NO346598B1 - Method for the preparation of amidines and amide manufactured by the method - Google Patents
Method for the preparation of amidines and amide manufactured by the method Download PDFInfo
- Publication number
- NO346598B1 NO346598B1 NO20201432A NO20201432A NO346598B1 NO 346598 B1 NO346598 B1 NO 346598B1 NO 20201432 A NO20201432 A NO 20201432A NO 20201432 A NO20201432 A NO 20201432A NO 346598 B1 NO346598 B1 NO 346598B1
- Authority
- NO
- Norway
- Prior art keywords
- group
- amidines
- formula
- reacting
- reacting components
- Prior art date
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- 150000001409 amidines Chemical class 0.000 title claims description 72
- 150000001408 amides Chemical class 0.000 title claims description 44
- 238000000034 method Methods 0.000 title claims description 30
- 238000002360 preparation method Methods 0.000 title claims description 19
- 239000002904 solvent Substances 0.000 claims description 29
- 238000006243 chemical reaction Methods 0.000 claims description 27
- 150000001412 amines Chemical class 0.000 claims description 24
- 125000003118 aryl group Chemical group 0.000 claims description 23
- 229910052739 hydrogen Inorganic materials 0.000 claims description 21
- 239000001257 hydrogen Substances 0.000 claims description 21
- 239000003054 catalyst Substances 0.000 claims description 20
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims description 17
- 150000004696 coordination complex Chemical class 0.000 claims description 13
- 229910052760 oxygen Inorganic materials 0.000 claims description 12
- 125000000923 (C1-C30) alkyl group Chemical group 0.000 claims description 11
- 239000004927 clay Substances 0.000 claims description 10
- 229910052717 sulfur Inorganic materials 0.000 claims description 10
- 125000005842 heteroatom Chemical group 0.000 claims description 8
- 238000000746 purification Methods 0.000 claims description 7
- 125000002947 alkylene group Chemical group 0.000 claims description 6
- 150000004985 diamines Chemical class 0.000 claims description 6
- 238000005580 one pot reaction Methods 0.000 claims description 6
- FJKROLUGYXJWQN-UHFFFAOYSA-N 4-hydroxybenzoic acid Chemical compound OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 claims description 5
- 125000000320 amidine group Chemical group 0.000 claims description 5
- 125000003277 amino group Chemical group 0.000 claims description 5
- 150000001735 carboxylic acids Chemical class 0.000 claims description 5
- 150000002148 esters Chemical class 0.000 claims description 5
- 239000007858 starting material Substances 0.000 claims description 5
- IJFXRHURBJZNAO-UHFFFAOYSA-N 3-hydroxybenzoic acid Chemical compound OC(=O)C1=CC=CC(O)=C1 IJFXRHURBJZNAO-UHFFFAOYSA-N 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 4
- 125000000732 arylene group Chemical group 0.000 claims description 4
- 125000004178 (C1-C4) alkyl group Chemical group 0.000 claims description 3
- 229910018626 Al(OH) Inorganic materials 0.000 claims description 3
- 238000001953 recrystallisation Methods 0.000 claims description 3
- LODHFNUFVRVKTH-ZHACJKMWSA-N 2-hydroxy-n'-[(e)-3-phenylprop-2-enoyl]benzohydrazide Chemical compound OC1=CC=CC=C1C(=O)NNC(=O)\C=C\C1=CC=CC=C1 LODHFNUFVRVKTH-ZHACJKMWSA-N 0.000 claims description 2
- CHZCERSEMVWNHL-UHFFFAOYSA-N 2-hydroxybenzonitrile Chemical compound OC1=CC=CC=C1C#N CHZCERSEMVWNHL-UHFFFAOYSA-N 0.000 claims description 2
- UPHOPMSGKZNELG-UHFFFAOYSA-N 2-hydroxynaphthalene-1-carboxylic acid Chemical compound C1=CC=C2C(C(=O)O)=C(O)C=CC2=C1 UPHOPMSGKZNELG-UHFFFAOYSA-N 0.000 claims description 2
- SGHBRHKBCLLVCI-UHFFFAOYSA-N 3-hydroxybenzonitrile Chemical compound OC1=CC=CC(C#N)=C1 SGHBRHKBCLLVCI-UHFFFAOYSA-N 0.000 claims description 2
- CVNOWLNNPYYEOH-UHFFFAOYSA-N 4-cyanophenol Chemical compound OC1=CC=C(C#N)C=C1 CVNOWLNNPYYEOH-UHFFFAOYSA-N 0.000 claims description 2
- 229940090248 4-hydroxybenzoic acid Drugs 0.000 claims description 2
- JCJUKCIXTRWAQY-UHFFFAOYSA-N 6-hydroxynaphthalene-1-carboxylic acid Chemical compound OC1=CC=C2C(C(=O)O)=CC=CC2=C1 JCJUKCIXTRWAQY-UHFFFAOYSA-N 0.000 claims description 2
- YGSDEFSMJLZEOE-UHFFFAOYSA-N Salicylic acid Natural products OC(=O)C1=CC=CC=C1O YGSDEFSMJLZEOE-UHFFFAOYSA-N 0.000 claims description 2
- 229910052736 halogen Inorganic materials 0.000 claims description 2
- 125000005843 halogen group Chemical group 0.000 claims description 2
- 229920000768 polyamine Polymers 0.000 claims description 2
- 229960004889 salicylic acid Drugs 0.000 claims description 2
- 230000015572 biosynthetic process Effects 0.000 description 15
- 239000000203 mixture Substances 0.000 description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 15
- -1 amidine compounds Chemical class 0.000 description 14
- OSWPMRLSEDHDFF-UHFFFAOYSA-N methyl salicylate Chemical compound COC(=O)C1=CC=CC=C1O OSWPMRLSEDHDFF-UHFFFAOYSA-N 0.000 description 14
- 238000003786 synthesis reaction Methods 0.000 description 12
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 10
- 239000003063 flame retardant Substances 0.000 description 10
- 238000004519 manufacturing process Methods 0.000 description 9
- 238000010438 heat treatment Methods 0.000 description 8
- 229920000642 polymer Polymers 0.000 description 8
- 239000011541 reaction mixture Substances 0.000 description 8
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- 229960001047 methyl salicylate Drugs 0.000 description 7
- 238000003756 stirring Methods 0.000 description 7
- 125000001424 substituent group Chemical group 0.000 description 7
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 239000011230 binding agent Substances 0.000 description 6
- 230000001965 increasing effect Effects 0.000 description 6
- 238000002844 melting Methods 0.000 description 6
- 230000008018 melting Effects 0.000 description 6
- LXCFILQKKLGQFO-UHFFFAOYSA-N methylparaben Chemical compound COC(=O)C1=CC=C(O)C=C1 LXCFILQKKLGQFO-UHFFFAOYSA-N 0.000 description 6
