TW201306939A - 用於加氫甲醯化過程之配位基和催化劑體系 - Google Patents
用於加氫甲醯化過程之配位基和催化劑體系 Download PDFInfo
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- cyclobutane
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- 239000003446 ligand Substances 0.000 title claims abstract description 39
- 239000003054 catalyst Substances 0.000 title claims abstract description 24
- 238000007037 hydroformylation reaction Methods 0.000 title claims abstract description 22
- 238000000034 method Methods 0.000 title description 6
- XXROGKLTLUQVRX-UHFFFAOYSA-N allyl alcohol Chemical compound OCC=C XXROGKLTLUQVRX-UHFFFAOYSA-N 0.000 claims abstract description 22
- XGVSNOPGUGPUGA-UHFFFAOYSA-N cyclobutylmethylphosphane Chemical compound PCC1CCC1 XGVSNOPGUGPUGA-UHFFFAOYSA-N 0.000 claims abstract description 12
- 150000001336 alkenes Chemical class 0.000 claims abstract description 6
- 239000007983 Tris buffer Substances 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 10
- -1 3,5-dimethylphenyl Chemical group 0.000 claims description 9
- 239000012327 Ruthenium complex Substances 0.000 claims description 7
- CUJRVFIICFDLGR-UHFFFAOYSA-N acetylacetonate Chemical compound CC(=O)[CH-]C(C)=O CUJRVFIICFDLGR-UHFFFAOYSA-N 0.000 claims description 7
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 7
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 7
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 7
- 150000002923 oximes Chemical class 0.000 claims description 5
- 125000003545 alkoxy group Chemical group 0.000 claims description 4
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- IKTMDUUPAIDXQE-UHFFFAOYSA-N [2-[bis(3,5-dimethylphenyl)phosphanylmethyl]-3,4-bis(trityloxymethyl)cyclobutyl]methyl-bis(3,5-dimethylphenyl)phosphane Chemical compound CC1=CC(C)=CC(P(CC2C(C(COC(C=3C=CC=CC=3)(C=3C=CC=CC=3)C=3C=CC=CC=3)C2COC(C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)CP(C=2C=C(C)C=C(C)C=2)C=2C=C(C)C=C(C)C=2)C=2C=C(C)C=C(C)C=2)=C1 IKTMDUUPAIDXQE-UHFFFAOYSA-N 0.000 claims description 3
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims description 3
- 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 2
- RRKODOZNUZCUBN-CCAGOZQPSA-N (1z,3z)-cycloocta-1,3-diene Chemical compound C1CC\C=C/C=C\C1 RRKODOZNUZCUBN-CCAGOZQPSA-N 0.000 claims 1
- LMYKTNLGBUMKNF-UHFFFAOYSA-N ruthenium(1+) Chemical class [Ru+] LMYKTNLGBUMKNF-UHFFFAOYSA-N 0.000 claims 1
