CN114985002A - 用于烯烃氢甲酰化的双膦聚合物催化剂及其制备方法和应用 - Google Patents
用于烯烃氢甲酰化的双膦聚合物催化剂及其制备方法和应用 Download PDFInfo
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- CN114985002A CN114985002A CN202210606551.7A CN202210606551A CN114985002A CN 114985002 A CN114985002 A CN 114985002A CN 202210606551 A CN202210606551 A CN 202210606551A CN 114985002 A CN114985002 A CN 114985002A
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- Prior art keywords
- diphosphine
- polymer
- catalyst
- bisphosphine
- bromostyrene
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- VURFVHCLMJOLKN-UHFFFAOYSA-N diphosphane Chemical compound PP VURFVHCLMJOLKN-UHFFFAOYSA-N 0.000 title claims abstract description 108
- 229920000642 polymer Polymers 0.000 title claims abstract description 65
- 239000003054 catalyst Substances 0.000 title claims abstract description 49
- 238000007037 hydroformylation reaction Methods 0.000 title claims abstract description 27
- 150000001336 alkenes Chemical class 0.000 title claims abstract description 19
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 title claims abstract description 18
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 239000000178 monomer Substances 0.000 claims abstract description 28
- 229910052751 metal Inorganic materials 0.000 claims abstract description 27
- 239000002184 metal Substances 0.000 claims abstract description 27
- 239000003446 ligand Substances 0.000 claims abstract description 17
- 239000002904 solvent Substances 0.000 claims abstract description 17
- 229920001577 copolymer Polymers 0.000 claims abstract description 12
- 238000000034 method Methods 0.000 claims abstract description 8
- 239000002638 heterogeneous catalyst Substances 0.000 claims abstract description 6
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims abstract description 5
- 125000000524 functional group Chemical group 0.000 claims abstract description 5
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims abstract description 4
- 229920002554 vinyl polymer Polymers 0.000 claims abstract description 4
- 239000002149 hierarchical pore Substances 0.000 claims abstract description 3
