JP2009132697A - Method for inhibiting metal deposition from transition metal complex - Google Patents
Method for inhibiting metal deposition from transition metal complex Download PDFInfo
- Publication number
- JP2009132697A JP2009132697A JP2008283060A JP2008283060A JP2009132697A JP 2009132697 A JP2009132697 A JP 2009132697A JP 2008283060 A JP2008283060 A JP 2008283060A JP 2008283060 A JP2008283060 A JP 2008283060A JP 2009132697 A JP2009132697 A JP 2009132697A
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- Prior art keywords
- group
- reaction
- transition metal
- palladium
- phosphite
- Prior art date
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- 229910052723 transition metal Inorganic materials 0.000 title claims abstract description 88
- 150000003624 transition metals Chemical class 0.000 title claims abstract description 88
- 238000000034 method Methods 0.000 title claims abstract description 51
- 238000001465 metallisation Methods 0.000 title abstract description 21
- 230000002401 inhibitory effect Effects 0.000 title abstract 2
- 239000003054 catalyst Substances 0.000 claims abstract description 99
- 238000006243 chemical reaction Methods 0.000 claims abstract description 80
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 claims abstract description 61
- 125000003118 aryl group Chemical group 0.000 claims abstract description 60
- 239000003446 ligand Substances 0.000 claims abstract description 50
- 239000007788 liquid Substances 0.000 claims abstract description 35
- 150000002903 organophosphorus compounds Chemical class 0.000 claims abstract description 23
- 230000008569 process Effects 0.000 claims abstract description 6
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 221
- 229910052763 palladium Inorganic materials 0.000 claims description 107
- 229910052751 metal Inorganic materials 0.000 claims description 78
- 239000002184 metal Substances 0.000 claims description 78
- 125000004432 carbon atom Chemical group C* 0.000 claims description 40
- MWWXARALRVYLAE-UHFFFAOYSA-N 2-acetyloxybut-3-enyl acetate Chemical compound CC(=O)OCC(C=C)OC(C)=O MWWXARALRVYLAE-UHFFFAOYSA-N 0.000 claims description 38
- -1 allyl compound Chemical class 0.000 claims description 32
- 150000001875 compounds Chemical class 0.000 claims description 28
- 125000001424 substituent group Chemical group 0.000 claims description 28
- 238000006317 isomerization reaction Methods 0.000 claims description 25
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims description 22
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 claims description 16
- 238000001556 precipitation Methods 0.000 claims description 13
- 239000002994 raw material Substances 0.000 claims description 12
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 9
- 238000007037 hydroformylation reaction Methods 0.000 claims description 8
- 150000008300 phosphoramidites Chemical class 0.000 claims description 8
- 229910000073 phosphorus hydride Inorganic materials 0.000 claims description 8
- 229910052799 carbon Inorganic materials 0.000 claims description 7
- AQSJGOWTSHOLKH-UHFFFAOYSA-N phosphite(3-) Chemical class [O-]P([O-])[O-] AQSJGOWTSHOLKH-UHFFFAOYSA-N 0.000 claims description 7
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 6
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims description 5
- 238000007254 oxidation reaction Methods 0.000 claims description 5
- 238000005859 coupling reaction Methods 0.000 claims description 4
- 238000006356 dehydrogenation reaction Methods 0.000 claims description 4
- 238000005649 metathesis reaction Methods 0.000 claims description 4
- 238000006384 oligomerization reaction Methods 0.000 claims description 4
- 239000007795 chemical reaction product Substances 0.000 claims description 3
- 239000001257 hydrogen Substances 0.000 claims description 3
- 229910052739 hydrogen Inorganic materials 0.000 claims description 3
- 229910052697 platinum Inorganic materials 0.000 claims description 3
- 238000005937 allylation reaction Methods 0.000 claims description 2
- 150000003003 phosphines Chemical class 0.000 claims description 2
- 125000001183 hydrocarbyl group Chemical group 0.000 claims 1
- 239000012295 chemical reaction liquid Substances 0.000 abstract description 6
- 238000000151 deposition Methods 0.000 abstract description 2
- 230000008021 deposition Effects 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 87
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- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 18
- 235000019400 benzoyl peroxide Nutrition 0.000 description 18
- HXEQSCUBDIKNLN-UHFFFAOYSA-N ditert-butyl ethanediperoxoate Chemical compound CC(C)(C)OOC(=O)C(=O)OOC(C)(C)C HXEQSCUBDIKNLN-UHFFFAOYSA-N 0.000 description 18
- 238000009835 boiling Methods 0.000 description 15
- 238000001914 filtration Methods 0.000 description 14
- 125000000217 alkyl group Chemical group 0.000 description 13
- 238000001095 inductively coupled plasma mass spectrometry Methods 0.000 description 13
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- 238000004821 distillation Methods 0.000 description 12
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- 230000000052 comparative effect Effects 0.000 description 11
- 238000010438 heat treatment Methods 0.000 description 11
- 150000002940 palladium Chemical class 0.000 description 11
- 239000002904 solvent Substances 0.000 description 11
- YJVFFLUZDVXJQI-UHFFFAOYSA-L palladium(ii) acetate Chemical compound [Pd+2].CC([O-])=O.CC([O-])=O YJVFFLUZDVXJQI-UHFFFAOYSA-L 0.000 description 9
- 239000000047 product Substances 0.000 description 9
- 238000000926 separation method Methods 0.000 description 9
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- 125000003545 alkoxy group Chemical group 0.000 description 8
- 239000006227 byproduct Substances 0.000 description 8
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 7
- 229910001873 dinitrogen Inorganic materials 0.000 description 7
- 238000005984 hydrogenation reaction Methods 0.000 description 7
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 7
- JKIJEFPNVSHHEI-UHFFFAOYSA-N Phenol, 2,4-bis(1,1-dimethylethyl)-, phosphite (3:1) Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC=C1OP(OC=1C(=CC(=CC=1)C(C)(C)C)C(C)(C)C)OC1=CC=C(C(C)(C)C)C=C1C(C)(C)C JKIJEFPNVSHHEI-UHFFFAOYSA-N 0.000 description 6
- 238000001944 continuous distillation Methods 0.000 description 6
- 230000007423 decrease Effects 0.000 description 6
- 239000000706 filtrate Substances 0.000 description 6
- 239000007789 gas Substances 0.000 description 6
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- 125000005843 halogen group Chemical group 0.000 description 6
- 150000002430 hydrocarbons Chemical group 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- HVLLSGMXQDNUAL-UHFFFAOYSA-N triphenyl phosphite Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)OC1=CC=CC=C1 HVLLSGMXQDNUAL-UHFFFAOYSA-N 0.000 description 6
- YDRQWVZQEWLPTB-UHFFFAOYSA-N 2-hydroxybut-3-enyl acetate Chemical compound CC(=O)OCC(O)C=C YDRQWVZQEWLPTB-UHFFFAOYSA-N 0.000 description 5
- 125000004093 cyano group Chemical group *C#N 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 238000011084 recovery Methods 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 5
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 150000001721 carbon Chemical group 0.000 description 4
- 150000004696 coordination complex Chemical class 0.000 description 4
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 4
- 238000000354 decomposition reaction Methods 0.000 description 4
- 125000004185 ester group Chemical group 0.000 description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 4
- 125000001624 naphthyl group Chemical group 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [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 description 4
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 125000003277 amino group Chemical group 0.000 description 3
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 238000011109 contamination Methods 0.000 description 3
- 125000006165 cyclic alkyl group Chemical group 0.000 description 3
- 150000001993 dienes Chemical class 0.000 description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 3
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 3
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
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- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- RBYGDVHOECIAFC-UHFFFAOYSA-L acetonitrile;palladium(2+);dichloride Chemical compound [Cl-].[Cl-].[Pd+2].CC#N.CC#N RBYGDVHOECIAFC-UHFFFAOYSA-L 0.000 description 1
- 238000006137 acetoxylation reaction Methods 0.000 description 1
- 125000003668 acetyloxy group Chemical group [H]C([H])([H])C(=O)O[*] 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 125000002252 acyl group Chemical group 0.000 description 1
- BTGRAWJCKBQKAO-UHFFFAOYSA-N adiponitrile Chemical compound N#CCCCCC#N BTGRAWJCKBQKAO-UHFFFAOYSA-N 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- TWKVUTXHANJYGH-UHFFFAOYSA-L allyl palladium chloride Chemical class Cl[Pd]CC=C.Cl[Pd]CC=C TWKVUTXHANJYGH-UHFFFAOYSA-L 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- WXNOJTUTEXAZLD-UHFFFAOYSA-L benzonitrile;dichloropalladium Chemical compound Cl[Pd]Cl.N#CC1=CC=CC=C1.N#CC1=CC=CC=C1 WXNOJTUTEXAZLD-UHFFFAOYSA-L 0.000 description 1
- 125000006267 biphenyl group Chemical group 0.000 description 1
- ORDKJXVTZGLELC-UHFFFAOYSA-N bis(2-tert-butylphenyl) propyl phosphite Chemical compound P(OCCC)(OC1=C(C=CC=C1)C(C)(C)C)OC1=C(C=CC=C1)C(C)(C)C ORDKJXVTZGLELC-UHFFFAOYSA-N 0.000 description 1
- YNHIGQDRGKUECZ-UHFFFAOYSA-L bis(triphenylphosphine)palladium(ii) dichloride Chemical compound [Cl-].[Cl-].[Pd+2].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 YNHIGQDRGKUECZ-UHFFFAOYSA-L 0.000 description 1
- ITMIAZBRRZANGB-UHFFFAOYSA-N but-3-ene-1,2-diol Chemical compound OCC(O)C=C ITMIAZBRRZANGB-UHFFFAOYSA-N 0.000 description 1
- ZAWBQWCCSRWCHW-UHFFFAOYSA-N butyl bis(2-tert-butylphenyl) phosphite Chemical compound P(OCCCC)(OC1=C(C=CC=C1)C(C)(C)C)OC1=C(C=CC=C1)C(C)(C)C ZAWBQWCCSRWCHW-UHFFFAOYSA-N 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
- WXMZPPIDLJRXNK-UHFFFAOYSA-N butyl(diphenyl)phosphane Chemical compound C=1C=CC=CC=1P(CCCC)C1=CC=CC=C1 WXMZPPIDLJRXNK-UHFFFAOYSA-N 0.000 description 1
- 150000001728 carbonyl compounds Chemical class 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- HZEFWURFJZUWDE-UHFFFAOYSA-N cyclohexyl dihydrogen phosphite Chemical compound OP(O)OC1CCCCC1 HZEFWURFJZUWDE-UHFFFAOYSA-N 0.000 description 1
- ZXKWUYWWVSKKQZ-UHFFFAOYSA-N cyclohexyl(diphenyl)phosphane Chemical compound C1CCCCC1P(C=1C=CC=CC=1)C1=CC=CC=C1 ZXKWUYWWVSKKQZ-UHFFFAOYSA-N 0.000 description 1
- VPLLTGLLUHLIHA-UHFFFAOYSA-N dicyclohexyl(phenyl)phosphane Chemical compound C1CCCCC1P(C=1C=CC=CC=1)C1CCCCC1 VPLLTGLLUHLIHA-UHFFFAOYSA-N 0.000 description 1
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 description 1
- 238000006471 dimerization reaction Methods 0.000 description 1
- AAXGWYDSLJUQLN-UHFFFAOYSA-N diphenyl(propyl)phosphane Chemical compound C=1C=CC=CC=1P(CCC)C1=CC=CC=C1 AAXGWYDSLJUQLN-UHFFFAOYSA-N 0.000 description 1
- KWKXNDCHNDYVRT-UHFFFAOYSA-N dodecylbenzene Chemical compound CCCCCCCCCCCCC1=CC=CC=C1 KWKXNDCHNDYVRT-UHFFFAOYSA-N 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- SCWWUJMECBGKEH-UHFFFAOYSA-N hexyl diphenyl phosphite Chemical compound C=1C=CC=CC=1OP(OCCCCCC)OC1=CC=CC=C1 SCWWUJMECBGKEH-UHFFFAOYSA-N 0.000 description 1
- WHNGQRQJGDUZPJ-UHFFFAOYSA-N hexyl(diphenyl)phosphane Chemical compound C=1C=CC=CC=1P(CCCCCC)C1=CC=CC=C1 WHNGQRQJGDUZPJ-UHFFFAOYSA-N 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 150000002466 imines Chemical class 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 229910017053 inorganic salt Inorganic materials 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 125000000040 m-tolyl group Chemical group [H]C1=C([H])C(*)=C([H])C(=C1[H])C([H])([H])[H] 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 125000003261 o-tolyl group Chemical group [H]C1=C([H])C(*)=C(C([H])=C1[H])C([H])([H])[H] 0.000 description 1
- 239000013110 organic ligand Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 125000003854 p-chlorophenyl group Chemical group [H]C1=C([H])C(*)=C([H])C([H])=C1Cl 0.000 description 1
- 125000000636 p-nitrophenyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)[N+]([O-])=O 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 150000002941 palladium compounds Chemical class 0.000 description 1
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 1
- INIOZDBICVTGEO-UHFFFAOYSA-L palladium(ii) bromide Chemical compound Br[Pd]Br INIOZDBICVTGEO-UHFFFAOYSA-L 0.000 description 1
- GPNDARIEYHPYAY-UHFFFAOYSA-N palladium(ii) nitrate Chemical compound [Pd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O GPNDARIEYHPYAY-UHFFFAOYSA-N 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 125000004437 phosphorous atom Chemical group 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- APVDIAOSUXFJNU-UHFFFAOYSA-N rhodium(3+) phosphite Chemical compound [Rh+3].[O-]P([O-])[O-] APVDIAOSUXFJNU-UHFFFAOYSA-N 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 125000003808 silyl group Chemical group [H][Si]([H])([H])[*] 0.000 description 1
- 238000001577 simple distillation Methods 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 238000001256 steam distillation Methods 0.000 description 1
- 125000000542 sulfonic acid group Chemical group 0.000 description 1
- 125000000472 sulfonyl group Chemical group *S(*)(=O)=O 0.000 description 1
- MLFOVZVWGSASHO-UHFFFAOYSA-N tert-butyl bis(2-tert-butylphenyl) phosphite Chemical compound C=1C=CC=C(C(C)(C)C)C=1OP(OC(C)(C)C)OC1=CC=CC=C1C(C)(C)C MLFOVZVWGSASHO-UHFFFAOYSA-N 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 150000003623 transition metal compounds Chemical class 0.000 description 1
- XTTGYFREQJCEML-UHFFFAOYSA-N tributyl phosphite Chemical compound CCCCOP(OCCCC)OCCCC XTTGYFREQJCEML-UHFFFAOYSA-N 0.000 description 1
- TUQOTMZNTHZOKS-UHFFFAOYSA-N tributylphosphine Chemical compound CCCCP(CCCC)CCCC TUQOTMZNTHZOKS-UHFFFAOYSA-N 0.000 description 1
- WLPUWLXVBWGYMZ-UHFFFAOYSA-N tricyclohexylphosphine Chemical compound C1CCCCC1P(C1CCCCC1)C1CCCCC1 WLPUWLXVBWGYMZ-UHFFFAOYSA-N 0.000 description 1
- RXJKFRMDXUJTEX-UHFFFAOYSA-N triethylphosphine Chemical compound CCP(CC)CC RXJKFRMDXUJTEX-UHFFFAOYSA-N 0.000 description 1
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 1
- RMZAYIKUYWXQPB-UHFFFAOYSA-N trioctylphosphane Chemical compound CCCCCCCCP(CCCCCCCC)CCCCCCCC RMZAYIKUYWXQPB-UHFFFAOYSA-N 0.000 description 1
- BKHZQJRTFNFCTG-UHFFFAOYSA-N tris(2-methylphenyl) phosphite Chemical compound CC1=CC=CC=C1OP(OC=1C(=CC=CC=1)C)OC1=CC=CC=C1C BKHZQJRTFNFCTG-UHFFFAOYSA-N 0.000 description 1
- WXAZIUYTQHYBFW-UHFFFAOYSA-N tris(4-methylphenyl)phosphane Chemical compound C1=CC(C)=CC=C1P(C=1C=CC(C)=CC=1)C1=CC=C(C)C=C1 WXAZIUYTQHYBFW-UHFFFAOYSA-N 0.000 description 1
- 238000005292 vacuum distillation Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
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Abstract
Description
本発明は、遷移金属と有機配位子を有する遷移金属錯体を含有する溶液において、該遷移金属が析出するのを抑制する方法に関する。詳しくは、本発明は、遷移金属−有機リン含有リガンド錯体触媒を用いた水素化反応、異性化反応等の反応後の溶液中において、該遷移金属錯体触媒からの遷移金属析出を抑制する方法に関する。 The present invention relates to a method for suppressing precipitation of a transition metal in a solution containing a transition metal complex having a transition metal and an organic ligand. Specifically, the present invention relates to a method of suppressing transition metal precipitation from a transition metal complex catalyst in a solution after a reaction such as a hydrogenation reaction or an isomerization reaction using a transition metal-organophosphorus-containing ligand complex catalyst. .