- LENZDBCJOHFCAS-UHFFFAOYSA-N tris Chemical compound OCC(N)(CO)CO LENZDBCJOHFCAS-UHFFFAOYSA-N 0.000 claims 1
- PIAOXUVIBAKVSP-UHFFFAOYSA-N γ-hydroxybutyraldehyde Chemical compound OCCCC=O PIAOXUVIBAKVSP-UHFFFAOYSA-N 0.000 abstract description 15
- 238000006243 chemical reaction Methods 0.000 abstract description 11
- 239000010948 rhodium Substances 0.000 abstract description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 abstract description 6
- 229910052703 rhodium Inorganic materials 0.000 abstract description 2
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 abstract description 2
- 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 abstract 1
- 125000002524 organometallic group Chemical group 0.000 abstract 1
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 14
- JTMCAHGCWBGWRV-UHFFFAOYSA-N 3-hydroxy-2-methylpropanal Chemical compound OCC(C)C=O JTMCAHGCWBGWRV-UHFFFAOYSA-N 0.000 description 11
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 9
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 8
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 7
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 6
- 239000006227 byproduct Substances 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- NBBJYMSMWIIQGU-UHFFFAOYSA-N Propionic aldehyde Chemical compound CCC=O NBBJYMSMWIIQGU-UHFFFAOYSA-N 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 4
- YYROPELSRYBVMQ-UHFFFAOYSA-N 4-toluenesulfonyl chloride Chemical compound CC1=CC=C(S(Cl)(=O)=O)C=C1 YYROPELSRYBVMQ-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000012300 argon atmosphere Substances 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 3
- 239000011541 reaction mixture Substances 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- PMPVIKIVABFJJI-UHFFFAOYSA-N Cyclobutane Chemical compound C1CCC1 PMPVIKIVABFJJI-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- ZTQSAGDEMFDKMZ-UHFFFAOYSA-N butyric aldehyde Natural products CCCC=O ZTQSAGDEMFDKMZ-UHFFFAOYSA-N 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 239000012043 crude product Substances 0.000 description 2
- WPOPOPFNZYPKAV-UHFFFAOYSA-N cyclobutylmethanol Chemical compound OCC1CCC1 WPOPOPFNZYPKAV-UHFFFAOYSA-N 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000012454 non-polar solvent Substances 0.000 description 2