- 229920003226 polyurethane urea Polymers 0.000 description 6
- 229910052710 silicon Inorganic materials 0.000 description 6
- 239000010703 silicon Substances 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical group [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 5
- 229910052799 carbon Inorganic materials 0.000 description 5
- 238000002425 crystallisation Methods 0.000 description 5
- 150000002430 hydrocarbons Chemical class 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 235000019260 propionic acid Nutrition 0.000 description 5
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 5
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 4
- 239000001273 butane Substances 0.000 description 4
- 239000006185 dispersion Substances 0.000 description 4
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 4
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 4
- 229910000077 silane Inorganic materials 0.000 description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- VOPWNXZWBYDODV-UHFFFAOYSA-N Chlorodifluoromethane Chemical compound FC(F)Cl VOPWNXZWBYDODV-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 125000003545 alkoxy group Chemical group 0.000 description 3
- 229910021529 ammonia Inorganic materials 0.000 description 3
- 229920001400 block copolymer Polymers 0.000 description 3
- 230000008025 crystallization Effects 0.000 description 3
- 230000005595 deprotonation Effects 0.000 description 3
- 238000010537 deprotonation reaction Methods 0.000 description 3
- 238000003379 elimination reaction Methods 0.000 description 3
- ZHNUHDYFZUAESO-UHFFFAOYSA-N formamide Substances NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 229920000728 polyester Polymers 0.000 description 3
- 229920006395 saturated elastomer Polymers 0.000 description 3
- 229930195734 saturated hydrocarbon Natural products 0.000 description 3
- 229930195735 unsaturated hydrocarbon Natural products 0.000 description 3
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 2
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 2
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 2
- PNKUSGQVOMIXLU-UHFFFAOYSA-N Formamidine Chemical compound NC=N PNKUSGQVOMIXLU-UHFFFAOYSA-N 0.000 description 2
- 239000005642 Oleic acid Substances 0.000 description 2
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 2
- 239000006096 absorbing agent Substances 0.000 description 2
- 238000007605 air drying Methods 0.000 description 2
- 125000003368 amide group Chemical group 0.000 description 2
- RDOXTESZEPMUJZ-UHFFFAOYSA-N anisole Chemical compound COC1=CC=CC=C1 RDOXTESZEPMUJZ-UHFFFAOYSA-N 0.000 description 2
- 159000000032 aromatic acids Chemical class 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 235000014113 dietary fatty acids Nutrition 0.000 description 2
- 239000000539 dimer Substances 0.000 description 2
- 238000004299 exfoliation Methods 0.000 description 2
- 229930195729 fatty acid Natural products 0.000 description 2
- 239000000194 fatty acid Substances 0.000 description 2
- 150000004665 fatty acids Chemical class 0.000 description 2
- 150000003948 formamides Chemical class 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 230000001771 impaired effect Effects 0.000 description 2
- 230000001939 inductive effect Effects 0.000 description 2
- 239000000543 intermediate Substances 0.000 description 2
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 2
- 235000010270 methyl p-hydroxybenzoate Nutrition 0.000 description 2
- PHQOGHDTIVQXHL-UHFFFAOYSA-N n'-(3-trimethoxysilylpropyl)ethane-1,2-diamine Chemical compound CO[Si](OC)(OC)CCCNCCN PHQOGHDTIVQXHL-UHFFFAOYSA-N 0.000 description 2
- FATBGEAMYMYZAF-KTKRTIGZSA-N oleamide Chemical compound CCCCCCCC\C=C/CCCCCCCC(N)=O FATBGEAMYMYZAF-KTKRTIGZSA-N 0.000 description 2
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 238000001139 pH measurement Methods 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 description 1
- HJKLEAOXCZIMPI-UHFFFAOYSA-N 2,2-diethoxyethanamine Chemical compound CCOC(CN)OCC HJKLEAOXCZIMPI-UHFFFAOYSA-N 0.000 description 1
- MUGKPJBGLHSCED-UHFFFAOYSA-N 2-(1,4,7-triazonan-1-yl)ethanamine Chemical compound NCCN1CCNCCNCC1 MUGKPJBGLHSCED-UHFFFAOYSA-N 0.000 description 1
- GPGMFPCRRLUBRU-UHFFFAOYSA-N 2-methoxybenzoic acid;methyl 2-hydroxybenzoate Chemical compound COC(=O)C1=CC=CC=C1O.COC1=CC=CC=C1C(O)=O GPGMFPCRRLUBRU-UHFFFAOYSA-N 0.000 description 1
- WWYFPDXEIFBNKE-UHFFFAOYSA-M 4-carboxybenzyl alcohol Chemical compound OCC1=CC=C(C([O-])=O)C=C1 WWYFPDXEIFBNKE-UHFFFAOYSA-M 0.000 description 1
- QXSAKPUBHTZHKW-UHFFFAOYSA-N 4-hydroxybenzamide Chemical compound NC(=O)C1=CC=C(O)C=C1 QXSAKPUBHTZHKW-UHFFFAOYSA-N 0.000 description 1
- 125000005274 4-hydroxybenzoic acid group Chemical group 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 239000004606 Fillers/Extenders Substances 0.000 description 1
- BDAGIHXWWSANSR-UHFFFAOYSA-M Formate Chemical compound [O-]C=O BDAGIHXWWSANSR-UHFFFAOYSA-M 0.000 description 1
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- VDFCGVHHHJDPFQ-UHFFFAOYSA-N N-sulfonylmethanimidamide Chemical class N=CN=S(=O)=O VDFCGVHHHJDPFQ-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- SKZKKFZAGNVIMN-UHFFFAOYSA-N Salicilamide Chemical compound NC(=O)C1=CC=CC=C1O SKZKKFZAGNVIMN-UHFFFAOYSA-N 0.000 description 1
- 229910008051 Si-OH Inorganic materials 0.000 description 1
- 229910006358 Si—OH Inorganic materials 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 229910021502 aluminium hydroxide Inorganic materials 0.000 description 1
- VZTDIZULWFCMLS-UHFFFAOYSA-N ammonium formate Chemical compound [NH4+].[O-]C=O VZTDIZULWFCMLS-UHFFFAOYSA-N 0.000 description 1
- 230000003110 anti-inflammatory effect Effects 0.000 description 1
- 150000004982 aromatic amines Chemical class 0.000 description 1
- 238000010533 azeotropic distillation Methods 0.000 description 1
- 150000003937 benzamidines Chemical class 0.000 description 1