遷移金属とホスファイトリガンドなどの有機リン含有配位子とからなる錯体触媒は、多くの反応プロセスに使用されており、このような反応プロセスとしては、例えば、不飽和化合物の水素化反応、異性化反応、オレフィンのハイドロフォルミル化反応、オレフィンの二量化反応等が知られている。また、ハイドロフォルミル化反応の際、ロジウム−ホスファイトリガンド錯体触媒を構成するホスファイトリガンドが、副生する酸性物質により或いは加水分解等によって一部が分解されると、錯体が不安定となり反応溶液中に錯体触媒の金属が析出することから、副生する酸性化合物を除去することも知られている(特許文献1参照)。これらの反応に使用される錯体触媒における遷移金属、例えば、ロジウム(第8族)やパラジウム(第10族)等は反応後の反応溶液から分離され回収されている。しかし、実際の反応プロセスにおいて、反応工程内で錯体触媒から金属の析出が生ずると触媒金属の損失となるだけでなく、装置内の汚染の一因となり、例えば熱伝導度が低下するなど、円滑な操作上問題である。 Complex catalysts composed of transition metals and organophosphorus-containing ligands such as phosphite ligands are used in many reaction processes. Examples of such reaction processes include hydrogenation reactions of unsaturated compounds, isomerism. Reactions such as hydroforming, olefin hydroformylation, and olefin dimerization are known. In the hydroformylation reaction, if the phosphite ligand that constitutes the rhodium-phosphite ligand complex catalyst is partially decomposed by the by-product acidic substance or by hydrolysis, the complex becomes unstable. Since the metal of the complex catalyst is precipitated in the solution, it is also known to remove the by-product acidic compound (see Patent Document 1). Transition metals such as rhodium (Group 8) and palladium (Group 10) in the complex catalyst used in these reactions are separated and recovered from the reaction solution after the reaction. However, in the actual reaction process, if metal deposition from the complex catalyst occurs in the reaction process, it not only causes loss of the catalyst metal, but also contributes to contamination in the apparatus, for example, a decrease in thermal conductivity. Is a serious operational problem.
金属錯体触媒からの金属の析出は、そのリガンドが反応時或いは目的生成物等の分離・回収時に酸化などにより一部が分解して錯体が不安定となることが析出の一つの要因であるので、錯体触媒におけるリガンドの分解等を阻止して、安定化を図り、プロセス工程内での金属が析出することを抑制し、金属錯体触媒含有液として反応系外に取り出すことが求められている。
本発明は、有機リン配位子を含有する遷移金属錯体触媒を用いた反応後の反応液中における遷移金属の析出を抑制し、遷移金属錯体触媒はその含有液として反応系外に効率良く取り出す方法を提供するものである。 The present invention suppresses the precipitation of transition metal in the reaction solution after the reaction using the transition metal complex catalyst containing the organophosphorus ligand, and the transition metal complex catalyst is efficiently taken out of the reaction system as the containing solution. A method is provided.
本発明者らは、各種反応に使用されているホスファイトリガンド等を含有する遷移金属錯体触媒を用いた反応液中において、遷移金属の析出を防止するために反応後の反応液中の該遷移金属錯体の状態について鋭意研究した結果、これらの遷移金属錯体触媒のホスファイトリガンド等の配位子が、反応中或いは分離・回収中に酸化等により一部が分解し、それによって錯体が不安定となり、錯体の金属が析出し易くなるのが一因であることを見出した。さらに、反応液における遷移金属錯体を酸化防止剤としてのホスファイトで接触処理することにより該遷移金属錯体を安定化し、遷移金属の析出を防止し得ることを見出した。本発明は、かかる知見に基づき達成されたのである。 In the reaction solution using a transition metal complex catalyst containing a phosphite ligand or the like used in various reactions, the present inventors have made the transition in the reaction solution after the reaction in order to prevent the precipitation of the transition metal. As a result of earnest research on the state of metal complexes, some of these transition metal complex catalyst ligands such as phosphite ligands are decomposed by oxidation or the like during the reaction or during separation / recovery, which makes the complexes unstable. Thus, it has been found that one of the reasons is that the complex metal is easily deposited. Furthermore, it has been found that the transition metal complex in the reaction solution can be contact-treated with phosphite as an antioxidant to stabilize the transition metal complex and prevent precipitation of the transition metal. The present invention has been achieved based on such findings.
すなわち、本発明の要旨は、以下の各項に存する。
1:3価の有機リン化合物からなる配位子を有する第8〜10族遷移金属から選ばれる遷移金属の遷移金属錯体を含有する溶液を、該3価の有機リン化合物とは異なる芳香族ホスファイトと接触させ、該溶液中における遷移金属錯体からの金属析出を抑制することを特徴とする方法。
2:芳香族ホスファイトが下式(I)で示されることを特徴とする前記1項に記載の方法。
That is, the gist of the present invention resides in the following items.
1: A solution containing a transition metal complex of a transition metal selected from
2: The method according to item 1, wherein the aromatic phosphite is represented by the following formula (I):
3:芳香族ホスファイトは、式(I)における少なくとも1個のアリール基がそのオルト位に置換基を有することを特徴とする前記1又は2項に記載の方法。
4:芳香族ホスファイトは、式(I)における少なくとも1個のアリール基がオルト位に有する置換基は3級または4級炭素原子により結合する置換基であることを特徴とする前記3項に記載の方法。
5:芳香族ホスファイトは、式(I)中、3個のRは同一で、オルト位に3級または4級炭素原子により結合する置換基を有するフェニル基であることを特徴とする前記4項に記載の方法。
6:芳香族ホスファイトが単座のホスファイトであることを特徴とする前記1〜5項のいずれか一項に記載の方法。
3: The method according to
4: The aromatic phosphite is characterized in that the substituent which at least one aryl group in the formula (I) has in the ortho position is a substituent bonded by a tertiary or quaternary carbon atom. The method described.
5: The aromatic phosphite is a phenyl group having three substituents in the formula (I) and having a substituent bonded to the ortho position by a tertiary or quaternary carbon atom. The method according to item.
6: The method according to any one of 1 to 5 above, wherein the aromatic phosphite is a monodentate phosphite.
7:3価の有機リン化合物が、ホスフィン、ホスファイト及びホスホラアミダイトからなる群から選ばれる少なくとも一種であることを特徴とする前記1〜6項のいずれか一項に記載の方法。
8:3価の有機リン化合物が、複座のホスフィン、ホスファイト及びホスホラアミダイトからなる群から選ばれる少なくとも一種であることを特徴とする前記1〜7項のいずれか一項に記載の方法。
9:第8〜10族遷移金属がパラジウム又は白金であることを特徴とする前記1〜8項のいずれか一項に記載の方法。
10:3価の有機リン化合物からなる配位子及び第8〜10族遷移金属から選ばれる遷移金属を含有する遷移金属錯体を含有する溶液が、該遷移金属錯体を触媒として行われる異性化反応、水素化反応、ヒドロホルミル化反応、脱水素反応、オリゴメリゼーション、メタセシス、カップリング反応、或いはアリル化反応のいずれかの反応後の溶液であることを特徴とする前記1〜9項のいずれか一項に記載の方法。
7: The method according to any one of 1 to 6 above, wherein the trivalent organic phosphorus compound is at least one selected from the group consisting of phosphine, phosphite and phosphoramidite.
8: The method according to any one of 1 to 7 above, wherein the trivalent organophosphorus compound is at least one selected from the group consisting of bidentate phosphines, phosphites, and phosphoramidites. .
9: The method according to any one of 1 to 8 above, wherein the Group 8-10 transition metal is palladium or platinum.
An isomerization reaction in which a solution containing a transition metal complex containing a ligand composed of a trivalent organophosphorus compound and a transition metal selected from
11:3価の有機リン化合物からなる配位子及び第8〜10族遷移金属から選ばれる遷移金属を含有する遷移金属錯体を含有する溶液が、原料アリル化合物誘導体の異性化反応後の原料と異なるアリル化合物誘導体を含む溶液であることを特徴とする前記10項に記載の方法。
12:3価の有機リン化合物からなる配位子及び第8〜10族遷移金属から選ばれる遷移金属を含有する遷移金属錯体を含有する溶液が、アセトキシアリル化合物の異性化反応後の反応液であることを特徴とする前記10又は11項に記載の方法。
13:アセトキシアリル化合物が、ブタジエンの酸化ジアセトキシ化反応生成物から得られる3,4−ジアセトキシ−1−ブテンを主成分とする含有液であることを特徴とする前記12項に記載の方法。
11: A solution containing a ligand composed of a trivalent organophosphorus compound and a transition metal complex containing a transition metal selected from
12: A solution containing a transition metal complex containing a ligand composed of a trivalent organic phosphorus compound and a transition metal selected from
13: The method according to 12 above, wherein the acetoxyallyl compound is a liquid containing 3,4-diacetoxy-1-butene as a main component obtained from a butadiene diacetoxylation reaction product of butadiene.
本発明の方法によれば、有機リン配位子を含有する遷移金属錯体触媒を用いた反応後の反応液中において、遷移金属の析出を抑制して錯体を安定化するので、反応系内での金属のロスを生ずることなく該遷移金属錯体触媒を、その含有液として反応系外に効率良く取り出すことができ、装置内の汚染、熱伝導度の低下等を抑えることができる。 According to the method of the present invention, in the reaction solution after the reaction using the transition metal complex catalyst containing the organophosphorus ligand, the complex is stabilized by suppressing the precipitation of the transition metal. Thus, the transition metal complex catalyst can be efficiently taken out of the reaction system as its containing liquid without causing loss of the metal, and contamination in the apparatus, a decrease in thermal conductivity, and the like can be suppressed.
