SK286712B6 - Method of preparation of N-(1-phenylethyl)- N'-phenyl-1,4- phenylenediamine - Google Patents
Method of preparation of N-(1-phenylethyl)- N'-phenyl-1,4- phenylenediamine Download PDFInfo
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- SK286712B6 SK286712B6 SK1454-2003A SK14542003A SK286712B6 SK 286712 B6 SK286712 B6 SK 286712B6 SK 14542003 A SK14542003 A SK 14542003A SK 286712 B6 SK286712 B6 SK 286712B6
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- phenylenediamine
- phenyl
- aminodiphenylamine
- condensation
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- RRUHMDSGRHUALW-UHFFFAOYSA-N 1-n-phenyl-4-n-(1-phenylethyl)benzene-1,4-diamine Chemical compound C=1C=CC=CC=1C(C)NC(C=C1)=CC=C1NC1=CC=CC=C1 RRUHMDSGRHUALW-UHFFFAOYSA-N 0.000 title claims abstract description 20
- 238000000034 method Methods 0.000 title claims description 17
- 238000002360 preparation method Methods 0.000 title claims description 7
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims abstract description 66
- 239000003054 catalyst Substances 0.000 claims abstract description 38
- 230000005494 condensation Effects 0.000 claims abstract description 33
- 238000009833 condensation Methods 0.000 claims abstract description 32
- KWOLFJPFCHCOCG-UHFFFAOYSA-N Acetophenone Chemical compound CC(=O)C1=CC=CC=C1 KWOLFJPFCHCOCG-UHFFFAOYSA-N 0.000 claims abstract description 28
- 238000006243 chemical reaction Methods 0.000 claims abstract description 27
- ATGUVEKSASEFFO-UHFFFAOYSA-N p-aminodiphenylamine Chemical compound C1=CC(N)=CC=C1NC1=CC=CC=C1 ATGUVEKSASEFFO-UHFFFAOYSA-N 0.000 claims abstract description 25
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 21
- ITNVLPFJMMARHE-UHFFFAOYSA-N n-phenyl-4-(1-phenylethylideneamino)aniline Chemical compound C=1C=CC=CC=1C(C)=NC(C=C1)=CC=C1NC1=CC=CC=C1 ITNVLPFJMMARHE-UHFFFAOYSA-N 0.000 claims abstract description 19
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 13
- 239000001257 hydrogen Substances 0.000 claims abstract description 13
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 12
- 238000005984 hydrogenation reaction Methods 0.000 claims description 18
- 239000000203 mixture Substances 0.000 claims description 16
- -1 1-phenylethylidene Chemical group 0.000 claims description 12
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 8
- 238000006482 condensation reaction Methods 0.000 claims description 8
- 229910052802 copper Inorganic materials 0.000 claims description 8
- 239000010949 copper Substances 0.000 claims description 8
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 claims description 7
- 238000004821 distillation Methods 0.000 claims description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical group O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 5
- GXDVEXJTVGRLNW-UHFFFAOYSA-N [Cr].[Cu] Chemical compound [Cr].[Cu] GXDVEXJTVGRLNW-UHFFFAOYSA-N 0.000 claims description 5
- 239000002516 radical scavenger Substances 0.000 claims description 5
- 229940044174 4-phenylenediamine Drugs 0.000 claims description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 4
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical class [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 claims description 4
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 4
- NPXOKRUENSOPAO-UHFFFAOYSA-N Raney nickel Chemical compound [Al].[Ni] NPXOKRUENSOPAO-UHFFFAOYSA-N 0.000 claims description 4
- 230000002378 acidificating effect Effects 0.000 claims description 4
- 238000009903 catalytic hydrogenation reaction Methods 0.000 claims description 4
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical class O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 4
- WDZLHEZDMLOIOQ-UHFFFAOYSA-N 4-n-phenyl-4-n-(1-phenylethyl)benzene-1,4-diamine Chemical compound C=1C=CC=CC=1C(C)N(C=1C=CC(N)=CC=1)C1=CC=CC=C1 WDZLHEZDMLOIOQ-UHFFFAOYSA-N 0.000 claims description 3
