WO2021174522A1 - A method for the alkylation of amines - Google Patents
A method for the alkylation of amines Download PDFInfo
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- WO2021174522A1 WO2021174522A1 PCT/CN2020/078148 CN2020078148W WO2021174522A1 WO 2021174522 A1 WO2021174522 A1 WO 2021174522A1 CN 2020078148 W CN2020078148 W CN 2020078148W WO 2021174522 A1 WO2021174522 A1 WO 2021174522A1
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- Prior art keywords
- general formula
- metal
- compound
- metal element
- group
- Prior art date
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- 238000000034 method Methods 0.000 title claims abstract description 26
- 150000001412 amines Chemical class 0.000 title claims abstract description 21
- 230000029936 alkylation Effects 0.000 title abstract description 6
- 238000005804 alkylation reaction Methods 0.000 title abstract description 6
- 229910052751 metal Inorganic materials 0.000 claims abstract description 152
- 239000002184 metal Substances 0.000 claims abstract description 150
- 239000003054 catalyst Substances 0.000 claims abstract description 91
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 40
- 239000001257 hydrogen Substances 0.000 claims abstract description 38
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 claims abstract description 28
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 26
- 238000006243 chemical reaction Methods 0.000 claims description 56
- 239000010949 copper Substances 0.000 claims description 47
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 46
- 150000001875 compounds Chemical class 0.000 claims description 41
- -1 octylenediamine Chemical compound 0.000 claims description 25
- 150000002431 hydrogen Chemical class 0.000 claims description 20
- 239000007983 Tris buffer Substances 0.000 claims description 15
- 150000002602 lanthanoids Chemical class 0.000 claims description 13
- 229910052782 aluminium Inorganic materials 0.000 claims description 12
- 229910052802 copper Inorganic materials 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 12
- 229910052747 lanthanoid Inorganic materials 0.000 claims description 11
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 11
- 229910052804 chromium Inorganic materials 0.000 claims description 10
- 229910052710 silicon Inorganic materials 0.000 claims description 10
- 239000002904 solvent Substances 0.000 claims description 10
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 9
- 229910044991 metal oxide Inorganic materials 0.000 claims description 9
- 150000004706 metal oxides Chemical class 0.000 claims description 9
- 239000011701 zinc Substances 0.000 claims description 9
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 8
- 229910052749 magnesium Inorganic materials 0.000 claims description 8
- 229910052725 zinc Inorganic materials 0.000 claims description 8
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 7
- 229910052791 calcium Inorganic materials 0.000 claims description 7
- GKQPCPXONLDCMU-CCEZHUSRSA-N lacidipine Chemical compound CCOC(=O)C1=C(C)NC(C)=C(C(=O)OCC)C1C1=CC=CC=C1\C=C\C(=O)OC(C)(C)C GKQPCPXONLDCMU-CCEZHUSRSA-N 0.000 claims description 7
- 229910052748 manganese Inorganic materials 0.000 claims description 7
- 229910052759 nickel Inorganic materials 0.000 claims description 7
- AOHJOMMDDJHIJH-UHFFFAOYSA-N propylenediamine Chemical compound CC(N)CN AOHJOMMDDJHIJH-UHFFFAOYSA-N 0.000 claims description 7
- 229910052708 sodium Inorganic materials 0.000 claims description 7
- 229910052797 bismuth Inorganic materials 0.000 claims description 6
- 229910052799 carbon Inorganic materials 0.000 claims description 6
- QMXSDTGNCZVWTB-UHFFFAOYSA-N n',n'-bis(3-aminopropyl)propane-1,3-diamine Chemical compound NCCCN(CCCN)CCCN QMXSDTGNCZVWTB-UHFFFAOYSA-N 0.000 claims description 6
- 229910052712 strontium Inorganic materials 0.000 claims description 6
- MBYLVOKEDDQJDY-UHFFFAOYSA-N tris(2-aminoethyl)amine Chemical compound NCCN(CCN)CCN MBYLVOKEDDQJDY-UHFFFAOYSA-N 0.000 claims description 6
- 229910052787 antimony Inorganic materials 0.000 claims description 5
- 229910052789 astatine Inorganic materials 0.000 claims description 5
- RYXHOMYVWAEKHL-UHFFFAOYSA-N astatine atom Chemical compound [At] RYXHOMYVWAEKHL-UHFFFAOYSA-N 0.000 claims description 5
- 229910017052 cobalt Inorganic materials 0.000 claims description 5
- 239000010941 cobalt Substances 0.000 claims description 5
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 5
- 229910052742 iron Inorganic materials 0.000 claims description 5
- 239000010936 titanium Substances 0.000 claims description 5
- 229910052727 yttrium Inorganic materials 0.000 claims description 5
- 239000007868 Raney catalyst Substances 0.000 claims description 4
- 229910052768 actinide Inorganic materials 0.000 claims description 4
- 150000001255 actinides Chemical class 0.000 claims description 4
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 claims description 4
- 229910052785 arsenic Inorganic materials 0.000 claims description 4
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims description 4
- 229910052699 polonium Inorganic materials 0.000 claims description 4
- HZEBHPIOVYHPMT-UHFFFAOYSA-N polonium atom Chemical compound [Po] HZEBHPIOVYHPMT-UHFFFAOYSA-N 0.000 claims description 4
- 229910052714 tellurium Inorganic materials 0.000 claims description 4
- PORWMNRCUJJQNO-UHFFFAOYSA-N tellurium atom Chemical compound [Te] PORWMNRCUJJQNO-UHFFFAOYSA-N 0.000 claims description 4
- 229910052720 vanadium Inorganic materials 0.000 claims description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 3
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 claims description 3
- 229910052790 beryllium Inorganic materials 0.000 claims description 3
- VHRGRCVQAFMJIZ-UHFFFAOYSA-N cadaverine Chemical compound NCCCCCN VHRGRCVQAFMJIZ-UHFFFAOYSA-N 0.000 claims description 3
- 229910052793 cadmium Inorganic materials 0.000 claims description 3
- 239000011651 chromium Substances 0.000 claims description 3
- 229910052745 lead Inorganic materials 0.000 claims description 3
- 229910052758 niobium Inorganic materials 0.000 claims description 3
- 229910052700 potassium Inorganic materials 0.000 claims description 3
- KIDHWZJUCRJVML-UHFFFAOYSA-N putrescine Chemical compound NCCCCN KIDHWZJUCRJVML-UHFFFAOYSA-N 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- 229910052709 silver Inorganic materials 0.000 claims description 3
- 229910000564 Raney nickel Inorganic materials 0.000 claims description 2
- 125000003342 alkenyl group Chemical group 0.000 claims description 2
- 125000000304 alkynyl group Chemical group 0.000 claims description 2
- MRNZSTMRDWRNNR-UHFFFAOYSA-N bis(hexamethylene)triamine Chemical compound NCCCCCCNCCCCCCN MRNZSTMRDWRNNR-UHFFFAOYSA-N 0.000 claims description 2
- YQLZOAVZWJBZSY-UHFFFAOYSA-N decane-1,10-diamine Chemical compound NCCCCCCCCCCN YQLZOAVZWJBZSY-UHFFFAOYSA-N 0.000 claims description 2
- PWSKHLMYTZNYKO-UHFFFAOYSA-N heptane-1,7-diamine Chemical compound NCCCCCCCN PWSKHLMYTZNYKO-UHFFFAOYSA-N 0.000 claims description 2
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 claims description 2
- RTWNYYOXLSILQN-UHFFFAOYSA-N methanediamine Chemical compound NCN RTWNYYOXLSILQN-UHFFFAOYSA-N 0.000 claims description 2
- XIDCCVQQSRGENZ-UHFFFAOYSA-N methanetetramine Chemical compound NC(N)(N)N XIDCCVQQSRGENZ-UHFFFAOYSA-N 0.000 claims description 2
- 229910052750 molybdenum Inorganic materials 0.000 claims description 2
- BKHGFBHADSLTHZ-UHFFFAOYSA-N n',n'-bis(4-aminobutyl)butane-1,4-diamine Chemical compound NCCCCN(CCCCN)CCCCN BKHGFBHADSLTHZ-UHFFFAOYSA-N 0.000 claims description 2
- JNZCEYWMODDEQC-UHFFFAOYSA-N n',n'-bis(5-aminopentyl)pentane-1,5-diamine Chemical compound NCCCCCN(CCCCCN)CCCCCN JNZCEYWMODDEQC-UHFFFAOYSA-N 0.000 claims description 2
- SXJVFQLYZSNZBT-UHFFFAOYSA-N nonane-1,9-diamine Chemical compound NCCCCCCCCCN SXJVFQLYZSNZBT-UHFFFAOYSA-N 0.000 claims description 2
- 229910052702 rhenium Inorganic materials 0.000 claims description 2
- 229910052707 ruthenium Inorganic materials 0.000 claims description 2
- 229910052713 technetium Inorganic materials 0.000 claims description 2
- 229910052719 titanium Inorganic materials 0.000 claims description 2
- 229910052721 tungsten Inorganic materials 0.000 claims description 2
- 229910052726 zirconium Inorganic materials 0.000 claims description 2
- NPXOKRUENSOPAO-UHFFFAOYSA-N Raney nickel Chemical compound [Al].[Ni] NPXOKRUENSOPAO-UHFFFAOYSA-N 0.000 claims 1
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 abstract description 75
- UKODFQOELJFMII-UHFFFAOYSA-N pentamethyldiethylenetriamine Chemical compound CN(C)CCN(C)CCN(C)C UKODFQOELJFMII-UHFFFAOYSA-N 0.000 abstract description 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 66
- 229910052757 nitrogen Inorganic materials 0.000 description 51
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 33
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 25
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 24
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 18
- 239000011787 zinc oxide Substances 0.000 description 17
- 235000014692 zinc oxide Nutrition 0.000 description 17
- 238000003756 stirring Methods 0.000 description 16
- 125000004429 atom Chemical group 0.000 description 14
- 238000010438 heat treatment Methods 0.000 description 12
- 239000011575 calcium Substances 0.000 description 10
- 239000011777 magnesium Substances 0.000 description 10
- 150000002739 metals Chemical class 0.000 description 10
- 230000002829 reductive effect Effects 0.000 description 10
- 239000011734 sodium Substances 0.000 description 9
- 238000010521 absorption reaction Methods 0.000 description 8
- 239000003517 fume Substances 0.000 description 8
- 239000007788 liquid Substances 0.000 description 8
- 238000010907 mechanical stirring Methods 0.000 description 8
- 238000007789 sealing Methods 0.000 description 8
- 239000011541 reaction mixture Substances 0.000 description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 6
- 238000006722 reduction reaction Methods 0.000 description 6
- 229910052752 metalloid Inorganic materials 0.000 description 5
- 150000002738 metalloids Chemical class 0.000 description 5
- 125000004430 oxygen atom Chemical group O* 0.000 description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 4
- 229910006404 SnO 2 Inorganic materials 0.000 description 4
- BTANRVKWQNVYAZ-UHFFFAOYSA-N butan-2-ol Chemical compound CCC(C)O BTANRVKWQNVYAZ-UHFFFAOYSA-N 0.000 description 4
- 229910052738 indium Inorganic materials 0.000 description 4
- 239000011133 lead Substances 0.000 description 4
- 239000000395 magnesium oxide Substances 0.000 description 4
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 4
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 239000010457 zeolite Substances 0.000 description 4
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 3
- 229910004247 CaCu Inorganic materials 0.000 description 3
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 3
- 229910004298 SiO 2 Inorganic materials 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical group [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 3
- 229910052786 argon Inorganic materials 0.000 description 3
- 229910052788 barium Inorganic materials 0.000 description 3
- 229910052796 boron Inorganic materials 0.000 description 3
- 150000001721 carbon Chemical group 0.000 description 3