- 150000001558 benzoic acid derivatives Chemical class 0.000 description 1
- 239000003139 biocide Substances 0.000 description 1
- 230000001680 brushing effect Effects 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 239000008199 coating composition Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 125000005442 diisocyanate group Chemical group 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000002816 fuel additive Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 229920001002 functional polymer Polymers 0.000 description 1
- ZRALSGWEFCBTJO-UHFFFAOYSA-N guanidine group Chemical group NC(=N)N ZRALSGWEFCBTJO-UHFFFAOYSA-N 0.000 description 1
- 125000001072 heteroaryl group Chemical group 0.000 description 1
- 125000005241 heteroarylamino group Chemical group 0.000 description 1
- 238000000265 homogenisation Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 239000012442 inert solvent Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 239000004922 lacquer Substances 0.000 description 1
- 150000003951 lactams Chemical class 0.000 description 1
- 150000002596 lactones Chemical class 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- UZKWTJUDCOPSNM-UHFFFAOYSA-N methoxybenzene Substances CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 201000000980 schizophrenia Diseases 0.000 description 1
- 239000000779 smoke Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 229920001897 terpolymer Polymers 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 239000011135 tin Substances 0.000 description 1
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D207/00—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom
- C07D207/02—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D207/18—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having one double bond between ring members or between a ring member and a non-ring member
- C07D207/20—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having one double bond between ring members or between a ring member and a non-ring member with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C231/00—Preparation of carboxylic acid amides
- C07C231/10—Preparation of carboxylic acid amides from compounds not provided for in groups C07C231/02 - C07C231/08
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C235/00—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by oxygen atoms
- C07C235/42—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by oxygen atoms having carbon atoms of carboxamide groups bound to carbon atoms of six-membered aromatic rings and singly-bound oxygen atoms bound to the same carbon skeleton
- C07C235/44—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by oxygen atoms having carbon atoms of carboxamide groups bound to carbon atoms of six-membered aromatic rings and singly-bound oxygen atoms bound to the same carbon skeleton with carbon atoms of carboxamide groups and singly-bound oxygen atoms bound to carbon atoms of the same non-condensed six-membered aromatic ring
- C07C235/58—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by oxygen atoms having carbon atoms of carboxamide groups bound to carbon atoms of six-membered aromatic rings and singly-bound oxygen atoms bound to the same carbon skeleton with carbon atoms of carboxamide groups and singly-bound oxygen atoms bound to carbon atoms of the same non-condensed six-membered aromatic ring with carbon atoms of carboxamide groups and singly-bound oxygen atoms, bound in ortho-position to carbon atoms of the same non-condensed six-membered aromatic ring
- C07C235/60—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by oxygen atoms having carbon atoms of carboxamide groups bound to carbon atoms of six-membered aromatic rings and singly-bound oxygen atoms bound to the same carbon skeleton with carbon atoms of carboxamide groups and singly-bound oxygen atoms bound to carbon atoms of the same non-condensed six-membered aromatic ring with carbon atoms of carboxamide groups and singly-bound oxygen atoms, bound in ortho-position to carbon atoms of the same non-condensed six-membered aromatic ring having the nitrogen atoms of the carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms
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- C07C257/10—Compounds containing carboxyl groups, the doubly-bound oxygen atom of a carboxyl group being replaced by a doubly-bound nitrogen atom, this nitrogen atom not being further bound to an oxygen atom, e.g. imino-ethers, amidines with replacement of the other oxygen atom of the carboxyl group by nitrogen atoms, e.g. amidines
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- C08G77/22—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen
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Description
The present invention belongs to the technical field of synthesis of amidines and amides, and more particularly to one-pot manufacturing of amidines and amides. The present invention relates to a solvent free manufacturing of amidines and amides in a one-pot procedure. The products are formed in high yield and can be used in application areas such as components in paints and lacquers or as flame retardants without further purification. According to another aspect, the invention relates to an amide manufactured by said method.
Background
Amidines and amides are among others useful components in coating formulations, as additives in thermoplastics and as components in flame retardants. Solvents and/or metal complex catalysts are frequently used in order to ensure safe and reliable manufacturing processes. CN 110078642 A discloses an application of chlorodifluoromethane as a C1 source for synthesis of amidine compounds. Chlorodifluoromethane can be subjected to quadrupole bond cracking under a mild condition, and valuable amidine compounds can be obtained. Water and a solvent are added in the presence of chlorodifluoromethane. The amidine compounds can be obtained by one-step.