以下、本発明をより詳細に説明する。
本発明における遷移金属錯体触媒は、3価の有機リン化合物からなる配位子及び第8〜10族遷移金属から選ばれる遷移金属を含有する遷移金属錯体からなり、該配位子はP−C結合、P−O結合或いはP−N結合を有するものである。この様な遷移金属錯体触媒は、例えば、アリル化合物誘導体の異性化、不飽和化合物の水素化、オレフィンのヒドロホルミル化、脱水素、オレフィンのオリゴメリゼーション、メタセシス、カップリング反応、ジエンのヒドロシアン化(ブタジエンのアジポニトリル化)等の多くの製造プロセスに使用される公知の遷移金属錯体触媒である。
Hereinafter, the present invention will be described in more detail.
The transition metal complex catalyst in the present invention comprises a ligand composed of a trivalent organophosphorus compound and a transition metal complex containing a transition metal selected from
本発明における遷移金属錯体触媒が含有する、3価の有機リン化合物からなる配位子は、P−C結合、P−O結合或いはP−N結合を有する化合物であり、ホスフィン、ホスファイト、及びホスホラアミダイトから選ばれる単座及び複座の配位子が含まれる。 The ligand composed of a trivalent organophosphorus compound contained in the transition metal complex catalyst in the present invention is a compound having a P—C bond, a P—O bond or a P—N bond, such as phosphine, phosphite, and Monodentate and bidentate ligands selected from phosphoramidites are included.
ホスフィンとしては、トリアルキルホスフィン、アルキルジアリールホスフィン、ジアルキルアリールホスフィン、ジシクロアルキルアリールホスフィン、シクロアルキルジアリールホスフィン、トリアラルキルホスフィン、トリシクロアルキルホスフィン、及びトリアリールホスフィン等が挙げられ、例えば下記一般式(i)で示される。 Examples of the phosphine include trialkylphosphine, alkyldiarylphosphine, dialkylarylphosphine, dicycloalkylarylphosphine, cycloalkyldiarylphosphine, triaralkylphosphine, tricycloalkylphosphine, and triarylphosphine. i).
アリール基としては、フェニル基、ナフチル基、ジフェニル基等が挙げられ、アルキル基としては、炭素数1〜10のアルキル基、例えば、メチル基、エチル基、プロピル基、ブチル基、シクロヘキシル基等が挙げられる。また、これらの基が有し得る置換基としては、アルキル基、アルコキシ基、シリル基、アミノ基、アシル基、カルボキシ基、ハロゲン原子、スルホニル基、スルホン酸基、シアノ基、トリフルオロメチル基等が挙げられる。これらの中、フェニル基、ナフチル基などのアリール基が好ましい。
Examples of the aryl group include a phenyl group, a naphthyl group, and a diphenyl group. Examples of the alkyl group include an alkyl group having 1 to 10 carbon atoms, such as a methyl group, an ethyl group, a propyl group, a butyl group, and a cyclohexyl group. Can be mentioned. Examples of the substituent that these groups may have include an alkyl group, an alkoxy group, a silyl group, an amino group, an acyl group, a carboxy group, a halogen atom, a sulfonyl group, a sulfonic acid group, a cyano group, and a trifluoromethyl group. Is mentioned. Of these, aryl groups such as a phenyl group and a naphthyl group are preferred.
前記ホスフィンとして、具体的には、トリフェニルホスフィン、トリス−p−トリルホスフィン、トリス−p−メトキシフェニルホスフィン、トリス−p−フルオロフェニルホスフィン、トリス−p−クロルフェニルホスフィン、トリス−ジメチルアミノフェニルホスフィン、プロピルジフェニルホスフィン、t−ブチルジフェニルホスフィン、n−ブチルジフェニルホスフィン、n−ヘキシルジフェニルホスフィン、シクロヘキシルジフェニルホスフィン、ジシクロヘキシルフェニルホスフィン、トリシクロヘキシルホスフィン、トリメチルホスフィン、トリエチルホスフィン、トリブチルホスフィン、トリオクチルホスフィン等が挙げられる。 Specific examples of the phosphine include triphenylphosphine, tris-p-tolylphosphine, tris-p-methoxyphenylphosphine, tris-p-fluorophenylphosphine, tris-p-chlorophenylphosphine, and tris-dimethylaminophenylphosphine. Propyldiphenylphosphine, t-butyldiphenylphosphine, n-butyldiphenylphosphine, n-hexyldiphenylphosphine, cyclohexyldiphenylphosphine, dicyclohexylphenylphosphine, tricyclohexylphosphine, trimethylphosphine, triethylphosphine, tributylphosphine, trioctylphosphine, etc. It is done.
前記ホスファイトとしては、下記の式(1−1)及び(2−1)で表される単座及び2座の配位子が挙げられる。
前記ホスホラアミダイトとしては、下記の式(1−2)及び(2−2)〜(2−5)で表される単座及び2座の配位子が挙げられる。
Examples of the phosphite include monodentate and bidentate ligands represented by the following formulas (1-1) and (2-1).
Examples of the phosphoramidite include monodentate and bidentate ligands represented by the following formulas (1-2) and (2-2) to (2-5).
上記式中、Y1、Y2、Y3、Y4、Y5、Y6、Y7、Y8、及びY9は、それぞれ独立に鎖状若しくは環状アルキル基、アリール基又は複素環基を表し、これらの基は更に置換基を有していてもよい。また、Y2とY3、Y4とY5、Y6とY7、Y8とY9はそれぞれ互いに連結して環を形成していてもよい。nはメチレン鎖(−CH2−)の長さを示し、nは1〜10であり、好ましくは1〜5であり、特に好ましくは2〜4である。mはメチレン鎖の長さを示し、mは1〜5であり、好ましくは1〜3である。 In the above formula, Y 1 , Y 2 , Y 3 , Y 4 , Y 5 , Y 6 , Y 7 , Y 8 , and Y 9 are each independently a chain or cyclic alkyl group, aryl group, or heterocyclic group. And these groups may further have a substituent. Y 2 and Y 3 , Y 4 and Y 5 , Y 6 and Y 7 , and Y 8 and Y 9 may be connected to each other to form a ring. n is methylene chain (-CH 2 -) indicates the length of, n is 1 to 10, preferably 1 to 5, particularly preferably 2 to 4. m shows the length of a methylene chain, m is 1-5, Preferably it is 1-3.
R1及びR5は、それぞれ独立に水素原子、置換基を有していてもよい炭素数3〜20の2級又は3級炭化水素基を表し、R2、R3、R6、R7、R9及びR10は、それぞれ独立に置換基を有していてもよい炭素数1〜20の炭化水素基、又は置換基を有していてもよい炭素数1〜10のアルコキシ基を表し、R4及びR8は、それぞれ独立に水素原子、炭素数1〜4の炭化水素基、ハロゲン原子、又は炭素数1〜4のアルコキシ基を表す。 R 1 and R 5 each independently represent a hydrogen atom or a secondary or tertiary hydrocarbon group having 3 to 20 carbon atoms which may have a substituent, and R 2 , R 3 , R 6 , R 7 , R 9 and R 10 each independently represents a hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, or an alkoxy group having 1 to 10 carbon atoms which may have a substituent. , R 4 and R 8 each independently represents a hydrogen atom, a hydrocarbon group having 1 to 4 carbon atoms, a halogen atom, or an alkoxy group having 1 to 4 carbon atoms.
上記鎖状若しくは環状のアルキル基及びアルコキシ基のアルキル骨格部分は、通常、炭素数1〜20であり、好ましくは1〜14である。その具体例としては、例えばメチル基、エチル基、n−プロピル基、i−プロピル基、n−ブチル基、i−ブチル基、sec−ブチル基、t−ブチル基、ペンチル基、へキシル基、オクチル基、デシル基、シクロヘキシル基、シクロペンチル基等である。また、アルキル基が有し得る置換基としては、炭素数1〜10のアルコキシ基、炭素数6〜10のアリール基、アミノ基、シアノ基、炭素数2〜10のエステル基、ヒドロキシ基、及びハロゲン原子が挙げられる。 The chain skeleton or cyclic alkyl group and the alkyl skeleton portion of the alkoxy group usually have 1 to 20 carbon atoms, preferably 1 to 14 carbon atoms. Specific examples thereof include, for example, methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, sec-butyl group, t-butyl group, pentyl group, hexyl group, An octyl group, a decyl group, a cyclohexyl group, a cyclopentyl group, and the like. Examples of the substituent that the alkyl group may have include an alkoxy group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, an amino group, a cyano group, an ester group having 2 to 10 carbon atoms, a hydroxy group, and A halogen atom is mentioned.
上記アリール基は、炭素数が通常6〜20であり、好ましくは6〜14である。アリール基の具体例としては、フェニル基、ナフチル基が挙げられ、これらの基が有し得る置換基としては、水素原子、炭素数1〜20のアルキル基、炭素数1〜10のアルコキシ基、炭素数3〜20のシクロアルキル基、炭素数6〜20のアリール基、炭素数6〜20のアリーロキシ基、炭素数6〜20のアルキルアリール基、炭素数6〜20のアルキルアリーロキシ基、炭素数6〜20のアリールアルキル基、炭素数6〜20のアリールアルコキシ基、シアノ基、エステル基、ヒドロキシ基、および塩素、フッ素等のハロゲン原子が挙げられる。 The aryl group usually has 6 to 20 carbon atoms, preferably 6 to 14 carbon atoms. Specific examples of the aryl group include a phenyl group and a naphthyl group. Examples of the substituent that these groups may have include a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, A cycloalkyl group having 3 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aryloxy group having 6 to 20 carbon atoms, an alkylaryl group having 6 to 20 carbon atoms, an alkylaryloxy group having 6 to 20 carbon atoms, carbon Examples thereof include arylalkyl groups having 6 to 20 carbon atoms, arylalkoxy groups having 6 to 20 carbon atoms, cyano groups, ester groups, hydroxy groups, and halogen atoms such as chlorine and fluorine.
Y1〜Y9が置換基を有していてもよいアリール基である場合、具体例としては、フェニル基、2−メチルフェニル基、3−メチルフェニル基、4−メチルフェニル基、2,3−ジメチルフェニル基、2,4−ジメチルフェニル基、2,5−ジメチルフェニル基、2,6−ジメチルフェニル基、2−エチルフェニル基、2−イソプロピルフェニル基、2−t−ブチルフェニル基、2,4−ジ−t−ブチルフェニル基、2−クロロフェニル基、3−クロロフェニル基、4−クロロフェニル基、2,3−ジクロロフェニル基、2,4−ジクロロフェニル基、2,5−ジクロロフェニル基、3,4−ジクロロフェニル基、3,5−ジクロロフェニル基、4−トリフルオロメチルフェニル基、2−メトキシフェニル基、3−メトキシフェニル基、4−メトキシフェニル基、3,5−ジメトキシフェニル基、4−シアノフェニル基、4−ニトロフェニル基、トリフルオロメチルフェニル基、ペンタフルオロフェニル基、及び下記の(C−1)〜(C−8)の基などが挙げられる。 When Y 1 to Y 9 are aryl groups which may have a substituent, specific examples include phenyl group, 2-methylphenyl group, 3-methylphenyl group, 4-methylphenyl group, 2, 3 -Dimethylphenyl group, 2,4-dimethylphenyl group, 2,5-dimethylphenyl group, 2,6-dimethylphenyl group, 2-ethylphenyl group, 2-isopropylphenyl group, 2-t-butylphenyl group, 2 , 4-Di-t-butylphenyl group, 2-chlorophenyl group, 3-chlorophenyl group, 4-chlorophenyl group, 2,3-dichlorophenyl group, 2,4-dichlorophenyl group, 2,5-dichlorophenyl group, 3,4 -Dichlorophenyl group, 3,5-dichlorophenyl group, 4-trifluoromethylphenyl group, 2-methoxyphenyl group, 3-methoxyphenyl group, 4-metho Xiphenyl group, 3,5-dimethoxyphenyl group, 4-cyanophenyl group, 4-nitrophenyl group, trifluoromethylphenyl group, pentafluorophenyl group, and groups (C-1) to (C-8) below Etc.
本発明における遷移金属錯体触媒における第8〜10族の遷移金属としては、好ましくはルテニウム、ロジウム、ニッケル、パラジウム、白金等であり、特に好ましくはパラジウムである。該遷移金属は化合物の形態で供給されるが、具体的な化合物としては、例えば酢酸塩、硫酸塩、硝酸塩、ハライド塩、有機塩、無機塩、アセチルアセトナト化合物、アルケン配位化合物、アミン配位化合物、ピリジン配位化合物、一酸化炭素配位化合物、ホスフィン配位化合物、ホスファイト配位化合物等が挙げられる。 The group 8-10 transition metal in the transition metal complex catalyst in the present invention is preferably ruthenium, rhodium, nickel, palladium, platinum or the like, and particularly preferably palladium. The transition metal is supplied in the form of a compound. Specific compounds include, for example, acetate, sulfate, nitrate, halide salt, organic salt, inorganic salt, acetylacetonato compound, alkene coordination compound, amine coordination. A coordination compound, a pyridine coordination compound, a carbon monoxide coordination compound, a phosphine coordination compound, a phosphite coordination compound, and the like.