- 239000002253 acid Substances 0.000 claims description 3
- 229910000323 aluminium silicate Inorganic materials 0.000 claims description 3
- 235000012216 bentonite Nutrition 0.000 claims description 3
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 2
- 229910052804 chromium Inorganic materials 0.000 claims description 2
- 239000011651 chromium Substances 0.000 claims description 2
- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O GDVKFRBCXAPAQJ-UHFFFAOYSA-A 0.000 claims description 2
- 229910001701 hydrotalcite Inorganic materials 0.000 claims description 2
- 229960001545 hydrotalcite Drugs 0.000 claims description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 2
- 235000013980 iron oxide Nutrition 0.000 claims description 2
- VBMVTYDPPZVILR-UHFFFAOYSA-N iron(2+);oxygen(2-) Chemical class [O-2].[Fe+2] VBMVTYDPPZVILR-UHFFFAOYSA-N 0.000 claims description 2
- 229910052901 montmorillonite Inorganic materials 0.000 claims description 2
- 229910052763 palladium Inorganic materials 0.000 claims description 2
- 229910052697 platinum Inorganic materials 0.000 claims description 2
- 230000029936 alkylation Effects 0.000 claims 2
- 238000005804 alkylation reaction Methods 0.000 claims 2
- 239000005909 Kieselgur Substances 0.000 claims 1
- 238000010923 batch production Methods 0.000 claims 1
- NEFBYIFKOOEVPA-UHFFFAOYSA-K dicalcium phosphate Chemical class [Ca+2].[Ca+2].[O-]P([O-])([O-])=O NEFBYIFKOOEVPA-UHFFFAOYSA-K 0.000 claims 1
- 150000002431 hydrogen Chemical class 0.000 claims 1
- 229910044991 metal oxide Inorganic materials 0.000 claims 1
- 150000004706 metal oxides Chemical class 0.000 claims 1
- 229920001971 elastomer Polymers 0.000 abstract description 7
- 239000005060 rubber Substances 0.000 abstract description 7
- 238000006731 degradation reaction Methods 0.000 abstract description 4
- 239000000047 product Substances 0.000 description 15
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 9
- 150000004658 ketimines Chemical class 0.000 description 9
- 239000011541 reaction mixture Substances 0.000 description 9
- 150000004982 aromatic amines Chemical class 0.000 description 7
- 230000015572 biosynthetic process Effects 0.000 description 6
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 6
- 239000006227 byproduct Substances 0.000 description 5
- 238000005755 formation reaction Methods 0.000 description 5
- 239000013078 crystal Substances 0.000 description 4
- 150000002576 ketones Chemical class 0.000 description 4
- 239000000376 reactant Substances 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 3
- OUBMGJOQLXMSNT-UHFFFAOYSA-N N-isopropyl-N'-phenyl-p-phenylenediamine Chemical compound C1=CC(NC(C)C)=CC=C1NC1=CC=CC=C1 OUBMGJOQLXMSNT-UHFFFAOYSA-N 0.000 description 3
- 239000007868 Raney catalyst Substances 0.000 description 3
- 229910000564 Raney nickel Inorganic materials 0.000 description 3
- 238000004061 bleaching Methods 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 239000000706 filtrate Substances 0.000 description 3
- 150000004989 p-phenylenediamines Chemical class 0.000 description 3
- 230000001681 protective effect Effects 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 238000001953 recrystallisation Methods 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 238000010792 warming Methods 0.000 description 3
- 235000005074 zinc chloride Nutrition 0.000 description 3
- 239000011592 zinc chloride Substances 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 230000002929 anti-fatigue Effects 0.000 description 2
- 239000003963 antioxidant agent Substances 0.000 description 2
- 230000003078 antioxidant effect Effects 0.000 description 2
- 239000004927 clay Substances 0.000 description 2
- 239000007859 condensation product Substances 0.000 description 2
- 239000012043 crude product Substances 0.000 description 2
