CN114950551B - 用于烯烃氢甲酰化的单亚磷酸酯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单亚磷酸酯聚合物催化剂及其制备方法和应用 Download PDFInfo
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- CN114950551B CN114950551B CN202210588203.1A CN202210588203A CN114950551B CN 114950551 B CN114950551 B CN 114950551B CN 202210588203 A CN202210588203 A CN 202210588203A CN 114950551 B CN114950551 B CN 114950551B
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- 239000003054 catalyst Substances 0.000 title claims abstract description 40
- 238000007037 hydroformylation reaction Methods 0.000 title claims abstract description 35
- 229920000642 polymer Polymers 0.000 title claims abstract description 30
- 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 12
- 238000002360 preparation method Methods 0.000 title abstract description 39
- 239000003446 ligand Substances 0.000 claims abstract description 35
- 229910052751 metal Inorganic materials 0.000 claims abstract description 29
- 239000002184 metal Substances 0.000 claims abstract description 29
- 229920001577 copolymer Polymers 0.000 claims abstract description 28
- 239000002638 heterogeneous catalyst Substances 0.000 claims abstract description 19
- 239000000178 monomer Substances 0.000 claims abstract description 15
- 238000000034 method Methods 0.000 claims abstract description 11
- 150000001491 aromatic compounds Chemical class 0.000 claims abstract description 10
- 239000011148 porous material Substances 0.000 claims abstract description 10
- 229910052763 palladium Inorganic materials 0.000 claims abstract description 5
- 229910052703 rhodium Inorganic materials 0.000 claims abstract description 5
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 4
- 230000000379 polymerizing effect Effects 0.000 claims abstract description 4
- 230000001276 controlling effect Effects 0.000 claims abstract description 3
- 230000001105 regulatory effect Effects 0.000 claims abstract description 3
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 44
- -1 rh (CH 3COO)2 Chemical compound 0.000 claims description 29
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 claims description 22
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 21
- 238000006243 chemical reaction Methods 0.000 claims description 20
- 238000003756 stirring Methods 0.000 claims description 11
- 239000003960 organic solvent Substances 0.000 claims description 10
- 239000011261 inert gas Substances 0.000 claims description 9