- 238000012719 thermal polymerization Methods 0.000 claims abstract description 3
- 125000002947 alkylene group Chemical group 0.000 claims abstract 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 50
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 36
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 25
- KQJQPCJDKBKSLV-UHFFFAOYSA-N 1-bromo-3-ethenylbenzene Chemical compound BrC1=CC=CC(C=C)=C1 KQJQPCJDKBKSLV-UHFFFAOYSA-N 0.000 claims description 24
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- SSZOCHFYWWVSAI-UHFFFAOYSA-N 1-bromo-2-ethenylbenzene Chemical compound BrC1=CC=CC=C1C=C SSZOCHFYWWVSAI-UHFFFAOYSA-N 0.000 claims description 10
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims description 10
- -1 chlorophosphinyl alkane Chemical class 0.000 claims description 10
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- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 6
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- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 claims description 4
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- 230000000694 effects Effects 0.000 abstract description 5
- 229910000073 phosphorus hydride Inorganic materials 0.000 abstract description 3
- 238000007172 homogeneous catalysis Methods 0.000 abstract description 2
- 230000000379 polymerizing effect Effects 0.000 abstract 1
- 239000010948 rhodium Substances 0.000 description 16
- 230000015572 biosynthetic process Effects 0.000 description 15
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 15
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- SBWAJHLQMFBNIN-UHFFFAOYSA-N dichloro(2-dichlorophosphanylethyl)phosphane Chemical compound ClP(Cl)CCP(Cl)Cl SBWAJHLQMFBNIN-UHFFFAOYSA-N 0.000 description 7
- 238000011068 loading method Methods 0.000 description 7
- ISCGKQXZXYUYAW-UHFFFAOYSA-M magnesium;ethenylbenzene;bromide Chemical compound [Mg+2].[Br-].C=CC1=CC=C[C-]=C1 ISCGKQXZXYUYAW-UHFFFAOYSA-M 0.000 description 7
- 238000006116 polymerization reaction Methods 0.000 description 7
