CN116903789A - 含有双齿磷配体的多孔有机聚合物及其制备方法和应用 - Google Patents
含有双齿磷配体的多孔有机聚合物及其制备方法和应用 Download PDFInfo
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- 229920000620 organic polymer Polymers 0.000 title claims abstract description 23
- 239000003446 ligand Substances 0.000 title claims abstract description 22
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 title claims abstract description 20
- 229910052698 phosphorus Inorganic materials 0.000 title claims abstract description 20
- 239000011574 phosphorus Substances 0.000 title claims abstract description 20
- 238000002360 preparation method Methods 0.000 title claims abstract description 8
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- 229920000642 polymer Polymers 0.000 claims abstract description 17
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- 229910052723 transition metal Inorganic materials 0.000 claims abstract description 3
- 238000006243 chemical reaction Methods 0.000 claims description 52
- 238000003756 stirring Methods 0.000 claims description 12
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 5
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- 229940125904 compound 1 Drugs 0.000 claims description 4
- 229940125782 compound 2 Drugs 0.000 claims description 4
- 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 claims description 3
- 229910052739 hydrogen Inorganic materials 0.000 claims description 3
- 229910052751 metal Inorganic materials 0.000 claims description 3
- 239000000178 monomer Substances 0.000 claims description 3
- 125000003545 alkoxy group Chemical group 0.000 claims description 2
- 125000001589 carboacyl group Chemical group 0.000 claims description 2
- 229940126214 compound 3 Drugs 0.000 claims description 2
- 125000004185 ester group Chemical group 0.000 claims description 2
- 229910052736 halogen Inorganic materials 0.000 claims description 2
- 150000002367 halogens Chemical class 0.000 claims description 2
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- 150000002431 hydrogen Chemical class 0.000 claims description 2
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- 125000002560 nitrile group Chemical group 0.000 claims description 2
- FAIAAWCVCHQXDN-UHFFFAOYSA-N phosphorus trichloride Chemical compound ClP(Cl)Cl FAIAAWCVCHQXDN-UHFFFAOYSA-N 0.000 claims description 2