- 235000019253 formic acid Nutrition 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 238000002354 inductively-coupled plasma atomic emission spectroscopy Methods 0.000 description 3
- 229910052744 lithium Inorganic materials 0.000 description 3
- 239000011572 manganese Substances 0.000 description 3
- 229910052976 metal sulfide Inorganic materials 0.000 description 3
- 239000010955 niobium Substances 0.000 description 3
- 125000004433 nitrogen atom Chemical group N* 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- KBPLFHHGFOOTCA-UHFFFAOYSA-N 1-Octanol Chemical compound CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 description 2
- BBMCTIGTTCKYKF-UHFFFAOYSA-N 1-heptanol Chemical compound CCCCCCCO BBMCTIGTTCKYKF-UHFFFAOYSA-N 0.000 description 2
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 description 2
- LTPBRCUWZOMYOC-UHFFFAOYSA-N Beryllium oxide Chemical compound O=[Be] LTPBRCUWZOMYOC-UHFFFAOYSA-N 0.000 description 2
- ODINCKMPIJJUCX-UHFFFAOYSA-N Calcium oxide Chemical compound [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 2
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- NBBJYMSMWIIQGU-UHFFFAOYSA-N Propionic aldehyde Chemical compound CCC=O NBBJYMSMWIIQGU-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 229910003071 TaON Inorganic materials 0.000 description 2
- 229910010413 TiO 2 Inorganic materials 0.000 description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 2
- 229910021536 Zeolite Inorganic materials 0.000 description 2
- 150000001299 aldehydes Chemical class 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 150000001735 carboxylic acids Chemical class 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- MWKFXSUHUHTGQN-UHFFFAOYSA-N decan-1-ol Chemical compound CCCCCCCCCCO MWKFXSUHUHTGQN-UHFFFAOYSA-N 0.000 description 2
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 229910052733 gallium Inorganic materials 0.000 description 2
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 description 2
- PJXISJQVUVHSOJ-UHFFFAOYSA-N indium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[In+3].[In+3] PJXISJQVUVHSOJ-UHFFFAOYSA-N 0.000 description 2
- 229910052746 lanthanum Inorganic materials 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- HFLAMWCKUFHSAZ-UHFFFAOYSA-N niobium dioxide Chemical compound O=[Nb]=O HFLAMWCKUFHSAZ-UHFFFAOYSA-N 0.000 description 2
- ZWRUINPWMLAQRD-UHFFFAOYSA-N nonan-1-ol Chemical compound CCCCCCCCCO ZWRUINPWMLAQRD-UHFFFAOYSA-N 0.000 description 2
- 230000000737 periodic effect Effects 0.000 description 2
- 229910052703 rhodium Inorganic materials 0.000 description 2
- 239000010948 rhodium Substances 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000012086 standard solution Substances 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 229910052715 tantalum Inorganic materials 0.000 description 2
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- 239000005968 1-Decanol Substances 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 229910002521 CoMn Inorganic materials 0.000 description 1
- 229910052693 Europium Inorganic materials 0.000 description 1
- 229910005793 GeO 2 Inorganic materials 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- KWYHDKDOAIKMQN-UHFFFAOYSA-N N,N,N',N'-tetramethylethylenediamine Chemical compound CN(C)CCN(C)C KWYHDKDOAIKMQN-UHFFFAOYSA-N 0.000 description 1
- 229910052779 Neodymium Inorganic materials 0.000 description 1
- 229910052777 Praseodymium Inorganic materials 0.000 description 1
- 229910052772 Samarium Inorganic materials 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 229910002367 SrTiO Inorganic materials 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- GEIAQOFPUVMAGM-UHFFFAOYSA-N ZrO Inorganic materials [Zr]=O GEIAQOFPUVMAGM-UHFFFAOYSA-N 0.000 description 1
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- QVQLCTNNEUAWMS-UHFFFAOYSA-N barium oxide Inorganic materials [Ba]=O QVQLCTNNEUAWMS-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- ZTQSAGDEMFDKMZ-UHFFFAOYSA-N butyric aldehyde Natural products CCCC=O ZTQSAGDEMFDKMZ-UHFFFAOYSA-N 0.000 description 1
- 229910052792 caesium Inorganic materials 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- 239000000292 calcium oxide Substances 0.000 description 1
- 229910000420 cerium oxide Inorganic materials 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 125000001664 diethylamino group Chemical group [H]C([H])([H])C([H])([H])N(*)C([H])([H])C([H])([H])[H] 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 229910052730 francium Inorganic materials 0.000 description 1
- 229910052732 germanium Inorganic materials 0.000 description 1
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 1
- 239000010416 ion conductor Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910000311 lanthanide oxide Inorganic materials 0.000 description 1
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 1
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 230000011987 methylation Effects 0.000 description 1
- 238000007069 methylation reaction Methods 0.000 description 1
- 229910003455 mixed metal oxide Inorganic materials 0.000 description 1
- URKRYOHZWVRTIL-UHFFFAOYSA-N n',n'-bis[2-(diethylamino)ethyl]-n,n-diethylethane-1,2-diamine Chemical compound CCN(CC)CCN(CCN(CC)CC)CCN(CC)CC URKRYOHZWVRTIL-UHFFFAOYSA-N 0.000 description 1
- VMGSQCIDWAUGLQ-UHFFFAOYSA-N n',n'-bis[2-(dimethylamino)ethyl]-n,n-dimethylethane-1,2-diamine Chemical compound CN(C)CCN(CCN(C)C)CCN(C)C VMGSQCIDWAUGLQ-UHFFFAOYSA-N 0.000 description 1
- DTKANQSCBACEPK-UHFFFAOYSA-N n',n'-bis[3-(dimethylamino)propyl]-n,n-dimethylpropane-1,3-diamine Chemical compound CN(C)CCCN(CCCN(C)C)CCCN(C)C DTKANQSCBACEPK-UHFFFAOYSA-N 0.000 description 1
- LIGIARLVFBHRJF-UHFFFAOYSA-N n'-[2-(diethylamino)ethyl]-n,n,n'-triethylethane-1,2-diamine Chemical compound CCN(CC)CCN(CC)CCN(CC)CC LIGIARLVFBHRJF-UHFFFAOYSA-N 0.000 description 1
- XSCOFLWZKMBZFE-UHFFFAOYSA-N n'-[2-(dipropylamino)ethyl]-n,n,n'-tripropylethane-1,2-diamine Chemical compound CCCN(CCC)CCN(CCC)CCN(CCC)CCC XSCOFLWZKMBZFE-UHFFFAOYSA-N 0.000 description 1
- MUESDKXVLSXRPO-UHFFFAOYSA-N n,n,n',n'-tetra(propan-2-yl)ethane-1,2-diamine Chemical compound CC(C)N(C(C)C)CCN(C(C)C)C(C)C MUESDKXVLSXRPO-UHFFFAOYSA-N 0.000 description 1
- OROFXWIKMNHVSV-UHFFFAOYSA-N n,n,n',n'-tetra(propan-2-yl)propane-1,3-diamine Chemical compound CC(C)N(C(C)C)CCCN(C(C)C)C(C)C OROFXWIKMNHVSV-UHFFFAOYSA-N 0.000 description 1
- DIHKMUNUGQVFES-UHFFFAOYSA-N n,n,n',n'-tetraethylethane-1,2-diamine Chemical compound CCN(CC)CCN(CC)CC DIHKMUNUGQVFES-UHFFFAOYSA-N 0.000 description 1
- RCZLVPFECJNLMZ-UHFFFAOYSA-N n,n,n',n'-tetraethylpropane-1,3-diamine Chemical compound CCN(CC)CCCN(CC)CC RCZLVPFECJNLMZ-UHFFFAOYSA-N 0.000 description 1
- DMQSHEKGGUOYJS-UHFFFAOYSA-N n,n,n',n'-tetramethylpropane-1,3-diamine Chemical compound CN(C)CCCN(C)C DMQSHEKGGUOYJS-UHFFFAOYSA-N 0.000 description 1
- HVBXZPOGJMBMLN-UHFFFAOYSA-N n,n,n',n'-tetrapropylethane-1,2-diamine Chemical compound CCCN(CCC)CCN(CCC)CCC HVBXZPOGJMBMLN-UHFFFAOYSA-N 0.000 description 1
- FQELQRCSRAWQAB-UHFFFAOYSA-N n,n,n',n'-tetrapropylpropane-1,3-diamine Chemical compound CCCN(CCC)CCCN(CCC)CCC FQELQRCSRAWQAB-UHFFFAOYSA-N 0.000 description 1
- DUWWHGPELOTTOE-UHFFFAOYSA-N n-(5-chloro-2,4-dimethoxyphenyl)-3-oxobutanamide Chemical compound COC1=CC(OC)=C(NC(=O)CC(C)=O)C=C1Cl DUWWHGPELOTTOE-UHFFFAOYSA-N 0.000 description 1
- OHWSRBFDUQYYSN-UHFFFAOYSA-N n-[2-[di(propan-2-yl)amino]ethyl]-n,n',n'-tri(propan-2-yl)ethane-1,2-diamine Chemical compound CC(C)N(C(C)C)CCN(C(C)C)CCN(C(C)C)C(C)C OHWSRBFDUQYYSN-UHFFFAOYSA-N 0.000 description 1
- BFRGSJVXBIWTCF-UHFFFAOYSA-N niobium monoxide Inorganic materials [Nb]=O BFRGSJVXBIWTCF-UHFFFAOYSA-N 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 229910052755 nonmetal Inorganic materials 0.000 description 1
- 150000002843 nonmetals Chemical class 0.000 description 1
- 125000000962 organic group Chemical group 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229910052592 oxide mineral Inorganic materials 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 1
- RUDFQVOCFDJEEF-UHFFFAOYSA-N oxygen(2-);yttrium(3+) Chemical class [O-2].[O-2].[O-2].[Y+3].[Y+3] RUDFQVOCFDJEEF-UHFFFAOYSA-N 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 229910052705 radium Inorganic materials 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000006485 reductive methylation reaction Methods 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 229910052701 rubidium Inorganic materials 0.000 description 1
- 229910052706 scandium Inorganic materials 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- IATRAKWUXMZMIY-UHFFFAOYSA-N strontium oxide Inorganic materials [O-2].[Sr+2] IATRAKWUXMZMIY-UHFFFAOYSA-N 0.000 description 1
- 239000002887 superconductor Substances 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- LSGOVYNHVSXFFJ-UHFFFAOYSA-N vanadate(3-) Chemical class [O-][V]([O-])([O-])=O LSGOVYNHVSXFFJ-UHFFFAOYSA-N 0.000 description 1
- RNWHGQJWIACOKP-UHFFFAOYSA-N zinc;oxygen(2-) Chemical class [O-2].[Zn+2] RNWHGQJWIACOKP-UHFFFAOYSA-N 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
- C07C209/04—Preparation of compounds containing amino groups bound to a carbon skeleton by substitution of functional groups by amino groups
- C07C209/14—Preparation of compounds containing amino groups bound to a carbon skeleton by substitution of functional groups by amino groups by substitution of hydroxy groups or of etherified or esterified hydroxy groups
- C07C209/16—Preparation of compounds containing amino groups bound to a carbon skeleton by substitution of functional groups by amino groups by substitution of hydroxy groups or of etherified or esterified hydroxy groups with formation of amino groups bound to acyclic carbon atoms or to carbon atoms of rings other than six-membered aromatic rings
-
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/72—Copper
-
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/75—Cobalt
-
- 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
- B01J25/00—Catalysts of the Raney type
-
- 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
- B01J25/00—Catalysts of the Raney type
- B01J25/02—Raney nickel
Definitions
- the present invention pertains to a method for the alkylation of amines.
- N, N, N', N”, N”-pentamethyldiethylenetriamine is used in the formation of rigid foam polyurethane.
- Current technology for PMDTA production relies on the methylation of diethylenetriamine (DETA) in the presence of hydrogen by using formaldehyde as methyl source. This methodology is selective towards PMDTA.
- formaldehyde CMR compound raises HSE concerns.
- US Patent No. 5105013 teaches a process for the preparation of permethylated amines, particularly pentamethyldiethylenetriamine, by the reductive methylation of diethylenetriamine in the presence of hydrogen, formaldehyde aqueous solution, a catalyst, and a solvent. The reaction was carried out in two reaction phases and the flow rate of formaldehyde must be well controlled.
- the present invention therefore pertains to a method for preparing a compound having general formula (I) by reacting a compound having general formula (II) with an alcohol having general formula (III) in the presence of hydrogen and a metal catalyst:
- - R is an alkyl, alkenyl or alkynyl
- - n is an integer between 0 and 20
- - m is an integer between 1 and 3
- - p is an integer between 0 and 2
- the method of the invention enables to alkylate amines by using an environmentally friendly alkylation agent.