- 238000000921 elemental analysis Methods 0.000 description 2
- 239000004816 latex Substances 0.000 description 2
- 229920000126 latex Polymers 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 238000005932 reductive alkylation reaction Methods 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 239000003381 stabilizer Substances 0.000 description 2
- 238000006277 sulfonation reaction Methods 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 229920003051 synthetic elastomer Polymers 0.000 description 2
- 239000005061 synthetic rubber Substances 0.000 description 2
- PMJHHCWVYXUKFD-SNAWJCMRSA-N (E)-1,3-pentadiene Chemical compound C\C=C\C=C PMJHHCWVYXUKFD-SNAWJCMRSA-N 0.000 description 1
- XXYMSQQCBUKFHE-UHFFFAOYSA-N 4-nitro-n-phenylaniline Chemical compound C1=CC([N+](=O)[O-])=CC=C1NC1=CC=CC=C1 XXYMSQQCBUKFHE-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 239000005751 Copper oxide Substances 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 230000001476 alcoholic effect Effects 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 238000010533 azeotropic distillation Methods 0.000 description 1
- 239000000440 bentonite Substances 0.000 description 1
- 229910000278 bentonite Inorganic materials 0.000 description 1
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 229910000431 copper oxide Inorganic materials 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- RXKJFZQQPQGTFL-UHFFFAOYSA-N dihydroxyacetone Chemical compound OCC(=O)CO RXKJFZQQPQGTFL-UHFFFAOYSA-N 0.000 description 1
- 239000007884 disintegrant Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 239000002638 heterogeneous catalyst Substances 0.000 description 1
- 230000036571 hydration Effects 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 235000019691 monocalcium phosphate Nutrition 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- BHAAPTBBJKJZER-UHFFFAOYSA-N p-anisidine Chemical compound COC1=CC=C(N)C=C1 BHAAPTBBJKJZER-UHFFFAOYSA-N 0.000 description 1
- 235000010603 pastilles Nutrition 0.000 description 1
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 description 1
- PMJHHCWVYXUKFD-UHFFFAOYSA-N piperylene Natural products CC=CC=C PMJHHCWVYXUKFD-UHFFFAOYSA-N 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000005201 scrubbing Methods 0.000 description 1
- 239000013049 sediment Substances 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000004073 vulcanization Methods 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
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
- C07C209/24—Preparation of compounds containing amino groups bound to a carbon skeleton by reductive alkylation of ammonia, amines or compounds having groups reducible to amino groups, with carbonyl compounds
- C07C209/26—Preparation of compounds containing amino groups bound to a carbon skeleton by reductive alkylation of ammonia, amines or compounds having groups reducible to amino groups, with carbonyl compounds by reduction with hydrogen
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
Description
Vynález sa týka spôsobu prípravy N-(l-fenyletyl)-N'-fenyl-l,4-fenyléndiamínu najskôr kyslo katalyzovanou kondenzáciou 4-aminodifenylamínu s acetofenónom cez N-(l-fenyletylidén)-N'-fenyl-1,4-fenyléndiamin, ktorý sa následne katalytický hydrogenuje vodíkom na výsledný produkt, ktorý je použiteľný ako súčasť antidegradačných systémov gumových vulkanizátov.The present invention relates to a process for the preparation of N- (1-phenylethyl) -N'-phenyl-1,4-phenylenediamine first by acid-catalyzed condensation of 4-aminodiphenylamine with acetophenone via N- (1-phenylethylidene) -N'-phenyl-1,4- phenylenediamine, which is subsequently catalytically hydrogenated with hydrogen to give the final product, which is useful as part of an anti-degradation system of rubber vulcanizates.