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- 150000003254 radicals Chemical class 0.000 claims description 8
- 125000000524 functional group Chemical group 0.000 claims description 7
- 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 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 5
- 239000007789 gas Substances 0.000 claims description 5
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 4
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 4
- CUJRVFIICFDLGR-UHFFFAOYSA-N acetylacetonate Chemical compound CC(=O)[CH-]C(C)=O CUJRVFIICFDLGR-UHFFFAOYSA-N 0.000 claims description 4
- 238000009826 distribution Methods 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 4
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 4
- 229920002554 vinyl polymer Polymers 0.000 claims description 4
- 238000007334 copolymerization reaction Methods 0.000 claims description 3
- 239000012065 filter cake Substances 0.000 claims description 3
- 238000001914 filtration Methods 0.000 claims description 3
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 claims description 3
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 2
- NFHFRUOZVGFOOS-UHFFFAOYSA-N Pd(PPh3)4 Substances [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 claims description 2
- 229910002666 PdCl2 Inorganic materials 0.000 claims description 2
- RBYGDVHOECIAFC-UHFFFAOYSA-L acetonitrile;palladium(2+);dichloride Chemical compound [Cl-].[Cl-].[Pd+2].CC#N.CC#N RBYGDVHOECIAFC-UHFFFAOYSA-L 0.000 claims description 2
- 125000002947 alkylene group Chemical group 0.000 claims description 2
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 2
- SKWRXFAMSFJQRS-UHFFFAOYSA-N carbon monoxide;cobalt Chemical compound [Co].[O+]#[C-].[O+]#[C-] SKWRXFAMSFJQRS-UHFFFAOYSA-N 0.000 claims description 2
- IETKMTGYQIVLRF-UHFFFAOYSA-N carbon monoxide;rhodium;triphenylphosphane Chemical compound [Rh].[O+]#[C-].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 IETKMTGYQIVLRF-UHFFFAOYSA-N 0.000 claims description 2
- 238000011049 filling Methods 0.000 claims description 2
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 claims description 2
- JKDRQYIYVJVOPF-FDGPNNRMSA-L palladium(ii) acetylacetonate Chemical compound [Pd+2].C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O JKDRQYIYVJVOPF-FDGPNNRMSA-L 0.000 claims description 2
- 239000000725 suspension Substances 0.000 claims description 2
- 239000008096 xylene Substances 0.000 claims description 2