- 239000012300 argon atmosphere Substances 0.000 description 6
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 4
- IFVKYYDUXZQIJT-UHFFFAOYSA-N CC.ClPC1=CC=CC=C1 Chemical compound CC.ClPC1=CC=CC=C1 IFVKYYDUXZQIJT-UHFFFAOYSA-N 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- DNDMRSOUMYPBKS-UHFFFAOYSA-M Br[Mg]C1=C(C=C)C=CC=C1 Chemical compound Br[Mg]C1=C(C=C)C=CC=C1 DNDMRSOUMYPBKS-UHFFFAOYSA-M 0.000 description 3
- GGRQQHADVSXBQN-FGSKAQBVSA-N carbon monoxide;(z)-4-hydroxypent-3-en-2-one;rhodium Chemical compound [Rh].[O+]#[C-].[O+]#[C-].C\C(O)=C\C(C)=O GGRQQHADVSXBQN-FGSKAQBVSA-N 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 238000002390 rotary evaporation Methods 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- 238000005303 weighing Methods 0.000 description 3
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 2
- LVEYOSJUKRVCCF-UHFFFAOYSA-N 1,3-bis(diphenylphosphino)propane Chemical compound C=1C=CC=CC=1P(C=1C=CC=CC=1)CCCP(C=1C=CC=CC=1)C1=CC=CC=C1 LVEYOSJUKRVCCF-UHFFFAOYSA-N 0.000 description 2
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 2
- MPNFUAWYZWQOJU-UHFFFAOYSA-N C=CC(CCCP(C1=CC=CC=C1)C1=CC=CC=C1)(C=C)P(C1=CC=CC=C1)C1=CC=CC=C1 Chemical class C=CC(CCCP(C1=CC=CC=C1)C1=CC=CC=C1)(C=C)P(C1=CC=CC=C1)C1=CC=CC=C1 MPNFUAWYZWQOJU-UHFFFAOYSA-N 0.000 description 2
- RSWLDYYBTOZAHY-UHFFFAOYSA-N C=CC(CP(C1=CC=CC=C1)C1=CC=CC=C1)(CP(C1=CC=CC=C1)C1=CC=CC=C1)C=C Chemical class C=CC(CP(C1=CC=CC=C1)C1=CC=CC=C1)(CP(C1=CC=CC=C1)C1=CC=CC=C1)C=C RSWLDYYBTOZAHY-UHFFFAOYSA-N 0.000 description 2
- NSDZKIDSEBWXKB-UHFFFAOYSA-N ClP(CCCCP(C1=CC=CC=C1)C1=CC=CC=C1)Cl Chemical compound ClP(CCCCP(C1=CC=CC=C1)C1=CC=CC=C1)Cl NSDZKIDSEBWXKB-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- QILQKRYCXJFQLZ-UHFFFAOYSA-N dichloro(3-diphenylphosphanylpropyl)phosphane Chemical compound C=1C=CC=CC=1P(CCCP(Cl)Cl)C1=CC=CC=C1 QILQKRYCXJFQLZ-UHFFFAOYSA-N 0.000 description 2
- OEKLCAXLANZKPX-UHFFFAOYSA-N dichloro(dichlorophosphanylmethyl)phosphane Chemical compound ClP(Cl)CP(Cl)Cl OEKLCAXLANZKPX-UHFFFAOYSA-N 0.000 description 2
- 239000002815 homogeneous catalyst Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 2