Doterajší stav technikyBACKGROUND OF THE INVENTION
Medzi ekonomicky najpriaznivejší postup prípravy aralkylovaných p-fenyléndiamínov ako účinných antidegradantov pre gumové vulkanizáty patrí ich príprava z aromatických primárnych amínov a alifatických ketónov. Syntéza prebieha najskôr ako kyslo katalyzovaná kondenzácia amínu s ketónom, pričom táto rovnovážna reakcia sa obyčajne posúva v smere vzniku žiadaného produktu odstraňovaním v kondenzácii vznikajúcej vody pomocou vlastného vynášača vody, ktorým môže byť aj samotný ketón. Reakciou vzniknutý ketimín sa následne katalytický hydrogenuje vodíkom na alkylaromatický p-fenyléndiamín ako antidegradant.Among the most economically advantageous processes for the preparation of aralkylated p-phenylenediamines as effective antidegradants for rubber vulcanizates is their preparation from aromatic primary amines and aliphatic ketones. The synthesis proceeds first as the acid-catalyzed condensation of the amine with the ketone, and this equilibrium reaction is usually shifted towards the formation of the desired product by removal of the condensation of the water formed by its own water entrainer, which may also be the ketone itself. The resulting ketimine is then catalytically hydrogenated with hydrogen to an alkylaromatic p-phenylenediamine as an antidegradant.
Tak napríklad podľa SK P 278 291 podstata výroby alkylarylamínov redukčnou alkylácou aromatických amínov alifatickými ketónmi spočíva v tom, že zmes východiskového aromatického amínu a ketónu sa najskôr podrobí pôsobeniu heterogénneho katalyzátora a takto získaná reakčná zmes obsahujúca ketimín sa neskôr, aj v prítomnosti kondenzačného katalyzátora, hydrogenuje na meďnatom hydrogenačnom katalyzátore. Reakcia sa uskutočňuje bez odstraňovania reakčnej kondenzačnej vody, čo má za následok pomalší priebeh kondenzácie. Tento problém kondenzácie aromatickýh amínov s alifatickými ketónmi rieši ďalší SK P 278 068, podľa ktorého sa z východiskovej zmesi obsahujúcej aromatický amín, alifatický ketón a kyslý heterogénny katalyzátor voda odseparuje destiláciou v množstve 3 až 98 % stechiometrie a potom sa reakčná zmes hydrogenuje. Zmes postupuje do hydrogenácie bez 1 predchádzajúcej separácie ketimínu, čoho dôsledkom je zvýšený obsah vedľajších produktov po hydrogenácii.For example, according to SK P 278 291 the essence of the production of alkylarylamines by the reductive alkylation of aromatic amines with aliphatic ketones is that the mixture of the starting aromatic amine and ketone is first treated with a heterogeneous catalyst and the reaction mixture thus obtained containing ketimine is later hydrogenated. on a copper hydrogenation catalyst. The reaction is carried out without removing the reaction condensation water, resulting in a slower condensation run. This problem of condensation of aromatic amines with aliphatic ketones is solved by another method of separating from a starting mixture comprising an aromatic amine, an aliphatic ketone and an acidic heterogeneous water catalyst by distillation in an amount of 3 to 98% stoichiometry and then hydrogenating the reaction mixture. The mixture proceeds to hydrogenation without 1 prior separation of ketimine, resulting in an increased content of by-products after hydrogenation.