具体的なパラジウム化合物としては、パラジウム金属、酢酸パラジウム、トリフルオロ酢酸パラジウム、硫酸パラジウム、硝酸パラジウム、塩化パラジウム、臭化パラジウム、ヨウ化パラジウム、ビス(アセチルアセトナト)パラジウム、ジクロロシクロオクタジエンパラジウム、ジクロロビス(トリフェニルホスフィン)パラジウム、テトラキス(トリフェニルホスフィン)パラジウム、ビス(ジベンジリアセトン)パラジウム、カリウムテトラクロロバラグト、ナトリウムテトラクロロバラグト、ジクロロビス(ベンゾニトリル)パラジウム、ジクロロビス(アセトニトリル)パラジウム、及びその他のカルボキシレート化合物、オレフィン含有化合物、有機ホスフィン含有化合物、アリルパラジウムクロリドニ量体等が挙げられる。特に、価格及び取り扱いのし易さなどから、酢酸パラジウム、トリフルオロ酢酸パラジウム、ビス(アセチルアセトナト)パラジウム、テトラキス(トリフェニルホスフィン)パラジウム等が特に好適に用いられる。 Specific palladium compounds include palladium metal, palladium acetate, palladium trifluoroacetate, palladium sulfate, palladium nitrate, palladium chloride, palladium bromide, palladium iodide, bis (acetylacetonato) palladium, dichlorocyclooctadiene palladium, Dichlorobis (triphenylphosphine) palladium, tetrakis (triphenylphosphine) palladium, bis (dibenzylacetone) palladium, potassium tetrachlorobaraguto, sodium tetrachlorobaraguto, dichlorobis (benzonitrile) palladium, dichlorobis (acetonitrile) palladium, And other carboxylate compounds, olefin-containing compounds, organic phosphine-containing compounds, allyl palladium chloride dimers, and the like. In particular, palladium acetate, palladium trifluoroacetate, bis (acetylacetonato) palladium, tetrakis (triphenylphosphine) palladium, and the like are particularly preferably used because of cost and ease of handling.
本発明の遷移金属錯体における、上記配位子の添加量は、配位子中のリン原子のモル比が遷移金属錯体中の遷移金属の1モルに対して0.1〜1000が好ましく、より好ましくは1〜100であり、1〜10が特に好ましい。また、配位子として一種又は複数種の配位子が含まれていてもよい。遷移金属錯体の調製方法は、特に制限されず、例えば、該錯体を触媒とする反応時、遷移金属化合物と配位子化合物を所望の割合で溶媒中、加温することにより反応させて触媒含有液とすることが出来る。 In the transition metal complex of the present invention, the addition amount of the above ligand is preferably such that the molar ratio of the phosphorus atom in the ligand is 0.1 to 1000 with respect to 1 mol of the transition metal in the transition metal complex, Preferably it is 1-100, and 1-10 are especially preferable. Moreover, 1 type or multiple types of ligand may be contained as a ligand. The method for preparing the transition metal complex is not particularly limited. For example, during the reaction using the complex as a catalyst, the transition metal compound and the ligand compound are reacted by heating them in a desired ratio in a solvent to contain a catalyst. Can be liquid.
本発明においては、上記3価の有機リン化合物からなる配位子と第8〜10族の遷移金属を含む遷移金属錯体を含有する溶液と芳香族ホスファイトとを接触させるが、芳香族ホスファイトは、配位子である3価の有機リン化合物とは異なるものである。
In the present invention, a solution comprising a ligand composed of the above trivalent organophosphorus compound, a transition metal complex containing a transition metal of
遷移金属錯体触媒の金属析出は、該金属錯体触媒のホスファイトリガンド配位子が、反応中或いは分離・回収中に酸化されて錯体が不安定となることが一因である。従って、接触させる芳香族ホスファイトは上記金属錯体触媒の有する3価の有機リン化合物からなる配位子の酸化を防止し、それ自体が酸化される成分として機能するものであればよく、下記式(I)で示される芳香族ホスファイトが挙げられる。 One reason for the metal precipitation of the transition metal complex catalyst is that the phosphite ligand ligand of the metal complex catalyst is oxidized during the reaction or during separation / recovery and the complex becomes unstable. Therefore, the aromatic phosphite to be brought into contact is not limited as long as it prevents oxidation of the ligand composed of the trivalent organophosphorus compound of the metal complex catalyst and functions as a component to be oxidized itself. The aromatic phosphite shown by (I) is mentioned.
式(I)における炭化水素基は、アルキル基又はアリール基から選ばれる。アルキル基は、炭素数が通常1〜20、好ましくは1〜14の直鎖若しくは分岐のアルキル基又は環状のアルキル基であり、具体的なアルキル基としては、メチル基、エチル基、n−プロピル基、i−プロピル基、n−ブチル基、i−ブチル基、sec−ブチル基、t−ブチル基、ペンチル基、へキシル基、オクチル基、デシル基、シクロヘキシル基、シクロペンチル基等が挙げられる。また、アルキル基が有し得る置換基としては、炭素数1〜10のアルコキシ基、炭素数6〜10のアリール基、アミノ基、シアノ基、炭素数2〜10のエステル基、ヒドロキシ基、及びハロゲン原子等が挙げられる。
The hydrocarbon group in formula (I) is selected from an alkyl group or an aryl group. The alkyl group is a linear or branched alkyl group having 1 to 20 carbon atoms, preferably 1 to 14 carbon atoms, or a cyclic alkyl group. Specific examples of the alkyl group include a methyl group, an ethyl group, and n-propyl. Group, i-propyl group, n-butyl group, i-butyl group, sec-butyl group, t-butyl group, pentyl group, hexyl group, octyl group, decyl group, cyclohexyl group, cyclopentyl group and the like. Examples of the substituent that the alkyl group may have include an alkoxy group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, an amino group, a cyano group, an ester group having 2 to 10 carbon atoms, a hydroxy group, and A halogen atom etc. are mentioned.
アリール基は、炭素数が通常6〜20であり、好ましくは6〜14である。アリール基の具体例としては、フェニル基、ナフチル基が挙げられる。これらの基が有し得る置換基としては、水素原子、炭素数1〜20のアルキル基、炭素数1〜10のアルコキシ基、炭素数3〜20のシクロアルキル基、炭素数6〜10のアリール基、炭素数6〜20のアリーロキシ基、炭素数6〜20のアルキルアリール基、炭素数6〜20のアルキルアリーロキシ基、炭素数6〜20のアリールアルキル基、炭素数6〜20のアリールアルコキシ基、シアノ基、エステル基、ヒドロキシ基および、塩素、フッ素等のハロゲン原子が挙げられる。置換基として、好ましくは、i−プロピル基、i−ブチル基、sec−ブチル基、t−ブチル基、シクロヘキシル基であり、t−ブチル基が特に好ましい。 The aryl group usually has 6 to 20 carbon atoms, preferably 6 to 14 carbon atoms. Specific examples of the aryl group include a phenyl group and a naphthyl group. Examples of the substituent that these groups may have include a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, and an aryl having 6 to 10 carbon atoms. Group, aryloxy group having 6 to 20 carbon atoms, alkylaryl group having 6 to 20 carbon atoms, alkylaryloxy group having 6 to 20 carbon atoms, arylalkyl group having 6 to 20 carbon atoms, arylalkoxy group having 6 to 20 carbon atoms Group, cyano group, ester group, hydroxy group, and halogen atoms such as chlorine and fluorine. The substituent is preferably an i-propyl group, an i-butyl group, a sec-butyl group, a t-butyl group, or a cyclohexyl group, and a t-butyl group is particularly preferable.
芳香族ホスファイトとしては、式(I)における少なくとも1個のアリール基が、そのオルト位(2位又は6位)に置換基を有することが好ましく、オルト位に有する置換基は3級または4級炭素原子によりアリール基に結合する置換基であることが好ましい。特に好適な芳香族ホスファイトは、式(I)中、3個のRは同一で、オルト位に3級または4級炭素原子により結合する置換基を有するフェニル基であるホスファイトであり、また、芳香族ホスファイトは、単座のホスファイトであることが好ましい。特に、オルト位にt−ブチル基を有するフェニル基の単座ホスファイトが好ましい。 As the aromatic phosphite, it is preferable that at least one aryl group in the formula (I) has a substituent at the ortho position (the 2-position or 6-position), and the substituent at the ortho position is tertiary or 4 The substituent is preferably bonded to the aryl group through a secondary carbon atom. Particularly preferred aromatic phosphites are phosphites in which in the formula (I) three R's are identical and are phenyl groups having a substituent attached to the ortho position by a tertiary or quaternary carbon atom, The aromatic phosphite is preferably a monodentate phosphite. In particular, a monodentate phosphite of a phenyl group having a t-butyl group at the ortho position is preferable.
芳香族ホスファイトとして具体的には、トリフェニルホスファイト、トリス−o−トリルホスファイト、トリス−o−i−プロピルフェニルホスファイト、トリス−2−t−ブチルフェニルホスファイト、トリス−i−ブチルフェニルホスファイト、トリス−i−プロピルフェニルホスファイト、トリス−2,4−ジ−t−ブチルフェニルホスファイト、トリス−2,5−ジ−t−ブチルフェニルホスファイト、トリス−2,6−ジ−t−ブチルフェニルホスファイト、トリス−2,3−ジ−t−ブチルフェニルホスファイト、トリス−2,4−ジ−i−プロピルフェニルホスファイト、トリス−2,5−ジ−i−プロピルフェニルホスファイト、トリス−2,6−ジ−i−プロピルフェニルホスファイト、トリス−2,3−ジ−i−プロピルフェニルホスファイト、プロピルジ(2−t−ブチルフェニル)ホスファイト、t−ブチルジ(2−t−ブチルフェニル)ホスファイト、n−ブチルジ(2−t−ブチルフェニル)ホスファイト、n−ヘキシルジフェニルホスファイト、t−ブチルジ(2,4−t−ブチルフェニル)ホスファイト、n−ブチル−ジ(2,4−t−ブチルフェニル)ホスファイト、ジ(2,4−t−ブチルフェニル)シクロヘキシルホスファイト、トリス−2−t−ブチルシクロヘキシルホスファイト、ジ(2−t−ブチルシクロヘキシル)フェニルホスファイト等が挙げられる。これらの中、トリス−2−t−ブチルフェニルホスファイト、トリス−i−ブチルフェニルホスファイト、トリス−i−プロピルフェニルホスファイト、トリス−2,4−ジ-t−ブチルフェニルホスファイト、トリス−2,4−ジt−ブチルフェニルホスファイト等が好ましく、特にトリス−2,4−ジt−ブチルフェニルホスファイトが好ましい。 Specific examples of aromatic phosphites include triphenyl phosphite, tris-o-tolyl phosphite, tris-oi-propylphenyl phosphite, tris-2-t-butylphenyl phosphite, tris-i-butyl. Phenyl phosphite, tris-i-propylphenyl phosphite, tris-2,4-di-t-butylphenyl phosphite, tris-2,5-di-t-butylphenyl phosphite, tris-2,6-di -T-butylphenyl phosphite, tris-2,3-di-t-butylphenyl phosphite, tris-2,4-di-i-propylphenyl phosphite, tris-2,5-di-i-propylphenyl Phosphite, Tris-2,6-di-i-propylphenyl phosphite, Tris-2,3-di-i-propi Phenyl phosphite, propyl di (2-t-butylphenyl) phosphite, t-butyl di (2-t-butylphenyl) phosphite, n-butyl di (2-t-butylphenyl) phosphite, n-hexyl diphenyl phosphite T-butyldi (2,4-t-butylphenyl) phosphite, n-butyl-di (2,4-t-butylphenyl) phosphite, di (2,4-t-butylphenyl) cyclohexyl phosphite, Examples include tris-2-t-butylcyclohexyl phosphite and di (2-t-butylcyclohexyl) phenyl phosphite. Among these, tris-2-t-butylphenyl phosphite, tris-i-butylphenyl phosphite, tris-i-propylphenyl phosphite, tris-2,4-di-t-butylphenyl phosphite, tris- 2,4-di-t-butylphenyl phosphite is preferable, and tris-2,4-di-t-butylphenyl phosphite is particularly preferable.