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- IGZGPHCSICULHS-UHFFFAOYSA-N C=CC(C=CC=C1)=C1P(CCP(C1=CC=CC=C1)C1=C(C=C)C=CC=C1)C1=CC=CC=C1 Chemical compound C=CC(C=CC=C1)=C1P(CCP(C1=CC=CC=C1)C1=C(C=C)C=CC=C1)C1=CC=CC=C1 IGZGPHCSICULHS-UHFFFAOYSA-N 0.000 description 1
- OSGSLMLDGKAEBY-UHFFFAOYSA-N C=CC1=CC=CC(P(CCP(C2=CC=CC=C2)C2=CC(C=C)=CC=C2)C2=CC=CC=C2)=C1 Chemical compound C=CC1=CC=CC(P(CCP(C2=CC=CC=C2)C2=CC(C=C)=CC=C2)C2=CC=CC=C2)=C1 OSGSLMLDGKAEBY-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- BDAJJKOUELCFCA-UHFFFAOYSA-N ClC1=CPC(CC(PC=C2Cl)=C2Cl)=C1Cl Chemical compound ClC1=CPC(CC(PC=C2Cl)=C2Cl)=C1Cl BDAJJKOUELCFCA-UHFFFAOYSA-N 0.000 description 1
- WVDHCPNSOSHTSC-UHFFFAOYSA-N ClPC(CCC1=CC=CC=C1)P(Cl)Cl Chemical compound ClPC(CCC1=CC=CC=C1)P(Cl)Cl WVDHCPNSOSHTSC-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 238000005411 Van der Waals force Methods 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 238000004873 anchoring Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
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- 238000009835 boiling Methods 0.000 description 1
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- 150000004696 coordination complex Chemical class 0.000 description 1
- KIUIKWRHWKNTBP-UHFFFAOYSA-N dichloro(3-dichlorophosphanylpropyl)phosphane Chemical compound ClP(Cl)CCCP(Cl)Cl KIUIKWRHWKNTBP-UHFFFAOYSA-N 0.000 description 1
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- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
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- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
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- 239000004014 plasticizer Substances 0.000 description 1
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- 239000009719 polyimide resin Substances 0.000 description 1
- 229920005990 polystyrene resin Polymers 0.000 description 1
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- 239000010703 silicon Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