Ešte v širšom rozsahu kondenzáciu aromatických amínov, vrátane 4-aminodifenylamínu, s alifatickými ketónmi opisuje DE 2 901 863 A1 firmy Bayer, podľa ktorého sa ketimíny pripravujú z aromatických amínov vrátane 4-aminodifenylamínu a ketónov. Podľa SU P 183765 sa N-(l-fenyletyl)-N'-fenyl-l,4-fenyléndiamín pripravil redukčnou alkyláciou 4-aminodifenylamínu alebo C-nitrózo a 4-nitrodifenylamínu s acetofenónom za odstraňovania vody v jednom stupni za katalýzy zmesi chloridu zinočnatého a Raney niklu v prítomnosti vodíka. Katalýza chloridmi si vyžaduje nákladnú separáciu katalyzátora spojenú s vysokým obsahom solí v odpadových vodách. V predmetnom patente sa dokonca produkt separuje destiláciou pri teplote 200 - 220 °C, tlaku „4 torr“ v neuveriteľne vysokom výťažku 98 % na vstupujúci 4-aminodifenylamín. Podobne vysoké výťažky sú uvádzané vo viacerých prameňoch uvedených autorov používajúcich pri kondenzácii 4-aminodifenylamín s acetofenónom katalyzátor chlorid zinočnatý. Tak napríklad Bebich s Grinbergom publikovali v Dokladoch Akadémie Náuk ZSSR v roku 1965 161 č. 6 s. 1333-5 syntézu N-substituovaných aromatických amínov tak, že kondenzáciu 4-aminodifenylamínu s acetofenónom katalyzovali chloridom zinočnatým a toluén použili ako vynášač vody pri teplote 144 °C. Po jednej hodine reakcie sa všetka reakčná voda oddelila a potom sa oddestiloval toluén a nadbytočný acetofenón. Po ochladení mali byť vzniknuté kryštály odfiltrované (v skutočnosti vzniká, príklad 7 tejto PP, rýchlo tuhnúca tavenina kryštálov) a premyté alkoholom. Získalo sa 99 % teoretického množstva ketimínu. Je evidentné, že tento výťažok bol počítaný bez analýzy zloženia tohto surového produktu a započítané boli doň aj vedľajšie produkty a katalyzátor. Až potom bol produkt prekryštalizovaný z alkoholu a získal sa produkt s teplotou topenia 135 °C, ktorý sa hodnotil elementárnou analýzou. Výťažok prekryštalizácie však tiež nie je uvedený. Následne bol ketimín podrobený hydrogenácii bez uvedenia jeho vstupnej kvality, t. j. nie je známe, či bol hydrogenovaný surový produkt pripravený vo vysokom výťažku 99 % alebo prekryštalizovaný ketimín, ktorého zloženie sa takmer stotožnilo s teoretickým zložením. Ketimín sa hydrogenoval v prostredí alkoholu na meďnatochromitom katalyzátore pri teplote 140 °C. Po 40 minútach reakcie sa odfiltroval katalyzátor pri teplote 70 °C a produkt N-(l-fenyletyl)-N'-fenyl-1,4-fenyléndiamín sa získal v 91,5 % výťažku, s teplotou topenia 85,5 °C. Zloženie bolo hodnotené elementárnou analýzou, ktorá potvrdila zloženie blízke teoretickému, ale tiež až po prekryštalizácii. Postup je chránený aj SU pat. 156674 (1963) a 159858 (1964). Predmetný článok a patenty dokladujú dobrú katalytickú aktivitu Z11CI2 zdokumentovanú vysokým výťažkom produktu podloženú jeho zložením blízkym teoretickému, ale až po prekryštalizácii bez uvedenia jej výťažku. Dá sa predpokladať, že autori článku a uvedených patentov využili špičkovú techniku spred 40 rokov, ktorá nedovolila postrehnúť priebeh reakcií tvorby vedľajších produktov. Takisto v spomenutej práci sa okrem porovnania priebehu kondenzácie bez katalyzátora a s katalyzátorom pri jednej koncentrácii nevenovali iným vplyvom okrem dĺžky reakčného času.Even more broadly, condensation of aromatic amines, including 4-aminodiphenylamine, with aliphatic ketones is described in DE 2 901 863 A1 by Bayer, according to which ketimines are prepared from aromatic amines including 4-aminodiphenylamine and ketones. According to SU P 183765, N- (1-phenylethyl) -N'-phenyl-1,4-phenylenediamine was prepared by the reductive alkylation of 4-aminodiphenylamine or C-nitroso and 4-nitrodiphenylamine with acetophenone while removing the water in one step, catalysing the zinc chloride mixture and Raney nickel in the presence of hydrogen. Chloride catalysis requires costly catalyst separation associated with high salt content in wastewater. In the present patent, the product is even separated by distillation at a temperature of 200-220 ° C, a pressure of "4 torr" in an incredibly high yield of 98% to the incoming 4-aminodiphenylamine. Similarly high yields are reported in a number of sources by the authors using 4-aminodiphenylamine with acetophenone for the condensation of zinc chloride catalyst. For example, Bebich and Grinberg published the USSR Documents in 1965 161 no. 6 p. 1333-5 synthesis of N-substituted aromatic amines by catalyzing the condensation of 4-aminodiphenylamine with acetophenone with zinc chloride and using toluene as a water scavenger at 144 ° C. After one hour of reaction all of the reaction water was separated and then toluene and excess acetophenone were distilled off. After cooling, the crystals formed should be filtered off (in fact, Example 7 of this PP, a rapidly solidifying melt of crystals) and washed with alcohol. 