- 239000002904 solvent Substances 0.000 claims description 2
- 125000001273 sulfonato group Chemical group [O-]S(*)(=O)=O 0.000 claims description 2
- 125000000542 sulfonic acid group Chemical group 0.000 claims description 2
- 239000000758 substrate Substances 0.000 claims 3
- 150000003839 salts Chemical class 0.000 claims 2
- 229910002091 carbon monoxide Inorganic materials 0.000 claims 1
- 239000011261 inert gas Substances 0.000 claims 1
- -1 transition metal salts Chemical class 0.000 claims 1
- 230000003197 catalytic effect Effects 0.000 abstract description 9
- 150000001875 compounds Chemical class 0.000 abstract 1
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 22
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 22
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 18
- 230000015572 biosynthetic process Effects 0.000 description 15
- 238000003786 synthesis reaction Methods 0.000 description 15
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 description 14
- 239000007789 gas Substances 0.000 description 14
- 229910052757 nitrogen Inorganic materials 0.000 description 11
- 239000010948 rhodium Substances 0.000 description 11
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 description 9
- 239000003921 oil Substances 0.000 description 9
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 8
- 239000000047 product Substances 0.000 description 8
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 8
- 239000005457 ice water Substances 0.000 description 7
- 239000012299 nitrogen atmosphere Substances 0.000 description 4
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 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 description 3
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- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 229920001577 copolymer Polymers 0.000 description 3
- 239000003999 initiator Substances 0.000 description 3
- 125000004368 propenyl group Chemical group C(=CC)* 0.000 description 3
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- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 2
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
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- VVOAZFWZEDHOOU-UHFFFAOYSA-N magnolol Chemical compound OC1=CC=C(CC=C)C=C1C1=CC(CC=C)=CC=C1O VVOAZFWZEDHOOU-UHFFFAOYSA-N 0.000 description 2