- 229910021604 Rhodium(III) chloride Inorganic materials 0.000 claims 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims 1
- SONJTKJMTWTJCT-UHFFFAOYSA-K rhodium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Rh+3] SONJTKJMTWTJCT-UHFFFAOYSA-K 0.000 claims 1
- 238000000926 separation method Methods 0.000 abstract description 5
- 230000015572 biosynthetic process Effects 0.000 abstract description 3
- 238000003786 synthesis reaction Methods 0.000 abstract description 3
- 230000003197 catalytic effect Effects 0.000 abstract description 2
- KKJLGRFVBCOZKZ-UHFFFAOYSA-N ethenyl dihydrogen phosphite Chemical compound OP(O)OC=C KKJLGRFVBCOZKZ-UHFFFAOYSA-N 0.000 abstract 1
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 42
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 14
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 10
- FAIAAWCVCHQXDN-UHFFFAOYSA-N phosphorus trichloride Chemical compound ClP(Cl)Cl FAIAAWCVCHQXDN-UHFFFAOYSA-N 0.000 description 10
- 239000000243 solution Substances 0.000 description 10
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 9
- 239000010948 rhodium Substances 0.000 description 8
- 230000000694 effects Effects 0.000 description 7
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- FXEIWOUGVRUQNK-UHFFFAOYSA-N 5-ethenyl-2-methoxyphenol Chemical compound COC1=CC=C(C=C)C=C1O FXEIWOUGVRUQNK-UHFFFAOYSA-N 0.000 description 6
- 229910052786 argon Inorganic materials 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 4
- QHPQWRBYOIRBIT-UHFFFAOYSA-N 4-tert-butylphenol Chemical compound CC(C)(C)C1=CC=C(O)C=C1 QHPQWRBYOIRBIT-UHFFFAOYSA-N 0.000 description 4
- FZHSPPYCNDYIKD-UHFFFAOYSA-N 5-methoxysalicylaldehyde Chemical compound COC1=CC=C(O)C(C=O)=C1 FZHSPPYCNDYIKD-UHFFFAOYSA-N 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- OTVDXQWQYPAXTF-UHFFFAOYSA-N 2-tert-butyl-5-ethenylphenol Chemical compound CC(C)(C)C1=CC=C(C=C)C=C1O OTVDXQWQYPAXTF-UHFFFAOYSA-N 0.000 description 3
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 3
- 239000012300 argon atmosphere Substances 0.000 description 3
- 239000002815 homogeneous catalyst Substances 0.000 description 3
- DFXPGUZPIQYTNQ-UHFFFAOYSA-N 2-ethenyl-4-methoxyphenol Chemical compound COC1=CC=C(O)C(C=C)=C1 DFXPGUZPIQYTNQ-UHFFFAOYSA-N 0.000 description 2
- WOQYIZUOIZRPKT-UHFFFAOYSA-N 4-tert-butyl-2-ethenylphenol Chemical compound CC(C)(C)C1=CC=C(O)C(C=C)=C1 WOQYIZUOIZRPKT-UHFFFAOYSA-N 0.000 description 2