- the invention also concerns a mixture comprising:
- Fig. 1 is an image of temperature-yield curve of reaction of DETA with methanol over Pricat Cu 60/8P of Example 3;
- Fig. 2 is an image of H 2 pressure-yield curve of reaction of DETA with methanol over Pricat Cu 60/8P of Example 4;
- Fig. 3 is an image of time-yield curve of reaction of DETA with methanol over Pricat Cu 60/8P of Example 5;
- Fig. 4 is an image of mass ratio (Cat/DETA) -yield curve of reaction of DETA with methanol over Pricat Cu 60/8P of Example 6;
- Fig. 5 is an image of concentration (DETA in methanol) -yield curve of reaction of DETA with methanol over Pricat Cu 60/8P of Example 7.
- Ratios, concentrations, amounts, and other numerical data may be presented herein in a range format. It is to be understood that such a range format is used merely for convenience and brevity and should be interpreted flexibly to include not only the numerical values explicitly recited as the limits of the range, but also all the individual numerical values or sub-ranges encompassed within that range as if each numerical value or sub-range is explicitly recited.
- the compound having general formula (II) is a compound having general formula (IV) :
- n is an integer between 0 and 20, preferably between 0 and 9, and more preferably between 0 and 4.
- the compound having general formula (II) is a compound having general formula (V) :
- n is an integer between 0 and 20, preferably between 0 and 9, and more preferably between 0 and 4.
- the compound having general formula (II) is a compound having general formula (VI) :
- n is an integer between 0 and 20, preferably between 0 and 9, and more preferably between 0 and 4.
- the compound having general formula (II) can be selected from the group consisting of dimethylenetriamine, diethylenetriamine, dipropylenetriamine, dibutylenetriamine, dipentylenetriamine, dihexylenetriamine, diheptylenetriamine, dioctylenetriamine, dinonylenetriamine, didecylenetriamine, methylenediamine, ethylenediamine, propylenediamine, butylenediamine, pentylenediamine, hexylenediamine, heptylenediamine, octylenediamine, nonylenediamine, and decylenediamine, triaminomethylamine, tris (2-aminoethyl) amine, tris (3-aminopropyl) amine, tris (4-aminobutyl) amine, tris (5-aminopentyl) amine, tris (6-aminohexyl) amine, tris (7-aminoh
- the compound having general formula (II) can be selected from the group consisting of diethylenetriamine, dipropylenetriamine, dibutylenetriamine, dipentylenetriamine, ethylenediamine, propylenediamine, butylenediamine and pentylenediamine.
- R may be straight or branched. More preferably, R may be a C 1 -C 10 straight or branched alkyl.
- Examples of the alcohol having general formula (III) are methanol, ethanol, 1-propanol, 1-butanol, 1-pentanol, 1-hexanol, 1-heptanol, 1-octanol, 1-nonanol, 1-decanol, 2-propanol, 2-butanol and 3-butanol.
- the alcohol having general formula (III) can be selected from the group consisting of methanol, ethanol, 1-propanol and 2-propanol.
- the alcohol may comprise traces of corresponding aldehyde and/or carboxylic acid.
- methanol may comprise traces of formaldehyde and/or formic acid
- ethanol may comprise traces of acetaldehyde and/or acetic acid
- propanol may comprise traces of propionaldehyde and/or propanoic acid.
- the alcohol may contain 0.01-10000 ppm corresponding aldehyde and/or carboxylic acid.
- Preferred reactions of the present invention are the following:
- the metal catalyst may comprise at least one metal element in elemental form and/or at least one metal oxide of at least one metal element, wherein the metal element is selected from (i) elements of group IA except hydrogen, (ii) elements of group IIA, (iii) elements of group IIIA, (iv) elements of group IVA except carbon, (v) arsenic, antimony, bismuth, tellurium, polonium and astatine, (vi) elements of groups IB, IIB, IIIB, IVB, VB, VIB, VIIB and VIIIB, (vii) lanthanides and (viii) actinides.
- the metal element is selected from (i) elements of group IA except hydrogen, (ii) elements of group IIA, (iii) elements of group IIIA, (iv) elements of group IVA except carbon, (v) arsenic, antimony, bismuth, tellurium, polonium and astatine, (vi) elements of groups IB, IIB, IIIB, IVB, VB,
- the metal catalyst according to present invention can be a supported or unsupported catalyst.
- the support to the metal catalyst is not particularly limited. It can notably be a metal oxide chosen in the group consisting of aluminum oxide (Al 2 O 3 ) , silicon dioxide (SiO 2 ) , titanium oxide (TiO 2 ) , zirconium dioxide (ZrO 2 ) , calcium oxide (CaO) , magnesium oxide (MgO) , lanthanum oxide (La 2 O 3 ) , niobium dioxide (NbO 2 ) , cerium oxide (CeO 2 ) and mixtures thereof.
- Al 2 O 3 aluminum oxide
- SiO 2 silicon dioxide
- TiO 2 titanium oxide
- ZrO 2 zirconium dioxide
- CaO calcium oxide
- MgO magnesium oxide
- La 2 O 3 lanthanum oxide
- NbO 2 niobium dioxide
- CeO 2 cerium oxide
- the support can also be a zeolite.
- Zeolites are substances having a crystalline structure and a unique ability to change ions. People skilled in the art can easily understand how to obtain those zeolites by preparation method reported, such as zeolite L is described in US 4503023 or commercial purchase, such as ZSM available from ZEOLYST.
- the support of catalyst can even be Kieselguhr, clay or carbon.
- metals are the elements in the periodic system which are located left to the diagonal extending from boron (atomic number 5) to astatine (atomic number 85) ) .
- Metals of group IA Li, Na, K, Rb, Cs, Fr are also known as alkali metals and metals of group IIA (Be, Mg, Ca, Sr Ba and Ra) are generally referred to as alkaline earth metals.
- the metals of group IB, IIB, IIIB, IVB, VB, VIB, VIIB and VIIIB are often referred to as transition metals.
- This group comprises the elements with atomic number 21 to 30 (Sc to Zn) , 39 to 48 (Y to Cd) , 72 to 80 (Hf to Hg) and 104 to 112 (Hf to Cn) .
- the lanthanides encompass the metals with atomic number 57 to 71 and the actinides the metals with the atomic number 89 to 103.
- metalloids are sometimes also referred to as metalloids.
- the term metalloid is generally designating an element which has properties between those of metals and non-metals. Typically, metalloids have a metallic appearance but are relatively brittle and have a moderate electrical conductivity.
- the six commonly recognized metalloids are boron, silicon, germanium, arsenic, antimony, and tellurium.
- Other elements also recognized as metalloids include aluminum, polonium, and astatine. On a standard periodic table all of these elements may be found in a diagonal region of the p-block, extending from boron at one end, to astatine at the other (as indicated above) .
- the metal element is selected from elements of groups IA, IIA, IIIA, IVA, IB, IIB, IIIB, IVB, VB, VIB, VIIB and VIIIB. More preferably, the metal element is selected from elements of groups IA, IIA, IIIA, IVA, IB, IIB, VIB, VIIB and VIIIB.
- the metal catalyst comprises two, three, or four metal elements, which are present in elemental form and/or in metal oxide form.
- Metal oxide compounds comprise typically at least one oxygen atom and at least one metal atom which is chemically bound to the oxygen atom; the electronegativity of the oxygen atom is obviously higher than the electronegativity of the metal atom.
- the metal oxide compound of the present invention may be a single oxide or a mixed oxide.
- a single metal oxide is typically composed of one or more metal atom (s) of a same, unique metal element and one or more oxygen atom (s) .
- the metal atom comprised in the single metal oxide can be notably:
- Ln a lanthanide Ln, as in CeO 2 and in Ln 2 O 3 , or
- a mixed metal oxide is typically composed of one or more metal atom (s) of different metal elements and one or more oxygen atom (s) .
- Many metals can form mixed oxides with one or more other metals.
- Mixed oxide minerals appear in a great variety in nature and synthetic mixed oxides find use as components of different materials used in advanced technological applications.
- ZnO Al, ZnO: Cu, ZnO: Ag, ZnO: Ga, ZnO: Mg, ZnO: Cd, ZnO: In, ZnO: Sn, ZnO: Sc, ZnO: Y, ZnO: Co, ZnO: Mn, ZnO: Cr and ZnO: B
- cuprates superconductors such as YBa 2 Cu 3 O 7-x , Bi 2 Sr 2 CuO 6 , Bi 2 Sr 2 CaCu 2 O 8 , Bi 2 Sr 2 Ca 2 Cu 3 O 6 , Tl 2 Ba 2 CuO 6 , Tl 2 Ba 2 CaCu 2 O 8 , Tl 2 Ba 2 Ca 2 Cu 3 O 10 , TlBa 2 Ca 3 Cu 4 O 11 , HgBa 2 CuO 4 , HgBa 2 CaCu 2 O 6 and HgBa 2 Ca 2 Cu 3 O 8 ,
- A Ni, Mg, Mn, Fe, Co, Zn, Cu, Ca, Sr, Ba or Pb
- Ln represents a lanthanide metal
- perovskites such as LaGaO 3 , Na 1-x Bi x TiO 3 with 0 ⁇ x ⁇ 1,
- IGZO indium-gallium-zinc oxide
- ITO indium - mixed oxides of indium and tin, commonly referred to as ITO, which denotes a solid solution of indium (III) oxide (In 2 O 3 ) and tin (IV) oxide (SnO 2 ) , consisting essentially of or consisting of from 80 wt. %up to 95 wt. %of In 2 O 3 and from 5 wt. %to 20 wt. %of SnO 2 , in some cases about 90 wt. %In 2 O 3 and about 10 wt. %SnO 2 ; in particular for organic electronic device applications, ITO has been profitably used in the recent past.
- the metal catalyst according to the present invention can be Raney catalysts such as Raney nickel, Raney cobalt and Raney copper.
- the metal catalyst comprises Metal element A and optionally Metal element B, which are present in elemental form and/or in metal oxide form, wherein:
- Metal element A is at least one metal element selected from elements of groups IB and VIIIB, and
- Metal element B is at least one metal element selected from the group consisting of Al, Na, Mn, Mg, Si, Zn, Ni, Cr, K, Li, Cs, Be, Ca, Sr, Ba, Sc, Y, Ti, Zr, V, Nb, W, Mo, Tc, Re, Fe, Ru, Co, Ag, Cd, Hg, Ga, Pb, Bi, Ce, and mixtures thereof.
- Metal element A is Cu or Co and Metal element B is at least one metal element selected from the group consisting of Al, Na, Mn, Mg, Si, Zn, Ni, Cr and mixtures thereof.
- Metal element A can be supported on a support in this embodiment.
- Said support can be Al 2 O 3 , SiO 2 , TiO 2 , ZrO 2 , ZnO, MgO, NbO 2 , CeO 2 and mixtures thereof.
- the weight ratio of Metal element A based on the total weight of the catalyst is from 20 to 100 wt%.
- the metal catalyst may comprise Metal element A being Cu, and Metal element B being Al, Zn and Na.
- the weight ratio of Cu based on the total weight of the catalyst is from 35 to 55 wt%.
- the weight ratio of Al based on the total weight of the catalyst is from 3 to 7 wt%.
- the weight ratio of Zn based on the total weight of the catalyst is from10 to 30 wt%.
- the weight ratio of Na based on the total weight of the catalyst is from 0 to 1 wt%.
- the metal catalyst may comprise Metal element A being Cu, and Metal element B being Al and Mn.
- the weight ratio of Cu based on the total weight of the catalyst is from 40 to 65 wt%.
- the weight ratio of Al based on the total weight of the catalyst is from 20 to 40 wt%.
- the weight ratio of Mn based on the total weight of the catalyst is from 2 to 20 wt%.
- the metal catalyst may comprise Metal element A being Cu and Metal element B being Si.
- the weight ratio of Cu based on the total weight of the catalyst is from 85 to 100 wt%.
- the weight ratio of Si based on the total weight of the catalyst is from 0.005 to 10 wt%.
- the metal catalyst may comprise Metal element A being Cu, and Metal element B being Mg, Cr and Si.
- the weight ratio of Cu based on the total weight of the catalyst is from 60 to 90 wt%.
- the weight ratio of Mg based on the total weight of the catalyst is from 0 to 5 wt%.
- the weight ratio of Cr based on the total weight of the catalyst is from 0 to 3 wt%.
- the weight ratio of Si based on the total weight of the catalyst is from 0 to 10 wt%.