本発明における3価の有機リン化合物からなる配位子と第8〜10族の遷移金属を含む遷移金属錯体を含有する溶液としては、具体的には該遷移金属触媒を用いた反応により得られる反応液である。該遷移金属錯体触媒を用いた反応としては、例えば、アリル化合物誘導体の異性化、不飽和化合物の水素化、オレフィンのヒドロホルミル化、脱水素、オレフィンのオリゴメリゼーション、メタセシス、カップリング反応、ジエンのヒドロシアン化(ブタジエンのアジポニトリル化)等が挙げられる。特に、本発明では、該遷移金属錯体を触媒とするアリル化合物誘導体の異性化反応後の反応液が好ましく、ブタジエンの酸化アセトキシ化反応で得られるアセトキシアリル化合物、即ち3,4−ジアセトキシ−1−ブテンの1,4−ジアセトキシ−2−ブテンへの異性化反応の反応液が特に好ましい。
A solution containing a transition metal complex containing a ligand composed of a trivalent organophosphorus compound and a transition metal of
本発明の方法において、上記該遷移金属触媒を用いた反応により得られる反応液と芳香族ホスファイトとを接触させるが、反応液としては反応後の反応液そのままであっても反応液から生成物を除去した残留液或いは触媒を分離した触媒を含有する反応液であってもよく、特に反応後の反応液と接触させるのが好ましい。反応液と芳香族ホスファイトとの接触は、具体的には反応後の反応液に芳香族ホスファイト含有溶液または固体そのものを添加し、接触させることにより行われる。芳香族ホスファイトは固体そのものであっても、溶液であってもよいが、添加時の反応液との接触効率からあらかじめ均一に溶解させておいた方が好ましい。これにより、反応工程以降、反応液では遷移金属錯体触媒と芳香族ホスファイトが均一な溶液として工程内の配管内、蒸留塔等の装置内を移送されるので、配管内及び蒸留塔等の装置内での触媒金属の析出による金属ロス、工程系内での汚れの生成が抑制される。また、触媒金属は溶解した含有液として系外に取り出すことが出来、取り出された溶液は触媒処理(触媒回収或いは廃棄)に付される。触媒処理工程では、取り出された溶液をそのまま焼却する、金属回収の為に他場所に移送、或いはプラント内に設置された水中燃焼装置等により金属灰としての回収等が行われる。
反応液と芳香族ホスファイトとの混合物は、必要であれば加熱処理される。加熱処理温度は、通常20℃〜200℃、好ましくは80℃〜180℃である。この範囲を超えて高温で処理すると芳香族ホスファイト自身の熱分解が進行し、他方低温過ぎると反応液に対する芳香族ホスファイトの溶解度が下がり、金属の析出抑制効果が低下する。
In the method of the present invention, the reaction solution obtained by the reaction using the transition metal catalyst and an aromatic phosphite are brought into contact with each other. The residual liquid from which the catalyst has been removed or the reaction liquid containing the catalyst from which the catalyst has been separated may be used, and it is particularly preferable to contact the reaction liquid after the reaction. Specifically, the contact between the reaction solution and the aromatic phosphite is carried out by adding the aromatic phosphite-containing solution or the solid itself to the reaction solution after the reaction and bringing them into contact with each other. The aromatic phosphite may be a solid itself or a solution, but it is preferable that the aromatic phosphite is uniformly dissolved in advance from the contact efficiency with the reaction solution at the time of addition. Thereby, after the reaction step, the transition metal complex catalyst and the aromatic phosphite are transferred in the reaction solution as a uniform solution in the pipe in the process, in the apparatus such as the distillation tower, etc. The metal loss due to the deposition of the catalyst metal in the inside and the generation of dirt in the process system are suppressed. Further, the catalyst metal can be taken out of the system as a dissolved contained liquid, and the taken-out solution is subjected to catalyst treatment (catalyst recovery or disposal). In the catalyst treatment step, the extracted solution is incinerated as it is, transferred to another place for metal recovery, or recovered as metal ash by an underwater combustion device installed in the plant.
The mixture of reaction liquid and aromatic phosphite is heat-treated if necessary. The heat treatment temperature is usually 20 ° C to 200 ° C, preferably 80 ° C to 180 ° C. When the treatment is carried out at a high temperature exceeding this range, the thermal decomposition of the aromatic phosphite proceeds. On the other hand, when the treatment is too low, the solubility of the aromatic phosphite in the reaction solution is lowered, and the metal precipitation suppressing effect is lowered.
芳香族ホスファイトの選定基準としては、そのホスファイトが有する酸化防止機能を最大限発揮させるために、酸素以外の因子による分解を回避する必要があり、具体的には熱的あるいは化学的に容易に分解するホスファイトの使用は好ましくない。そのため、熱的に安定である芳香族ホスファイトが好ましく、さらに化学的な安定性を高めるためには、P−O結合が他の化学成分との反応によって開裂されるのを防止するために、芳香族環がそのP−O結合に対するオルト位に嵩高い置換基を有するホスファイトが好ましい。また通常は単座ホスファイトが複座ホスファイトよりも安価であり、機能上及びコストの観点から単座の芳香族ホスファイトが好ましい。 As a selection criterion for aromatic phosphites, it is necessary to avoid decomposition by factors other than oxygen in order to maximize the antioxidant function of the phosphites. The use of phosphites which decompose into Therefore, an aromatic phosphite that is thermally stable is preferred, and in order to further enhance chemical stability, in order to prevent the P—O bond from being cleaved by reaction with other chemical components, A phosphite in which the aromatic ring has a bulky substituent at the ortho position relative to its PO bond is preferred. In addition, monodentate phosphites are usually less expensive than double seat phosphites, and monodentate aromatic phosphites are preferred from the viewpoint of functionality and cost.
遷移金属触媒を用いた反応により得られる反応液へ芳香族ホスファイトを添加して接触させる場合、反応液に対する芳香族ホスファイトの割合は、反応液に含まれる遷移金属触媒の種類、量等により異なるが、通常、遷移金属触媒の金属1モル量に対して1モル等量〜1000モル等量であり、好ましくは2モル等量〜50モル等量である。添加量が、この割合を超えて少なすぎると、金属の析出抑制効果が得られず、他方多すぎても添加量に見合う効果は得られないので、コスト上好ましくない。 When aromatic phosphite is added to the reaction solution obtained by the reaction using the transition metal catalyst and brought into contact, the ratio of the aromatic phosphite to the reaction solution depends on the type and amount of the transition metal catalyst contained in the reaction solution. Although it is different, it is usually 1 mol equivalent to 1000 mol equivalent, preferably 2 mol equivalent to 50 mol equivalent, relative to 1 mol metal of the transition metal catalyst. If the amount added exceeds this ratio and is too small, the effect of suppressing the precipitation of metal cannot be obtained. On the other hand, if the amount added is too large, an effect commensurate with the amount added cannot be obtained.
添加される芳香族ホスファイト溶液における濃度は、該芳香族ホスファイトの種類によっても異なるが、通常50重量ppm〜1重量%であり、好ましくは100重量ppm〜5000重量ppmである。 The concentration in the aromatic phosphite solution to be added varies depending on the type of the aromatic phosphite, but is usually 50 ppm to 1% by weight, preferably 100 ppm to 5000 ppm by weight.
以下に、遷移金属錯体触媒を用いたアセトキシアリル化合物の異性化反応後の反応液を、芳香族ホスファイトと接触させる方法を説明する。
アセトキシアリル化合物としての3,4−ジアセトキシ−1−ブテン類及び/又は1,4−ジアセトキシ−2−ブテン類をブタジエン等の共役ジエン類の酸化ジアセトキシ化反応により製造する方法は公知である。最も一般的には、パラジウム系触媒の存在下、ブタジエン、酢酸及び酸素を反応させて1,4−ジアセトキシ−2−ブテン及び3,4−ジアセトキシ−1−ブテンを製造するが、その反応液には、通常これらのジアセトキシブテン類の加水分解物である1−アセトキシ−4−ヒドロキシ−2−ブテン、3−ヒドロキシ−4−アセトキシ−1−ブテン、4−ヒドロキシ−3−アセトキシ−1−ブテンなども含まれている。
Below, the method of making the reaction liquid after the isomerization reaction of the acetoxyallyl compound using a transition metal complex catalyst contact with aromatic phosphite is demonstrated.
Methods for producing 3,4-diacetoxy-1-butenes and / or 1,4-diacetoxy-2-butenes as acetoxyallyl compounds by oxidative diacetoxylation reaction of conjugated dienes such as butadiene are known. Most commonly, 1,4-diacetoxy-2-butene and 3,4-diacetoxy-1-butene are produced by reacting butadiene, acetic acid and oxygen in the presence of a palladium-based catalyst. Are usually hydrolysates of these diacetoxybutenes, such as 1-acetoxy-4-hydroxy-2-butene, 3-hydroxy-4-acetoxy-1-butene, 4-hydroxy-3-acetoxy-1-butene Etc. are also included.
異性化反応に原料として供給される3,4−ジアセトキシ−1−ブテンとしては、純品の他、上記ブタジエンのジアセトキシ化反応後の反応液そのもの、あるいは酢酸、水などの3,4−ジアセトキシ−1−ブテンよりも低沸点の副生物の少なくとも一部を蒸留などにより除去したもの、あるいは3,4−ジアセトキシ−1−ブテンよりも高沸点の副生物の一部あるいは全量を蒸留などにより除去したもの、更には低沸点の副生物及び高沸点副生物の双方を一部あるいは全量を除去したもの等である。本発明の方法では、これらを「3,4−ジアセトキシ−1−ブテンを主成分とする含有液」として使用する。通常、本発明で使用する「3,4−ジアセトキシ−1−ブテンを主成分とする含有液」は、1,4−ジアセトキシ−2−ブテンも含有するが、その他に、3,4−ジアセトキシ−1−ブテンの加水分解物である3−ヒドロキシ−4−アセトキシ−1−ブテン、4−ヒドロキシ−3−アセトキシ−1−ブテン及び/又は3,4−ジヒドロキシ−1−ブテン、更に1,4−ジアセトキシ−2−ブテンの加水分解物である1−アセトキシ−4−ヒドロキシ−2−ブテン及び/又は1,4−ジヒドロキシ−2−ブテンを含んでいても差し支えない。 As 3,4-diacetoxy-1-butene supplied as a raw material for the isomerization reaction, in addition to pure products, the reaction solution itself after diacetoxylation reaction of butadiene, or 3,4-diacetoxy- such as acetic acid and water A product obtained by removing at least a part of by-products having a lower boiling point than 1-butene by distillation or the like, or a part or whole amount of a by-product having a higher boiling point than 3,4-diacetoxy-1-butene was removed by distillation or the like. In addition, the low boiling point by-product and the high boiling point by-product are partially or completely removed. In the method of the present invention, these are used as “containing liquid containing 3,4-diacetoxy-1-butene as a main component”. Usually, the “containing liquid mainly composed of 3,4-diacetoxy-1-butene” used in the present invention also contains 1,4-diacetoxy-2-butene, but in addition, 3,4-diacetoxy- 3-Hydroxy-4-acetoxy-1-butene, 4-hydroxy-3-acetoxy-1-butene and / or 3,4-dihydroxy-1-butene, which are hydrolysates of 1-butene, and 1,4- It may contain 1-acetoxy-4-hydroxy-2-butene and / or 1,4-dihydroxy-2-butene, which is a hydrolyzate of diacetoxy-2-butene.
上述のアセトキシアリル化合物等の異性化反応において触媒として使用される遷移金属錯体としては、配位子として好ましくはホスファイト或いはホスホラアミダイト、特に好ましくはホスホラアミダイトとパラジウムとの錯体触媒である。遷移金属錯体の使用量は、反応原料であるアセトキシアリル化合物に対して0.001重量ppm〜1000重量ppmであり、好ましくは0.001〜100重量ppm、特に好ましくは0.01〜100重量ppmの範囲である。 The transition metal complex used as a catalyst in the isomerization reaction of the acetoxyallyl compound described above is preferably a phosphite or phosphoramidite as a ligand, particularly preferably a complex catalyst of phosphoramidite and palladium. The amount of the transition metal complex used is 0.001 to 1000 ppm by weight, preferably 0.001 to 100 ppm by weight, particularly preferably 0.01 to 100 ppm by weight, based on the reaction raw material acetoxyallyl compound. Range.
異性化反応を実施する温度は、通常20〜200℃であり、好ましくは80〜180℃、特に好ましくは100℃〜160℃である。反応温度が高すぎると、遷移金属錯体触媒のメタル化による劣化が進行し、活性の消失が起こり、また反応温度が低すぎた場合には、反応速度が低下し、長大な反応器が必要となってしまう。 The temperature for carrying out the isomerization reaction is usually 20 to 200 ° C, preferably 80 to 180 ° C, particularly preferably 100 ° C to 160 ° C. If the reaction temperature is too high, deterioration of the transition metal complex catalyst due to metalization proceeds, loss of activity occurs, and if the reaction temperature is too low, the reaction rate decreases and a long reactor is required. turn into.
異性化反応を実施する圧力は、通常1気圧であるが、減圧下又は加圧下であっても構わないが、1気圧〜10気圧が好ましく、特に好ましくは1〜3気圧である。反応圧力が低すぎると反応温度の低下に伴い触媒活性が低下し、反応圧力が高すぎると反応器コストが増大してしまう。 The pressure for carrying out the isomerization reaction is usually 1 atm, but it may be under reduced pressure or under pressure, but it is preferably 1 atm to 10 atm, particularly preferably 1 to 3 atm. If the reaction pressure is too low, the catalytic activity decreases as the reaction temperature decreases, and if the reaction pressure is too high, the reactor cost increases.