99% of the theoretical amount of ketimine was obtained. Obviously, this yield was calculated without analyzing the composition of the crude product and also included by-products and catalyst. Only then was the product recrystallized from alcohol to give a product with a melting point of 135 ° C, which was evaluated by elemental analysis. However, the yield of recrystallization is also not indicated. Subsequently, the ketimine was subjected to hydrogenation without indicating its input quality, i.e. the ketidine. j. it is not known whether the hydrogenated crude product was prepared in a high yield of 99% or recrystallized ketimine, whose composition almost coincided with the theoretical composition. Ketimine was hydrogenated in an alcoholic environment on a copper-chromium catalyst at 140 ° C. After 40 minutes of reaction, the catalyst was filtered off at 70 ° C and the product N- (1-phenylethyl) -N'-phenyl-1,4-phenylenediamine was obtained in 91.5% yield, m.p. 85.5 ° C. The composition was evaluated by elemental analysis, which confirmed the composition close to theoretical but also after recrystallization. The procedure is also protected by SU pat. 156674 (1963) and 159858 (1964). The present article and patents illustrate the good catalytic activity of Z11Cl2, documented by the high yield of the product supported by its composition close to theoretical, but only after recrystallization without indicating its yield. It can be assumed that the authors of the article and the aforementioned patents used cutting-edge technology 40 years ago that did not allow to observe the reactions of by-product formation. Also in the aforementioned work, besides comparing the course of the condensation without catalyst and with the catalyst at one concentration, they did not deal with any effects other than the length of the reaction time.
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Tieto reakcie na rozdiel od hlavnej reakcie tvorby N-(l-fenyletyl)-N'-fenyl-l,4-fenyléndiamínu si vyžadujú iné entalpické nároky. Tento parameter je ako kontrolovateľný cez rýchlosť oddestilovávaného rozpúšťadla ako vynášača reakčnej vody.These reactions, unlike the major N- (1-phenylethyl) -N'-phenyl-1,4-phenylenediamine formation reaction, require other enthalpy demands. This parameter is as controllable via the rate of the distilled solvent as the reaction water scavenger.
Použitie samotného N-(l-fenyletyl)-N'-fenyl-l,4-fenyléndiamínu ako stabilizátora latexov syntetických kaučukov resp. antidegradantov gumových vulkanizátov je známe z minulosti, tak napríklad stabilizácia latexu 1,3-pentadienu je chránená japonským patentom JP 53072055 (1976), kde sú porovnávané jeho účinky stabilizácie s účinkami fosfitových stabilizátorov. Podobne sú známe antidegradačné vlastnosti N-(l-fenyletyl)-N'-fenyl-l,4-fenyléndiamínu v gumových vulkanizátoch proti ozónovému starnutiu pomocou viacerých samostatných derivátov p-fenyléndiamínu, resp. anizidínu, ZSSR pat. 156674 (1963). Lehocký P.: „Migration rates of antiozonants in vulcanizates“ Rubberchem 2001, Brussels, Belgium, Apr. 3-4 2001, naznačil aj kombináciu migrujúcich derivátov p-fenyléndiamínu typu IPPD, resp. 6PPD s podstatne pomalšie migrujúcim N-(l-fenyletyl)-N'-fenyl-l,4-fenyléndiamínom a kombinácia N-(l-fenyletyl)-N'-fenyl-l,4-fenyléndiamínu s N,N1-bis(a-metylbenzyl)-p-fenyléndiamínom je spomenutá v ZSSR pat. 156674 (1963).The use of N- (1-phenylethyl) -N'-phenyl-1,4-phenylenediamine alone as a latex stabilizer for synthetic rubbers, resp. antidegradants of rubber vulcanizates are known in the past, for example, the stabilization of 1,3-pentadiene latex is protected by Japanese patent JP 53072055 (1976), where its stabilizing effects are compared with those of phosphite stabilizers. Similarly, the anti-degradation properties of N- (1-phenylethyl) -N'-phenyl-1,4-phenylenediamine in rubber vulcanizates against ozone aging are known using several separate p-phenylenediamine derivatives, respectively. anisidine, USSR Pat. 156674 (1963). Lehocký P .: "Migration rates of antiozonants in vulcanizates" Rubberchem 2001, Brussels, Belgium, Apr. 3-4 2001, also indicated a combination of migrating p-phenylenediamine derivatives of the IPPD type, respectively. 6PPD with substantially slower migrating N- (1-phenylethyl) -N'-phenyl-1,4-phenylenediamine and a combination of N- (1-phenylethyl) -N'-phenyl-1,4-phenylenediamine with N, N 1 -bis (α-methylbenzyl) -p-phenylenediamine is mentioned in USSR Pat. 156674 (1963).