WO 17105449 A1 describes methods of synthesis of amidines, amidine-metal complexes, thin metal films formed using amidine-metal complexes on semiconductor devices, and semiconductor devices and systems with thin metal films formed using amidine-metal complexes. The synthesis comprises solvents.
US 9988482 BB and EP 3131992 B1 disclose a catalyst containing at least one amidine or guanidine group, which is bound to a siloxane residue. At room temperature, the catalyst is liquid, odourless and suitable as a cross-linking catalyst for curable compositions, in particular for silane group-containing compositions. It is particularly good at accelerating the hardening of such compositions without impairing stability in storage, and displays little volatility but good compatibility. Lanthanum(lll)-trifiuoromethanesulfonate is used as metal complex catalyst in the synthesis of the catalyst containing an amidine group.
KR 790000508 B1 discloses a process for the manufacture of N, N'-disubstituted amidines with anti-inflammatory activity. An imino-compound is reacted with amines in organic solvent.
WO 2004/087124 discloses amidine compounds for treating schizophrenia. Manufacturing of such amidine compounds is feasible by condensation of amine with substituted formamide in a solvent.
EP 2264012 A1 discloses heteroarylamidines and their use in micro-organisms control. A process for the preparation of the heteroarylamidines comprises the conversion of a heteroarylamine with either aminoacetal, amide or amine/orthoformate in solvent.
DE 1267467 discloses the preparation of cyclic amidines by a condensation reaction of dicarboxylic acid semi-amide with diamine in hydrocarbon solvent. The cyclic amidines are useful as fuel additives and biocides.
DE 2036181 discloses a method for the preparation of benzamidines wherein benziminochlorides are reacted with aromatic amines in an inert solvent.
DE 2256755 A1 discloses a method for preparation of amidines by reacting silylated amides or lactams with ammonia or amines. Mercury, tin, zinc and titanium chloride are used as catalyst and toluene, xylene, chlorobenzene and anisole as solvent.
EP 0617054 B1 discloses amine functional polymers which are vinyl based terpolymers made up of randomly linked units with formamidine or formamidinium formate, formamide and either amine or ammonium formate as functional groups. The polymers are prepared by aqueous hydrolysis of poly(N-vinylformamide) at a temperature in the range of 90 °C to 175 °C, preferably in the presence of a minor amount of ammonia or volatile amine.
EP0919555A1 a process for preparing a bicyclic amidine by reacting a lactone and a diamine. Water formed during the elimination reaction is distilled from the reaction mixture together with a considerable excess of diamine, which acts as non-reacting solvent.
US 7247749 discloses the synthesis of an amidine catalyst by conversion of fluorinated nitrile with ammonia at high pressure.
WO0078725 A1 provides a process for preparing amidines starting from carboxylic acid derivatives, in which the carboxylic acid containing moiety is attached to a sp<3>-, or sp<2>- or sphybridized carbon atom. The sp<2>-hybridized carbon atom, to which the carboxylic acid containing moiety is attached to may be part of an aromatic or heteroaromatic or olefinic system. The process comprises use of solvent and purification of intermediates.
EP2260078 B1, WO 2006045713, EP 1740643 B1, EP 1756202 B1, EP 1943293 B1 and EP 3341339 B1 disclose methods for preparing polymers comprising siloxane. The methods comprise conversion of amine bound to hydrolysed siloxane with carboxylic acid derivates. Considerable amounts of solvent are used for lowering viscosity and removal of water or alcohol from elimination reactions. EP 1943293 B1 claims a hybrid polymer which is suitable as UV absorber. The disclosed data for the preparation of the UV-absorber shows that the product is a mixture of solvent, hybrid polymer with claimed amide structure and hybrid polymer with claimed amidine structure.
For sake of completeness, the following publications should also be referenced:
NO 20190822 A;
Ostrowska K: N-Alkyl-, N-Aryl-, and N-hetaryl-substituted amidines (imidamides), Science of Synthesis (2005), 22, 379-488;
Chandna N et al: Metal- and solvent-free synthesis of N-sulfonylformamidines, journal is The Royal Society of Chemistry 2013, Green Chemistry;
US 20170081348 A1;
Zhang Feng et al: Metal- and solvent-free synthesis of amides using substitute formamides as an amino source under mild conditions, Scientific Reports, published online 26. February 2019.
None of the prior art discloses methods for the preparation of amidines without using solvents and/or metal complex catalysts. Amidine products manufactured by these methods require frequently purification from solvents and catalyst residue. Stripping and recrystallization may be applied. Apart from its negative environmental impact such purification is time consuming and costly. Hence, the useful industrial application of such amidine products is frequently impaired. There is a need for methods for manufacturing of amidines without using solvents and/or metal complex catalysts.
Objects
It is therefore an object of the present invention to provide a method for preparation of amidines, in which neither the use of solvent nor the use of metal complex catalyst is mandatory.
It is a further object to provide a method for conversion of amidines to amides. It is still a further object to provide amidines and amides, which essentially are free of solvent residues and metal complex catalyst residues without a need of post-reactor purification.
The present invention
The above mentioned objects are achieved by a method as defined in claim 1.
According to another aspect, the present invention concerns an amide as defined by claim 6.
Preferred embodiments of the different aspects of the invention are disclosed by the dependent claims.
The preparation of amidines by conversion of two moles of amine and one mole carboxylic acid derivative is known. Since a C=N double bond and a C-N single bond have to be formed, at least one of the moles of amine has to be primary. The other may be either primary or secondary. Suitable amines, which later on may be called first reacting components, may be selected among the group of amines in formula 1.
Formula 1: Suitable amines for amidine synthesis
R1, R2 and R4 are selected independently from each other from C1-C30 alkyl, C5-C30 aryl, C6-C30 alkylated aryl. Branched, linear, saturated and unsaturated hydrocarbon chains Cn may be applied since these differences do not influence the preparation of amidines in a significant way. C-C and C-H bonds may optionally be interrupted by one or more heteroatoms selected from the group consisting of O, S and NH.