- the metal catalyst may comprise Metal element A being Cu, and Metal element B being Al and Si.
- the weight ratio of Cu based on the total weight of the catalyst is from 40 to 80 wt%.
- the weight ratio of Al based on the total weight of the catalyst is from 0 to 6 wt%.
- the weight ratio of Si based on the total weight of the catalyst is from 0 to 10 wt%
- the metal catalyst may comprise Metal element A being Cu, and Metal element B being Ni and Si.
- the weight ratio of Cu based on the total weight of the catalyst is from 45 to 95 wt%.
- the weight ratio of Ni based on the total weight of the catalyst is from 0 to 10 wt%.
- the weight ratio of Si based on the total weight of the catalyst is from 0 to 10 wt%.
- the metal catalyst may comprise Metal element A being Cu, and Metal element B being Cr and Si.
- the weight ratio of Cu based on the total weight of the catalyst is from 50 to 95 wt%.
- the weight ratio of Cr based on the total weight of the catalyst is from 0 to 40 wt%.
- the weight ratio of Si based on the total weight of the catalyst is from 0 to 10 wt%.
- the metal catalyst according to the present invention can further comprise at least one metal sulphide compound.
- metal sulphide compounds comprise typically at least one sulphur atom and at least one metal atom which is chemically bound to the sulphur atom; the electronegativity of the sulphur atom is obviously higher than the electronegativity of the metal atom.
- the (or at least one) metal atom comprised in the metal sulphide compound can be notably:
- the metal catalyst according to the present invention can further comprise at least one metal carbide compound.
- Metal carbide compounds comprise typically at least one carbon atom and at least one metal atom which is chemically bound to the carbon atom; the electronegativity of the carbon atom is obviously higher than the electronegativity of the metal atom.
- the (or at least one) metal atom comprised in the metal carbide compound can be notably:
- LaC 2 lanthanum percarbide
- Ln 2 C 3 sesquicarbide, wherein Ln denotes a lanthanide
- the metal catalyst according to the present invention can further comprise at least one metal nitride compound.
- Metal nitride compounds comprise typically at least one nitrogen atom and at least one metal atom which is chemically bound to the nitrogen atom; the electronegativity of the nitrogen atom is obviously higher than the electronegativity of the metal atom.
- the (or at least one) metal atom comprised in the metal nitride compound can be notably:
- the metal nitride is an oxynitride (i.e. a compound that qualifies as metal nitride compound and as metal oxide compound) . Examples thereof are:
- TaON tantalum oxynitride
- perovskite oxynitrides such as CaTaO 2 N, SrTaO 2 N, BaTaO 2 N, LaTaON 2 and BaNbO 2 N, and
- the metal catalyst is composed of metal element in elemental form and/or metal oxide.
- the metal catalyst according to the present invention can be obtained by pre-reduction of commercial catalysts, such as T-4489 P, T-8031 P from Süd-Chemie, T-4419 P from Clariant and Pricat CU 60/35 P, Pricat CU 50/8 P, Pricat 60/8 P from Johnson Matthey.
- commercial catalysts such as T-4489 P, T-8031 P from Süd-Chemie, T-4419 P from Clariant and Pricat CU 60/35 P, Pricat CU 50/8 P, Pricat 60/8 P from Johnson Matthey.
- the skilled person can pre-reduce the commercial catalysts by some well-known ways.
- the metal catalyst can be obtained by in situ-reduction. That is to say, the commercial catalysts can be in situ-reduced during the reaction of the compound having general formula (II) with the alcohol having general formula (III) in the presence of hydrogen.
- the weight ratio of the metal catalyst to the compound having general formula (II) is from 0.1 to 10 and preferably from 0.2 to 2.
- the weight ratio of the compound having general formula (II) to the alcohol having general formula (III) may be from 0.0001 to 0.1 and preferably from 0.001 to 0.05.
- the alcohol having general formula (III) is the reactant and also the only solvent of the compound having general formula (II) .
- the reaction may also be carried out in the presence of a second solvent other than the alcohol having general formula (III) as long as the second solvent does not participate in the reaction in place of the alcohol.
- solvent examples include water, formaldehyde (traces) , formic acid (traces) , benzene, toluene, dimethyl ether, etc.
- the concentration of the compound having general formula (II) in the solvent may be from 0.01wt%to 9wt%, preferably from 0.1wt%to 5wt%and more preferably from 0.1wt%to 2.5wt%.
- reaction of the compound having general formula (II) with the alcohol having general formula (III) is desirably carried out under a hydrogen pressure in a range of 15-70 bar, and more preferably 20-50 bar.
- hydrogen may be added during the reaction to make up for the consumption or continuously circulated through the reaction zone.
- the reaction may be carried out in the presence of an inert atmosphere such as N 2 or Ar.
- the reaction time may be from 4 to 24h and preferably from 10 to 20h.
- the reaction temperature may be from 140°C to 220°C and preferably from 180°C to 200°C.
- the invention also concerns a mixture comprising:
- the mixture may further comprise a second solvent selected from the group consisting of water, formaldehyde, formic acid, benzene, toluene and dimethyl ether.
- a second solvent selected from the group consisting of water, formaldehyde, formic acid, benzene, toluene and dimethyl ether.
- the mixture may further comprise a compound having general formula (I) .
- the compound having general formula (I) , the compound having general formula (II) , the alcohol having general formula (III) , the metal catalyst and the solvent have the same meaning as above defined.
- a gas mixture consisting of H 2 /Ar or H 2 /N 2 in 1/3 to 1/10 ratio is flew through the tube from one outlet to another which is connected directly to the atmosphere.
- the tube is weighed with and without catalyst to get the real weight ofthe catalyst.
- the catalyst is used freshly after reduction, or kept in a glove box filled with argon.
- the autoclave was well sealed under nitrogen, and purged by hydrogen 10 bar and evacuated for 10 times, finally purged with 30 bar of hydrogen.
- the sealing ofthe reactor is checked by waiting 1 hour at room temperature without stirring, and if the pressure remains unchanged then the reactor is well-sealed. Then the reactor was stirred with mechanical stirring for 1 hour at ambient temperature to allow the absorption of the hydrogen, followed by heating up to 200°C for 10 hours with 500 rounds/min stirring speed.
- the reactor was cooled down to ambient temperature and the hydrogen gas was evacuated carefully in fume hood.
- To the reaction mixture was added internal standard bisphenyl with accurate weight. After complete dissolving of bisphenyl, the liquid was firstly weighed and then filtered and analyzed by GC. The conversion and yields were calculated using internal standard calibration.
- the autoclave was well sealed under nitrogen, and purged by hydrogen 10 bar and evacuated for 10 times, finally purged with 30 bar of hydrogen.
- the sealing of the reactor is checked by waiting 1 hour at room temperature without stirring, and if the pressure remains unchanged then the reactor is well-sealed. Then the reactor was stirred with mechanical stirring for 1 hour at ambient temperature to allow the absorption of the hydrogen, followed by heating up to 200°C for 20 hours with 500 rounds/min stirring speed.
- the reactor was cooled down to ambient temperature and the hydrogen gas was evacuated carefully in fume hood. The liquid was firstly weighed and then filtered and analyzed by GC affording 28%yield of PMDTA.
- the autoclave was well sealed under nitrogen, and purged by hydrogen 10 bar and evacuated for 10 times, finally purged with 50 bar of hydrogen.
- the sealing of the reactor is checked by waiting 1 hour at room temperature without stirring, and if the pressure remains unchanged then the reactor is well-sealed. Then the reactor was stirred with mechanical stirring for 1 hour at ambient temperature to allow the absorption of the hydrogen, followed by heating up to the temperatures described in Table 4 for 10 hours with 500 rounds/min stirring speed.
- the reactor was cooled down to ambient temperature and the hydrogen gas was evacuated carefully in fume hood.
- To the reaction mixture was added internal standard bisphenyl with accurate weight. After complete dissolving of bisphenyl, the liquid was firstly weighed and then filtered and analyzed by GC. The conversion and yields were calculated using internal standard calibration.
- the autoclave was well sealed under nitrogen, and purged by hydrogen 10 bar and evacuated for 10 times, finally purged with hydrogen till the pressures described in Table 5.
- the sealing of the reactor is checked by waiting 1 hour at room temperature without stirring, and if the pressure remains unchanged then the reactor is well-sealed. Then the reactor was stirred with mechanical stirring for 1 hour at ambient temperature to allow the absorption of the hydrogen, followed by heating up to 200°C for 10 hours with 500 rounds/min stirring speed.
- the reactor was cooled down to ambient temperature and the hydrogen gas was evacuated carefully in fume hood.
- To the reaction mixture was added internal standard bisphenyl with accurate weight. After complete dissolving of bisphenyl, the liquid was firstly weighed and then filtered and analyzed by GC. The conversion and yields were calculated using internal standard calibration.
- Pre-reduced copper containing catalyst Pricat 60/8P was weighed (0.12g) .
- a clean autoclave was charged under nitrogen after vacuum&nitrogen exchanges for 3 times, catalyst was transferred into autoclave immediately.
- the autoclave was well sealed under nitrogen, and purged by hydrogen 10 bar and evacuated for 10 times, finally purged with 50 bar of hydrogen.
- the sealing of the reactor is checked by waiting 1 hour at room temperature without stirring, and if the pressure remains unchanged then the reactor is well-sealed. Then the reactor was stirred with mechanical stirring for 1 hour at ambient temperature to allow the absorption of the hydrogen, followed by heating up to 200°C for time described in Table 6 with 500 rounds/min stirring speed.
- the reactor was cooled down to ambient temperature and the hydrogen gas was evacuated carefully in fume hood.
- To the reaction mixture was added internal standard bisphenyl with accurate weight. After complete dissolving of bisphenyl, the liquid was firstly weighed and then filtered and analyzed by GC. The conversion and yields were calculated using internal standard calibration.
- Pre-reduced copper containing catalyst Pricat 60/8P was weighed to a certain amount described in Table 7. A clean autoclave was charged under nitrogen after vacuum&nitrogen exchanges for 3 times, catalyst was transferred into autoclave immediately.
- the autoclave was well sealed under nitrogen, and purged by hydrogen 10 bar and evacuated for 10 times, finally purged with 50 bar of hydrogen.
- the sealing of the reactor is checked by waiting 1 hour at room temperature without stirring, and if the pressure remains unchanged then the reactor is well-sealed. Then the reactor was stirred with mechanical stirring for 1 hour at ambient temperature to allow the absorption of the hydrogen, followed by heating up to 200°C for 10 hours with 500 rounds/min stirring speed.
- the reactor was cooled down to ambient temperature and the hydrogen gas was evacuated carefully in fume hood.
- To the reaction mixture was added internal standard bisphenyl with accurate weight. After complete dissolving of bisphenyl, the liquid was firstly weighed and then filtered and analyzed by GC. The conversion and yields were calculated using internal standard calibration.
- Pre-reduced copper containing catalyst Pricat 60/8P was weighed (0.13 g) . A clean autoclave was charged under nitrogen after vacuum&nitrogen exchanges for 3 times, catalyst was transferred into autoclave immediately.
- the autoclave was well sealed under nitrogen, and purged by hydrogen 10 bar and evacuated for 10 times, finally purged with 40 bar of hydrogen.
- the sealing of the reactor is checked by waiting 1 hour at room temperature without stirring, and if the pressure remains unchanged then the reactor is well-sealed. Then the reactor was stirred with mechanical stirring for 1 hour at ambient temperature to allow the absorption of the hydrogen, followed by heating up to 200°C for 20 hours with 500 rounds/min stirring speed.
- the reactor was cooled down to ambient temperature and the hydrogen gas was evacuated carefully in fume hood.
- To the reaction mixture was added internal standard bisphenyl with accurate weight. After complete dissolving of bisphenyl, the liquid was firstly weighed and then filtered and analyzed by GC. The conversion and yields were calculated using internal standard calibration.
- Pre-reduced copper containing catalyst Pricat 60/8P was weighed (0.12 g) . A clean autoclave was charged under nitrogen after vacuum&nitrogen exchanges for 3 times, catalyst was transferred into autoclave immediately.
- the autoclave was well sealed under nitrogen, and purged by hydrogen 10 bar and evacuated for 10 times, finally purged with 50 bar of hydrogen.