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- 230000009286 beneficial effect Effects 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
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- OVTCUIZCVUGJHS-UHFFFAOYSA-N dipyrrin Chemical compound C=1C=CNC=1C=C1C=CC=N1 OVTCUIZCVUGJHS-UHFFFAOYSA-N 0.000 description 1
- 239000003480 eluent Substances 0.000 description 1
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- 239000000543 intermediate Substances 0.000 description 1
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- 239000002923 metal particle Substances 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 238000009987 spinning Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- UYUUAUOYLFIRJG-UHFFFAOYSA-N tris(4-methoxyphenyl)phosphane Chemical compound C1=CC(OC)=CC=C1P(C=1C=CC(OC)=CC=1)C1=CC=C(OC)C=C1 UYUUAUOYLFIRJG-UHFFFAOYSA-N 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
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- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
- B01J31/189—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms containing both nitrogen and phosphorus as complexing atoms, including e.g. phosphino moieties, in one at least bidentate or bridging ligand
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Abstract
本发明公开了一类含有双齿磷配体的多孔有机聚合物及其制备方法和应用。所述聚合物是具有如下通式Ⅰ:上述聚合物是通过将:通式化合物与或
Description
技术领域
本发明涉及一类有机聚合物及其制备方法和应用。具体说,是涉及一类含有双齿磷配体的多孔有机聚合物及其制备方法和应用,属于有机化学技术领域。
技术背景
氢甲酰化反应是指烯烃和CO/H2在催化剂的作用下生成醛的过程。烯烃氢甲酰化反应是工业上合成醛的重要方法,醛类化合物是非常有价值的精细化学品,也是重要的合成中间体。实现非均相催化烯烃的氢甲酰化反应,则可以有效解决催化剂回收、循环和污染等问题。多孔有机聚合物(POPs)作为一类新兴的高分子材料,因高比表面积、稳定的骨架和可控的结构而受到广泛的研究兴趣;并在多相催化领域中取得了长足的进展。由膦配体单体构建的POPs具有以下特点:(1)在聚合物骨架中高浓度的膦配体能负载金属,回收催化剂;(2)有效调节金属中心周围的空间效益和电子效益,有助于催化剂的选择性和活性提高;(3)能够有效分散金属颗粒,形成单原子活性位点。因此,近年来多种含膦POPs材料被合成并用于多相催化中。通过溶剂热烯烃聚合是合成含膦多孔有机聚合物的主要方法之一。然而仍然存在着原料昂贵、合成过程繁杂和废弃物多等问题。本专利以天然产物厚朴酚为原料,通过三步反应成功合成了一种含有双齿磷配体的多孔有机聚合物。该聚合物负载铑构建的非均相催化剂在烯烃的氢甲酰化反应中的表现出高的催化活性、选择性和循环性。
发明内容
本发明的目的是提供一类含有双齿磷配体的多孔有机聚合物及其制备方法和应用,为非均相催化烯烃氢甲酰化增添一类新催化剂。
一类含有双齿磷配体的多孔有机聚合物,其具有如下结构通式I:
上述通式中:
R1、R2、R3、R4分别选自C1~C10的烷烃基、C1~C10的烷氧基、
R5、R6、R7、R8、R9、R10分别独立选自氢、磺酸基、卤素、腈基、C1~C12的烷烃基、C1~C10的烷酰基、C1~C10的酯基、C1~C10的磺酸酯基;
R分别来自单体单元;
n:m比例为1:1~1:100;
所述的一类含有双齿磷配体的多孔有机聚合物,其特征在于:聚合物I由化合物1与R'进行聚合反应得到;反应通式如下所示:
所述通式中化合物1由化合物2与磷氯进行反应得到;反应通式如下所示:
所述通式中化合物2由化合物3异构反应得到;反应通式如下所示:
上述通式中的R1、R2、R3、R4、R5、R6、R7、R8、R9、R10及R的含义均同权利要求1中所述;R'分别选自
所述的一类含有双齿磷配体的多孔有机聚合物的应用,其特征在于:用于催化烯烃的氢甲酰化反应;
所述的应用,其特征在于:一类含有双齿磷配体的多孔有机聚合物与过渡金属盐形成I/Rh催化剂,然后用于催化烯烃的氢甲酰化反应;
所述的应用,其特征在于,一类含有双齿磷配体的多孔有机聚合物选自如下结构:
与现有技术相比,本发明具有如下显著效果:
1.本发明提供的含有双齿磷配体的多孔有机聚合物负载催化剂,以天然产物为原料、合成步骤绿色、制备方法简单。
2.本发明提供的含有双齿磷配体的多孔有机聚合物负载催化剂,用于烯烃的氢甲酰化反应,反应条件温和,收率可高达78%,适于规模化生产,具有实用价值。
具体实施方式
下面结合实施例对本发明作进一步详细、完整地说明。
下述实施例中所用的丙烯基联苯二酚通过如下方法制备而得,具体为:
1)二酚的制备
在氮气保护下,反应瓶中加入原料1.0g,Rh(acac)(CO)2(1mg,0.004mmol),三(4-甲氧苯基)膦(4.22mg,0.012mmol),EtOH(4mL),100℃加热72小时,产物经柱层析分离提纯得到丙烯基联苯二酚。产物表征如下:1H NMR(500MHz,CDCl3)δ7.29(dd,J=8.5,1.5Hz,2H),7.23(d,J=1.5Hz,2H),6.95(d,J=8.5Hz,2H),6.36(d,J=15.5Hz,2H),6.13(m,2H),5.70(d,J=28.5Hz,2H),1.88(dd,J=19.5,7.0Hz,6H).
2)合成
在氮气气氛下,向20mL的Schlenk管里分别加入二吡咯磷氯(297.9mg,1.5mmol),无水三乙胺(0.21mL,1.5mmol)和无水四氢呋喃(2mL),降温至0℃,滴加丙烯基联苯二酚(200mg,0.75mmol)无水四氢呋喃(2mL)溶液,缓慢升温至室温并搅拌过夜,停止反应,减压旋去溶剂,柱层析(淋洗剂:乙酸乙酯:石油醚=1/20)分离得到无色油状物421.1mg。产物表征如下:1H NMR(500MHz,CDCl3)δ7.23(d,J=6.5Hz,4H),6.79(d,J=9.0Hz,2H),6.73(s,8H),6.35(d,J=15.5Hz,2H),6.24(s,8H),6.16(m,2H),1.91–1.84(m,6H).
3)聚合物I1合成
在氮气气氛下,向10mL的旋塞瓶中分别加入无水四氢呋喃(3.0mL),共聚单元(60mg,0.102mmol)和/>(172.8mg,0.51mmol)。最后加入5.0mg的引发剂AIBN。室温下搅拌10min后,在100℃下反应24h,产物经离心分离,四氢呋喃洗涤(3×3mL)旋蒸后得白色的固体(201.2mg)。
4)聚合物I2合成
在氮气气氛下,向10mL的旋塞瓶中分别加入无水四氢呋喃(3.0mL),共聚单元(60.2mg,0.102mmol)和二乙烯苯(66.4mg,0.51mmol)。最后加入5.0mg的引发剂AIBN。室温下搅拌10min后,在100℃下反应24h,产物经离心分离,四氢呋喃洗涤(3×3mL)旋蒸后得白色的固体(108.4mg)。
5)聚合物I3合成
在氮气气氛下,向10mL的旋塞瓶中分别加入无水四氢呋喃(3.0mL),共聚单元(60.2mg,0.102mol)和/>(196.1mg,0.51mmol)。最后加入5.0mg的引发剂AIBN。室温下搅拌10min后,在100℃下反应24h,产物经离心分离,四氢呋喃洗涤(3×3mL)旋蒸后得白色的固体(201.3mg)
6)聚合物I1/Rh催化剂的合成
在氮气气氛下,向一100mL的Schlenk管里分别加入(90mg),Rh(acac)(CO)2(3.4mg,0.0132mmol)和无水甲苯(5mL)。在氮气保护下室温下搅拌24h后,用无水THF洗涤反应产物后离心分离,如此离心洗涤三次。最后,减压旋蒸出去甲苯,再用油泵抽3h,得到催化剂(85mg)。
7)聚合物I1/Rh催化剂催化1-己烯催化量S/C=1x104的氢甲酰化反应
在手套箱里,向100mL反应釜加入催化剂(5mg)和无水1-己烯(0.46mL,3.67mmol)。然后充入CO置换釜内氮气三次,再充入CO(10atm)和H2(10atm),油浴90℃下搅拌反应3h。反应完成后,用冰水浴冷却反应釜至室温,缓慢放掉合成气,加入癸烷(49uL)作为内标物,搅拌均匀后测气相。正异比为50.5,直链醛的收率为78.0%,TON为9000。
8)聚合物I1/Rh催化剂催化1-己烯催化量S/C=20x104的氢甲酰化反应
在手套箱里,向100mL反应釜加入催化剂(5.0mg)和无水1-己烯(9.11mL,73.4mmol)。然后充入CO置换釜内氮气三次,再充入CO(10atm)和H2(10atm),油浴90℃下搅拌反应10h。反应完成后,用冰水浴冷却反应釜至室温,缓慢放掉合成气,然后充入CO(10atm)和H2(10atm),继续反应3h,如此反应2次。最后,加入癸烷(49uL)作为内标物,搅拌均匀后测气相。正异比为12.1,直链醛的摩尔百份含量为77.3%,TON为16.7×104。