- ZVCQQLGWGRTXGC-UHFFFAOYSA-N 5-tert-butyl-2-hydroxybenzaldehyde Chemical compound CC(C)(C)C1=CC=C(O)C(C=O)=C1 ZVCQQLGWGRTXGC-UHFFFAOYSA-N 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical class C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 2
- 229930040373 Paraformaldehyde Natural products 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- 239000007983 Tris buffer Substances 0.000 description 2
- 150000001299 aldehydes Chemical class 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 238000001246 colloidal dispersion Methods 0.000 description 2
- 238000007210 heterogeneous catalysis Methods 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- LSEFCHWGJNHZNT-UHFFFAOYSA-M methyl(triphenyl)phosphanium;bromide Chemical compound [Br-].C=1C=CC=CC=1[P+](C=1C=CC=CC=1)(C)C1=CC=CC=C1 LSEFCHWGJNHZNT-UHFFFAOYSA-M 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- NWVVVBRKAWDGAB-UHFFFAOYSA-N p-methoxyphenol Chemical compound COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 description 2
- 229920002866 paraformaldehyde Polymers 0.000 description 2
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- FTBGIBKQXBYFKS-UHFFFAOYSA-N O1CCCC1.P(Cl)(Cl)Cl Chemical compound O1CCCC1.P(Cl)(Cl)Cl FTBGIBKQXBYFKS-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000001460 carbon-13 nuclear magnetic resonance spectrum Methods 0.000 description 1
- 239000012876 carrier material Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- TWWJJVNUZQLCPD-UHFFFAOYSA-N diphenylphosphane;methane Chemical compound C.C=1C=CC=CC=1PC1=CC=CC=C1 TWWJJVNUZQLCPD-UHFFFAOYSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 238000007172 homogeneous catalysis Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- ZOGYOOUMDVKYLM-UHFFFAOYSA-N phosphane phosphorous acid Chemical compound P.OP(O)O ZOGYOOUMDVKYLM-UHFFFAOYSA-N 0.000 description 1
- 238000001394 phosphorus-31 nuclear magnetic resonance spectrum Methods 0.000 description 1
- 229910052573 porcelain Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- LPNYRYFBWFDTMA-UHFFFAOYSA-N potassium tert-butoxide Chemical compound [K+].CC(C)(C)[O-] LPNYRYFBWFDTMA-UHFFFAOYSA-N 0.000 description 1
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000012719 thermal polymerization Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
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Abstract