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical compound CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 description 2
- 239000002798 polar solvent Substances 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 2
- RKQZLPCYBYUNPD-UHFFFAOYSA-N (triphenyl-$l^{5}-phosphanylidene)methanone Chemical compound C=1C=CC=CC=1P(C=1C=CC=CC=1)(=C=O)C1=CC=CC=C1 RKQZLPCYBYUNPD-UHFFFAOYSA-N 0.000 description 1
- WDYVUKGVKRZQNM-UHFFFAOYSA-N 6-phosphonohexylphosphonic acid Chemical compound OP(O)(=O)CCCCCCP(O)(O)=O WDYVUKGVKRZQNM-UHFFFAOYSA-N 0.000 description 1
- 108010010803 Gelatin Proteins 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical group CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- HYBBKUAYLJOAIQ-UHFFFAOYSA-N 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 Chemical compound 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 HYBBKUAYLJOAIQ-UHFFFAOYSA-N 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- CZPWVGJYEJSRLH-UHFFFAOYSA-N Pyrimidine Chemical compound C1=CN=CN=C1 CZPWVGJYEJSRLH-UHFFFAOYSA-N 0.000 description 1
- OATYEVJXAXMWIA-UHFFFAOYSA-K [Cl-].C1=CC=CCCCC1.[Ru+3].[Cl-].[Cl-] Chemical compound [Cl-].C1=CC=CCCCC1.[Ru+3].[Cl-].[Cl-] OATYEVJXAXMWIA-UHFFFAOYSA-K 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- GPFIUEZTNRNFGD-UHFFFAOYSA-N bis(3,5-dimethylphenyl)phosphane Chemical compound CC1=CC(C)=CC(PC=2C=C(C)C=C(C)C=2)=C1 GPFIUEZTNRNFGD-UHFFFAOYSA-N 0.000 description 1
- 239000001273 butane Substances 0.000 description 1
- 150000008280 chlorinated hydrocarbons Chemical class 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 239000000539 dimer Substances 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 239000003480 eluent Substances 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 229920000159 gelatin Polymers 0.000 description 1
- 239000008273 gelatin Substances 0.000 description 1
- 235000019322 gelatine Nutrition 0.000 description 1
- 235000011852 gelatine desserts Nutrition 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 230000011987 methylation Effects 0.000 description 1
- 238000007069 methylation reaction Methods 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 125000005328 phosphinyl group Chemical group [PH2](=O)* 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 150000003283 rhodium Chemical class 0.000 description 1
- 150000003303 ruthenium Chemical class 0.000 description 1