- the sealing of the reactor is checked by waiting 1 hour at room temperature without stirring, and ifthe pressure remains unchanged then the reactor is well-sealed. Then the reactor was stirred with mechanical stirring for 1 hour at ambient temperature to allow the absorption of the hydrogen, followed by heating up to 200°C for 10 hours with 500 rounds/min stirring speed.
- the reactor was cooled down to ambient temperature and the hydrogen gas was evacuated carefully in fume hood.
- To the reaction mixture was added internal standard bisphenyl with accurate weight. After complete dissolving of bisphenyl, the liquid was firstly weighed and then filtered and analyzed by GC. The conversion and yields were calculated using internal standard calibration. The yield of PMDTA was 68.1%.
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Abstract
The present invention pertains to a method for the alkylation of amines. In particular, the present invention relates to a method for preparing N, N, N', N", N"-pentamethyldiethylenetriamine by reacting diethylenetriamine with methanol in the presence of hydrogen and a metal catalyst.
Description
The present invention pertains to a method for the alkylation of amines.
N, N, N', N”, N”-pentamethyldiethylenetriamine (PMDTA) is used in the formation of rigid foam polyurethane. Current technology for PMDTA production relies on the methylation of diethylenetriamine (DETA) in the presence of hydrogen by using formaldehyde as methyl source. This methodology is selective towards PMDTA. However, the use of formaldehyde (CMR compound) raises HSE concerns.
For example, US Patent No. 5105013 teaches a process for the preparation of permethylated amines, particularly pentamethyldiethylenetriamine, by the reductive methylation of diethylenetriamine in the presence of hydrogen, formaldehyde aqueous solution, a catalyst, and a solvent. The reaction was carried out in two reaction phases and the flow rate of formaldehyde must be well controlled.
Hence, there is still a need to develop an environmentally friendly process to prepare PMDTA in high yield and selectivity, which can overcome the drawbacks in prior arts.
SUMMARY OF THE INVENTION
The present invention therefore pertains to a method for preparing a compound having general formula (I) by reacting a compound having general formula (II) with an alcohol having general formula (III) in the presence of hydrogen and a metal catalyst:
wherein:
- R is an alkyl, alkenyl or alkynyl,
- n is an integer between 0 and 20,
- m is an integer between 1 and 3,
- p is an integer between 0 and 2, and
- p+m=3.
The method of the invention enables to alkylate amines by using an environmentally friendly alkylation agent.
Advantageously, it is not necessary to control the flow rate of alkylation agent by using the method according to the present invention.
The invention also concerns a mixture comprising:
(i) A compound having general formula (II) ,
(ii) An alcohol having general formula (III) ,
(iii) Hydrogen, and
(iv) A metal catalyst.
BRIEF DESCRIPTION OF DRAWINGS
Fig. 1 is an image of temperature-yield curve of reaction of DETA with methanol over Pricat Cu 60/8P of Example 3;
Fig. 2 is an image of H
2 pressure-yield curve of reaction of DETA with methanol over Pricat Cu 60/8P of Example 4;
Fig. 3 is an image of time-yield curve of reaction of DETA with methanol over Pricat Cu 60/8P of Example 5;
Fig. 4 is an image of mass ratio (Cat/DETA) -yield curve of reaction of DETA with methanol over Pricat Cu 60/8P of Example 6;
Fig. 5 is an image of concentration (DETA in methanol) -yield curve of reaction of DETA with methanol over Pricat Cu 60/8P of Example 7.
DEFINITIONS
Throughout the description, including the claims, the term "comprising one" should be understood as being synonymous with the term "comprising at least one" , unless otherwise specified, and "between" should be understood as being inclusive of the limits.
As used herein, the terminology " (C
n-C
m) " in reference to an organic group, wherein n and m are both integers, indicates that the group may contain from n carbon atoms to m carbon atoms per group.
The articles “a” , “an” and “the” are used to refer to one or to more than one (i.e., to at least one) of the grammatical object of the article.
The term “and/or” includes the meanings “and” , “or” and also all the other possible combinations of the elements connected to this term.
It is specified that, in the continuation of the description, unless otherwise indicated, the values at the limits are included in the ranges of values which are given.
Ratios, concentrations, amounts, and other numerical data may be presented herein in a range format. It is to be understood that such a range format is used merely for convenience and brevity and should be interpreted flexibly to include not only the numerical values explicitly recited as the limits of the range, but also all the individual numerical values or sub-ranges encompassed within that range as if each numerical value or sub-range is explicitly recited.
DETAILS OF THE INVENTION
In some embodiments, the compound having general formula (II) is a compound having general formula (IV) :
wherein n is an integer between 0 and 20, preferably between 0 and 9, and more preferably between 0 and 4.
In some embodiments, the compound having general formula (II) is a compound having general formula (V) :
wherein n is an integer between 0 and 20, preferably between 0 and 9, and more preferably between 0 and 4.
In some embodiments, the compound having general formula (II) is a compound having general formula (VI) :
wherein n is an integer between 0 and 20, preferably between 0 and 9, and more preferably between 0 and 4.
The compound having general formula (II) can be selected from the group consisting of dimethylenetriamine, diethylenetriamine, dipropylenetriamine, dibutylenetriamine, dipentylenetriamine, dihexylenetriamine, diheptylenetriamine, dioctylenetriamine, dinonylenetriamine, didecylenetriamine, methylenediamine, ethylenediamine, propylenediamine, butylenediamine, pentylenediamine, hexylenediamine, heptylenediamine, octylenediamine, nonylenediamine, and decylenediamine, triaminomethylamine, tris (2-aminoethyl) amine, tris (3-aminopropyl) amine, tris (4-aminobutyl) amine, tris (5-aminopentyl) amine, tris (6-aminohexyl) amine, tris (7-aminoheptyl) amine, tris (8-aminooctyl) amine, tris (9-aminononyl) amine and tris (10-aminodecyl) amine.
Preferably, the compound having general formula (II) can be selected from the group consisting of diethylenetriamine, dipropylenetriamine, dibutylenetriamine, dipentylenetriamine, ethylenediamine, propylenediamine, butylenediamine and pentylenediamine.
Preferably, R may be straight or branched. More preferably, R may be a C
1-C
10 straight or branched alkyl.
Examples of the alcohol having general formula (III) are methanol, ethanol, 1-propanol, 1-butanol, 1-pentanol, 1-hexanol, 1-heptanol, 1-octanol, 1-nonanol, 1-decanol, 2-propanol, 2-butanol and 3-butanol.
Preferably, the alcohol having general formula (III) can be selected from the group consisting of methanol, ethanol, 1-propanol and 2-propanol.
The alcohol may comprise traces of corresponding aldehyde and/or carboxylic acid. For example, methanol may comprise traces of formaldehyde and/or formic acid, ethanol may comprise traces of acetaldehyde and/or acetic acid, and propanol may comprise traces of propionaldehyde and/or propanoic acid. In a specific embodiment, the alcohol may contain 0.01-10000 ppm corresponding aldehyde and/or carboxylic acid.
Preferred reactions of the present invention are the following:
- Reaction of diethylenetriamine with methanol to produce N, N, N', N”, N”-pentamethyldiethylenetriamine;
- Reaction of diethylenetriamine with ethanol to produce N, N, N', N”, N”-pentaethyldiethylenetriamine;
- Reaction of diethylenetriamine with 1-propanol to produce N, N, N', N”, N”-pentapropyldiethylenetriamine;
- Reaction of diethylenetriamine with 2-propanol to produce N, N, N', N”, N”-pentaisopropyldiethylenetriamine;
- Reaction of dipropylenetriamine with methanol to produce N, N, N', N”, N”-pentamethyldipropylenetriamine;
- Reaction of dipropylenetriamine with ethanol to produce N, N, N', N”, N”-pentaethyldipropylenetriamine;
- Reaction of dipropylenetriamine with 1-propanol to produce N, N, N', N”, N”-pentapropyldipropylenetriamine;
- Reaction of dipropylenetriamine with 2-propanol to produce N, N, N', N”, N”-pentaisopropyldipropylenetriamine;
- Reaction of ethylenediamine with methanol to produce N, N, N', N'-tetramethylethane-1, 2-diamine;
- Reaction of ethylenediamine with ethanol to produce N, N, N', N'-tetraethylethane-1, 2-diamine;
- Reaction of ethylenediamine with 1-propanol to produce N, N, N', N'-tetrapropylethane-1, 2-diamine;
- Reaction of ethylenediamine with 2-propanol to produce N, N, N', N'-tetraisopropylethane-1, 2-diamine;
- Reaction of propylenediamine with methanol to produce N, N, N', N'-tetramethylpropane-1, 3-diamine;
- Reaction of propylenediamine with ethanol to produce N, N, N', N'-tetraethylpropane-1, 3-diamine;
- Reaction of propylenediamine with 1-propanol to produce N, N, N', N'-tetrapropylpropane-1, 3-diamine;
- Reaction of propylenediamine with 2-propanol to produce N, N, N', N'-tetraisopropylpropane-1, 3-diamine;
- Reaction of tris (2-aminoethyl) amine with methanol to produce tris [2- (dimethylamino) ethyl] amine;
- Reaction of tris (2-aminoethyl) amine with ethanol to tris [2- (diethylamino) ethyl] amine;
- Reaction of tris (2-aminoethyl) amine with 1-propanol to produce tris [2- (di-n-propylamino) ethyl] amine;
- Reaction of tris (2-aminoethyl) amine with 2-propanol to produce tris [2- (di-iso-propylamino) ethyl] amine.
- Reaction of tris (3-aminopropyl) amine with methanol to produce tris [3- (dimethylamino) propyl] amine;
- Reaction of tris (3-aminopropyl) amine with ethanol to tris [3- (diethylamino) propyl] amine;
- Reaction of tris (3-aminopropyl) amine with 1-propanol to produce tris [3- (di-n-propylamino) propyl] amine;
- Reaction of tris (3-aminopropyl) amine with 2-propanol to produce tris [3- (di-iso-propylamino) propyl] amine.
The metal catalyst may comprise at least one metal element in elemental form and/or at least one metal oxide of at least one metal element, wherein the metal element is selected from (i) elements of group IA except hydrogen, (ii) elements of group IIA, (iii) elements of group IIIA, (iv) elements of group IVA except carbon, (v) arsenic, antimony, bismuth, tellurium, polonium and astatine, (vi) elements of groups IB, IIB, IIIB, IVB, VB, VIB, VIIB and VIIIB, (vii) lanthanides and (viii) actinides.
The metal catalyst according to present invention can be a supported or unsupported catalyst.
The support to the metal catalyst is not particularly limited. It can notably be a metal oxide chosen in the group consisting of aluminum oxide (Al
2O
3) , silicon dioxide (SiO
2) , titanium oxide (TiO
2) , zirconium dioxide (ZrO
2) , calcium oxide (CaO) , magnesium oxide (MgO) , lanthanum oxide (La
2O
3) , niobium dioxide (NbO
2) , cerium oxide (CeO
2) and mixtures thereof.
The support can also be a zeolite. Zeolites are substances having a crystalline structure and a unique ability to change ions. People skilled in the art can easily understand how to obtain those zeolites by preparation method reported, such as zeolite L is described in US 4503023 or commercial purchase, such as ZSM available from ZEOLYST.
The support of catalyst can even be Kieselguhr, clay or carbon.
For the avoidance of doubt, the different groups of elements are herein numbered in accordance with the CAS system.
Generally, metals are the elements in the periodic system which are located left to the diagonal extending from boron (atomic number 5) to astatine (atomic number 85) ) .
Metals of group IA (Li, Na, K, Rb, Cs, Fr) are also known as alkali metals and metals of group IIA (Be, Mg, Ca, Sr Ba and Ra) are generally referred to as alkaline earth metals.
The metals of group IB, IIB, IIIB, IVB, VB, VIB, VIIB and VIIIB are often referred to as transition metals. This group comprises the elements with atomic number 21 to 30 (Sc to Zn) , 39 to 48 (Y to Cd) , 72 to 80 (Hf to Hg) and 104 to 112 (Hf to Cn) .
The lanthanides encompass the metals with atomic number 57 to 71 and the actinides the metals with the atomic number 89 to 103.