本发明涉及一种用于烯烃氢甲酰化的单亚磷酸酯聚合物催化剂及其制备方法和应用,所述单亚磷酸酯聚合物催化剂是由活性金属组分和单亚磷酸酯共聚物组成的多相催化剂,其中所述活性金属组分是Rh、Co和Pd中的一种或几种,所述单亚磷酸酯共聚物是由含乙烯基的单亚磷酸酯配体单体与含有烯烃基官能团的芳烃化合物通过调控单体投入比例,经溶剂热聚合法聚合后生成的具有大比表面积和多级孔结构的共聚物。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%。本发明催化剂的制备路线短,合成收率高,具有优异的催化性能且催化剂与产品易分离,适用于烯烃氢甲酰化反应。
Description
技术领域
本发明涉及一种用于烯烃氢甲酰化的单亚磷酸酯聚合物催化剂及其制备方法和应用,属于多相催化技术领域。
背景技术
氢甲酰化反应是将烯烃转化为醛的反应,醛基可进一步反应生成醇、酸、胺等化合物,每年全世界经由氢甲酰化技术生产的化学品超过1千万吨。均相催化体因具有高的反应活性和选择性广泛应用于氢甲酰化工业生产,但均相催化剂存在与产物分离困难的问题。多相催化剂相比均相催化剂最大的优点是催化剂与产物易分离,目前多相催化剂存在的主要问题是反应条件苛刻,反应活性相对较低等。目前氢甲酰化主要研究的热点集中在开发一种新型的多相化催化剂,使其既具有多相催化的催化剂与产物易分离的优点,又具有均相催化的高反应活性。
US4252678报道了一种含有Rh等活性金属的胶态分散体的制备方法,将活性金属组分以1.0~20.0nm的胶态分散体与采用羟基封端的(苯乙烯/丁二烯)功能化共聚物组成的催化剂体系,并应用于1-己烯的氢甲酰化反应。但该催化剂没有解决催化剂与产物分离困难的问题。
CN102281948A报道了一种聚合物负载的过渡金属催化剂络合物及使用方法,制备了具有较窄分子量分布的能溶的聚合物负载的Rh催化剂。但是这种工艺的最大弊端是催化剂制备过程复杂。催化剂制备需要先控制官能单体和苯乙烯等合成可溶性的聚合物,再引入配体,最后负载Rh活性金属。且催化剂与产物的分离效果以及反应活性有待提升。
发明内容
为了解决现有技术存在的上述问题,本发明提供一种用于烯烃氢甲酰化的单亚磷酸酯聚合物催化剂及其制备方法和应用。
本发明具体通过如下技术方案予以实现:
本发明提供了一种用于烯烃氢甲酰化的单亚磷酸酯聚合物催化剂,该单亚磷酸酯聚合物催化剂由活性金属组分和单亚磷酸酯共聚物组成,其中所述活性金属组分是Rh、Co和Pd中的一种或几种,所述单亚磷酸酯共聚物是由含乙烯基的单亚磷酸酯配体单体与含有烯烃基官能团的芳烃化合物通过调控单体投入比例,经溶剂热聚合法聚合后生成的具有大比表面积和多级孔结构的共聚物,所述共聚物比表面积为100~2000m2/g,孔容为0.1~5.0cm3/g,孔径分布在0.2~100.0nm。所述活性金属组分在所述单亚磷酸酯聚合物催化剂总重量中占0.01~10.0%。
在一个优选实施方案中,所述金属组分在所述单亚磷酸酯聚合物总重量中占0.01~5.0%。
在一个优选实施方案中,所述单亚磷酸酯配体是乙烯基单齿亚磷酸酯;所述含有烯烃基官能团的芳烃化合物为三(4-乙烯基苯)基膦、苯乙烯、二乙烯基苯中的一种或几种的混合物。
所述单亚磷酸酯配体单体是选自以下单体中的一种或多种:
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:
本发明还提供一种上述单亚磷酸酯聚合物催化剂的制备方法,所述方法包括:
I.高压反应釜中,将共聚单体单亚磷酸酯配体和含有烯烃基官能团的芳烃化合物按比例(摩尔比0.01:1~100:1)溶于有机溶剂,再加入自由基引发剂,充入压力0.1MPa~5.0MPa的惰性气体,加热至60~150℃,搅拌聚合0.5~50小时后,在50~80℃减压条件下脱除溶剂,即得到所述单亚磷酸酯共聚物;
II.将所述单亚磷酸酯共聚物置于溶有活性金属组分的有机溶剂中,在0~100℃和惰性气体保护氛围下搅拌0.5~50小时,然后在室温下过滤,滤饼真空脱除有机溶剂,即得到所述由单亚磷酸酯共聚物上负载活性金属组分的多相催化剂单亚磷酸酯聚合物催化剂。
所述步骤I)和II)中使用的有机溶剂是甲醇、乙醇、甲苯、二甲苯、四氢呋喃、二氧六环、二氯甲烷或三氯甲烷中的一种或几种的混合物;
所述步骤I)中所述单亚磷酸酯膦配体为含乙烯基的单亚磷酸酯配体单体,所述烯烃基官能团的芳烃化合物为三(4-乙烯基苯)基膦、苯乙烯、二乙烯基苯中的一种或几种的混合物;
所述步骤I)中共聚单体单亚磷酸酯配体和含有烯烃基官能团的芳烃化合物比例优选摩尔比0.01:1~30:1。
所述步骤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,所述自由基引发剂与所述共聚单体的重量比为1:100~1:5,优选1:50~1:10。
所述步骤I)中优选惰性气体氩气、氮气中的一种,充入压力优选0.1MPa~2.0MPa,加热温度80~150℃,搅拌0.5~24小时。
所述步骤II)中优选惰性气体氩气、氮气中的一种,温度10~60℃,搅拌0.5~24小时。
所述步骤III)中活性金属组分为Rh、Co和Pd的活性金属组分中的一种或两种以上,其中Rh的活性金属组分为RhCl3、Rh(CH3COO)2、RhH(CO)(PPh3)3、Rh(CO)2(acac);Co的活性金属组分为CoCl2、Co(CH3COO)2、Co(CO)2(acac);Pd的活性金属组分为PdCl2、Pd(CH3COO)2、Pd(acac)2、Pd(PPh3)4、PdCl2(CH3CN)2。
本发明还提供一种上述多相催化剂在烯烃氢甲酰化反应中的应用,优选,应用在装填有所述多相催化剂的固定床、悬浮床或釜式反应器中,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。
本发明产生的有益效果包括但不限于以下方面:
本发明的单亚磷酸酯共聚物型多相催化剂与现有的氢甲酰化催化剂相比,催化剂制备方法简单,单程收率高;所述共聚物通过两种或多种单体不同比例共聚调控聚合物的多级孔结构,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的聚合物载体材料。所述活性金属组分与聚合物中P形成化学配体键使得活性组分以单原子分散的状态存在,使得催化剂具有高活性高稳定性;该方法制备得到的催化剂兼具了均相亚磷酸酯配体的高活性以及多相催化剂与产品易分离的优点。
附图说明
图1为三(2-乙烯基-4-叔丁基苯基)亚磷酸酯配体(L1)的1H NMR谱;
图2为三(2-乙烯基-4-叔丁基苯基)亚磷酸酯配体(L1)的13C NMR谱;
图3为三(2-乙烯基-4-叔丁基苯基)亚磷酸酯配体(L1)的31P NMR谱。
具体实施方式
下面将通过具体实施例对本发明做进一步描述,但本发明的保护范围并不仅局限于此。
实施例1:
(1)三(2-乙烯基-4-叔丁基苯基)亚磷酸酯配体(L1)的制备:如图1所示,三步反应均在氩气条件下进行,具体以4-叔丁基苯酚为原料,使用多聚甲醛、无水氯化镁、三乙胺,在干燥四氢呋喃中回流4小时,得到2-羟基-5叔丁基苯甲醛,收率96%;以甲基三苯基溴化膦及叔丁基醇钾在干燥四氢呋喃中室温预制得到磷叶立德试剂,加入上述得到的2-羟基-5叔丁基苯甲醛,室温搅拌12小时,得到2-羟基-5叔丁基苯乙烯,收率83%;将上述得到的2-羟基-5叔丁基苯乙烯,溶于含有三乙胺的干燥四氢呋喃中,0℃条件下,滴加三氯化磷四氢呋喃溶液,室温搅拌12小时,得到三(2-乙烯基-4-叔丁基苯基)亚磷酸酯配体(L1),收率87%。
(2)含膦有机共聚物的制备:高压反应釜中,将3g单亚磷酸酯配体L1和1g三(4-乙烯基苯)基膦溶于50ml四氢呋喃溶剂中,向上述溶液中加入自由基引发剂偶氮二异丁腈:充入压力1MPa的惰性气体,搅拌条件下,加热到120℃,反应24小时;上述聚合后溶液冷却至室温,60℃真空脱除溶剂,得到L1和三(4-乙烯基苯)基膦有机多孔共聚物。
(3)多相催化剂的制备:惰性气体分为下,将25mg乙酰丙酮二羰基铑的溶于20ml四氢呋喃中,加入1g上述含膦有机共聚物,在30℃和惰性气体保护氛围下搅12小时,然后在室温下过滤,滤饼真空脱除有机溶剂,即得到所述由含膦有机共聚物上负载活性金属组分的多相催化。
(4)固定床氢甲酰化反应:将1g所述多相催化剂装填于固定床反应器中,两端封填惰性瓷球,1-己烯原料通过计量泵流量为0.2mL/min进入反应器,控制合成气(CO:H2:=1:1)空速2000h-1,其中反应温度为90℃,反应压力为1.8MPa。产物含量以及剩余原料量采用气相色谱仪分析。反应结果如表1所示。
实施例2:
替换步骤(2)含膦有机共聚物的制备过程中使用溶剂为二氧六环:
具体在实施例2中,除了步骤(2)含膦有机共聚物的制备过程,将3g单亚磷酸酯配体L1和1g三(4-乙烯基苯)基膦溶于50ml二氧六环溶剂中,其余的制备步骤和氢甲酰化反应条件与实施例1相同。
实施例3:
调整聚合物单体共聚比例:
具体在实施例3中,除了步骤(2)含膦有机共聚物的制备步骤中“将2g单亚磷酸酯配体L1和2g三(4-乙烯基苯)基膦”替代“将3g单亚磷酸酯配体L1和1g三(4-乙烯基苯)基膦”溶于50ml四氢呋喃溶剂中外,其余的制备步骤和氢甲酰化反应条件与实施例1相同。
实施例4:
含0.5wt%Rh的多相催化剂制备:
具体在实施例4中,除了步骤(3)多相催化剂的制备过程,“称取12.5mg乙酰丙酮二羰基铑”替代“25mg乙酰丙酮二羰基铑”溶于20ml四氢呋喃中外,其余的制备步骤和氢甲酰化反应条件与实施例1相同。
实施例5:
更换单亚磷酸酯共聚单体:
具体在实施例5中,除了步骤(2)含膦有机共聚物的制备过程,使用苯乙烯单体代替三(4-乙烯基苯)基膦单体外,其余的制备步骤和氢甲酰化反应条件与实施例1相同。
实施例6:
使用L2配体代替L1配体进行催化剂的制备:
步骤(1)中三(3-乙烯基-4-叔丁基苯基)亚磷酸酯(L2)的制备:在氩气条件下,将3-乙烯基-4-叔丁基苯酚溶于含有三乙胺的干燥四氢呋喃中,0℃条件下,滴加三氯化磷四氢呋喃溶液,室温搅拌12小时,得到三(3-乙烯基-4-叔丁基苯基)亚磷酸酯(L2)。其中,3-乙烯基-4-叔丁基苯酚与三乙胺的摩尔比为1:1,3-乙烯基-4-叔丁基苯酚与三氯化磷的摩尔比为3:1,收率85.3%。
其余的制备步骤和氢甲酰化反应条件与实施例1相同。
实施例7:
使用L3配体代替L1配体进行催化剂的制备:
步骤(1)中三(2-叔丁基-5-乙烯基苯基)亚磷酸酯(L3)的制备:在氩气条件下,将2-叔丁基-5-乙烯基苯酚溶于含有三乙胺的干燥四氢呋喃中,0℃条件下,滴加三氯化磷四氢呋喃溶液,室温搅拌12小时,得到三(2-叔丁基-5-乙烯基苯基)亚磷酸酯(L3)。其中,2-叔丁基-5-乙烯基苯酚与三乙胺的摩尔比为1:1,2-叔丁基-5-乙烯基苯酚与三氯化磷的摩尔比为3:1,收率82.3%。
其余的制备步骤和氢甲酰化反应条件与实施例1相同。
实施例8:
使用L4配体代替L1配体进行催化剂的制备:
步骤(1)三(2-乙烯基-4-甲氧基苯基)亚磷酸酯(L4)配体的制备:三步反应均在氩气条件下进行,具体以4-甲氧基苯酚为原料,使用多聚甲醛,无水氯化镁,三乙胺,在干燥四氢呋喃中回流4小时,得到2-羟基-5甲氧基苯甲醛,收率93.2%;以甲基三苯基溴化膦及叔丁基醇钾在干燥四氢呋喃中室温预制得到磷叶立德试剂,加入上述得到的2-羟基-5甲氧基苯甲醛,室温搅拌12小时,得到2-羟基-5甲氧基苯乙烯,收率75.7%;将上述得到的2-羟基-5甲氧基苯乙烯,溶于含有三乙胺的干燥四氢呋喃中,0℃条件下,滴加三氯化磷四氢呋喃溶液,室温搅拌12小时,得到三(2-乙烯基-4-甲氧基苯基)亚磷酸酯(L4),收率80.2%。
其余的制备步骤和氢甲酰化反应条件与实施例1相同。
实施例9:
使用L6配体代替L1配体进行催化剂的制备:
步骤(1)中三(2-甲氧基-5-乙烯基苯基)亚磷酸酯(L6)的制备:在氩气条件下,将2-甲氧基-5-乙烯基苯酚溶于含有三乙胺的干燥四氢呋喃中,0℃条件下,滴加三氯化磷四氢呋喃溶液,室温搅拌12小时,得到三(2-甲氧基-5-乙烯基苯基)亚磷酸酯(L6)。其中,2-甲氧基-5-乙烯基苯酚与三乙胺的摩尔比为1:1,2-甲氧基-5-乙烯基苯酚与三氯化磷的摩尔比为3:1,收率75.2%。
其余的制备步骤和氢甲酰化反应条件与实施例1相同。
实施例10:
使用L11配体代替L1配体进行催化剂的制备:
步骤(1)间位取代的二乙烯基1,2-双(二苯基膦)甲烷(L11)的制备:在氩气条件下,将4-叔丁基苯酚和三乙胺溶于干燥四氢呋喃中,0℃温度下,滴加三氯化磷四氢呋喃溶液,室温搅拌12小时后加热回流3小时,反应液冷却后过滤,滤液减压蒸馏蒸出未反应的三氯化磷后用无水四氢呋喃溶解,将以上溶液于0℃条件下滴加到3-乙烯基-4-叔丁基苯酚和三乙胺溶于干燥四氢呋喃中,室温搅拌12小时,得到4叔丁基苯基-二(3-乙烯基-4-叔丁基苯基)亚磷酸酯(L11)。其中,4-叔丁基苯酚与三氯化磷的摩尔比为1:10,4-叔丁基苯酚与三乙胺的摩尔比为1:2,3-乙烯基-4-叔丁基苯酚与三乙胺的摩尔比为1:2。
收率84.5%。
其余的制备步骤和氢甲酰化反应条件与实施例1相同。
表1实施例中合成的多相催化剂催化1-己烯氢甲酰化反应结果
实施例 | 1-己烯转化率% | 醛选择性% | 正异比 |
实施例1 | 99.5 | 97.2 | 14.3 |
实施例2 | 99.3 | 97.3 | 14.2 |
实施例3 | 99.1 | 94.7 | 9.6 |
实施例4 | 83.5 | 98.4 | 17.8 |
实施例5 | 98.2 | 97.6 | 15.5 |
实施例6 | 97.5 | 95.2 | 10.5 |
实施例7 | 95.3 | 98.3 | 8.2 |
实施例8 | 99.3 | 92.7 | 7.7 |
实施例9 | 93.1 | 95.4 | 12.8 |
实施例10 | 96.2 | 91.6 | 16.5 |
Claims (8)
1.一种单亚磷酸酯聚合物催化剂在1-己烃氢甲酰化反应中的应用,其特征在于,所述单亚磷酸酯聚合物催化剂是由活性金属组分和单亚磷酸酯共聚物组成的多相催化剂,其中所述活性金属组分是金属Rh、Co和Pd中的一种或多种,所述单亚磷酸酯共聚物通过两种或多种单体不同比例共聚调控聚合物的多级孔结构,所述单亚磷酸酯共聚物单体为含乙烯基的单亚磷酸酯配体单体中的一种或多种和含有烯烃基官能团的芳烃化合物中的一种或多种,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%;
其中所述单亚磷酸酯配体单体是选自以下各项中的一种或多种:
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:
2.一种权利要求1所述的单亚磷酸酯聚合物催化剂在1-己烯氢甲酰化反应中的应用,其特征在于,所述方法包括:
I.高压反应釜中,将共聚单体单亚磷酸酯配体和含有烯烃基官能团的芳烃化合物按摩尔比为0.01:1~100:1的比例溶于有机溶剂,再加入自由基引发剂,充入压力0.1MPa~5.0MPa的惰性气体,加热至60~150℃,搅拌聚合0.5~50小时后,在50~80℃减压条件下脱除有机溶剂,得到所述单亚磷酸酯共聚物;
II.将所述单亚磷酸酯共聚物置于溶有活性金属组分的有机溶剂中,在0~100℃和惰性气体保护氛围下搅拌0.5~50小时,然后在室温下过滤,滤饼真空脱除有机溶剂,即得到所述由单亚磷酸酯共聚物上负载活性金属组分的多相催化剂。
3.根据权利要求2所述的单亚磷酸酯聚合物催化剂在1-己烯氢甲酰化反应中的应用,其特征在于,步骤I)和II)中使用的有机溶剂是甲醇、乙醇、甲苯、二甲苯、四氢呋喃、二氧六环、二氯甲烷和三氯甲烷中的一种或多种的混合物。
4.根据权利要求2所述的单亚磷酸酯聚合物催化剂在1-己烯氢甲酰化反应中的应用,其特征在于,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、偶氮二异丁腈和偶氮二异庚腈的一种或多种,所述自由基引发剂与所述共聚单体的质量比为1:100~1:5。
5.根据权利要求2所述的单亚磷酸酯聚合物催化剂在1-己烯氢甲酰化反应中的应用,其特征在于,步骤II)中活性金属组分为所述的活性组分为Rh、Co和Pd的一种或两种以上,其中Rh的活性金属组分为RhCl3、Rh(CH3COO)2、
RhH(CO)(PPh3)3、Rh(CO)2(acac);其中Co的活性金属组分为CoCl2、Co(CH3COO)2、Co(CO)2(acac);其中Pd的活性金属组分为PdCl2、Pd(CH3COO)2、Pd(acac)2、Pd(PPh3)4、PdCl2(CH3CN)2。
6.根据权利要求2所述的单亚磷酸酯聚合物催化剂在1-己烯氢甲酰化反应中的应用,其特征在于,所述步骤I)中共聚单体单亚磷酸酯配体和含有烯烃基官能团的芳烃化合物的摩尔比为0.01:1~30:1。
7.根据权利要求2所述的单亚磷酸酯聚合物催化剂在1-己烯氢甲酰化反应中的应用,其特征在于,所述自由基引发剂与所述共聚单体的重量比为1:50~1:10。
8.根据权利要求7所述的单亚磷酸酯聚合物催化剂在1-己烯氢甲酰化反应中的应用,其特征在于,所述的烯烃氢甲酰化反应中在装填有所述单亚磷酸酯聚合物催化剂的反应器为固定床、悬浮床或釜式反应器,烯烃氢甲酰化反应的反应条件为: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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