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- 239000004711 α-olefin Substances 0.000 description 1
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- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/06—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing polymers
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- 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
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
本发明公开了一种用于烯烃氢甲酰化的双膦聚合物催化剂及其制备方法和应用。该双膦聚合物催化剂是由活性金属组分和双膦共聚物组成形成的多相催化剂,其中所述双膦共聚物通过两种或多种单体以不同比例共聚调控聚合物的多级孔结构,所述双膦共聚物单体为含乙烯基的双膦配体单体与含有烯烃基官能团的芳烃化合物两种或多种经溶剂热聚合法聚合得到。本发明双膦聚合物催化剂保留了均相催化活性高、选择性好的优点,且多孔结构中柔性链连接的双膦结构,提高了活性金属与膦多配体配位的比例,提高了活性金属在催化剂中的稳定性。
Description
技术领域
本发明属于催化剂制备与应用领域,具体涉及双膦聚合物催化剂制备及其在非均相烯烃氢甲酰化反应中的应用。
背景技术
烯烃氢甲酰化反应是目前工业生产中应用规模最大的均相催化反应之一,利用该反应可生产增塑剂醇、表面活性剂醇、羧酸等多种高附加值含氧化学品,全球总产量达到2000万吨/年。然而,目前工业化的烯烃氢甲酰化工艺多为均相催化的气液相反应过程。从氢甲酰化反应诞生之日起,均相催化剂与产物的分离循环问题一直限制其发展。
在均相催化过程中,以高碳烯烃作为氢甲酰化反应的原料存在较大的问题,原因在于高碳醛产物沸点很高,需要高温条件才能将产物分离,而氢甲酰化催化剂在高温分离过程中极易分解。通过均相催化剂的多相化可以解决催化剂的分离问题,这方面已经进行了大量的研究。
氢甲酰化均相催化剂的多相化一个方向是将金属或金属配合物负载在固体载体上,使得催化剂与产物容易分离。根据载体类型的不同,可分为无机载体和有机载体。无机载体主要为大比表面积的活性炭、二氧化硅以及氧化铝等。有机载体主要为聚苯乙烯树脂、聚酰亚胺树脂等。由于以上载体与金属之间的一般为弱相互作用的范德华力,使得金属在载体上吸附不牢固,容易在反应过程中流失。并且由于反应体系中配体浓度较低,使得催化体系的选择性不高。
专利CN 103521268A公布了一种锚合配体和助剂双重修饰的负载金属催化剂,催化剂以SiO2、Al2O3、MCM-14等分子筛为载体,配体选用能与硅羟基作用的含N或P的有机配体。属于有机无机杂化型载体,用于烯烃氢甲酰化反应。但整体催化活性较低,乙烯氢甲酰化活性只有<300TOFh-1的反应速率。
专利CN112892602A公布了一种间位含有乙烯基的三苯基膦类多孔有机聚合物型催化剂,在进行1-辛烯的氢甲酰化反应时,正异比较高,可达到15.5。但该催化剂体系中聚合物的聚合单体是单一的单齿膦配体,在形成聚合物后,结构完全呈现刚性,与铑等中心活性金属难以形成稳定的多配位构型,存在金属流失的问题。
发明内容
本发明为克服现有烯烃均相氢甲酰化技术中非均相催化剂反应活性低及存在活性金属流失问题。提供一种多孔双膦聚合物催化剂,该催化剂保留了均相催化活性高、选择性好的优点,且多孔结构中柔性链连接的双膦结构,提高了活性金属与膦多配体配位的比例,提高了活性金属在催化剂中的稳定性。
本发明所要解决的技术问题具体采用如下技术方案予以实现:
一种用于烯烃氢甲酰化反应的双膦聚合物催化剂,所述双膦聚合物催化剂是由活性金属组分和双膦共聚物形成的多相催化剂,所述活性金属组分是金属Rh、Co和Pd中的一种或几种,所述双膦共聚物通过两种或多种单体以不同比例共聚调控聚合物的多级孔结构,所述双膦共聚物单体为含乙烯基的双膦配体单体与含有烯烃基官能团的芳烃化合物两种或多种,经溶剂热聚合法聚合后得到比表面积为100~2000m2/g,孔容为0.1~5.0cm3/g,孔径分布在0.2~100.0nm的聚合物。所述活性金属组分在所述多相催化剂总重量中占0.01~10.0%;
所述双膦配体单体是选自以下各项中的一种或多种:
上述结构式中n的范围为1~4之间的自然数;
所述含有烯烃基官能团的芳烃化合物选自以下各项中的一种或多种:
在上述所述的双膦聚合物催化剂中,其中双膦配体单体的制备步骤为:
将溴代苯乙烯加到含有镁粉的四氢呋喃中,在25~60℃下搅拌,滤除未反应的镁粉得到乙烯基苯基溴化镁溶液;取氯膦基烷烃加入到制得的上述格氏试剂中,再在25~60℃下反应2小时,即得到双膦配体单体L1-L8;所述溴代苯乙烯选自3-溴苯乙烯或2-溴苯乙烯中的一种,所述氯膦基烷烃选自1,2-双(二氯膦基)烷烃,1-二氯膦基-3-苯基氯膦基烷烃,1-二氯膦基-3-二苯基膦基烷烃或1,2-双(苯基氯膦基)烷烃中的一种;所述溴代苯乙烯与镁粉的摩尔比为1.0:2.0~1.0:1.0,溴代苯乙烯与氯膦基烷烃的摩尔比为1.0:0.50~1.0:0.10。
优选,活性金属组分在所述双膦聚合物催化剂总重量中占0.005~2.0%。
优选,所述双膦聚合物的比表面积为150~1500m2/g,孔容为0.1~5.0cm3/g,孔径分布在0.2~100.0nm。
本发明还进一步提供了上述双膦聚合物催化剂的一种制备方法,包括:
I)水热反应釜中,将双膦配体单体溶于有机溶剂,再加入自由基引发剂,加热至60~150℃反应0.5~50小时;
II)将步骤I)结束后过滤,滤饼在减压加热下脱除溶剂,即得到所述双膦聚合物;
III)将所述双膦聚合物置于溶有活性金属组分的有机溶剂中,在60~150℃和惰性气体保护氛围下搅拌0.5~20小时,然后在室温下过滤,即得到所述由双膦聚合物上负载活性金属组分的催化剂。
优选,步骤I)和III)中使用的有机溶剂是甲醇、乙醇、甲苯、二甲苯、二氧六环、四氢呋喃或二氯甲烷中的一种或几种的混合物;步骤I)中使用的自由基引发剂是过氧化二苯甲酰、叔丁基过氧化氢、偶氮二异丁腈或偶氮二异庚腈的一种或几种。进一步优选,所述有机溶剂是甲苯、二氧六环或四氢呋喃。
进一步优选,所述自由基引发剂与所述有机配体单体的重量比为1:100~1:5。
本发明还进一步提供了上述的双膦聚合物催化剂在烯烃氢甲酰化反应中的应用,其中,应用在装填有所述双膦聚合物催化剂的固定床中,使烯烃原料与CO/H2混合气进行所述烯烃氢甲酰化反应,其中反应温度为40~200℃,反应压力为0.1~10.0MPa,气体体积空速为100~10000h-1。
与现有技术相比,本发明具有如下显著效果:
1.本发明提供的多孔有机双膦聚合物负载氢甲酰化催化剂,用于混合α烯烃氢甲酰化制高碳醛反应,具有高活性、高选择性和催化剂易循环回用的优点。
2.本发明提供的多孔有机双膦聚合物负载催化剂制备方法简单,合成收率高,易于实现规模化生产。
本发明的其他特征和优点将在随后的具体实施方式部分予以详细说明。
具体实施方式
以下对本发明的具体实施方式进行详细说明。应当理解的是,此处所描述的具体实施方式仅用于说明和解释本发明,并不用于限制本发明。
实施例1
间位取代的四乙烯基1,2-双(二苯基膦)乙烷(L1n2)的制备步骤为:
(1)将3-溴苯乙烯加入到含有镁粉的四氢呋喃中,然后在25℃下搅拌3小时,滤除未反应的镁粉得到3-乙烯基苯基溴化镁溶液;
(2)将1,2-双(二氯膦基)乙烷加入到制得的格氏试剂中,在25℃下反应2小时,即得到间位取代的四乙烯基1,2-双(二苯基膦)乙烷。
其中,3-溴苯乙烯与镁粉的摩尔比为1:1.1,3-溴苯乙烯与1,2-双(二氯膦基)乙烷的摩尔比为1:0.25。
多孔双膦聚合物POL-L1n2合成
在氩气气氛下,向100mL的水热反应釜中分别加入无水四氢呋喃(20mL),间位取代的四乙烯基1,2-双(二苯基膦)乙烷(2.0mmo1),二乙烯基苯(2.0mmo1)和偶氮二异丁腈引发剂((0.2mmo1)。室温下搅拌后在100℃下聚合24小时,产物经离心分离,四氢呋喃洗涤,旋蒸脱除溶剂后得白色多孔双膦聚合物。
多孔双膦聚合物负载铑催化剂Rh-POL-L1n2的合成
称取Rh(acac)(CO)2(3mg)溶于四氢呋喃(20mL)中,加入1.0克上述制得的多孔双膦聚合物,在氩气保护下室温搅拌24小时。离心分离后,用甲苯洗涤产物,室温条件下真空抽除溶剂,即获得适用于烯烃氢甲酰化反应的多孔双膦聚合物负载铑催化剂。
实施例2
邻位取代的四乙烯基1,2-双(二苯基膦)乙烷(L2n2)的制备步骤为:
(1)取2-溴苯乙烯加到含有镁粉的四氢呋喃中,然后在25℃下搅拌3小时,滤除未反应的镁粉得到2-乙烯基苯基溴化镁溶液;
(2)取双(二氯磷氢基)甲烷加入到制得的格氏试剂中,再在25℃下反应3小时,即得到邻位取代的四乙烯基1,2-双(二苯基膦)乙烷。
其中,2-溴苯乙烯与镁粉的摩尔比为1:1.1,2-溴苯乙烯与1,2-双(二氯膦基)乙烷的摩尔比为1:0.25。
基于单体L1n2的多孔双膦聚合物合成与铑负载参照实施例1,只是将聚合步骤中的溶剂更换为二氧六环。
实施例3
间位取代的三乙烯基1,3-双(二苯基膦)丙烷(L3n3)的制备步骤为:
(1)取3-溴苯乙烯加到含有镁粉的四氢呋喃中,然后在25℃下搅拌3小时,滤除未反应的镁粉得到3-乙烯基苯基溴化镁溶液;
(2)取1-二氯膦基-3-苯基氯膦基丙烷加入到制得的格氏试剂中,再在60℃下反应2小时,即得到间位取代的三乙烯基1,3-双(二苯基膦)丙烷。