異性化反応は、通常液相中で行われ、該異性化反応は溶媒の存在下、又は非存在下のいずれでも実施可能である。溶媒を使用する場合、好ましい溶媒として、触媒及び原料化合物を溶解するものであれば使用可能であり特に限定はされない。溶媒の具体例としては、ジグライム、ジフェニルエーテル、ジベンジルエーテル、ジアリルエーテル、テトラヒドロフラン(THF)、ジオキサン等のエーテル類;N−メチル−2−ピロリドン、N,N−ジメチルホルムアミド、N,N−ジメチルアセトアミド等のアミド類;シクロヘキサノン等のケトン類;酢酸n−ブチル、γ−ブチロラクトン、ジ(n−オクチル)フタレイト等のエステル類;トルエン、キシレン、ドデシルベンゼン等の芳香族炭化水素類;n−ペンタン、n−ヘキサン、n−へプタン、n−オクタン等の脂肪族炭化水素類;異性化反応で生成する副生物そのもの;または原料であるアリル化合物誘導体そのもの;生成物であるアリル化合物そのもの;原料アリル化合物の脱離基に由来する化合物等が挙げられる。特に好ましい溶媒として、原料であるアリル化合物そのもの、生成物であるアリル化合物そのもの等が挙げられる。 The isomerization reaction is usually performed in a liquid phase, and the isomerization reaction can be performed in the presence or absence of a solvent. When a solvent is used, it can be used as a preferable solvent as long as it dissolves the catalyst and the raw material compound, and is not particularly limited. Specific examples of the solvent include ethers such as diglyme, diphenyl ether, dibenzyl ether, diallyl ether, tetrahydrofuran (THF) and dioxane; N-methyl-2-pyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide Amides such as cyclohexanone; esters such as n-butyl acetate, γ-butyrolactone, di (n-octyl) phthalate; aromatic hydrocarbons such as toluene, xylene and dodecylbenzene; n-pentane; Aliphatic hydrocarbons such as n-hexane, n-heptane, and n-octane; by-products generated by isomerization reaction itself; or allyl compound derivatives themselves as raw materials; allyl compounds themselves as products; raw allyl compounds And the like derived from the leaving group. Particularly preferred solvents include allyl compounds themselves as raw materials, allyl compounds themselves as products, and the like.
溶媒の使用量は特に限定されないが、異性化反応は主に分子内反応で進行するため、従来と比較してより少ない溶媒量で行うことが望ましい。通常、原料であるアリル化合物誘導体の合計重量に対して0〜10重量倍以下、好ましくは0〜5重量倍以下、最も好ましくは0〜1重量倍以下である。溶媒量が多すぎる場合には反応速度が低下する。 The amount of the solvent used is not particularly limited, but the isomerization reaction proceeds mainly by an intramolecular reaction, so it is desirable to carry out with a smaller amount of solvent compared to the conventional method. Usually, it is 0-10 weight times or less with respect to the total weight of the allyl compound derivative which is a raw material, Preferably it is 0-5 weight times or less, Most preferably, it is 0-1 weight times or less. When the amount of the solvent is too large, the reaction rate decreases.
異性化反応を実施する際の反応方式として、撹拌型の完全混合反応器やプラグフロー型の反応器を用いて、連続方式、半連続方式または回分方式のいずれでも行うことができる。反応器内の気相部は、溶媒、原料化合物、反応生成物、反応副生物、触媒分解物等に由来する蒸気以外は、アルゴンや窒素等の不活性ガスで形成されていることが望ましい。特に空気の漏れ込み等による酸素の混入が触媒劣化、即ちリン化合物の酸化消失の原因となるため、その量を極力低減させることが望ましい。 As a reaction system for carrying out the isomerization reaction, a continuous type, semi-continuous type or batch type can be carried out using a stirring type complete mixing reactor or a plug flow type reactor. The gas phase part in the reactor is preferably formed of an inert gas such as argon or nitrogen other than the vapor derived from the solvent, the raw material compound, the reaction product, the reaction byproduct, the catalyst decomposition product, and the like. In particular, oxygen contamination due to air leakage or the like causes catalyst deterioration, that is, oxidation loss of the phosphorus compound. Therefore, it is desirable to reduce the amount as much as possible.
異性化反応器から連続的に流出する反応液に、反応器出口近傍の配管に設けられた供給口から芳香族ホスファイトの溶液を注入する。芳香族ホスファイト溶液の注入は、連続的、間欠的のいずれでもよいが、連続的に供給するのが好ましい。芳香族ホスファイトが供給された反応液は、3,4−ジアセトキシ−1−ブテンの異性化反応により得られた生成物(1,4−ジアセトキシ−2−ブテン)を異性化反応液から分離するための分離工程(蒸留塔)に移送され、蒸留分離される。生成物の分離には、慣用の分離操作を採用することができ、具体的には、単蒸留、減圧蒸留、薄膜蒸留、水蒸気蒸留等の蒸留操作のほか、気液分離、蒸発(エバポレーション)、ガスストリッピング、ガス吸収及び抽出等の分離操作が挙げられる。各分離操作は、各々独立の工程で行ってもよく、2つ以上の成分の分離を同時に行ってもよい。なお、生成物、更には原料アリル化合物等を分離した後の残液は、前述した触媒処理に付すことができる。 An aromatic phosphite solution is injected into a reaction solution continuously flowing out from the isomerization reactor from a supply port provided in a pipe near the reactor outlet. The aromatic phosphite solution may be injected continuously or intermittently, but is preferably supplied continuously. The reaction solution supplied with the aromatic phosphite separates the product (1,4-diacetoxy-2-butene) obtained by the isomerization reaction of 3,4-diacetoxy-1-butene from the isomerization reaction solution. Is transferred to a separation step (distillation tower) for distillation. For separation of products, conventional separation operations can be employed. Specifically, in addition to distillation operations such as simple distillation, vacuum distillation, thin film distillation, steam distillation, etc., gas-liquid separation and evaporation (evaporation) And separation operations such as gas stripping, gas absorption and extraction. Each separation operation may be performed in an independent process, or two or more components may be separated at the same time. In addition, the residual liquid after isolate | separating a product, a raw material allyl compound, etc. can be attached | subjected to the catalyst process mentioned above.
上記異性化反応以外の反応として、オレフィンのハイドロフォルミル化反応が挙げられる。オレフィンのハイドロフォルミル化反応は、通常、オレフィンとオキソガス(一酸化炭素と水素の混合ガス)とを、遷移金属(例えば、Rh,Pd等)と有機リン化合物からなる配位子とを含む金属錯体触媒を用いて、溶媒の存在下或いは不存在下反応させることにより行われる。触媒の使用量は、反応基質1モルに対し、通常0.1ppmモル以上、好ましくは1ppmモル以上であり、0.2モル%以下、好ましくは0.1モル%以下である。反応温度は、通常、−20℃〜150℃、好ましくは0℃〜100℃であり、反応圧力は、通常0.01MPa〜30MPa、好ましくは0.05MPa〜20MPaである。 As a reaction other than the isomerization reaction, a hydroformylation reaction of olefin can be mentioned. The hydroformylation reaction of an olefin usually involves an olefin, an oxo gas (a mixed gas of carbon monoxide and hydrogen), a metal containing a transition metal (eg, Rh, Pd, etc.) and a ligand composed of an organophosphorus compound. The reaction is carried out using a complex catalyst in the presence or absence of a solvent. The amount of the catalyst used is usually 0.1 ppm mol or more, preferably 1 ppm mol or more, and 0.2 mol% or less, preferably 0.1 mol% or less, relative to 1 mol of the reaction substrate. The reaction temperature is usually −20 ° C. to 150 ° C., preferably 0 ° C. to 100 ° C., and the reaction pressure is usually 0.01 MPa to 30 MPa, preferably 0.05 MPa to 20 MPa.
また、他の反応として、上記遷移金属錯体触媒を用いたオレフィン、カルボニル化合物、イミン化合物等の水素化反応が挙げられる。水素化反応における該触媒の使用量は、反応基質1モルに対し、通常0.1ppmモル以上、好ましくは1ppmモル以上であり、0.2モル%以下、好ましくは0.1モル%以下である。反応温度は、通常、−20℃〜150℃、好ましくは0℃〜100℃であり、水素分圧は、通常0.001MPa〜30MPa、好ましくは0.01MPa〜20MPaである。
本発明の方法は、上記の反応例より得られる反応液に適用することにより反応液から遷移金属含有溶液を支障なく取り出すことが出来る。
Moreover, hydrogenation reaction of the olefin, carbonyl compound, imine compound, etc. using the said transition metal complex catalyst is mentioned as another reaction. The amount of the catalyst used in the hydrogenation reaction is usually 0.1 ppm mol or more, preferably 1 ppm mol or more, and 0.2 mol% or less, preferably 0.1 mol% or less with respect to 1 mol of the reaction substrate. . The reaction temperature is usually −20 ° C. to 150 ° C., preferably 0 ° C. to 100 ° C., and the hydrogen partial pressure is usually 0.001 MPa to 30 MPa, preferably 0.01 MPa to 20 MPa.
By applying the method of the present invention to the reaction solution obtained from the above reaction example, the transition metal-containing solution can be taken out from the reaction solution without any trouble.
次に、本発明の方法を実施例及び比較例により更に詳細に説明するが、本発明はこれらの実施例に限定されるものではない。 Next, the method of the present invention will be described in more detail with reference to Examples and Comparative Examples, but the present invention is not limited to these Examples.
参考例1
Pd−Te触媒1kgの存在下に、ブタジエン0.21kg/hr、酢酸2.94kg/hr、6%酸素/94%窒素混合ガス0.34kg/hrを流通させ、80℃、6MPaの条件でアセトキシ化反応させて、1,4−ジアセトキシ−2−ブテンが81重量%、3,4−ジアセトキシ−1−ブテンが9重量%、3−ヒドロキシ−4−アセトキシ−1−ブテンが2重量%、酢酸3重量%、その他3,4−ジアセトキシ−1−ブテンよりも沸点の低い成分が3重量%、及び3,4−ジアセトキシ−1−ブテンよりも沸点の高い成分が2重量%を含む混合液を得た。
Reference example 1
In the presence of 1 kg of Pd-Te catalyst, 0.21 kg / hr of butadiene, 2.94 kg / hr of acetic acid, 0.34 kg / hr of a mixed gas of 6% oxygen / 94% nitrogen were passed, and acetoxy was obtained at 80 ° C. and 6 MPa. To give 81% by weight of 1,4-diacetoxy-2-butene, 9% by weight of 3,4-diacetoxy-1-butene, 2% by weight of 3-hydroxy-4-acetoxy-1-butene, acetic acid A mixed liquid containing 3% by weight, 3% by weight of other components having a lower boiling point than 3,4-diacetoxy-1-butene, and 2% by weight of a component having a higher boiling point than 3,4-diacetoxy-1-butene Obtained.
参考例2
参考例1で得た混合液11Lを連続蒸留により3,4−ジアセトキシ−1−ブテン含有液と、1,4−ジアセトキシ−2−ブテン含有液とに分離した。尚、蒸留には40段のオルダーショウ蒸留塔を使用した。連続蒸留は、塔頂圧力は20mmHg、還流比は3、塔頂温度は95℃、塔底温度は151℃の温度範囲において保持し、150cc/hrの流量で塔底から20段の位置に混合液を連続導入し、塔頂部から27cc/hrで連続留出を行い、塔底から123cc/hrで連続抜き出しを行なった。本連続蒸留により、塔底から1,4−ジアセトキシ−2−ブテン含有液を缶出液として得、塔頂から3,4−ジアセトキシ−1−ブテン含有液を留出液として得た。得られた3,4−ジアセトキシ−1−ブテン含有液は、3,4−ジアセトキシ−1−ブテンが45重量%、3−ヒドロキシ−4−アセトキシ−1−ブテンが11重量%、酢酸が22重量%、その他3,4−ジアセトキシ−1−ブテンよりも沸点の低い成分が20重量%、及び3,4−ジアセトキシ−1−ブテンよりも沸点の高い成分が2重量%を含む混合液であった。また、該3,4−ジアセトキシ−1−ブテン含有液の1,4−ジアセトキシ−2−ブテン含有量は1重量%以下であった。
Reference example 2
11 L of the mixed liquid obtained in Reference Example 1 was separated into a 3,4-diacetoxy-1-butene-containing liquid and a 1,4-diacetoxy-2-butene-containing liquid by continuous distillation. For distillation, a 40-stage Oldershaw distillation column was used. In continuous distillation, the pressure at the top of the column is 20 mmHg, the reflux ratio is 3, the temperature at the top is 95 ° C, the temperature at the bottom is 151 ° C, and is mixed at the 20th stage from the bottom with a flow rate of 150 cc / hr. The liquid was continuously introduced, continuously distilled from the top of the column at 27 cc / hr, and continuously extracted from the bottom of the column at 123 cc / hr. By this continuous distillation, a 1,4-diacetoxy-2-butene-containing liquid was obtained as a bottoms from the tower bottom, and a 3,4-diacetoxy-1-butene-containing liquid was obtained as a distillate from the tower top. The resulting 3,4-diacetoxy-1-butene-containing liquid was 45% by weight of 3,4-diacetoxy-1-butene, 11% by weight of 3-hydroxy-4-acetoxy-1-butene, and 22% by weight of acetic acid. %, A component having a lower boiling point than 3,4-diacetoxy-1-butene is 20% by weight, and a component having a higher boiling point than 3,4-diacetoxy-1-butene is 2% by weight. . Further, the 1,4-diacetoxy-2-butene content in the 3,4-diacetoxy-1-butene-containing liquid was 1% by weight or less.