Some of the elements encompassed by the description above and understood to be metals for the purpose of the present invention, are sometimes also referred to as metalloids. The term metalloid is generally designating an element which has properties between those of metals and non-metals. Typically, metalloids have a metallic appearance but are relatively brittle and have a moderate electrical conductivity. The six commonly recognized metalloids are boron, silicon, germanium, arsenic, antimony, and tellurium. Other elements also recognized as metalloids include aluminum, polonium, and astatine. On a standard periodic table all of these elements may be found in a diagonal region of the p-block, extending from boron at one end, to astatine at the other (as indicated above) .
Preferably, the metal element is selected from elements of groups IA, IIA, IIIA, IVA, IB, IIB, IIIB, IVB, VB, VIB, VIIB and VIIIB. More preferably, the metal element is selected from elements of groups IA, IIA, IIIA, IVA, IB, IIB, VIB, VIIB and VIIIB.
In some embodiments, the metal catalyst comprises two, three, or four metal elements, which are present in elemental form and/or in metal oxide form.
Metal oxide compounds comprise typically at least one oxygen atom and at least one metal atom which is chemically bound to the oxygen atom; the electronegativity of the oxygen atom is obviously higher than the electronegativity of the metal atom.
The metal oxide compound of the present invention may be a single oxide or a mixed oxide.
A single metal oxide is typically composed of one or more metal atom (s) of a same, unique metal element and one or more oxygen atom (s) .
The metal atom comprised in the single metal oxide can be notably:
- a metal of group IA, as in Li
2O, Na
2O, K
2O, Rb
2O and Cs
2O
- a metal of group IIA, as in BeO, MgO, CaO, SrO and BaO
- a metal of group IIIA, as in B
2O
3, Al
2O
3, Ga
2O
3, In
2O
3 and Tl
2O
3
- a metal of group IVA, as in SiO
2, GeO
2, SnO
2, Sn
2O
3, Sn
3O
4 and PbO
2
- arsenic as in As
2O
3, antimony as in Sb
2O
3, bismuth as in Bi
2O
3, tellurium as in TeO
2, or polonium as in PoO
2
- a metal of group IB, as in CuO, Cu
2O, AgO, Ag
2O
2, Ag
2O
3 and Ag
3O
4
- a metal of group IIB, as in ZnO, CdO and HgO
- a metal of group IIIB, as in Sc
2O
3 and Y
2O
3
- a metal of group IVB, as in TiO
2 and ZrO
2
- a metal of group VB, as in VO
2, V
2O
5, Nb
2O
5, Ta
2O
5
- a metal of group VIB, as in Cr
2O
3, MoO
3, MoO
2 and WO
3
- a metal of group VIIB, as in Tc
2O
7, ReO
2, ReO
3, Re
2O
7, MnO, Mn
2O
3, Mn
3O
4 and Mn
2O
7
- a metal of group VIIIB, as in FeO, Fe
2O
3, Fe
3O
4, CoO, Co
3O
4, NiO, PdO and RuO
2
- a lanthanide Ln, as in CeO
2 and in Ln
2O
3, or
- an actinide, as in ThO
2.
A mixed metal oxide is typically composed of one or more metal atom (s) of different metal elements and one or more oxygen atom (s) . Many metals can form mixed oxides with one or more other metals. Mixed oxide minerals appear in a great variety in nature and synthetic mixed oxides find use as components of different materials used in advanced technological applications.
Only by way of example a number of mixed oxides are described below:
- transparent conducting doped zinc oxides, such as ZnO: Al, ZnO: Cu, ZnO: Ag, ZnO: Ga, ZnO: Mg, ZnO: Cd, ZnO: In, ZnO: Sn, ZnO: Sc, ZnO: Y, ZnO: Co, ZnO: Mn, ZnO: Cr and ZnO: B
- cuprates superconductors, such as YBa
2Cu
3O
7-x, Bi
2Sr
2CuO
6, Bi
2Sr
2CaCu
2O
8, Bi
2Sr
2Ca
2Cu
3O
6, Tl
2Ba
2CuO
6, Tl
2Ba
2CaCu
2O
8, Tl
2Ba
2Ca
2Cu
3O
10, TlBa
2Ca
3Cu
4O
11, HgBa
2CuO
4, HgBa
2CaCu
2O
6 and HgBa
2Ca
2Cu
3O
8,
- ACrO
4 with A=Zn, Cd, Cu, Ca, Pb, Ba or Sr
- AWO
4 and AMoO
4 where A=Ni, Mg, Mn, Fe, Co, Zn, Cu, Ca, Sr, Ba or Pb
- ATaO
4 and ANbO
4 where A=Cr, Fe, Rh or V
- ASbO
4 where A=Al, Cr, Fe, Rh or Ga
- AVO
4 where A=Cr, Fe, Al, In, Bi, Fe or Al
- Y
1-x-yGd
xLn
yBO
3 where Ln represents a lanthanide metal, 0<x<1 and 0<y<1
- A
3NbO
7 where A=Bi, Y or a lanthanide metal
- perovskites, such as LaGaO
3, Na
1-xBi
xTiO
3 with 0<x<1,
- perovskite oxides, such as La
1-xSr
xMeO
3-δ (Me=Co or Cu) with 0<x<1,
- ion conductors, such as Bi
2V
1.9Cu
0.1O
5.35, Ge
0.9Gd
0.1O
1.95 or La
0.9Sr
0.1Ga
0.8Mg
0.2O
2.85, (ZrO
2)
0.9 (Y
2O
3)
0.1
- CuZnFe
2O
4, CoMn
2O
4, PbCrO
4
- Zr
1-xTi
xO
2, Ba
6Ti
17O
40, BaZrO
3, PbTiO
3, SrTiO
3, Ba
1-xSr
xTiO
3, PbZrO
3, PbTi
1-xZr
xO
3 where 0<x<1
- doped yttrium oxides and lanthanide oxides, namely Y
2O
3: Ln and Ln
2O
3: Ln wherein Ln is a lanthanide atom,
- titanium-tin mixed oxide Sn
1-xTi
xO
2 with 0<x<1,
- yttrium, rhodium or lanthanide niobates, tantalates and vanadates A
1-xX
xMeO
4 where A=Y, Rh or Ln, X=Bi or Ln provided A and X are different from each other, Ln represents a lanthanide atom, Me=Nb, Ta or V and 1≥x>0
- indium-gallium-zinc oxide (IGZO) of formula InGaZn
2O
5
- transparent conducting Delafossite CuFeO
2 and other related ternary compounds of Delafossite structure of general chemical formula A
xX
yO
z where A is Ag, Pd or Pt and X is Co, Cr, Sr, Ba, Al, Ga, In, Sc, Y, La, Pr, Nd, Sm or Eu, and wherein x, y and z values are depending on the oxidation states of A and X
- transparent conducting Delafossite-type quaternary compounds: CuA
2/3Sb
1/3O
2 where A=Mn, Ca, Al, AgA
2/3Sb
1/3O
2 (A=Ni, Zn) , and
- mixed oxides of indium and tin, commonly referred to as ITO, which denotes a solid solution of indium (III) oxide (In
2O
3) and tin (IV) oxide (SnO
2) , consisting essentially of or consisting of from 80 wt. %up to 95 wt. %of In
2O
3 and from 5 wt. %to 20 wt. %of SnO
2, in some cases about 90 wt. %In
2O
3 and about 10 wt. %SnO
2; in particular for organic electronic device applications, ITO has been profitably used in the recent past.
In one preferred embodiment, the metal catalyst according to the present invention can be Raney catalysts such as Raney nickel, Raney cobalt and Raney copper.
In another preferred embodiment, the metal catalyst comprises Metal element A and optionally Metal element B, which are present in elemental form and/or in metal oxide form, wherein:
- Metal element A is at least one metal element selected from elements of groups IB and VIIIB, and
- Metal element B is at least one metal element selected from the group consisting of Al, Na, Mn, Mg, Si, Zn, Ni, Cr, K, Li, Cs, Be, Ca, Sr, Ba, Sc, Y, Ti, Zr, V, Nb, W, Mo, Tc, Re, Fe, Ru, Co, Ag, Cd, Hg, Ga, Pb, Bi, Ce, and mixtures thereof.
Preferably, Metal element A is Cu or Co and Metal element B is at least one metal element selected from the group consisting of Al, Na, Mn, Mg, Si, Zn, Ni, Cr and mixtures thereof.
In this embodiment, Metal element A can be supported on a support in this embodiment. Said support can be Al
2O
3, SiO
2, TiO
2, ZrO
2, ZnO, MgO, NbO
2, CeO
2 and mixtures thereof.
The weight ratio of Metal element A based on the total weight of the catalyst is from 20 to 100 wt%.
In some embodiments, the metal catalyst may comprise Metal element A being Cu, and Metal element B being Al, Zn and Na. The weight ratio of Cu based on the total weight of the catalyst is from 35 to 55 wt%. The weight ratio of Al based on the total weight of the catalyst is from 3 to 7 wt%. The weight ratio of Zn based on the total weight of the catalyst is from10 to 30 wt%. The weight ratio of Na based on the total weight of the catalyst is from 0 to 1 wt%.
In some embodiments, the metal catalyst may comprise Metal element A being Cu, and Metal element B being Al and Mn. The weight ratio of Cu based on the total weight of the catalyst is from 40 to 65 wt%. The weight ratio of Al based on the total weight of the catalyst is from 20 to 40 wt%. The weight ratio of Mn based on the total weight of the catalyst is from 2 to 20 wt%.
In some embodiments, the metal catalyst may comprise Metal element A being Cu and Metal element B being Si. The weight ratio of Cu based on the total weight of the catalyst is from 85 to 100 wt%. The weight ratio of Si based on the total weight of the catalyst is from 0.005 to 10 wt%.
In some embodiments, the metal catalyst may comprise Metal element A being Cu, and Metal element B being Mg, Cr and Si. The weight ratio of Cu based on the total weight of the catalyst is from 60 to 90 wt%. The weight ratio of Mg based on the total weight of the catalyst is from 0 to 5 wt%. The weight ratio of Cr based on the total weight of the catalyst is from 0 to 3 wt%. The weight ratio of Si based on the total weight of the catalyst is from 0 to 10 wt%.
In some embodiments, the metal catalyst may comprise Metal element A being Cu, and Metal element B being Al and Si. The weight ratio of Cu based on the total weight of the catalyst is from 40 to 80 wt%. The weight ratio of Al based on the total weight of the catalyst is from 0 to 6 wt%. The weight ratio of Si based on the total weight of the catalyst is from 0 to 10 wt%
In some embodiments, the metal catalyst may comprise Metal element A being Cu, and Metal element B being Ni and Si. The weight ratio of Cu based on the total weight of the catalyst is from 45 to 95 wt%. The weight ratio of Ni based on the total weight of the catalyst is from 0 to 10 wt%. The weight ratio of Si based on the total weight of the catalyst is from 0 to 10 wt%.
In some embodiments, the metal catalyst may comprise Metal element A being Cu, and Metal element B being Cr and Si. The weight ratio of Cu based on the total weight of the catalyst is from 50 to 95 wt%. The weight ratio of Cr based on the total weight of the catalyst is from 0 to 40 wt%. The weight ratio of Si based on the total weight of the catalyst is from 0 to 10 wt%.
The metal catalyst according to the present invention can further comprise at least one metal sulphide compound.
Then, metal sulphide compounds comprise typically at least one sulphur atom and at least one metal atom which is chemically bound to the sulphur atom; the electronegativity of the sulphur atom is obviously higher than the electronegativity of the metal atom.
The (or at least one) metal atom comprised in the metal sulphide compound can be notably:
- a metal of group IA, as in Li
2S, Li
2CdSnS
4
- a metal of group IIA, as in BaGa
2GeS
6
- a metal of group IIIA, as in CuInS
2or Cu
2ZnSnS
4 (CZTS)
- a metal of group IVA, as in PbS or Pb
2S
3
- antimony as in Sb
2S
3, or bismuth as in Bi
2S
3
- a metal of group IB as in CuS, Cu
2S or Ag
2S
- a metal of group IIB as in ZnS, CdS or PbHgS
- a metal of group IVB, as in TiS
2
- a metal of group VB, as in NbS
2
- a metal of group VIB, as in MoS
2
- a metal of group VIIB, as in FeS
2 or Co
9S
8
- a metal of group VIIIB, as in CoN, FeN, Co
3N or Ni
3N
2, or
- a lanthanide, as in LaN or LaTaON
2.
The metal catalyst according to the present invention can further comprise at least one metal carbide compound.