R1, R2 and R4 may optionally be bound to one or more silicon-based substituent of formula 2.
Formula 2: Silicon based substituent
R5-R7 are chosen among C1-C8 alkoxy, C1-C30 alkyl, C5-C30 aryl and C6-C30 alkylated aryl, X1 is O, R3 is H, C1-C30 alkyl, C5-C30 aryl, C6-C30 alkylated aryl and two of R1, R2 and R4 may be covalently be bound to each other and form ring structures.
Suitable carboxylic acid derivatives, which later on may be called second reacting components, may be selected among the group in formula 3.
Formula 3: Suitable carboxylic acid derivatives for amidine synthesis
X1, X2 and X3 are independently from one another selected from a group consisting of O, S and NH. R1 is chosen from C1-C30 alkyl, C5-C30 aryl, C6-C30 alkylated aryl, wherein branched, linear, saturated and unsaturated hydrocarbon chains Cn may be applied. C-C and C-H bonds may optionally be interrupted by one or more heteroatoms chosen among the group of O, S and NH. R5 is chosen among C1-C8 alkoxy, C1-C30 alkyl, C5-C30 aryl and C6-C30 alkylated aryl.
The prepared amidines are shown in formula 4 (a) and (b).
Formula 4a and b: Structures of prepared amidines
R1, R2 and R4 are independently from each other C1-C30 alkyl, C5-C30 aryl, C6-C30 alkylated aryl wherein branched, linear, saturated and unsaturated hydrocarbon chains Cn may be applied. C-C and C-H bonds may optionally be interrupted by one or more heteroatoms chosen among the group of O, S and NH.
At least one carboxylic acid derivative has to be soluble in at least one of the amines or vice versa and together with all optionally remaining amines and carboxylic acid derivatives form a solution at a temperature where the amount of formed amidines is negligible. The preparation is a fast and convenient a one-pot reaction process. Studies in a stainless steel vessel equipped with stirrer, distillation cooler and warmed by inductive heating showed that the elimination reaction progress measured by received distillate can be easily controlled by tuning the power transfer into the inductive heating unit. Neither the use of solvent nor the use of metal complex catalyst is necessary.
It is well known that carboxylic acid derivatives which are C3 and higher esters can be prepared by conversion of carboxylic acids with C3 and higher alcohols and azeotropic distillation of formed water. Carboxylic acid derivatives, which are C3 and higher esters, have usually lower melting points than the corresponding carboxylic acids. Carboxylic acid derivatives which are C3 and higher esters may therefore be more suitable for the amidine synthesis according to the present invention than the corresponding carboxylic acids.
In a first embodiment at least one of the first reacting components or at least one of the second reacting components preferably has a dynamic viscosity of less than 20 mPa*s at 150 °C, more preferred of less than 20 mPa*s at 100 °C and most preferred of less than 20 mPa*s at 50 °C. Lower viscosity at a given temperature facilitates the homogenisation of the reaction mixture and thus increases the progress of the reaction and shortens the batch time of the one pot reaction process.
In a second embodiment the temperature at which the solution of all reaction components is formed is preferably less than 180 °C, more preferred less than 120 °C and most preferred of less than 60 °C. Similar to the first embodiment a lower temperature at which the solution of all reaction components is formed increases the progress of the reaction and shortens the batch time of the one pot reaction process.
In a third embodiment clay is added to the reacting components at an amount of up to 70% w/w, more preferred up to 10% w/w and most preferred about 1% w/w of the total mass of starting material. The addition of clay to the first and second reacting components provided surprisingly transparent products, especially when 2- or 4-hydroxybenzoic esters have been used as second reacting component. The high transparency of the obtained amidines indicates an excellent dispersion of the clay in the amidine matrix and possibly exfoliation of the layered structure in the clay.
In a forth embodiment at least one of the amines which serve as first reacting components is covalently bound to an at least partially hydrolysable silane. At least one R2 and R4 are bound to one or more silicon-based substituent of formula 2.
Formula 2: Silicon based substituent
R5-R7 are chosen among C1-C8 alkoxy, C1-C30 alkyl, C5-C30 aryl and C6-C30 alkylated aryl, X1 is O. Silicon based substituents introduced by amines as first reacting compounds provide the possibility to crosslink the obtained amidine by state-of-the-art hydrolysis Si-OR groups and condensation of the formed Si-OH groups. Silicon based substituents facilitate the chemical bond to inorganic minerals such as fillers, pigments and other HO-functionalized materials, too.
In a fifth embodiment, at least one of the first reacting components comprises at least two amine groups, which are covalently bound to each other. The respective diamine, triamine, oligoamine or polyamine may arise from covalent bonding of at least two of R1, R2 or R4 and are at least partly described by formula 6.
Formula 5: First reacting components comprising at least two amine groups
L is a linkage group selected among the group of C2-C30 alkylene, C2-C30 alkylene comprising one or more double bonds or one or more triple bonds, C7-C30 aryl-substituted alkylene, C5-C30 arylene, C6-C30 alkylated arylene and optionally interrupted by heteroatoms chosen among the group of O, S and NH and optionally substituted by halogen.
L may also be the linkage group of formula 6.
Formula 6: Linkage group in first reacting components comprising at least two amine groups
R<1>-R<4 >are independently from each other selected among the group of H, C1-C4 alkyl, SiO(OH) and Al(OH)2. C1-C4 alkyl refers to non-hydrolysed siloxane, H refers to hydrolysed but not condensed siloxane, , SiO(OH) refers to hydrolysed and condensed siloxane, Al(OH)2 refers to hydrolysed and condensed siloxane in the presence of aluminium oxide or hydroxide matter.