其中,3-溴苯乙烯与镁粉的摩尔比为1:1.1,3-溴苯乙烯与1,3-双(二氯膦基)丙烷的摩尔比为1:0.34。
基于单体L3n3的多孔双膦聚合物合成与铑负载参照实施例1。
实施例4
间位取代的四乙烯基1,2-双(二苯基膦)甲烷(L1n1)的制备步骤为:
(1)取3-溴苯乙烯加到含有镁粉的四氢呋喃中,然后在25℃下搅拌3小时,滤除未反应的镁粉得到3-乙烯基苯基溴化镁溶液;
(2)取双(二氯膦基)甲烷加入到制得的格氏试剂中,再在25℃下反应2小时,即得到间位取代的四乙烯基-双(二苯基膦)甲烷。
其中,3-溴苯乙烯与镁粉的摩尔比为1:1.5,3-溴苯乙烯与双(二氯膦基)甲烷的摩尔比为1:0.25。
基于单体L1n1的多孔双膦聚合物合成与铑负载参照实施例1,只是将聚合步骤中的溶剂更换为二氧六环。
实施例5
间位取代的二乙烯基1,3-双(二苯基膦)丙烷(L5n3)的制备步骤为:
(1)取3-溴苯乙烯加到含有镁粉的四氢呋喃中,然后在25℃下搅拌3小时,滤除未反应的镁粉得到3-乙烯基苯基溴化镁溶液;
(2)取1-二氯膦基-3-二苯基膦基丙烷加入到制得的格氏试剂中,再在40℃下反应2小时,即得到间位取代的二乙烯基1,3-双(二苯基膦)丙烷。
其中,3-溴苯乙烯与镁粉的摩尔比为1:1.2,3-溴苯乙烯与1-二氯膦基-3-二苯基膦基丙烷的摩尔比为1:0.25。
基于单体L5n3的多孔双膦聚合物合成与铑负载参照实施例1,只是将聚合步骤中的溶剂更换为二氧六环。
实施例6
邻位取代的二乙烯基1,4-双(二苯基膦)丁烷(L6n4)的制备步骤为:
(1)取2-溴苯乙烯加到含有镁粉的四氢呋喃中,然后在25℃下搅拌3小时,滤除未反应的镁粉得到2-乙烯基苯基溴化镁溶液;
(2)取1-二氯膦基-4-二苯基膦基丁烷加入到制得的格氏试剂中,再在40℃下反应2小时,即得到邻位取代的二乙烯基1,4-双(二苯基膦)丁烷。
其中,2-溴苯乙烯与镁粉的摩尔比为1:1.2,2-溴苯乙烯与1-二氯膦基-4-二苯基膦基丁烷的摩尔比为1:0.25。
基于单体L6n4的多孔双膦聚合物合成与铑负载参照实施例1,只是将聚合步骤中的溶剂更换为二氧六环。
实施例7
1,2-二(3-乙烯基苯基-苯基膦)乙烷(L7n2)的制备步骤为:
(1)取3-溴苯乙烯加到含有镁粉的四氢呋喃中,然后在25℃下搅拌3小时,滤除未反应的镁粉得到3-乙烯基苯基溴化镁溶液;
(2)取1,2-双(苯基氯膦)乙烷加入到制得的格氏试剂中,再在60℃下反应3小时,即得到1,2-二(3-乙烯基苯基-苯基膦)乙烷。
其中,3-溴苯乙烯与镁粉的摩尔比为1:1.1,3-溴苯乙烯与1,2-双(苯基氯膦)乙烷的摩尔比为1:0.25。
基于单体L7n2的多孔双膦聚合物合成与铑负载参照实施例1,只是将聚合步骤中的溶剂更换为二氧六环。
实施例8
1,2-二(2-乙烯基苯基-苯基膦)乙烷(L8n2)的制备步骤为:
(1)取2-溴苯乙烯加到含有镁粉的四氢呋喃中,然后在25℃下搅拌3小时,滤除未反应的镁粉得到2-乙烯基苯基溴化镁溶液;
(2)取1,2-双(苯基氯膦)乙烷加入到制得的格氏试剂中,再在60℃下反应3小时,即得到1,2-二(2-乙烯基苯基-苯基膦)乙烷。
其中,2-溴苯乙烯与镁粉的摩尔比为1:1.1,3-溴苯乙烯与1,2-双(苯基氯膦)乙烷的摩尔比为1:0.25。
基于单体L8n2的多孔双膦聚合物合成与铑负载参照实施例1,只是将聚合步骤中的溶剂更换为二氧六环。
实施例9
间位取代的四乙烯基1,2-双(二苯基膦)乙烷(L1n2)的制备步骤为:
(3)将3-溴苯乙烯加入到含有镁粉的四氢呋喃中,然后在25℃下搅拌3小时,滤除未反应的镁粉得到3-乙烯基苯基溴化镁溶液;
(4)将1,2-双(二氯膦基)乙烷加入到制得的格氏试剂中,在25℃下反应2小时,即得到间位取代的四乙烯基1,2-双(二苯基膦)乙烷。
其中,3-溴苯乙烯与镁粉的摩尔比为1:1.1,3-溴苯乙烯与1,2-双(二氯膦基)乙烷的摩尔比为1:0.25。
多孔双膦聚合物POL-L1n2-TPP合成
在氩气气氛下,向100mL的水热反应釜中分别加入无水四氢呋喃(20mL),间位取代的四乙烯基1,2-双(二苯基膦)乙烷(2.0mmo1),三(4-乙烯基苯)基膦(2.0mmo1)和偶氮二异丁腈引发剂((0.2mmo1)。室温下搅拌后在100℃下聚合24小时,产物经离心分离,四氢呋喃洗涤,旋蒸脱除溶剂后得白色多孔双膦聚合物。
多孔双膦聚合物负载铑催化剂Rh-POL-L1n2-TPP的合成
称取Rh(acac)(CO)2(3mg)溶于四氢呋喃(20mL)中,加入1.0克上述制得的多孔双膦聚合物,在氩气保护下室温搅拌24小时。离心分离后,用甲苯洗涤产物,室温条件下真空抽除溶剂,即获得适用于烯烃氢甲酰化反应的多孔双膦聚合物负载铑催化剂。
实施例10
间位取代的四乙烯基1,2-双(二苯基膦)乙烷(L1n2)的制备步骤为:
(5)将3-溴苯乙烯加入到含有镁粉的四氢呋喃中,然后在25℃下搅拌3小时,滤除未反应的镁粉得到3-乙烯基苯基溴化镁溶液;