- 239000011877 solvent mixture Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- JBWKIWSBJXDJDT-UHFFFAOYSA-N triphenylmethyl chloride Chemical compound C=1C=CC=CC=1C(C=1C=CC=CC=1)(Cl)C1=CC=CC=C1 JBWKIWSBJXDJDT-UHFFFAOYSA-N 0.000 description 1
- 125000002221 trityl group Chemical group [H]C1=C([H])C([H])=C([H])C([H])=C1C([*])(C1=C(C(=C(C(=C1[H])[H])[H])[H])[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 1
- 230000035899 viability Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 238000003809 water extraction Methods 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
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- 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
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- 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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- 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
- C07F9/50—Organo-phosphines
- C07F9/5027—Polyphosphines
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- B—PERFORMING OPERATIONS; TRANSPORTING
- 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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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/24—Phosphines, i.e. phosphorus bonded to only carbon atoms, or to both carbon and hydrogen atoms, including e.g. sp2-hybridised phosphorus compounds such as phosphabenzene, phosphole or anionic phospholide ligands
- B01J31/2404—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring
- B01J31/2409—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring with more than one complexing phosphine-P atom
- B01J31/2414—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring with more than one complexing phosphine-P atom comprising aliphatic or saturated rings
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- C07C43/04—Saturated ethers
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Abstract
本發明涉及用於短鏈和長鏈烯烴的加氫甲醯化過程的配位基和催化劑體系，較佳的是用於烯丙醇的加氫甲醯化以生產4-羥基丁醛。在此揭露的配位基係全反式膦甲基-環丁烷配位基，例如像是全反式-1,2,3,4-四[雙-(3,5-二甲苯基)膦甲基]-環丁烷。該催化劑體系包括與一種有機金屬的銠錯合物結合的該等全反式膦甲基-環丁烷配位基，這種銠錯合物例如像是二羰基乙醯丙酮銠(I)。本發明的配位基和催化劑體系可以應用到烯烴的加氫甲醯化中，特別是烯丙醇的加氫甲醯化，並且還提供了改進的選擇性和高反應產率。
Description
本發明涉及在短鏈和長鏈烯烴的加氫甲醯化過程中使用的多種新穎的配位基和催化劑體系，比如用於生產4-羥基丁醛的烯丙醇的加氫甲醯化。本文揭露了該等配位基和催化劑的製備和它們在加氫甲醯化反應中的用途。