9)聚合物I1/Rh催化剂催化1-己烯催化量S/C=1x104的氢甲酰化反应循环测试。
在手套箱里,向100mL反应釜加入催化剂(50mg)和无水1-己烯(4.6mL,36.7mmol)。然后充入CO置换釜内氮气三次,再充入CO(10atm)和H2(10atm),油浴90℃下搅拌反应3h。反应完成后,用冰水浴冷却反应釜至室温,缓慢放掉合成气,将反应体系离心分离出上层产物和下层催化剂。分离出的催化剂在手套箱里加入反应釜内和加入无水1-己烯(4.6mL,36.7mmol)。然后充入CO置换釜内氮气三次,再充入CO(10atm)和H2(10atm),油浴90℃下搅拌反应3h。上层产物加入癸烷(49uL)作为内标物,搅拌均匀后测气相。如此循环10次。在十次反应过程中,醛的收率均能保持在70%以上。
10)聚合物I1/Rh催化剂催化1-辛烯催化量S/C=1x104的异构化/氢甲酰化反应。
在手套箱里,向100mL反应釜加入催化剂(5mg)和无水2-辛烯(0.57ml,3.67mmol)。然后充入CO置换釜内氮气三次,再充入CO(10atm)和H2(10atm),油浴90℃下搅拌反应3h。反应完成后,用冰水浴冷却反应釜至室温,缓慢放掉合成气,加入癸烷(49uL)作为内标物,搅拌均匀后测气相。正异比为40,直链醛的收率为71.0%,TON为8000。
11)聚合物I1/Rh催化剂催化2-辛烯催化量S/C=1x104的异构化/氢甲酰化反应。
在手套箱里,向100mL反应釜加入催化剂(5mg)和无水2-辛烯(0.57mL,3.67mmol)。然后充入CO置换釜内氮气三次,再充入CO(10atm)和H2(10atm),油浴90℃下搅拌反应3h。反应完成后,用冰水浴冷却反应釜至室温,缓慢放掉合成气,加入癸烷(49uL)作为内标物,搅拌均匀后测气相。正异比为7,直链醛的收率为57.7%,TON为6000。
12)聚合物I2/Rh催化剂催化1-己烯催化量S/C=1x104的氢甲酰化反应
在手套箱里,向100mL反应釜加入催化剂(4mg)和无水1-己烯(0.46mL,3.67mmol)。然后充入CO置换釜内氮气三次,再充入CO(10atm)和H2(10atm),油浴90℃下搅拌反应3h。反应完成后,用冰水浴冷却反应釜至室温,缓慢放掉合成气,加入癸烷(49uL)作为内标物,搅拌均匀后测气相。正异比为49,直链醛的收率为76.0%,TON为8500。
13)聚合物I3/Rh催化剂催化1-己烯催化量S/C=1x104的氢甲酰化反应
在手套箱里,向100mL反应釜加入催化剂(5.3mg)和无水1-己烯(0.46mL,3.67mmol)。然后充入CO置换釜内氮气三次,再充入CO(10atm)和H2(10atm),油浴90℃下搅拌反应3h。反应完成后,用冰水浴冷却反应釜至室温,缓慢放掉合成气,加入癸烷(49uL)作为内标物,搅拌均匀后测气相。正异比为46,直链醛的收率为72%,TON为8200。
上实施例仅用以说明本发明的技术方案,而非对其进行限制;尽管参照前述实施例对本发明进行了详细的说明,对于本领域的普通技术人员来说,依然可以对前述实施例所记载的技术方案进行修改,或者对其中部分技术特征进行等同替换;而这些修改或替换,并不使相应技术方案的本质脱离本发明所要求保护的技术方案的精神和范围。
Claims (7)
1.一类含有双齿磷配体的多孔有机聚合物,其具有如下结构通式I:
上述通式中:
R1、R2、R3、R4分别选自C1~C10的烷烃基、C1~C10的烷氧基、
R5、R6、R7、R8、R9、R10分别独立选自氢、磺酸基、卤素、腈基、C1~C12的烷烃基、C1~C10的烷酰基、C1~C10的酯基、C1~C10的磺酸酯基;
R分别来自单体单元;
n:m比例为1:1~1:100。
2.权利要求1所述的一类含有双齿磷配体的多孔有机聚合物,其特征在于:聚合物I由化合物1与R'进行聚合反应得到;反应通式如下所示:
所述通式中化合物1由化合物2与磷氯进行反应得到;反应通式如下所示:
所述通式中化合物2由化合物3异构反应得到;反应通式如下所示:
上述通式中的R1、R2、R3、R4、R5、R6、R7、R8、R9、R10及R的含义均同权利要求1中所述;R'分别选自
3.一种根据权利要求1所述的一类含有双齿磷配体的多孔有机聚合物的应用,其特征在于:用于催化烯烃的氢甲酰化反应。
4.根据权利要求3所述的应用,其特征在于:一类含有双齿磷配体的多孔有机聚合物与过渡金属盐形成I/Rh催化剂,然后用于催化烯烃的氢甲酰化反应。
5.根据权利要求4所述的应用,其特征在于,一类含有双齿磷配体的多孔有机聚合物选自如下结构:
6.根据权利要求4所述的应用,其特征在于,I/Rh催化剂制备包括如下步骤:在惰性气体下,将一类含有双齿磷配体的多孔有机聚合物与Rh(acac)(CO)2金属盐质量比为1:1~500:1加入甲苯中,在0~100℃搅拌反应0.1~20小时,除去溶剂,得到I/Rh催化剂。
7.根据权利要求4所述的应用,其特征在于:将I/Rh催化剂用于催化烯烃的氢甲酰化反应的操作如下:在惰性气氛下,向含有催化剂的反应釜中加入烯烃底物、CO和H2,在0~300℃条件下进行氢甲酰化反应;所述烯烃底物为端烯烃或内烯烃;所述烯烃底物与催化剂中Rh盐的摩尔比为100:1~100000:1,CO压力为0.5~200大气压,H2压力为0.5~200大气压。
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