(6)将1,2-双(二氯膦基)乙烷加入到制得的格氏试剂中,在25℃下反应2小时,即得到间位取代的四乙烯基1,2-双(二苯基膦)乙烷。
其中,3-溴苯乙烯与镁粉的摩尔比为1:1.1,3-溴苯乙烯与1,2-双(二氯膦基)乙烷的摩尔比为1:0.25。
多孔双膦聚合物POL-L1n2-ST合成
在氩气气氛下,向100mL的水热反应釜中分别加入无水四氢呋喃(20mL),间位取代的四乙烯基1,2-双(二苯基膦)乙烷(2.0mmo1),苯乙烯(2.0mmo1)和偶氮二异丁腈引发剂((0.2mmo1)。室温下搅拌后在100℃下聚合24小时,产物经离心分离,四氢呋喃洗涤,旋蒸脱除溶剂后得白色多孔双膦聚合物。
多孔双膦聚合物负载铑催化剂Rh-POL-L1n2-ST的合成
称取Rh(acac)(CO)2(3mg)溶于四氢呋喃(20mL)中,加入1.0克上述制得的多孔双膦聚合物,在氩气保护下室温搅拌24小时。离心分离后,用甲苯洗涤产物,室温条件下真空抽除溶剂,即获得适用于烯烃氢甲酰化反应的多孔双膦聚合物负载铑催化剂。
评价方法
将上述制备的1.0g多孔双膦聚合物负载铑催化剂装入5mL固定床反应器中,两端封填惰性瓷球。1-己烯用微量恒流泵以流量为0.2mL/min进入反应器,控制合成气(H2:CO=1:1)空速1000h-1,在反应温度90℃,压力的1.5MPa条件下进行氢甲酰化反应。产物冷却后用气相色谱分析,结果如表1所示。
表1实施例1-10中合成的催化剂催化1-己烯氢甲酰化反应结果
Claims (9)
1.一种用于烯烃氢甲酰化反应的双膦聚合物催化剂,其特征在于,所述双膦聚合物催化剂是由活性金属组分和双膦共聚物形成的多相催化剂,所述活性金属组分是金属Rh、Co和Pd中的一种或几种,所述双膦共聚物通过两种或多种单体以不同比例共聚调控聚合物的多级孔结构,所述双膦共聚物单体为含乙烯基的双膦配体单体与含有烯烃基官能团的芳烃化合物两种或多种,经溶剂热聚合法聚合后得到比表面积为100~2000m2/g,孔容为0.1~5.0cm3/g,孔径分布在0.2~100.0nm的聚合物。所述活性金属组分在所述多相催化剂总重量中占0.01~10.0%;
其中所述双膦配体单体是选自以下各项中的一种或多种:
上述结构式中n的范围为1~4之间的自然数;
所述含有烯烃基官能团的芳烃化合物选自以下各项中的一种或多种:
2.根据权利要求1所述的双膦聚合物催化剂,其特征在于,所述的双膦配体单体由如下制备步骤制得:
将溴代苯乙烯加到含有镁粉的四氢呋喃中,在25~60℃下搅拌,滤除未反应的镁粉得到乙烯基苯基溴化镁溶液;取氯膦基烷烃加入到制得的所述乙烯基苯基溴化镁溶液中,再在25~60℃下反应2小时,即得到双膦配体单体L1-L8;所述溴代苯乙烯选自3-溴苯乙烯或2-溴苯乙烯中的一种,所述氯膦基烷烃选自1,2-双(二氯膦基)烷烃,1-二氯膦基-3-苯基氯膦基烷烃,1-二氯膦基-3-二苯基膦基烷烃或1,2-双(苯基氯膦基)烷烃中的一种;所述溴代苯乙烯与镁粉的摩尔比为1.0:2.0~1.0:1.0,溴代苯乙烯与氯膦基烷烃的摩尔比为1.0:0.50~1.0:0.10。
3.根据权利要求1所述的双膦聚合物催化剂,其特征在于,所述活性金属组分在所述双膦聚合物催化剂总重量中占0.005~2.0%。
4.根据权利要求1所述的双膦聚合物催化剂,其特征在于,所述双膦聚合物的比表面积为150~1500m2/g,孔容为0.1~5.0cm3/g,孔径分布在0.2~100.0nm。
5.一种制备权利要求1所述的双膦聚合物催化剂的方法,其特征在于,包括:
I.水热反应釜中,将双膦配体单体溶于有机溶剂,再加入自由基引发剂,加热至60~150℃反应0.5~50小时;
II.将步骤I)结束后过滤,滤饼在减压加热下脱除溶剂,即得到所述双膦聚合物;
III.将所述双膦聚合物置于溶有活性金属组分的有机溶剂中,在60~150℃和惰性气体保护氛围下搅拌0.5~20小时,然后在室温下过滤,即得到所述由双膦聚合物上负载活性金属组分的催化剂。
6.根据权利要求5所述的方法,其特征在于,步骤I)和III)中使用的有机溶剂是甲醇、乙醇、甲苯、二甲苯、二氧六环、四氢呋喃或二氯甲烷中的一种或几种的混合物;步骤I)中使用的自由基引发剂是过氧化二苯甲酰、叔丁基过氧化氢、偶氮二异丁腈或偶氮二异庚腈的一种或几种。
7.根据权利要求6所述的方法,其特征在于,所述有机溶剂是甲苯、二氧六环或四氢呋喃。
8.根据权利要求5所述的方法,其特征在于,所述自由基引发剂与所述有机配体单体的重量比为1:100~1:5。
9.根据权利要求1所述的双膦聚合物催化剂在烯烃氢甲酰化反应中的应用,其特征在于,在装填有所述双膦聚合物催化剂的固定床中,使烯烃原料与CO/H2混合气进行所述烯烃氢甲酰化反应,其中反应温度为40~200℃,反应压力为0.1~10.0MPa,气体体积空速为100~10000h-1。
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