丙酮二羰基铑(简写Rh(acac)(CO)2)、Rh(acac)(C2H4)、[Rh(C2H4)2Cl]2、[Rh(cod)Cl]2、[Rh(CO)2Cl]2、HRh(CO)(PPh3)3和RhPPh3(acac)(CO)中的一种或多种,优选Rh(acac)(CO)2和/或HRh(CO)(PPh3)3,更优选Rh(acac)(CO)2其;中,acac代表乙酰丙酮、cod代表1,5-环辛二烯。
本发明中,所述催化剂中铑与膦配体的摩尔比为1:1-1:100,优选1:10-1:20。
本发明中,所述催化剂的用量为1-1000ppm,优选10-100ppm,基于α-烯烃、催化剂的总重量。
本发明中,所述催化剂的膦配体的制备方法,包括以下步骤:
(1)、化合物1和正丁基锂、PCl3反应制取化合物2,
(2)、化合物2和2,4-取代苯酚锂反应制取膦配体;
(3)、反应结束后通过过滤旋蒸即可得到高纯度膦配体。
化合物1和化合物2的结构分别如下:
作为优选的方案,膦配体制备方法的步骤(2)中,以所述2,4-取代苯酚锂为2,4-二甲基苯酚锂为例,所述膦配体的合成路线如下所示:
本发明方法适用于C3-C10的直链或支链α-烯烃,优选C3-C10的直链α-烯烃的氢甲酰化,更优选1-丁烯、丙烯、1-戊烯、1-己烯、1-庚烯。
本发明的有益效果在于:
本发明在催化剂中引入的新型膦配体可以显著提高Rh/亚磷酸酯正异比、选择性,并且能维持较高的催化活性,有利于提高工艺的经济性,减少后系统能耗和催化剂活性组分铑的用量,取得了较好的技术效果。
具体实施方式
气相色谱仪:SHIMADZU GC-2010Plus,色谱柱Agilent WAX:30m×320μm×0.25μm;进样口温度:280℃,升温程序:50℃保持1分钟,15℃/min到230℃保持10分钟;检测器温度:230℃。
核磁分析仪器:Bruker AVANCEII-400,氢谱:PROTON256碳谱:C13CPD;
化合物1:武汉鹏和,纯度≥98.0wt%。
实施例1
化合物2的合成:
-20℃下向化合物1(1.0mol,351.95g)的己烷溶液中滴加正丁基锂溶液(2.0mol,1.2L),滴加完毕,保持-20℃反应1小时。向反应液中滴加PCl3(2.0mol,271.76g),滴加完毕,升至室温反应1小时。反应完毕,离心过滤,旋转蒸发出去溶剂,真空干燥得到化合物2黄色固体。
实施例2
合成膦配体L1:
0℃下向化合物2(1.0mol,395.93g)的正己烷溶液中滴加2,4-二甲基苯酚锂正己烷溶液(4.0mol,2.5L),滴加完毕,升至室温反应0.5小时。反应完毕,离心过滤,旋转蒸发出去溶剂,50℃下真空干燥5小时,得到膦配体L1 739.3g,收率99.2%。
配体L1核磁表征数据如下:1H NMR:δ1.72(s,6H,C(CH3)2),2.15,2.34(s,24H,Ph-CH3),6.70~7.30(m,20H,Ph-H)。13C NMR:δ152.7,150.6,137.2(d,JP-C=40Hz),132.3,131.5,130.9,128.7,127.4,119.1(Ph-C),42.4(-C(CH3)2),30.9(-C(CH3)2),21.6,15.7(Ph-CH3)。31P NMR:δ20.4。
实施例3~7
合成膦配体L2~L6
根据实施例1的合成方法,改变步骤(2)的反应物2,4-取代苯酚锂分别为 合成膦配体L2~L6。
实施例8
1-丁烯氢甲酰化反应
将Rh(acac)(CO)2(0.7mmol,181.0mg)、膦配体L1 7.0mmol、1-丁烯6.0L加入10.0L高压釜中,密闭反应器,用一定压力的合成气(H2/CO=1)将反应器置换三次以后,用电磁驱动的机械搅拌器搅拌,加热升温至釜内温100℃,通入合成气至总压为5.0MPa,在100℃,5.0MPa的条件下反应2h,反应过程中保持压力恒定。反应结束后,取出反应釜置于冷水中快速冷却停止反应.反应产物用色质联用仪定性分析,气相色谱仪定量分析,采用校正归一法定量。烯烃转化率100%,醛的选择性98.7%,正异比90:1。