In a sixth embodiment the carboxylic acid derivatives selected as second reacting components are selected from a group consisting of 2-hydroxybenzoic acid, 3-hydroxybenzoic acid, 4-hydroxybenzoic acid, 2-hydroxynaphtoic acid, 3-hydroxynaphtoic acid, 4-hydroxynaphtoic acid, 6-hydroxynaphtoic acid and esters or amides thereof, 2-hydroxybenzonitrile, 3-hydroxybenzonitrile, 4-hydroxybenzonitrile, 2-hydroxynaphtonitrile, 3- hydroxynaphtonitrile, 4-hydroxynaphtonitrile and 6-hydroxynaphtonitrile. Hydroxy-substituted aromatic acids as second reacting components provide a number of interesting properties of the prepared amidines: low oxygen diffusion materials, fire retardant materials, materials comprising clay with excellent dispersion and possibly exfoliation, water soluble or dispersible materials by using at least partial deprotonation of the hydroxyl aromatic group. Several of these properties are connected to the formation of intermolecular hydrogen bonds beyond the formation of hydrogen bonds between amidine groups.
In a seventh embodiment the conversion of first reacting components and second reacting components is about quantitative without addition of facilitating components selected from the group of solvents and metal complex catalysts. First reacting components comprising at least two amine groups have shown to provide a fast and about quantitative reaction with second reacting components, especially with hydroxy-substituted aromatic acids. Siloxane moieties are also instrumental in providing fast and about quantitative reaction. Similarly, the addition of clay provides a fast and about quantitative reaction. In contrast to metal complex catalysts clay is frequently accepted and sometimes appreciated if its dispersion in the amidine product is excellent.
In an eighth embodiment the solvent free prepared amidine is converted with at least another reacting component selected among the group of carboxylic acids in order to obtain two amides per amidine group. An example starting from amidine formation is shown below.
Conversion of methyl salicylate with ethylene diamine to a salicylamidine. Water and methanol are distilled off.
Conversion of the salicylamidine with propionic acid to an intermediate
The final diamide as product of the conversion of the salicylamidine with propionic acid
Another example in which amidine synthesized from siloxane functionalised monoamine and hydroxybenzoic acid is converted with fatty acid is shown below.
Conversion of amidine with fatty acid
Amidine or amide as manufactured according to the present invention may in bulk form intermolecular hydrogen bonds. The influence of hydrogen bonds on crystallisation behaviour is known from block copolymers such as polyurethaneurea (PUU) block copolymers. PUU block copolymers are made up of soft segments based on polyether or polyester and hard segments based on the reaction of diisocyanate and diamine extender. They can be divided into polyetherand polyester-based PUU depending on the soft segments used. Polyester-based PUU have stronger hydrogen bonds between hard and soft segments for phase mixing than polyetherbased PUU. The hydrogen bonds cause an increased cohesion between the hard and soft segments with increasing hard segment contents, and higher hard-soft segment mixing present in these systems may also prevent the crystallization of the soft segments (Hydrogen bonding and crystallization behaviour: Xiu Yuying et al. POLYMER, 1992, Volume 33, Number 6).
Intermolecular hydrogen bonds between amidines or amides may have a major influence on the crystallisation behaviour of these amidines or amides. The amorphous parts in amidines or amides will increase. Amorphous domains in the solidified amidines or amides are likely to withhold solvent residues and metal complex catalysts. As a result, a post-reactor purification by recrystallization or stripping might be impaired. It is therefore a considerable advantage of the present invention to provide a safe and convenient high yield method for the preparation of solvent free and metal complex catalyst free amidines and amides.
It is expected that the influence of hydrogen bonds increases with increasing molecular weight of the amidine or amide. In a ninth embodiment the molecular weight of the amidine or amide is preferably at least 1000 g/mole, more preferred at least 1500 g/mole and most preferred at least 2000 g/mole.
Most application areas of polymeric amidines and amides require processing as neat materials or in mixtures. Useful molecular weight for such processing is frequently below 500000 g/mole. In a tenth embodiment the molecular weight of the amidine is preferably less than 200000 g/mole, more preferred less than 100000 g/mole and most preferred less than 50000 g/mole.
An eleventh embodiment are amidines represented by the dimer in formula 7a or the polymer in formula 7b.
Formula 7: Amidines according to the present invention
The number n is an integer of 8-200 and R<1>-R<5 >is H or OH. The amidines are made from substituted or non-substituted benzoic acid derivatives as second reaction components and tetraethylene tetraamine and polyvinylamine as first reacting components.
A twelfth embodiment are amides represented by the dimer in formula 8a or the polymer in formula 8b.
Formula 8: Amides according to the present invention
The number n is an integer of 8-200, R<1>-R<5 >is H or OH, R<6 >is C1-C30 alkyl, C5-C30 aryl, C6-C30 alkylated aryl and optionally interrupted by heteroatoms chosen among the group of O, S and NH. A strong advantage of the present invention is to provide amides with two different substituents on the amide group. By choosing R<3 >as OH, which is easy deprotonable, and R<6 >as linolenic which is air drying a water soluble or dispersible air-drying binder of excellent weathering stability would be obtained.
Yet another embodiment is the use of amidines according to the present invention as flame retardants. The amidines have a considerable content of nitrogen and a low content of oxygen, which both are important properties of flame retardants. Even more important is the low content of combustible solvent in the amidines. For many applications of flame retardant materials, a single burning item test (SBI) according to EN 13823 is mandatory. Fire retardant building products are not allowed to be sold without a passed SBI. A critical parameter of the SBI is the initial fire growth rate (FIGRA) which must not exceed 120 W/s after 0.2 MJ and after 0.4 MJ of total heat release (THR). Typical solvents used in binder manufacturing give an energy release of 27-43 MJ/kg. A hydrocarbon with a boiling point of 170 °C at 1013 mbar can frequently only with considerable efforts be removed from a binder, which is used in a flame retardant coating. Amounts of 5% w/w in the binder are not rare. In the SBI of for example a wallboard about 1 m<2 >of the board is exposed to a butane flame of 40 kW. A frequently used amount of binder in this type of SBI is 300 g/m<2>. This means 15 g of solvent or 0.6 MJ of total heat release. The butane flame is about 1000 °C and an evaporation and combustion of the solvent within a few tenths of seconds is very likely. This would easily lead to a FIGRA > 120 W/s between 0.2 MJ and 0.6 MJ heat release. As a consequence, the SBI test would be failed, even if all other parameters such as THR after 600 seconds and smoke generation are well within the limit.