Cieľom predloženého vynálezu je spôsob prípravy, ktorý odstraňuje nevýhody spomenutých riešení.It is an object of the present invention to provide a method of preparation which overcomes the disadvantages of said solutions.
Podstata vynálezuSUMMARY OF THE INVENTION
Spomenuté nedostatky odstraňuje spôsob prípravy N-(l-fenyletyl)-N'-fenyl-l,4-fenyléndiamínu s čistotou minimálne 96,1 % hmotn. kondenzáciou acetofenónu so 4-amínodifenylamínom v prítomnosti katalyzátora za zvýšenej teploty pri súčasnom odstraňovaní reakciou vznikajúcej vody prostredníctvom jej vynášača, čím vznikne N-(l-fenyletylidén)-N'-fenyl-l,4-fenyléndiamín, ktorý sa podrobí katalytickej hydrogenácii vodíkom. Podstata predmetného spôsobu spočíva v tom, že kyslo katalyzovaná kondenzačná reakcia sa uskutočňuje do neúplnej (50 až 90 %) konverzie 4-aminodifenylamínu reakčnou rýchlosťou kontrolovanou cez rýchlosť oddestilovávania rozpúšťadla, výhodne toluénu, ktoré je vynášačom vody, z kondenzácie v rozpätí 0,8 až 3 kh'1 toluénu na 1 kg 4-aminodifenylamínu, pričom reakciou vzniknutý N-(l-fenyletylidén)-N'-fenyl-l,4-fenyléndiamín sa následne katalytický hydrogenuje vodíkom na N-(l-fenyletyl)-N'-fenyl-l,4-fenyléndiamín s požadovanou čistotou.The above disadvantages are overcome by a process for the preparation of N- (1-phenylethyl) -N'-phenyl-1,4-phenylenediamine having a purity of at least 96.1% by weight. by condensation of acetophenone with 4-aminodiphenylamine in the presence of a catalyst at elevated temperature while removing the reaction of the resulting water via its scavenger to produce N- (1-phenylethylidene) -N'-phenyl-1,4-phenylenediamine, which is subjected to catalytic hydrogenation with hydrogen. The process is characterized in that the acid-catalyzed condensation reaction is carried out to incomplete (50-90%) conversion of 4-aminodiphenylamine at a reaction rate controlled through the rate of distillation of a solvent, preferably water-borne toluene, from a condensation in the range of 0.8 to 3 kh & apos ; of toluene per kg of 4-aminodiphenylamine, whereby the resulting N- (1-phenylethylidene) -N'-phenyl-1,4-phenylenediamine is catalytically hydrogenated with hydrogen to N- (1-phenylethyl) -N'- phenyl-1,4-phenylenediamine of the desired purity.