实施例9~12
氢甲酰化反应
根据实施例8实验方法,分别对丙烯、1-戊烯、1-己烯、1-庚烯进行氢甲酰化反应,反应结果详见表1。
表1
实施例13~17
根据实施例8实验方法,进行1-丁烯的氢甲酰化反应,仅改变催化剂的用量、催化剂中膦配体与Rh(acac)(CO)2的比例、反应温度、压力等条件,分别进行氢甲酰化反应,其中催化剂的用量是基于α-烯烃和催化剂的总重量,反应结果详见表2。
表2
实施例18~22
根据实施例8实验方法,改变膦配体分别为L2-L6,并分别进行1-丁烯氢甲酰化反应,反应结果详见表3。
表3
实施例 | 膦配体 | 转化率% | 选择性% | 正异比 |
18 | L2 | 100 | 99.5 | 90:1 |
19 | L3 | 99.7 | 98.9 | 95:1 |
20 | L4 | 98.9 | 98.5 | 90:1 |
21 | L5 | 98.5 | 99.0 | 85:1 |
22 | L6 | 99.0 | 98.2 | 88:1 |
对比例1
根据实施例8实验方法,将催化剂中的配体更换为三苯基膦,进行氢甲酰化反应,烯烃转化率80.5%,醛的选择性85.5%,正异比60:1。
对比例2
根据实施例8实验方法,将催化剂中的配体更换为Ar3P,进行氢甲酰化反应,烯烃转化率85.0%,醛的选择性80.0%,正异比50:1。
Claims (14)
1.一种烯烃氢甲酰化制备醛的方法,α-烯烃、合成气在催化剂作用下进行氢甲酰化反应,生成包括醛的产物;所述催化剂包括铑络合物、膦配体,所述膦配体结构如通式L所示:
其中,R1-R8分别独立地代表C1-C10的烷基、C5-C12的环烷基;
所述α-烯烃选自C3-C10的直链或支链α-烯烃。
2.根据权利要求1所述的方法,其特征在于,所述通式L中R1-R8相同。
3.根据权利要求1所述的方法,其特征在于,所述膦配体为L1、L2、L3、L4、L5和L6中的一种或多种,所述L1-L6的结构式如下所示:
4.根据权利要求1所述的方法,其特征在于,所述的铑络合物选自Rh(acac)(CO)2、Rh(acac)(C2H4)、[Rh(C2H4)2Cl]2、[Rh(cod)Cl]2、[Rh(CO)2Cl]2、HRh(CO)(PPh3)3和RhPPh3(acac)(CO)中的一种或多种;其中,acac代表乙酰丙酮、cod代表1,5-环辛二烯。
5.根据权利要求1所述的方法,其特征在于,所述催化剂中铑与膦配体的摩尔比为1:1-1:100。
6.根据权利要求5所述的方法,其特征在于,所述催化剂中铑与膦配体的摩尔比为1:10-1:20。
7.根据权利要求1-6中任一项所述的方法,其特征在于,所述催化剂的用量为1-1000ppm,基于α-烯烃和催化剂的总重量。
8.根据权利要求7所述的方法,其特征在于,所述催化剂的用量为10-100ppm,基于α-烯烃和催化剂的总重量。
9.根据权利要求1-6任一项所述的方法,其特征在于,所述氢甲酰化反应温度50~200℃,反应压力表压2~10MPa。
10.根据权利9所述的方法,其特征在于,所述氢甲酰化反应温度100~150℃,反应压力表压4~6MPa。
11.根据权利要求1-6任一项所述的方法,其特征在于,所述催化剂的膦配体的制备方法,包括以下步骤:
(1)、化合物1和正丁基锂、PCl3反应制取化合物2,
(2)、化合物2和2,4-取代苯酚锂反应制取膦配体;
化合物1和化合物2的结构分别如下:
12.根据权利要求1-6中任一项所述的方法,其特征在于,所述催化剂通过铑络合物和膦配体在合成气氛围下原位配位使用。
13.根据权利要求1-6中任一项所述的方法,其特征在于,所述α-烯烃选自C3-C10的直链α-烯烃。
14.根据权利要求13所述的方法,其特征在于,所述α-烯烃选自1-丁烯、丙烯、1-戊烯、1-己烯、1-庚烯。
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