It is a significant advantage of the present invention that solvent free flame retardant binders can be obtained.
Examples to support the patent claims
Example 1:
Preparation of salicylamidine from methyl salicylate and ethylene diamine. Water and methanol are distilled off. Salicylamidine has strong intramolecular hydrogen bonds between the phenolic HO-group and the amidine group. The molecular structure is about plane and easily crystallizing due to the intramolecular hydrogen bonds.
2 moles of diethylene amine (is introduced in a 1000 ml 3-necked reaction flask and mixed with 2 moles of methyl salicylate. A clear solution is obtained at room temperature. The mixture is heated to 180 °C under stirring and about 100 g of distillate is collected. A clear slightly yellow and product is obtained. Melting range is 200 °C – 205 °C.
Example 2:
Preparation of N-(2-N’-propylamidoethyl)-salicylic amide from salicylamidine and propionic acid. N-(2-N’-propylamidoethyl)-salicylic amide has strong intermolecular hydrogen bonds between the phenolic HO-group and the amide groups.
2 moles of freshly prepared salicylamidine are at around 150 °C and prior to its crystallization mixed with 2 moles of propionic acid. After initial turbidity, a clear, slightly yellow product is obtained after heating to 190 °C under stirring. No distillate of propionic acid (boiling point 141 °C) is collected. Melting range is 85 °C – 88 °C. N-(2-N’-propylamidoethyl)-salicylic amide is not easily crystallizing due to the intermolecular hydrogen bonds. However, wires of 100-500 µm diameter and several tenths of centimetre can be easily drawn. This is a strong indication for the presence of intermolecular hydrogen bonds.
Example 3:
The reactions in example 1 and example 2 have been characterized by measurement of pH values. 0.1 moles of each mixture of starting materials and each product have been dispersed or dissolved in 100 ml of water by high shear mixing. The obtained dispersions or solutions have been directly measured with a calibrated pH electrode. Table 1 shows the measured pH values and an explanation for the measured pH values on the base of the expected chemical structures of starting materials and products.
Table 1: pH values and explanation
pH measurement clearly indicates an about quantitative conversion from amine to amidine and finally to amide.
Example 4:
Preparation amidines from an amine, which is covalently bound to hydrolysable silane and 4-hydroxybenzoic acid methyl ester
2 moles of 3-aminopropyltriethoxysilane are introduced in a 1000 ml 3-necked reaction flask and heated to 80 °C under stirring.1 mole of 4-hydroxymethylbenzoate is added as powder within 5-10 minutes. Heating is increased and the reaction mixture becomes clear at 120 °C. The reaction mixture is slowly heated to 180 °C and about 50 g of distillate is collected. A clear colourless and slightly viscous amidine is obtained.
After cooling to 60 °C 3 moles of H2O are added under vigorous stirring within 10-20 minutes. A clear product with reduced viscosity is obtained.
0.5 mole oleic acid are added and the mixture with initial turbidity becomes clear upon heating to 180 °C. A polymeric amide is formed with alternating groups of 4-hydroxybenzoic amid and oleic amide on a propylene-siloxane core.
The product is insoluble in water. However, after deprotonation of 40 mole percentage of the hydroxyl groups with NaOH a homogenous easy flowing mixture with water is obtained. The pH value of the mixture is 10.0. The dry content of the mixture measured as loss on dry at 120 °C is 60% w/w.
Example 5:
Preparation amidines from an amine, which is covalently bound to hydrolysable silane and methyl salicylate
1 mole of N-(2-Aminoethyl)-3-aminopropyl-trimethoxysilane is introduced in a 1000 ml 3-necked reaction flask and heated to 80 °C under stirring.1 mole of methyl salicylate is added within 5-10 minutes. Heating is increased and the reaction mixture becomes clear at 120 °C. The reaction mixture is slowly heated to 180 °C and about 50 g of distillate is collected. A clear colourless and slightly viscous amidine is obtained.
After cooling to 60 °C 3 moles of H2O are added under vigorous stirring within 10-20 minutes. A clear product with reduced viscosity is obtained.
0.5 mole oleic acid are added and the mixture with initial turbidity becomes clear upon heating to 180 °C. A polymeric amide is formed with alternating groups of 2-hydroxybenzoic amid and oleic amide on a propylene-siloxane core.
The product is insoluble in water. However, after deprotonation of 40 mole% of the hydroxyl groups with NaOH a homogenous easy flowing mixture with water is obtained. The pH value of the mixture is 9.6. The dry content of the mixture measured as loss on dry at 120 °C is 58% w/w.
Example 6
Burning test of cardboard
Packaging type cardboard (ca.300 g/m<2>) has been coated with amidines obtained in Example 4 and 5 (Amidine Ex4, Ex5) and the corresponding amides (Amide Ex4, Ex5) and subjected to flame testing. The cardboard samples are about 8 cm in width and 20 cm in length. They are coated by brushing two times on the front side, which is exposed to the flame and one time on the backside. Drying has been performed for 10 min in an air stream at 80°C.
Flame: butane lighter with about 20 mm flame, top of flame in contact with cardboard sample for 60 seconds.
Table 2: Weight of burning test samples before and after fire test
A clear difference between the uncoated reference and the amidine coated samples has been found. The amidine-coated samples were self-extinguishing within 5 seconds after removal of the butane flame and showed a maximum flame height of 5 cm. The amidine-coated samples are suitable as flame retardant coatings. The amide-coated samples do not show a significant flame retardancy compared to the uncoated cardboard.