参考例3
参考例2で得た3,4−ジアセトキシ−1−ブテン含有液300kgを連続蒸留により3,4−ジアセトキシ−1−ブテンよりも沸点の低い成分の大部分を分離した。尚、蒸留には規則充填物TM−700M(MCパック)を5m充填した充填塔を使用した(HETP140mm/NTP)。塔頂圧力は100mmHg、還流比は3、塔頂温度は77℃、塔底温度は144℃の温度において保持し、20kg/hrの流量で塔底から2610mmの位置に連続導入し、塔頂部から7.6kg/hrで連続留出を行い、塔底から580mmの位置から側流として11.4kg/hr、塔底から1kg/hrで連続抜き出しを行なった。本連続蒸留により、塔頂から3,4−ジアセトキシ−1−ブテンよりも沸点の低い成分を留出液として得た。該留出中には酢酸が71重量%、3,4−ジアセトキシ−1−ブテンが0.18重量%(蒸留塔に導入する3,4−ジアセトキシアリル化合物量の0.17重量%に相当)、その他、3,4−ジアセトキシ−1−ブテンよりも沸点の低い成分21重量%含まれていた。また塔底からの抜き出した液中には3,4−ジアセトキシ−1−ブテンが70重量%、3−ヒドロキシ−4−アセトキシ−1−ブテンが9重量%、その他3,4−ジアセトキシ−1−ブテンよりも沸点の低い成分が3重量%、3,4−ジアセトキシ−1−ブテンよりも沸点の高い成分が18重量%を含まれていた。また、側流からの抜き出した液中には3,4−ジアセトキシ−1−ブテンが69重量%、3−ヒドロキシ−4−アセトキシ−1−ブテンが15重量%、その他3,4−ジアセトキシ−1−ブテンよりも沸点の低い成分が4重量%、3,4−ジアセトキシ−1−ブテンよりも沸点の高い成分が12重量%を含む精製3,4−ジアセトキシ−1−ブテンを得た。
Reference example 3
Most of the components having a boiling point lower than that of 3,4-diacetoxy-1-butene were separated by continuous distillation of 300 kg of the 3,4-diacetoxy-1-butene-containing liquid obtained in Reference Example 2. For distillation, a packed tower packed with 5 m of regular packing TM-700M (MC pack) was used (HETP 140 mm / NTP). The tower top pressure is 100 mmHg, the reflux ratio is 3, the tower top temperature is 77 ° C., the tower bottom temperature is 144 ° C., and continuously introduced at a flow rate of 20 kg / hr at a position 2610 mm from the tower bottom. Continuous distillation was carried out at 7.6 kg / hr, and continuous extraction was carried out at 11.4 kg / hr as a side flow from a position 580 mm from the tower bottom and 1 kg / hr from the tower bottom. By this continuous distillation, a component having a boiling point lower than 3,4-diacetoxy-1-butene was obtained as a distillate from the top of the column. During the distillation, 71% by weight of acetic acid and 0.18% by weight of 3,4-diacetoxy-1-butene (corresponding to 0.17% by weight of the amount of 3,4-diacetoxyallyl compound introduced into the distillation column) In addition, 21% by weight of a component having a boiling point lower than that of 3,4-diacetoxy-1-butene was contained. In the liquid extracted from the column bottom, 3,4-diacetoxy-1-butene was 70% by weight, 3-hydroxy-4-acetoxy-1-butene was 9% by weight, and other 3,4-diacetoxy-1- The component having a boiling point lower than that of butene was 3% by weight, and the component having a boiling point higher than that of 3,4-diacetoxy-1-butene was 18% by weight. In the liquid extracted from the side stream, 3,4-diacetoxy-1-butene was 69% by weight, 3-hydroxy-4-acetoxy-1-butene was 15% by weight, and other 3,4-diacetoxy-1 A purified 3,4-diacetoxy-1-butene containing 4% by weight of a component having a lower boiling point than butene and 12% by weight of a component having a higher boiling point than 3,4-diacetoxy-1-butene was obtained.
実施例1
窒素ガス雰囲気下、ガラス製フラスコに酢酸パラジウム(3.2 mg)、下記式(1)で表される配位子(上記(B−3)で表される配位子 31.2 mg、パラジウム金属に対して2モル等量)及び参考例3で塔底から得られた3,4−ジアセトキシ−1−ブテン含有液75gを添加し、80℃で1時間加熱撹拌して溶解し、パラジウム触媒溶液を調製した。このパラジウム触媒溶液中の溶存パラジウム金属濃度をICP−MS(Inductively Coupled Plasma Mass Spectrometry)により測定した結果、金属パラジウム濃度は20重量ppmであった。このパラジウム触媒液2ccに下式(2)で示されるDBPO[トリス(2,4−ジ−t−ブチルフェニル)ホスファイト]を添加(5.0 mg、パラジウム金属に対して20モル等量)し、常圧下175℃で27時間加熱した。加熱後の触媒溶液を目粗さが8μmのフィルターを用いて濾過を行い、濾液中に残存溶解するパラジウム濃度をICP−MSにより測定した。その結果、加熱ろ過後の残存溶解パラジウム金属濃度は、20重量ppmであった。加熱前の初期濃度と残存溶解濃度により、パラジウム金属の溶存残存率を算出した。その結果、パラジウム金属の溶存残存率は100%であり、Pdメタル析出率は0%であった。
Example 1
Under a nitrogen gas atmosphere, palladium acetate (3.2 mg) in a glass flask, a ligand represented by the following formula (1) (ligand represented by the above (B-3) 31.2 mg,
溶存残存率(%)= 残存溶解濃度/初期濃度
Pdメタル化量(重量ppm) = 初期濃度(20ppm)−残存溶解濃度
Pdメタル析出率(%)=[Pdメタル化量]/[初期濃度]
Dissolved residual rate (%) = residual dissolved concentration / initial concentration Pd metalation amount (weight ppm) = initial concentration (20 ppm) -residual dissolved concentration Pd metal precipitation rate (%) = [Pd metalization amount] / [initial concentration]
比較例1
(ブランクテスト)
上記実施例1において、パラジウム触媒溶液にDBPOを添加せずに常圧下、175℃で加熱した以外は同様にして実施した。その結果、加熱ろ過後の残存溶解パラジウム金属濃度は、6重量ppmであり、Pdメタル析出率は70%であった。
Comparative Example 1
(Blank test)
The same procedure as in Example 1 was performed except that the palladium catalyst solution was heated at 175 ° C. under normal pressure without adding DBPO. As a result, the residual dissolved palladium metal concentration after heat filtration was 6 ppm by weight, and the Pd metal deposition rate was 70%.
比較例2
(DBPOとトリフェニルホスフィンの効果比較)
上記実施例1において、パラジウム触媒溶液にDBPOを添加せず、代わりにトリフェニルホスフィンを添加(0.4mg、パラジウム金属に対して4モル等量)し、常圧下175℃で加熱した以外は同様にして実施した。その結果、加熱ろ過後の残存溶解パラジウム金属濃度は、2重量ppmであり、Pdメタル析出率は90%であった。
Comparative Example 2
(Comparison effect of DBPO and triphenylphosphine)
In Example 1 above, DBPO was not added to the palladium catalyst solution, but instead triphenylphosphine was added (0.4 mg, 4 molar equivalents with respect to palladium metal), and the same was carried out at 175 ° C. under normal pressure. Was carried out. As a result, the residual dissolved palladium metal concentration after heat filtration was 2 ppm by weight, and the Pd metal deposition rate was 90%.
実施例2
(トリフェニルホスフィン1000重量ppm存在条件)
窒素ガス雰囲気下、ガラス製フラスコに酢酸パラジウム(7.9mg)、上記式(1)で表される配位子(78.8mg、パラジウム金属に対して2モル等量)、トリフェニルホスフィン(76.5mg、触媒溶液中のトリフェニルホスフィン濃度1000重量ppm)、及び参考例3で側流から得られた3,4−ジアセトキシ−1−ブテン含有液75gを添加し、80℃で1時間加熱撹拌して溶解し、パラジウム触媒溶液を調製した。このパラジウム触媒溶液中の溶存パラジウム金属濃度をICP−MSにより測定した結果、金属パラジウム濃度は54重量ppmであった。このパラジウム触媒液2ccに前記式(2)で表されるDBPO[トリス(2,4−ジ−t−ブチルフェニル)ホスファイト]を添加(12.6mg、パラジウム金属に対して20モル等量)し、常圧下175℃で10時間加熱した。加熱後の触媒溶液を目粗さが8μmのフィルターを用いて濾過を行い、濾液中に残存溶解するパラジウム濃度をICP−MSにより測定した。その結果、加熱ろ過後の残存溶解パラジウム金属濃度は、52重量ppmであった。加熱前の初期濃度と残存濃度により、パラジウム金属の溶存残存率を算出した。その結果、パラジウム金属の溶存残存率は96%であり、Pdメタル析出率は4%であった。
Example 2
(Presence condition of 1000 ppm by weight of triphenylphosphine)
Under a nitrogen gas atmosphere, palladium acetate (7.9 mg), a ligand represented by the above formula (1) (78.8 mg, 2 molar equivalents relative to palladium metal), triphenylphosphine (76 0.5 mg, triphenylphosphine concentration in the catalyst solution of 1000 ppm by weight), and 75 g of 3,4-diacetoxy-1-butene-containing liquid obtained from the side stream in Reference Example 3 were added, and the mixture was heated and stirred at 80 ° C. for 1 hour. And dissolved to prepare a palladium catalyst solution. As a result of measuring the dissolved palladium metal concentration in this palladium catalyst solution by ICP-MS, the metal palladium concentration was 54 ppm by weight. DBPO [Tris (2,4-di-t-butylphenyl) phosphite] represented by the above formula (2) was added to 2 cc of this palladium catalyst solution (12.6 mg, 20 molar equivalents relative to palladium metal). And heated at 175 ° C. under normal pressure for 10 hours. The heated catalyst solution was filtered using a filter having a coarseness of 8 μm, and the concentration of palladium dissolved in the filtrate was measured by ICP-MS. As a result, the residual dissolved palladium metal concentration after heat filtration was 52 ppm by weight. The dissolved residual rate of palladium metal was calculated from the initial concentration and residual concentration before heating. As a result, the dissolved residual rate of palladium metal was 96%, and the Pd metal deposition rate was 4%.
実施例3
上記実施例2において、DBPO添加量を(6.3mg、パラジウム金属に対して10モル等量)とした以外は同様にして実施した。その結果、加熱ろ過後の残存溶解パラジウム金属濃度は、50重量ppmであり、Pdメタル析出率は7%であった。
Example 3
The same procedure as in Example 2 was performed except that the DBPO addition amount was (6.3 mg, 10 mol equivalent to palladium metal). As a result, the residual dissolved palladium metal concentration after heat filtration was 50 ppm by weight, and the Pd metal deposition rate was 7%.
実施例4
上記実施例2において、パラジウム触媒溶液にDBPOに代えてトリフェニルホスファイト[P(OPh)3]を添加(5μl、パラジウム金属に対して4モル等量)して、常圧下、175℃で加熱した以外は同様にして実施した。その結果、加熱ろ過後の残存溶解パラジウム金属濃度は、23重量ppmであり、Pdメタル析出率は57%であった。
Example 4
In Example 2 above, triphenyl phosphite [P (OPh) 3 ] was added to the palladium catalyst solution instead of DBPO (5 μl, 4 molar equivalents relative to palladium metal) and heated at 175 ° C. under normal pressure. The same operation was performed except that. As a result, the residual dissolved palladium metal concentration after heat filtration was 23 ppm by weight, and the Pd metal deposition rate was 57%.
実施例5
窒素ガス雰囲気下、ガラス製フラスコに酢酸パラジウム(5.0 mg)、上記式(1)で表される配位子(48.4 mg、パラジウム金属に対して2モル等量)、トリフェニルホスフィン(12.4mg、触媒溶液中のトリフェニルホスフィン濃度500重量ppm)及び参考例3で塔底から得られた3,4−ジアセトキシ−1−ブテン含有液24gを添加し、80℃で1時間加熱撹拌して溶解し、パラジウム触媒溶液を調製した。このパラジウム触媒液3ccに上記式(2)で示されるDBPO[トリス(2,4−ジ−t−ブチルフェニル)ホスファイト]を1重量%含む3,4−ジアセトキシ−1−ブテン含有液を1.8g添加(パラジウム金属に対して20モル等量)した。このパラジウム触媒溶液中の溶存パラジウム金属濃度をICP−MSにより測定した結果、金属パラジウム濃度は59重量ppmであった。このパラジウム触媒溶液を常圧下175℃で10時間加熱した。加熱後の触媒溶液を目粗さが8μmのフィルターを用いて濾過を行い、濾液中に残存溶解するパラジウム濃度をICP−MSにより測定した。その結果、加熱ろ過後の残存溶解パラジウム金属濃度は、55重量ppmであった。加熱前の初期濃度と残存濃度により、パラジウム金属の溶存残存率を算出した。その結果、パラジウム金属の溶存残存率は93%であり、Pdメタル析出率は7%であった。
Example 5
Under a nitrogen gas atmosphere, palladium acetate (5.0 mg), a ligand represented by the above formula (1) (48.4 mg, 2 molar equivalents relative to palladium metal), triphenylphosphine in a glass flask (12.4 mg, concentration of triphenylphosphine in catalyst solution 500 ppm by weight) and 3,4-diacetoxy-1-butene-containing liquid 24 g obtained from the tower bottom in Reference Example 3 were added and heated at 80 ° C. for 1 hour. The mixture was dissolved by stirring to prepare a palladium catalyst solution. A 3,4-diacetoxy-1-butene-containing liquid containing 1% by weight of DBPO [tris (2,4-di-t-butylphenyl) phosphite] represented by the above formula (2) in 3 cc of this palladium catalyst liquid 1 0.8 g was added (20 molar equivalent to palladium metal). As a result of measuring the dissolved palladium metal concentration in this palladium catalyst solution by ICP-MS, the metal palladium concentration was 59 ppm by weight. The palladium catalyst solution was heated at 175 ° C. for 10 hours under normal pressure. The heated catalyst solution was filtered using a filter having a coarseness of 8 μm, and the concentration of palladium dissolved in the filtrate was measured by ICP-MS. As a result, the residual dissolved palladium metal concentration after heat filtration was 55 ppm by weight. The dissolved residual rate of palladium metal was calculated from the initial concentration and residual concentration before heating. As a result, the dissolved residual rate of palladium metal was 93%, and the Pd metal deposition rate was 7%.