烯丙醇的加氫甲醯化已被公知並得以工業化應用(見例如USP 4,064,145；USP 4,215,077；USP 4,238,419；USP 4,678,857；USP 5,290,743)。在該等過程中，烯丙醇與CO/H2氣體混合物進行反應，生成4-羥基丁醛(HBA)。在藉由蒸餾去除了不希望的副產品後，HBA以一種已知的方式氫化生成1,4-丁二醇(BDO)。
近來，已經將銠錯合物與雙膦配位基例如DIOP(2,3-O-異亞丙基-2,3-二羥基-1,4-雙-[雙(3,5-二甲基苯)膦基]-丁烷)應用到加氫甲醯化反應中。
這種生產方式的一普遍缺點就是形成了不希望的副產物。具體地，和希望的線性產物一起，同時形成的還有同分異構的分支產物3-羥基-2-甲基丙醛(HMPA)和其他C3副產物(例如正丙醇和丙醛)。這對該方法的經濟可行性有負面的影響。
本發明提供了多種膦配位基，該等膦配位基在環丁烷配位基的基礎上包含至少兩個反式配位的(3,5-二烷基-苯基)膦甲基基團。在另一方面，本發明提供了多種催化劑體系，該等催化劑體系形成了一種銠錯合物以及所述包含至少兩個反式配位的(3,5-二烷基-苯基)膦甲基基團的環丁烷配位基。
本發明提供的配位基和催化劑體系允許在烯丙醇的加氫甲醯化過程中達到多個更優的HBA：HMPA比例，並且因此改善了其選擇性同時提高了反應產率。
一般而言，本發明中揭露的膦配位基可以定義為：具有式[A]的膦甲基-環丁烷
其中R1為烷基，較佳的是甲基，乙基或丙基R2係H或一個烷氧基基團，R3和R4彼此獨立地分別為CH2OR1、CH2O-芳烷基、CH2OH、CH2-[P(3,5-R1,R1-4-R2-苯基)2]或CH2O-(CH2-CH2-O)m-H(其中m為1至1000之間的整數
)。
較佳的是，[A]係一全反式-膦甲基-環丁烷衍生物，並且該等膦配位基為具有式[A]的全反式-膦甲基-環丁烷，其中R1係甲基，乙基或丙基，R2係H，R3和R4彼此獨立地分別是CH2OR1、CH2OH或CH2-[P(3,5-R1,R1-4-R2-苯基)2]另外較佳的是具有以下組合物的配位基[A]：全反式-1,2,3,4-四[雙-(3,5-二甲苯基)膦甲基]-環丁烷，以及全反式-1,2,3-三[雙-(3,5-二甲苯基)膦甲基]-4-(甲氧甲基)-環丁烷，全反式-1,2,3-三[雙-(3,5-二甲苯基)膦甲基]-4-(羥甲基)-環丁烷，全反式-1,2,3-三[雙-(3,5-二甲苯基)膦甲基]-4-[CH2-(O-CH2-CH2-O)mH]-環丁烷(其中m為1至1000之間的整數)。該等配位基可以用作單獨的化合物或者以混合物的形式使用或者作為配位基組合使用。
在還另一較佳的實施方式中，該等膦配位基係具有式[A]的全反式-膦甲基-環丁烷，其中R1係甲基，乙基或丙基，R2係H，
R3和R4係CH2-[P(3,5-R1,R1-4-R2-苯基)2]。
除了具有式[A]的膦配位基之外，本發明的催化劑和催化劑體系還包括一種銠錯合物。適合的銠錯合物的實例包括二羰基乙醯丙酮銠(I)[Rh(CO)2acac]、三(三苯基膦)羰基氫化銠[Rh(PPh)3(CO)H]、羰基(三苯基膦)銠-乙醯丙酮[Rh(CO)(PPh3)acac]、(環辛二烯)氯化銠(I)二聚體[(COD)RhCl]2和乙基己酸銠(III)。較佳的銠錯合物係二羰基乙醯丙酮銠(I)。
在本發明的實踐中，使用這種銠錯合物的量為在反應混合物中Rh的濃度範圍在約0.05到100 mg Rh/l之間，較佳的是0.1到25 mg Rh/l。更低的Rh濃度可能會降低反應速率和反應產率。
膦甲基-環丁烷配位基和銠錯合物的莫耳比一般為在0.5：1到10：1的範圍之間，較佳的是在1：1到5：1範圍之間。通常，膦甲基-環丁烷配位基和銠錯合物在添加烯烴化合物(例如，烯丙醇)之後再加入到反應混合物中。
通常，這種烯烴化合物例如烯丙醇的加氫甲醛化係在均相下進行的。可以使用極性和/或非極性溶劑。可以使用的極性溶劑有，例如乙醇、正丙醇、異丙醇、正丁醇、和異丁醇。適合使用的非極性溶劑係芳香烴或脂肪烴，例如苯、甲苯或二甲苯。通常，在該過程中應用的該等溶劑應能夠溶解所使用的銠錯合物。
基本上，本發明的配位基和催化劑體系可以用於長鏈
和短鏈烯烴的加氫甲醛化反應。作為短鏈烯烴的一實例，在此可以提及的是乙烯、丙烯、1-丁烯、異丁烯、1-戊烯等。
較佳的是，本發明的配位基和催化劑體系可以應用於烯丙醇的加氫甲醛化當中。在這個具體的應用中，該配位基和催化劑體系允許達到更有利的HBA：HMPA比例，從而提供改進的選擇性和高反應產率。
本發明的另外一方面係包含具有式[A]的配位基的催化劑體系的用途，該等具有式[A]的配位基允許加氫甲醯化過程的多個不同實施方式。
具有式[A]配位基(該等配位基具有多個聚醚基團(例如CH2O-(CH2-CH2-O)m-H，其中m為1到1000之間的整數))的新型的親水型催化劑體系可以在膜反應器中使用，從而允許在加氫甲醛化之後反應產物可以被連續地分離。
該加氫甲醛化在習知技術中已知的反應條件下進行反應，典型地是在20℃至120℃範圍內的溫度和2至20 bar範圍內的壓強下進行。取決於已有設備，可以藉由適合的預備實驗來確定最優性能。
所使用的合成氣體混合物(CO/氫)莫耳比CO：H2約是1：1，但這個比率可以根據實施方式而做出相當大的改變。
反應時間為在0.5到4小時的範圍內。反應開始時，基於溶劑或者溶劑混合物，丙烯醇濃度為5%至50%，較
佳的是10%至25%。
反應結束後，將HBA、HMPA和其他副產品從催化劑中分離出來，較佳的是藉由水萃取。
在隨後的一步驟中，對HBA(以及HMPA)進行氫化以得到相應的二羥基化合物，並且對粗產物分餾以得到所希望的純1,4-丁二醇(BDO)。