Example 7
Preparation of amidines from an amine, which is covalently bound to hydrolysable silane and methyl salicylate in the presence of clay
1 mole of N-(2-Aminoethyl)-3-aminopropyl-trimethoxysilane is introduced in a 1000 ml 3-necked reaction flask and heated to 80 °C under stirring.10 g of clay (montmorillonite K-10, Aldrich) is added. Thereafter 1 mole of methyl salicylate is added within 5-10 minutes. Heating is increased and the reaction mixture becomes clear at 120 °C. The reaction mixture is slowly heated to 180 °C and about 50 g of distillate is collected. A transparent and slightly viscous amidine is obtained.
Example 8
Preparation of amidines and amides with methyl 4-hydroxybenzoate as carboxylic acid derivative
Two amidines and two amides thereof have been prepared similar to the procedures in example 1 and example 2. Starting materials, melting range and observations are shown in table 3.
Table 3:
The use of methyl 4-hydroxybenzoate provides products in which intramolecular hydrogen bonds are not possible. This is in contrast to the use of methyl 2-hydroxybenzoate (methyl salicylate) in example 1 where intramolecular hydrogen bonds dominate in the product. The absence of intramolecular hydrogen bonds leads in this case to the stronger presence of intermolecular hydrogen bonds. The melting behaviour and feasibility of drawing wires from molten product can be explained by the presence of intermolecular hydrogen bonds.
The extreme temperature stability of example 8c in combination with a melting range comparable to thermoplastic resins reflects the presence of intramolecular hydrogen bonds, too.
Claims (7)
1. Method for the preparation of amidines of formula (4a) or formula (4b)
where R1, R2 and R4 independently from each other are selected from a group consisting of C1-C30 alkyl, C5-C30 aryl, C6-C30 alkylated aryl and optionally interrupted by heteroatoms selected from the group consisting of O, S and NH,R3 is H, C1-C30 alkyl, C5-C30 aryl, C6-C30 alkylated aryl where two of R1, R2 and R4 may be covalently be bound to each other and form ring structures, where neither the use of solvent nor the use of metal complex catalyst is mandatory, characterized in that said amidines are prepared in a one-pot reaction process from one or more first reacting components consisting of amines of formula (1)
and one or more second reacting components consisting of carboxylic acid derivatives of formula (3)
wherein X1, X2 and X3 are independently from one another selected from a group comprising O, S and NH,
wherein at least one of the second reacting components is soluble in at least one of the first reacting components or vice versa and together with all remaining first and second reacting components form a solution at a temperature where the amount of formed amidines is negligible,
wherein the molar ratio of reacting amine groups in the first reacting components to reacting carboxylic acid derivative groups in the second reacting components is typically 2:1,
wherein said amidines are converted with at least another reacting component selected among the group of carboxylic acids, thereby obtaining two amides per amidine group.
2. The method according to claim 1, characterized in that clay is added to the reacting components at an amount of up to 70% w/w, more preferred up to 10% w/w and most preferred about 1% w/w of the total mass of starting material.
3. The method according to any one of the previous claims, characterized in that at least two amines in formula (IV) are covalently bound to each other via at least two of R1, R2 or R4 and that the respective diamine, triamine, oligoamine or polyamine at least partly is described by formula (6):
wherein L is selected among the group of C2-C30 alkylene, C2-C30 alkylene comprising one or more double bonds or one or more triple bonds, C7-C30 arylsubstituted alkylene, C5-C30 arylene, C6-C30 alkylated arylene and optionally interrupted by heteroatoms chosen among the group of O, S and NH and optionally substituted by halogen or wherein L is selected to be formula (7)
wherein R<1>-R<4 >independently from each other are selected among the group of H, C1-C4 alkyl, SiO(OH) and Al(OH)2.
4. The method according to any one of the previous claims, characterized in that the carboxylic acid derivatives selected as second reacting components are selected from a group consisting of 2-hydroxybenzoic acid, 3-hydroxybenzoic acid, 4-hydroxybenzoic acid, 2-hydroxynaphtoic acid, 3-hydroxynaphtoic acid, 4-hydroxynaphtoic acid, 6-hydroxynaphtoic acid and esters or amides thereof, 2-hydroxybenzonitrile, 3-hydroxybenzonitrile, 4-hydroxybenzonitrile,
2-hydroxynaphtonitrile, 3- hydroxynaphtonitrile, 4-hydroxynaphtonitrile and
6-hydroxynaphtonitrile.
5. The method according to any one of the previous claims, characterized in that the conversion of first reacting components and second reacting components is about quantitative without addition of facilitating components selected from the group of solvents and metal complex catalysts.
6. Amide as manufactured according to the method of any of claims 1-5, wherein the amide molecules in bulk form intermolecular hydrogen bonds, thereby impairing a post-reactor purification by recrystallization or stripping and wherein the molecular weight of the amidine or amide is preferably at least 1000 g/mole, more preferred at least 1500 g/mole and most preferred at least 2000 g/mole.
7. Amide according to claim 10-12, characterized in that it is represented by formula (9a) or (9b)
wherein n is an integer of 8-200, R<1>-R<5 >is H or OH, R<6 >is C1-C30 alkyl, C5-C30 aryl, C6-C30 alkylated aryl and optionally interrupted by heteroatoms chosen among the group of O, S and NH.
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NO20201432A NO346598B1 (en) | 2020-12-23 | 2020-12-23 | Method for the preparation of amidines and amide manufactured by the method |
EP21852073.2A EP4267552A1 (en) | 2020-12-23 | 2021-12-23 | Amides and solvent free method for their manufacture |
PCT/NO2021/050281 WO2022139593A1 (en) | 2020-12-23 | 2021-12-23 | Amidines and solvent free method for their manufacture |
PCT/NO2021/050282 WO2022139594A1 (en) | 2020-12-23 | 2021-12-23 | Amides and solvent free method for their manufacture |
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