比較例3
上記実施例2において、パラジウム触媒溶液にDBPOを添加しないこと以外は同様にして実施した。その結果、加熱ろ過後の残存溶解パラジウム金属濃度は、4重量ppmであり、Pdメタル析出率は93%であった。
Comparative Example 3
In Example 2, the same procedure was performed except that DBPO was not added to the palladium catalyst solution. As a result, the residual dissolved palladium metal concentration after heat filtration was 4 ppm by weight, and the Pd metal deposition rate was 93%.
比較例4
上記実施例2において、パラジウム触媒溶液にDBPOに代えてトリn−ブチルホスファイト[P(OnBu)3]を添加(5μl、パラジウム金属に対して4モル等量)した以外は同様にして実施した。その結果、加熱ろ過後の残存溶解パラジウム金属濃度は、2重量ppmであり、Pdメタル析出率は96%であった。
Comparative Example 4
The same procedure as in Example 2 was performed except that tri-n-butyl phosphite [P (OnBu) 3 ] was added to the palladium catalyst solution instead of DBPO (5 μl, 4 molar equivalents relative to palladium metal). . As a result, the residual dissolved palladium metal concentration after heating filtration was 2 ppm by weight, and the Pd metal deposition rate was 96%.
上記実施例1〜5、比較例1〜4の結果を纏めて表1に示す。 The results of Examples 1 to 5 and Comparative Examples 1 to 4 are summarized in Table 1.
実施例6
窒素ガス雰囲気下、ガラス製フラスコに酢酸パラジウム(2.2 mg)、上記式(3)で表される配位子(上記(B−3)で表される配位子 19.5 mg、パラジウム金属に対して2モル等量)及び参考例3で側流から得られた3,4−ジアセトキシ−1−ブテン含有液20gを添加し、80℃で1時間加熱撹拌して溶解し、パラジウム触媒溶液を調製した。このパラジウム触媒溶液中の溶存パラジウム金属濃度をICP−MSにより測定した結果、金属パラジウム濃度は42重量ppmであった。このパラジウム触媒液3ccに式(2)で示されるDBPO[トリス(2,4−ジ−t−ブチルフェニル)ホスファイト]を添加(19mg、パラジウム金属に対して20モル等量)し、常圧下175℃で10時間加熱した。加熱後の触媒溶液を目粗さが8μmのフィルターを用いて濾過を行い、濾液中に残存溶解するパラジウム濃度をICP−MSにより測定した。その結果、加熱ろ過後の残存溶解パラジウム金属濃度は、41重量ppmであった。加熱前の初期濃度と残存濃度により、パラジウム金属の溶存残存率を算出した。その結果、パラジウム金属の溶存残存率は98%であり、Pdメタル析出率は2%であった。
Example 6
Under a nitrogen gas atmosphere, palladium acetate (2.2 mg) in a glass flask, a ligand represented by the above formula (3) (a ligand represented by the above (B-3) 19.5 mg,
比較例5
上記実施例6において、パラジウム触媒溶液にDBPOを添加しないこと以外は同様にして実施した。その結果、加熱ろ過後の残存溶解パラジウム金属濃度は、0重量ppmであり、Pdメタル析出率は100%であった。
Comparative Example 5
In Example 6, the same procedure was performed except that DBPO was not added to the palladium catalyst solution. As a result, the residual dissolved palladium metal concentration after heat filtration was 0 ppm by weight, and the Pd metal deposition rate was 100%.
実施例7
窒素ガス雰囲気下、ガラス製フラスコに酢酸パラジウム(2.2mg)、上記式(3)で表される配位子(19.5mg、パラジウム金属に対して2モル等量)、トリフェニルホスフィン(20mg、触媒溶液中のトリフェニルホスフィン濃度1000重量ppm)、及び参考例3で側流から得られた3,4−ジアセトキシ−1−ブテン含有液20gを添加し、80℃で1時間加熱撹拌して溶解し、パラジウム触媒溶液を調製した。このパラジウム触媒溶液中の溶存パラジウム金属濃度をICP−MSにより測定した結果、金属パラジウム濃度は42重量ppmであった。このパラジウム触媒液2ccに前記式(2)で表されるDBPO[トリス(2,4−ジ−t−ブチルフェニル)ホスファイト]を添加(19mg、パラジウム金属に対して20モル等量)し、常圧下175℃で10時間加熱した。加熱後の触媒溶液を目粗さが8μmのフィルターを用いて濾過を行い、濾液中に残存溶解するパラジウム濃度をICP−MSにより測定した。その結果、加熱ろ過後の残存溶解パラジウム金属濃度は、40重量ppmであった。加熱前の初期濃度と残存濃度により、パラジウム金属の溶存残存率を算出した。その結果、パラジウム金属の溶存残存率は96%であり、Pdメタル析出率は4%であった。
Example 7
Under a nitrogen gas atmosphere, palladium acetate (2.2 mg), a ligand represented by the above formula (3) (19.5 mg, 2 molar equivalents relative to palladium metal), triphenylphosphine (20 mg) in a glass flask. The triphenylphosphine concentration in the catalyst solution is 1000 ppm by weight), and 20 g of the 3,4-diacetoxy-1-butene-containing liquid obtained from the side stream in Reference Example 3 is added, and the mixture is heated and stirred at 80 ° C. for 1 hour. It dissolved and the palladium catalyst solution was prepared. As a result of measuring the dissolved palladium metal concentration in this palladium catalyst solution by ICP-MS, the metal palladium concentration was 42 ppm by weight. DBPO [Tris (2,4-di-t-butylphenyl) phosphite] represented by the above formula (2) was added to 2 cc of this palladium catalyst solution (19 mg, 20 mol equivalent to palladium metal), Heated at 175 ° C. for 10 hours under normal pressure. The heated catalyst solution was filtered using a filter having a coarseness of 8 μm, and the concentration of palladium dissolved in the filtrate was measured by ICP-MS. As a result, the residual dissolved palladium metal concentration after heat filtration was 40 ppm by weight. The dissolved residual rate of palladium metal was calculated from the initial concentration and residual concentration before heating. As a result, the dissolved residual rate of palladium metal was 96%, and the Pd metal deposition rate was 4%.
比較例6
上記実施例7において、パラジウム触媒溶液にDBPOを添加しないこと以外は同様にして実施した。その結果、加熱ろ過後の残存溶解パラジウム金属濃度は、0重量ppmであり、Pdメタル析出率は100%であった。
Comparative Example 6
In Example 7, the same procedure was performed except that DBPO was not added to the palladium catalyst solution. As a result, the residual dissolved palladium metal concentration after heat filtration was 0 ppm by weight, and the Pd metal deposition rate was 100%.
実施例8
窒素ガス雰囲気下、ガラス製フラスコに酢酸パラジウム(5.1 mg)、上記式(3)で表される配位子(46.2 mg、パラジウム金属に対して2モル等量)、トリフェニルホスフィン(12.7mg、触媒溶液中のトリフェニルホスフィン濃度500重量ppm)及び参考例3で側流から得られた3,4−ジアセトキシ−1−ブテン含有液24gを添加し、80℃で1時間加熱撹拌して溶解し、パラジウム触媒溶液を調製した。このパラジウム触媒液3ccに上記式(2)で示されるDBPO[トリス(2,4−ジ−t−ブチルフェニル)ホスファイト]を1重量%含む3,4−ジアセトキシ−1−ブテン含有液を1.8g添加(パラジウム金属に対して20モル等量)した。このパラジウム触媒溶液中の溶存パラジウム金属濃度をICP−MSにより測定した結果、金属パラジウム濃度は58重量ppmであった。このパラジウム触媒溶液を常圧下175℃で10時間加熱した。加熱後の触媒溶液を目粗さが8μmのフィルターを用いて濾過を行い、濾液中に残存溶解するパラジウム濃度をICP−MSにより測定した。その結果、加熱ろ過後の残存溶解パラジウム金属濃度は、56重量ppmであった。加熱前の初期濃度と残存濃度により、パラジウム金属の溶存残存率を算出した。その結果、パラジウム金属の溶存残存率は97%であり、Pdメタル析出率は3%であった。
上記実施例6〜8、比較例5〜6の結果を纏めて表2に示す。
Example 8
Under a nitrogen gas atmosphere, palladium acetate (5.1 mg), a ligand represented by the above formula (3) (46.2 mg, 2 molar equivalents relative to palladium metal), triphenylphosphine were placed in a glass flask. (12.7 mg, triphenylphosphine concentration in the catalyst solution: 500 ppm by weight) and 24 g of 3,4-diacetoxy-1-butene-containing liquid obtained from the side stream in Reference Example 3 were added and heated at 80 ° C. for 1 hour. The mixture was dissolved by stirring to prepare a palladium catalyst solution. A 3,4-diacetoxy-1-butene-containing liquid containing 1% by weight of DBPO [tris (2,4-di-t-butylphenyl) phosphite] represented by the above formula (2) in 3 cc of this palladium catalyst liquid 1 0.8 g was added (20 molar equivalent to palladium metal). As a result of measuring the dissolved palladium metal concentration in this palladium catalyst solution by ICP-MS, the metal palladium concentration was 58 ppm by weight. The palladium catalyst solution was heated at 175 ° C. for 10 hours under normal pressure. The heated catalyst solution was filtered using a filter having a coarseness of 8 μm, and the concentration of palladium dissolved in the filtrate was measured by ICP-MS. As a result, the residual dissolved palladium metal concentration after heat filtration was 56 ppm by weight. The dissolved residual rate of palladium metal was calculated from the initial concentration and residual concentration before heating. As a result, the dissolved residual rate of palladium metal was 97%, and the Pd metal deposition rate was 3%.
The results of Examples 6-8 and Comparative Examples 5-6 are summarized in Table 2.
(減圧条件下でのDBPOによるパラジウム金属のメタル析出抑制)
窒素ガス雰囲気下、ガラス製フラスコに酢酸パラジウム(21mg)、上記式(1)で表される配位子(200mg、パラジウム金属に対して2モル等量)、トリフェニルホスフィン(49mg、触媒溶液中のトリフェニルホスフィン濃度10重量ppm)及び参考例3で塔底から得られた3,4−ジアセトキシ−1−ブテン含有液)400ccを装入し、80℃で1時間加熱撹拌を行い、触媒溶液を調製し、金属パラジウム濃度として50重量ppm 含有する反応液を得た。蓋付き容器に得られた反応液及び上記式(2)で示されるDBPO(1.22g、パラジウム金属に対して20モル等量)を装入し、蓋をして密閉した後、減圧下(300〜380torr)、165℃まで昇温した。同温度を維持しながら、165℃に到達した時点(time=0)から、所定時間毎に反応液中のパラジウム濃度を測定し、経時変化を観測した。その結果を図1に示す。
なお、パラジウム濃度は、IPC−MSにより測定した。また、パラジウム溶存残存率(%)は反応液中の初期濃度に対する割合である。
(Inhibition of metal deposition of palladium metal by DBPO under reduced pressure conditions)
Under a nitrogen gas atmosphere, palladium acetate (21 mg), a ligand represented by the above formula (1) (200 mg, 2 molar equivalents relative to palladium metal), triphenylphosphine (49 mg, in a catalyst solution) in a glass flask Of triphenylphosphine of 10 ppm by weight) and 3,4-diacetoxy-1-butene-containing liquid obtained from the tower bottom in Reference Example 3) were charged, and the mixture was heated and stirred at 80 ° C. for 1 hour to obtain a catalyst solution. And a reaction solution containing 50 ppm by weight of metal palladium was obtained. The reaction solution obtained in a container with a lid and DBPO represented by the above formula (2) (1.22 g, 20 molar equivalents relative to palladium metal) were charged, sealed with a lid, and then under reduced pressure ( 300-380 torr), and the temperature was increased to 165 ° C. While maintaining the same temperature, the palladium concentration in the reaction solution was measured every predetermined time from the time of reaching 165 ° C. (time = 0), and the change with time was observed. The result is shown in FIG.
The palladium concentration was measured by IPC-MS. Further, the palladium dissolved residual rate (%) is a ratio to the initial concentration in the reaction solution.
比較例7
上記実施例3において、DBPOを添加しなかった以外は、実施例3と同様にしてパラジウム濃度の経時変化を観測し、その結果を図1に示した。
Comparative Example 7
In Example 3, except that DBPO was not added, the time-dependent change in the palladium concentration was observed in the same manner as in Example 3, and the results are shown in FIG.
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