Metal carbide compounds comprise typically at least one carbon atom and at least one metal atom which is chemically bound to the carbon atom; the electronegativity of the carbon atom is obviously higher than the electronegativity of the metal atom.
The (or at least one) metal atom comprised in the metal carbide compound can be notably:
- a metal of group IA, as in Na
2C
2 (sodium percarbide) and Li
4C
3 (lithium sequicarbide)
- a metal of group IIA, as in Be
2C, CaC
2 (calcium percarbide) and Mg
2C
3 (magnesium sesquicarbide)
- a metal of group IIIA, as in B
4C which is an example of a covalent carbide
- a metal of group IVA, as in SiC which is another example of a covalent carbide
- bismuth, as in BiC
- a metal of group IVB, as in TiC and HfC
- a metal of group VB, as in TaC and VC
- a metal of group VIB, as in Cr
3C
2, Mo
2C
5 and WC
- a metal of group VIIIB, as in Fe
3C, or
- a lanthanide, as in LaC
2 (lanthanum percarbide) and Ln
2C
3 (sesquicarbide, wherein Ln denotes a lanthanide) .
The metal catalyst according to the present invention can further comprise at least one metal nitride compound.
Metal nitride compounds comprise typically at least one nitrogen atom and at least one metal atom which is chemically bound to the nitrogen atom; the electronegativity of the nitrogen atom is obviously higher than the electronegativity of the metal atom.
The (or at least one) metal atom comprised in the metal nitride compound can be notably:
- a metal of group IA, as in Li
3N, or in LiMoN
2 and Li
7MnN
4 lithium transition metal nitrides
- a metal of group IIA, as in CaTaO
2N, SrTaO
2N, BaTaO
2N or BaNbO
2N
- a metal of group IIIA, as in AlN, InN or GaN
- a metal of group IVA, as in Si
3N
4 or Si
2N
2O
- a metal of group IIIB, as in ScN or YN
- a metal of group IVB, as in TiN, ZrN or HfN
- a metal of group VB, as in TaON
- a metal of group VIB, as in CrN, Cr
2N, MoN, Mo
2N, WN, W
2N
- a metal of group VIIB, as in Li
7MnN
4, TcN
- a metal of group VIIIB, as in CoN, FeN, Co
3N, Ni
3N
2, or
- a lanthanide, as in LaN or LaTaON
2.
In some embodiments, the metal nitride is an oxynitride (i.e. a compound that qualifies as metal nitride compound and as metal oxide compound) . Examples thereof are:
- tantalum oxynitride (TaON)
- perovskite oxynitrides, such as CaTaO
2N, SrTaO
2N, BaTaO
2N, LaTaON
2 and BaNbO
2N, and
- silicon oxynitride (Si
2N
2O) .
In a preferred embodiment, the metal catalyst is composed of metal element in elemental form and/or metal oxide.
The metal catalyst according to the present invention can be obtained by pre-reduction of commercial catalysts, such as T-4489 P, T-8031 P from Süd-Chemie, T-4419 P from Clariant and Pricat CU 60/35 P, Pricat CU 50/8 P, Pricat 60/8 P from Johnson Matthey. The skilled person can pre-reduce the commercial catalysts by some well-known ways.
Alternatively, the metal catalyst can be obtained by in situ-reduction. That is to say, the commercial catalysts can be in situ-reduced during the reaction of the compound having general formula (II) with the alcohol having general formula (III) in the presence of hydrogen.
The weight ratio of the metal catalyst to the compound having general formula (II) is from 0.1 to 10 and preferably from 0.2 to 2.
The weight ratio of the compound having general formula (II) to the alcohol having general formula (III) may be from 0.0001 to 0.1 and preferably from 0.001 to 0.05.
According to the method of the present invention, in a preferred embodiment, the alcohol having general formula (III) is the reactant and also the only solvent of the compound having general formula (II) . It can understood by the skilled person that the reaction may also be carried out in the presence of a second solvent other than the alcohol having general formula (III) as long as the second solvent does not participate in the reaction in place of the alcohol. Examples of such solvent are water, formaldehyde (traces) , formic acid (traces) , benzene, toluene, dimethyl ether, etc.
The concentration of the compound having general formula (II) in the solvent may be from 0.01wt%to 9wt%, preferably from 0.1wt%to 5wt%and more preferably from 0.1wt%to 2.5wt%.
Although not specifically limited, the reaction of the compound having general formula (II) with the alcohol having general formula (III) is desirably carried out under a hydrogen pressure in a range of 15-70 bar, and more preferably 20-50 bar. Optionally, hydrogen may be added during the reaction to make up for the consumption or continuously circulated through the reaction zone.
The reaction may be carried out in the presence of an inert atmosphere such as N
2 or Ar.
The reaction time may be from 4 to 24h and preferably from 10 to 20h.
The reaction temperature may be from 140℃ to 220℃ and preferably from 180℃ to 200℃.
The invention also concerns a mixture comprising:
(i) A compound having general formula (II) ,
(ii) An alcohol having general formula (III) ,
(iii) Hydrogen, and
(iv) A metal catalyst.
The mixture may further comprise a second solvent selected from the group consisting of water, formaldehyde, formic acid, benzene, toluene and dimethyl ether.
The mixture may further comprise a compound having general formula (I) .
The compound having general formula (I) , the compound having general formula (II) , the alcohol having general formula (III) , the metal catalyst and the solvent have the same meaning as above defined.
EXAMPLES
The technical features and technical effects of the present invention will be further described below in conjunction with the following examples so that the skilled in the art would fully understand the present invention. It will be readily understood by the skilled in the art that the examples herein are for illustrative purposes only and the scope of the present invention is not limited thereto.
Materials
- Cu based catalyst (T-4489 P) from Süd-Chemie
- Cu based catalyst (T-8031 P) from Süd-Chemie
- Cu based catalyst (Pricat CU 60/35 P) Johnson Matthey
- Cu based catalyst (Pricat 60/8 P) Johnson Matthey
- Cu based catalyst (T-4419 P) from Clariant
- Raney Cobalt from W.R. Grace
Table 1 ICP results
Analytical equipment information:
Perkin Elmer ICP-OES 8000
Electric balance with 0.0001g precision
IKA heating plate
1 mL transfer pipette
100 μL transfer pipette
50ml ICP tube
Software of ICP: Winlab32 for ICP Version 5.4.0.0687
Analytical conditions:
- Preparation: Weigh 50mg sample, add 3ml H
3PO
4 and 3ml H
2SO
4, heat at 280C with heating plate, until sample totally dissolved, when the solution left until 3-4 ml, dilute with DI water and add 10ppm Sc as an internal standard solution to 50ml. Then dilute 10 times to test high concentration elements.
- Reagents and Solution: Distilled de-ionized Ultra High Quality (UHQ chemical resistivity: 18MΩcm
-1) water (Millipore) , Phosphoric acid, AR grade, 85%, Sulfuric acid, AR grade, 98%ICP multi-element standard solution IV, Merck
- Instrument setting: Perkin Elemer 8000 ICP-OES was used for the determination of three elements. The operation parameters of ICP-OES were set as recommended by the manufacturer. The ICP-OES operating conditions are listed in Table 2.
Table 2 ICP operating parameters
Pre-reduction of catalysts:
Weigh Cu based catalyst in Table 1 into a glass tube with 2 outlets, one of which is then connected to a gas tube from one side, and the part containing catalyst is surrounded by a programmable heating oven.
At room temperature, a gas mixture consisting of H
2/Ar or H
2/N
2 in 1/3 to 1/10 ratio is flew through the tube from one outlet to another which is connected directly to the atmosphere.
After 10 minutes of gas flow, heat the oven with a program at a 1℃/min speed from room temperature to 200℃, and keep at 200℃ 0.5-4 hours depending on the amount ofcatalyst.
After the reduction, stop heating and let the temperature reduced to room temperature. Purge the reduced catalyst with pure nitrogen or argon for 10 minutes at room temperature, and plug the both outlets of the tube with rubber stopper immediately.
The tube is weighed with and without catalyst to get the real weight ofthe catalyst.
The catalyst is used freshly after reduction, or kept in a glove box filled with argon.
Example 1:
Pre-reduced copper containing catalyst described in Table 3 was weighed (0.13g) . Aclean autoclave was charged under nitrogen after vacuum&nitrogen exchanges for 3 times, catalyst was transferred into autoclave immediately.
Methanol (1.2 mol, 48mL) and then DETA (1.8 mmol, 0.18g) were charged into autoclave under nitrogen subsequently.
The autoclave was well sealed under nitrogen, and purged by hydrogen 10 bar and evacuated for 10 times, finally purged with 30 bar of hydrogen. The sealing ofthe reactor is checked by waiting 1 hour at room temperature without stirring, and if the pressure remains unchanged then the reactor is well-sealed. Then the reactor was stirred with mechanical stirring for 1 hour at ambient temperature to allow the absorption of the hydrogen, followed by heating up to 200℃ for 10 hours with 500 rounds/min stirring speed. The reactor was cooled down to ambient temperature and the hydrogen gas was evacuated carefully in fume hood. To the reaction mixture was added internal standard bisphenyl with accurate weight. After complete dissolving of bisphenyl, the liquid was firstly weighed and then filtered and analyzed by GC. The conversion and yields were calculated using internal standard calibration.
Table 3 Effects of different catalysts on reaction
Example 2:
Cobalt containing catalyst Raney Cobalt without reduction was weighed (catalyst/DETA wt/wt=1: 1) and washed with methanol. A clean autoclave was charged under nitrogen after vacuum&nitrogen exchanges for 3 times, catalyst was transferred into autoclave immediately.
Methanol (0.75 mol, 30mL) and then DETA (1.8 mmol, 0.18g) were charged into autoclave under nitrogen subsequently.
The autoclave was well sealed under nitrogen, and purged by hydrogen 10 bar and evacuated for 10 times, finally purged with 30 bar of hydrogen. The sealing of the reactor is checked by waiting 1 hour at room temperature without stirring, and if the pressure remains unchanged then the reactor is well-sealed. Then the reactor was stirred with mechanical stirring for 1 hour at ambient temperature to allow the absorption of the hydrogen, followed by heating up to 200℃ for 20 hours with 500 rounds/min stirring speed. The reactor was cooled down to ambient temperature and the hydrogen gas was evacuated carefully in fume hood. The liquid was firstly weighed and then filtered and analyzed by GC affording 28%yield of PMDTA.
Example 3:
Pre-reduced copper containing catalyst Pricat 60/8P was weighed (0.13g) . A clean autoclave was charged under nitrogen after vacuum&nitrogen exchanges for 3 times, catalyst was transferred into autoclave immediately.
Methanol (1.2 mol, 48mL) and then DETA (1.8 mmol, 0.18g) were charged into autoclave under nitrogen subsequently.
The autoclave was well sealed under nitrogen, and purged by hydrogen 10 bar and evacuated for 10 times, finally purged with 50 bar of hydrogen. The sealing of the reactor is checked by waiting 1 hour at room temperature without stirring, and if the pressure remains unchanged then the reactor is well-sealed. Then the reactor was stirred with mechanical stirring for 1 hour at ambient temperature to allow the absorption of the hydrogen, followed by heating up to the temperatures described in Table 4 for 10 hours with 500 rounds/min stirring speed. The reactor was cooled down to ambient temperature and the hydrogen gas was evacuated carefully in fume hood. To the reaction mixture was added internal standard bisphenyl with accurate weight. After complete dissolving of bisphenyl, the liquid was firstly weighed and then filtered and analyzed by GC. The conversion and yields were calculated using internal standard calibration.
Table 4 Influence of temperature on the reaction
Example 4:
Pre-reduced copper containing catalyst Pricat 60/8P was weighed (0.13g) . A clean autoclave was charged under nitrogen after vacuum&nitrogen exchanges for 3 times, catalyst was transferred into autoclave immediately.
Methanol (1.2 mol, 48mL) and then DETA (1.8 mmol, 0.18g) were charged into autoclave under nitrogen subsequently.
The autoclave was well sealed under nitrogen, and purged by hydrogen 10 bar and evacuated for 10 times, finally purged with hydrogen till the pressures described in Table 5. The sealing of the reactor is checked by waiting 1 hour at room temperature without stirring, and if the pressure remains unchanged then the reactor is well-sealed. Then the reactor was stirred with mechanical stirring for 1 hour at ambient temperature to allow the absorption of the hydrogen, followed by heating up to 200℃ for 10 hours with 500 rounds/min stirring speed. The reactor was cooled down to ambient temperature and the hydrogen gas was evacuated carefully in fume hood. To the reaction mixture was added internal standard bisphenyl with accurate weight. After complete dissolving of bisphenyl, the liquid was firstly weighed and then filtered and analyzed by GC. The conversion and yields were calculated using internal standard calibration.