下面的例子進一步對本發明進行說明：
a)製備全反式1,2-雙[雙-(3,5-二甲苯基)膦甲基]-3,4-雙(三苯甲基氧甲基)-環丁烷
將88 mg(0.5 mmol)的全反式-1,2,3,4-四(羥甲基)環丁烷溶於3 ml無水吡啶，並且在0℃在劇烈攪拌下加入251 mg(0.9 mmol)三苯甲基氯。將該反應混合物置於0℃攪拌過夜。然後在混合物內加入10 ml水並用乙酸乙酯(3×5 ml)萃取，之後用MgSO4乾燥並在一旋轉式蒸發器裡蒸乾。
用色譜分析法(矽膠)分離粗產品。(洗脫液：乙酸乙酯：乙烷1：3→2：3→乙酸乙酯：甲醇95：5)。
獲得的主要產物為114 mg(理論上34%的)全反式-1,2-雙(羥甲基)-3,4-雙(三苯甲基氧甲基)-環丁烷。
用習知技術已知的方式，該化合物的兩個OH-基團被甲苯磺酸化並與LiP(3,5-二甲苯基)2反應來生成全反式1,2-雙[雙-(3,5-二甲苯基)膦甲基]-3,4-雙(三苯甲基氧甲基)-環丁烷。在另外的步驟中(任選)，這兩個三苯甲基可以被移除或者可以換成烷基或者烷氧基。
b)製備全反式-1,2,3,4-四[雙-(3,5-二甲苯基)膦甲基]-環丁烷
將原料化合物全反式-1,2,3,4-四(羥甲基)環丁烷用本身已知的方法，在一種氯代烴溶劑(例如二氯甲烷)中的堿的存在下(例如，嘧啶)，在堿的存在下藉由與4當量的對甲苯磺醯氯(p-甲苯磺酸氯)反應從而進行甲苯磺酸化。將這種四-甲苯磺酸化的化合物分離，並且將溶劑在真空中去除。
在下一步驟中，這種四-甲苯磺酸化的化合物與4當量的LiP(3,5-二甲苯基)2在乾燥的醚溶劑(例如EG/DME混合物)中反應生成全反式-四-膦甲基-環丁烷配位基。
氬氣氣氛下，在4 ml乾燥並脫氣的甲基叔丁基醚中，16 mmol全反式-1,2,3,4-四[雙-(3,5-二甲苯基)膦甲基]-環丁烷與[Rh(CO)2(acac)](8 mmol)反應。
將得到的溶液在氬氣氣氛下注射到高壓釜中並用CO：H2為1：1的混合物沖洗。藉由一側臂將溶於15 ml乙醇中的1 ml丙烯醇溶液加入，並且這個反應在40 bar的壓力以及120℃的溫度下進行。生成了理論上97%的、比率約為14：1的HBA+HMPA(HBA/HMPA選擇性=93.3%)。
該等實驗都是在一個60 ml的高壓釜中，在氬氣氣氛下、65℃溫度以及合成氣體(CO/H2=1：1)壓力p=20 bar時進行。反應時間為120分鐘。向高壓釜中的[Rh(CO)2acac](1當量或4.3×10-5莫耳)添加溶於15 g乾燥脫氣的甲苯中的對應的膦配位基(2當量或8.6×10-5莫耳)溶液。該高壓釜在20 bar時加壓，然後加熱至65℃並且注入該丙烯醇(3.5 ml)。120分鐘之後，氣體攝入完成並且冷卻該高壓釜。得到的溶液用氣相色譜分析進行處理從而測定反應產物4-羥基-丁醛(HBA)以及3-羥基-2-甲基丙醛(HMPA)。由產品峰面積(HBA)對副產品峰面積(HMPA)的比率來確定選擇性。該等結果在表1中進行了概括：
如可在表1中所見，本發明提供的配位基和催化劑體系允許在烯丙醇的加氫甲醯化過程中達到多個更優的HBA：HMPA比例，並且因此改善了其選擇性同時提高了反應產率。
Claims (11)
- 一種膦甲基-環丁烷配位基，該膦甲基-環丁烷配位基具有式[A]
- 如申請專利範圍第1項所述之膦甲基-環丁烷配位基，其中R1係甲基，乙基或丙基，R2係H，R3和R4係CH2-[P(3,5-R1,R1-4-R2-苯基)2]。
- 如申請專利範圍第1項所述之膦甲基-環丁烷配位基，選自下組，該組由以下各項組成：全反式-1,2,3,4-四[雙-(3,5-二甲苯基)膦甲基]-環丁烷、全反式-1,2,3-三[雙-(3,5-二甲苯基)膦甲基]-4-(甲氧甲基)-環丁烷、全反式-1,2,3-三[雙-(3,5-二甲苯基)膦甲基]-4-(羥甲基)-環丁烷、 全反式1,2-雙[雙-(3,5-二甲苯基)膦甲基]-3,4-雙(三苯甲基氧甲基)-環丁烷和全反式-1,2,3-三[雙-(3,5-二甲苯基)膦甲基]-4-[CH2-(O-CH2-CH2-O)mH]-環丁烷，以及它們的混合物和組合，其中m為1至1000之間的整數。
- 一種用於烯烴的加氫甲醛化反應的催化劑體系，包括一種銠錯合物以及一種具有式[A]的膦甲基-環丁烷配位基
- 如申請專利範圍第4的催化劑體系，其中R1係甲基，乙基或丙基，R2係H，R3和R4係CH2-[P(3,5-R1,R1-4-R2-苯基)2]。
- 如申請專利範圍第4項所述之催化劑體系，其中該銠錯合物選自下組，該組由以下各項組成：二羰基乙醯丙 酮銠(I)[Rh(CO)2acac]、三(三苯基膦)羰基氫化銠[Rh(PPh)3(CO)H]、羰基(三苯基膦)銠-乙醯丙酮[Rh(CO)(PPh3)acac]、環辛二烯基氯化銠(I)二聚體[(COD)RhCl]2和乙基己酸銠(III)，以及它們的混合物和組合。
- 如申請專利範圍第4項所述之催化劑體系，其中該銠錯合物係二羰基乙醯丙酮銠(I)[Rh(CO)2acac]。
- 如申請專利範圍第4項所述之催化劑體系，其中該膦甲基-環丁烷配位基選自下組，該組由以下各項組成：全反式-1,2,3,4-四[雙-(3,5-二甲苯基)膦甲基]-環丁烷、全反式-1,2,3-三[雙-(3,5-二甲苯基)膦甲基]-4-(甲氧甲基)-環丁烷、全反式-1,2,3-三[雙-(3,5-二甲苯基)膦甲基]-4-(羥甲基)-環丁烷、全反式1,2-雙[雙-(3,5-二甲苯基)膦甲基]-3,4-雙(三苯甲基氧甲基)-環丁烷和全反式-1,2,3-三[雙-(3,5-二甲苯基)膦甲基]-4-[CH2-(O-CH2-CH2-O)mH]-環丁烷，以及它們的混合物以及組合，其中m為1至1000之間的整數。
- 如申請專利範圍第4項所述之催化劑體系，其中膦甲基-環丁烷配位基和銠錯合物的莫耳比率範圍係0.5：1至10：1。
- 如申請專利範圍第1至3項中任一項所述之膦甲基-環丁烷配位基用於烯丙醇的加氫甲醯化之用途。
- 如申請專利範圍第4至9項中任一項所述之催化劑體系用於烯丙醇的加氫甲醯化之用途。
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| WO2020242977A1 (en) * | 2019-05-31 | 2020-12-03 | Lyondell Chemical Technology, L.P. | High linear selectivity ligand for allyl alcohol hydroformylation |
| CN112457165A (zh) * | 2019-09-06 | 2021-03-09 | 南京延长反应技术研究院有限公司 | 一种烯丙醇加氢制备1，4-丁二醇的强化系统及工艺 |
| CN110975941B (zh) * | 2019-12-17 | 2022-08-05 | 万华化学集团股份有限公司 | 一种氢甲酰化反应催化剂组合物及丙烯氢甲酰化反应制备醛的方法 |
| CN113061149B (zh) * | 2021-03-29 | 2022-04-22 | 万华化学集团股份有限公司 | 一种互配型配体和氢甲酰化催化剂、及二元醇的制备方法 |
| CN116440953A (zh) * | 2023-02-28 | 2023-07-18 | 中海油天津化工研究设计院有限公司 | 一种羰基合成催化剂及其制备方法与应用 |
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| US4215077A (en) | 1978-02-09 | 1980-07-29 | Kuraray Co., Ltd. | Hydroformylation of olefins |
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- 2012-05-25 BR BR112013030262A patent/BR112013030262A2/pt not_active Application Discontinuation
- 2012-05-25 RU RU2013157751/04A patent/RU2013157751A/ru not_active Application Discontinuation
- 2012-05-25 BR BR112013029852A patent/BR112013029852A2/pt not_active Application Discontinuation
- 2012-05-25 CN CN201280025524.5A patent/CN103562213A/zh active Pending
- 2012-05-25 EP EP12726043.8A patent/EP2714700A1/en not_active Withdrawn
- 2012-05-25 WO PCT/EP2012/059850 patent/WO2012163837A1/en active Application Filing
- 2012-05-25 CA CA2835744A patent/CA2835744A1/en not_active Abandoned
- 2012-05-28 TW TW101118986A patent/TW201306939A/zh unknown
Also Published As
| Publication number | Publication date |
|---|---|
| US9108912B2 (en) | 2015-08-18 |
| WO2012163837A1 (en) | 2012-12-06 |
| US8791305B2 (en) | 2014-07-29 |
| BR112013029852A2 (pt) | 2016-12-20 |
| WO2012163831A1 (en) | 2012-12-06 |
| EP2714700A1 (en) | 2014-04-09 |
| CN103748102A (zh) | 2014-04-23 |
| RU2013157751A (ru) | 2015-07-10 |
| BR112013030262A2 (pt) | 2016-12-06 |
| US20140114090A1 (en) | 2014-04-24 |
| EP2714699A1 (en) | 2014-04-09 |
| CN103562213A (zh) | 2014-02-05 |
| US20140243558A1 (en) | 2014-08-28 |
| CA2835744A1 (en) | 2012-12-06 |
| JP2014524889A (ja) | 2014-09-25 |
| JP2014520089A (ja) | 2014-08-21 |
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