Table 5 Influence of pressure on the reaction
Example 5:
Pre-reduced copper containing catalyst Pricat 60/8P was weighed (0.12g) . A clean autoclave was charged under nitrogen after vacuum&nitrogen exchanges for 3 times, catalyst was transferred into autoclave immediately.
Methanol (1.2 mol, 48mL) and then DETA (1.8 mmol, 0.18g) were charged into autoclave under nitrogen subsequently.
The autoclave was well sealed under nitrogen, and purged by hydrogen 10 bar and evacuated for 10 times, finally purged with 50 bar of hydrogen. The sealing of the reactor is checked by waiting 1 hour at room temperature without stirring, and if the pressure remains unchanged then the reactor is well-sealed. Then the reactor was stirred with mechanical stirring for 1 hour at ambient temperature to allow the absorption of the hydrogen, followed by heating up to 200℃ for time described in Table 6 with 500 rounds/min stirring speed. The reactor was cooled down to ambient temperature and the hydrogen gas was evacuated carefully in fume hood. To the reaction mixture was added internal standard bisphenyl with accurate weight. After complete dissolving of bisphenyl, the liquid was firstly weighed and then filtered and analyzed by GC. The conversion and yields were calculated using internal standard calibration.
Table 6 Influence of reaction time on the reaction
Example 6:
Pre-reduced copper containing catalyst Pricat 60/8P was weighed to a certain amount described in Table 7. A clean autoclave was charged under nitrogen after vacuum&nitrogen exchanges for 3 times, catalyst was transferred into autoclave immediately.
Methanol (1.2 mol, 48mL) and then DETA (1.8 mmol, 0.18g) were charged into autoclave under nitrogen subsequently.
The autoclave was well sealed under nitrogen, and purged by hydrogen 10 bar and evacuated for 10 times, finally purged with 50 bar of hydrogen. The sealing of the reactor is checked by waiting 1 hour at room temperature without stirring, and if the pressure remains unchanged then the reactor is well-sealed. Then the reactor was stirred with mechanical stirring for 1 hour at ambient temperature to allow the absorption of the hydrogen, followed by heating up to 200℃ for 10 hours with 500 rounds/min stirring speed. The reactor was cooled down to ambient temperature and the hydrogen gas was evacuated carefully in fume hood. To the reaction mixture was added internal standard bisphenyl with accurate weight. After complete dissolving of bisphenyl, the liquid was firstly weighed and then filtered and analyzed by GC. The conversion and yields were calculated using internal standard calibration.
Table 7 Influence of the amount of catalyst on the reaction
Example 7:
Pre-reduced copper containing catalyst Pricat 60/8P was weighed (0.13 g) . A clean autoclave was charged under nitrogen after vacuum&nitrogen exchanges for 3 times, catalyst was transferred into autoclave immediately.
Methanol (1.2 mol, 48mL) and then DETA with a certain quantity described in Table 8 were charged into autoclave under nitrogen subsequently.
The autoclave was well sealed under nitrogen, and purged by hydrogen 10 bar and evacuated for 10 times, finally purged with 40 bar of hydrogen. The sealing of the reactor is checked by waiting 1 hour at room temperature without stirring, and if the pressure remains unchanged then the reactor is well-sealed. Then the reactor was stirred with mechanical stirring for 1 hour at ambient temperature to allow the absorption of the hydrogen, followed by heating up to 200℃ for 20 hours with 500 rounds/min stirring speed. The reactor was cooled down to ambient temperature and the hydrogen gas was evacuated carefully in fume hood. To the reaction mixture was added internal standard bisphenyl with accurate weight. After complete dissolving of bisphenyl, the liquid was firstly weighed and then filtered and analyzed by GC. The conversion and yields were calculated using internal standard calibration.
Table 8 Influence of the concentration of DETA on the reaction
Example 8:
Pre-reduced copper containing catalyst Pricat 60/8P was weighed (0.12 g) . A clean autoclave was charged under nitrogen after vacuum&nitrogen exchanges for 3 times, catalyst was transferred into autoclave immediately.
Methanol (1.2 mol, 48mL) and then DETA (2.7 mmol, 0.28 g) were charged into autoclave under nitrogen subsequently.
The autoclave was well sealed under nitrogen, and purged by hydrogen 10 bar and evacuated for 10 times, finally purged with 50 bar of hydrogen. The sealing of the reactor is checked by waiting 1 hour at room temperature without stirring, and ifthe pressure remains unchanged then the reactor is well-sealed. Then the reactor was stirred with mechanical stirring for 1 hour at ambient temperature to allow the absorption of the hydrogen, followed by heating up to 200℃ for 10 hours with 500 rounds/min stirring speed. The reactor was cooled down to ambient temperature and the hydrogen gas was evacuated carefully in fume hood. To the reaction mixture was added internal standard bisphenyl with accurate weight. After complete dissolving of bisphenyl, the liquid was firstly weighed and then filtered and analyzed by GC. The conversion and yields were calculated using internal standard calibration. The yield of PMDTA was 68.1%.
Claims (15)
- A method for preparing a compound having general formula (I) by reacting a compound having general formula (II) with an alcohol having general formula (III) in the presence of hydrogen and a metal catalyst:
wherein:- R is an alkyl, alkenyl or alkynyl,- n is an integer between 0 and 20,- m is an integer between 1 and 3,- p is an integer between 0 and 2, and- p+m=3. - The method according to claim 1, wherein R is a C 1-C 10 straight or branched alkyl.
- The method according to claim 1 or 2, wherein the compound having general formula (II) is a compound having general formula (IV) , (V) or (VI) :
wherein n is an integer between 0 and 20. - The method according to any one of claims 1 to 3, wherein the compound having general formula (II) is selected from the group consisting of dimethylenetriamine, diethylenetriamine, dipropylenetriamine, dibutylenetriamine, dipentylenetriamine, dihexylenetriamine, diheptylenetriamine, dioctylenetriamine, dinonylenetriamine, didecylenetriamine, methylenediamine, ethylenediamine, propylenediamine, butylenediamine, pentylenediamine, hexylenediamine, heptylenediamine, octylenediamine, nonylenediamine, and decylenediamine, triaminomethylamine, tris (2-aminoethyl) amine, tris (3-aminopropyl) amine, tris (4-aminobutyl) amine, tris (5-aminopentyl) amine, tris (6-aminohexyl) amine, tris (7-aminoheptyl) amine, tris (8-aminooctyl) amine, tris (9-aminononyl) amine and tris (10-aminodecyl) amine.
- The method according to any one of claims 1 to 4, wherein the metal catalyst comprises at least one metal element in elemental form and/or at least one metal oxide of at least one metal element, wherein the metal element is selected from (i) elements of group IA except hydrogen, (ii) elements of group IIA, (iii) elements of group IIIA, (iv) elements of group IVA except carbon, (v) arsenic, antimony, bismuth, tellurium, polonium and astatine, (vi) elements of groups IB, IIB, IIIB, IVB, VB, VIB, VIIB and VIIIB, (vii) lanthanides and (viii) actinides.
- The method according to any one of claims 1 to 5, wherein the metal catalyst is Raney catalysts such as Raney nickel, Raney cobalt and Raney copper.
- The method according to any one of claims 1 to 5, wherein the metal catalyst comprises Metal element A and optionally Metal element B, which are present in elemental form and/or in metal oxide form, wherein:- Metal element A is at least one metal element selected from elements of groups IB and VIIIB, and- Metal element B is at least one metal element selected from the group consisting of Al, Na, Mn, Mg, Si, Zn, Ni, Cr, K, Li, Cs, Be, Ca, Sr, Ba, Sc, Y, Ti, Zr, V, Nb, W, Mo, Tc, Re, Fe, Ru, Co, Ag, Cd, Hg, Ga, Pb, Bi, Ce and mixtures thereof.
- The method according to claim 7, wherein:- Metal element A is Cu or Co, and- Metal element B is at least one metal element selected from the group consisting of Al, Na, Mn, Mg, Si, Zn, Ni, Cr and mixtures thereof.
- The method according to any one of claims 1 to 8, wherein the weight ratio of the metal catalyst to the compound having general formula (II) is from 0.1 to 10 and preferably from 0.2 to 2.
- The method according to any one of claims 1 to 9, wherein the weight ratio of the compound having general formula (II) to the alcohol having general formula (III) is from 0.0001 to 0.1 and preferably from 0.001 to 0.05.
- The method according to any one of claims 1 to 10, wherein the reaction is carried out in the presence of a solvent and the concentration of the compound having general formula (II) in the solvent is from 0.01wt%to 9wt%, preferably from 0.1wt%to 5wt%and more preferably from 0.1wt%to 2.5wt%.
- The method according to any one of claims 1 to 11, wherein the reaction of the compound having general formula (II) with the alcohol having general formula (III) is carried out under a hydrogen pressure in a range of 20-50bar.
- The method according to any one of claims 1 to 12, wherein the reaction time of the compound having general formula (II) with the alcohol having general formula (III) is from 10 to 20 h.
- The method according to any one of claims 1 to 13, wherein the reaction temperature is from 180℃ to 200℃.
- A mixture comprising:(i) A compound having general formula (II) ,(ii) An alcohol having general formula (III) ,(iii) Hydrogen, and(iv) A metal catalyst.
Priority Applications (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP20922861.8A EP4114820A4 (en) | 2020-03-06 | 2020-03-06 | A method for the alkylation of amines |
| PCT/CN2020/078148 WO2021174522A1 (en) | 2020-03-06 | 2020-03-06 | A method for the alkylation of amines |
| CN202080098151.9A CN115210214A (en) | 2020-03-06 | 2020-03-06 | Process for alkylating amines |
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| Application Number | Priority Date | Filing Date | Title |
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| PCT/CN2020/078148 WO2021174522A1 (en) | 2020-03-06 | 2020-03-06 | A method for the alkylation of amines |
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|---|---|
| EP (1) | EP4114820A4 (en) |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1984873A (en) * | 2004-05-13 | 2007-06-20 | 巴斯福股份公司 | Method for the continuous production of an amine |
| CN101489979A (en) * | 2006-07-14 | 2009-07-22 | 巴斯夫欧洲公司 | Method for producing an amine |
| CN107074735A (en) * | 2014-11-10 | 2017-08-18 | 罗地亚经营管理公司 | For reacting the method to form amine by direct aminatin |
-
2020
- 2020-03-06 WO PCT/CN2020/078148 patent/WO2021174522A1/en unknown
- 2020-03-06 EP EP20922861.8A patent/EP4114820A4/en active Pending
- 2020-03-06 CN CN202080098151.9A patent/CN115210214A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1984873A (en) * | 2004-05-13 | 2007-06-20 | 巴斯福股份公司 | Method for the continuous production of an amine |
| CN101489979A (en) * | 2006-07-14 | 2009-07-22 | 巴斯夫欧洲公司 | Method for producing an amine |
| CN107074735A (en) * | 2014-11-10 | 2017-08-18 | 罗地亚经营管理公司 | For reacting the method to form amine by direct aminatin |
Non-Patent Citations (3)
| Title |
|---|
| JIA-MIN HUANG，ET.AL.: "N-Alkylation of Ethylenediamine with Alcohols Catalyzed by CuO-NiO/γ-Al2O3", CHEMICAL PAPERS, vol. 66, no. 4, 31 December 2012 (2012-12-31), pages 304 - 307, XP035021878, ISSN: 0366-6352, DOI: 10.2478/s11696-012-0140-8 * |
| See also references of EP4114820A4 * |
| TETSU YAMAKAWA，ET. AL.: "Alkylation of Ethylenediamine with Alcohols by Use of Cu-based Catalysts in the Liquid Phase", CATALYSIS COMMUNICATIONS., vol. 5, no. 6, 13 April 2004 (2004-04-13), pages 291 - 295, XP055027567, ISSN: 1566-7367, DOI: 10.1016/j.catcom.2004.03.004 * |
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| EP4114820A1 (en) | 2023-01-11 |
| CN115210214A (en) | 2022-10-18 |
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