Reakcia acetofenónu so 4-aminodifenylamínom sa uskutočňuje pri vzájomnom molovom pomere 0,8 až 10: 1 a hydrogenácia pri molovompomere vodíka kN-(l-fenyletylidén)-N'-fenyl-l,4-fenyléndiamínuje 1 až 100 : 1. Namiesto východiskových surovín je možné použiť aj ich prekurzory, t. j. organické alebo anorganické soli surovín, prípadne látky umožňujúce jednoduchou reakciou, napr. redukciou, oxidáciou, hydratácíou, dehydratáciou vznik samotných surovín a priebeh kondenzačnej reakcie acetofenónu so 4-aminodifenylamínom a/alebo následnej hydrogenačnej reakcie. Premenu prekurzorov na suroviny je možné uskutočňovať aj priamo v reakčnej zmesi súbežne s priebehom hlavnej kondenzačnej alebo hydrogenačnej reakcie.The reaction of acetophenone with 4-aminodiphenylamine is carried out at a molar ratio of 0.8 to 10: 1 and hydrogenation at a molar ratio of hydrogen to N- (1-phenylethylidene) -N'-phenyl-1,4-phenylenediamine is 1 to 100: 1. it is also possible to use their precursors, e.g. j. organic or inorganic salts of the raw materials, optionally substances allowing simple reactions, e.g. reduction, oxidation, hydration, dehydration, the formation of the raw materials themselves and the course of the condensation reaction of acetophenone with 4-aminodiphenylamine and / or the subsequent hydrogenation reaction. The conversion of the precursors to the raw materials can also be carried out directly in the reaction mixture in parallel with the course of the main condensation or hydrogenation reaction.
Ako kondenzačné katalyzátory sa použijú kyslé, heterogénne prírodné a/alebo syntetické hlinitokremičitany, prírodné a/alebo syntetické zeolity, montmorilonity, klinoptylolyty alebo bentonity, alebo z nich vyrobené produkty majúce kyslý charakter pod názvom Bieliaca hlinka, Nobelin FF, kde je bentonit aktivovaný kyselinou chlorovodíkovou, Jeltar 100, Jeltar 200, Jeltar 300 pripravené z bentonitu aktivovaného kyselinou sírovou, podobne ako sú pripravené katalyzátory typu Fulcate 22B, kyslé anorganické soli a oxidy, ako napríklad kyslé fosforečnany vápenaté a oxidy medi alebo oxidohydroxidy medi nanesené na rôznych nosičoch, prípadne zmesi oxidov kovov predstavujúcich Adkinsove katalyzátory pozostávajúce z oxidov medi, chrómu a železa v množstve 0,01 až 20 % hmotnostných vzťahované na 4-aminodifenylamín.The condensation catalysts used are acidic, heterogeneous natural and / or synthetic aluminosilicates, natural and / or synthetic zeolites, montmorillonites, clinoptylolytes or bentonites, or products made therefrom having the acidic character under the name Bleaching Clay, Nobelin FF, where bentonite is activated by hydrochloric acid , Jeltar 100, Jeltar 200, Jeltar 300 prepared from sulfuric acid-activated bentonite, similar to those prepared by Fulcate 22B catalysts, acid inorganic salts and oxides such as acid calcium phosphates and copper oxides or copper oxide hydroxohydroxides deposited on various supports or mixtures of oxides metals representing Adkins catalysts consisting of copper, chromium and iron oxides in an amount of 0.01 to 20% by weight based on 4-aminodiphenylamine.
Ako hydrogenačný katalyzátor sa použije buď meďnatochromitý Adkinsov katalyzátor a/alebo hydrogenačný katalyzátor meď na kremeline, alebo Raney nikel, alebo paládium, alebo platina nanesené na aktívnom uhlí v množstve 0,01 až 10 %, v hmotnostnom pomere 0,001 až 1 vzťahované na N-(l-fenyletylidén)-N'-fenyl-1,4-fenyléndiaminu.The hydrogenation catalyst used is either a copper-chromium Adkins catalyst and / or a copper hydrogenation catalyst on silica, or Raney nickel, or palladium, or platinum deposited on activated carbon in an amount of 0.01 to 10% in a weight ratio of 0.001 to 1 based on N- (l-phenylethylidene) -N'-phenyl-1,4-phenylenediamine.
Zistilo sa, že je výhodné, keď sa teplota kondenzácie udržuje v rozmedzí od 50 do 150 °C a teplota hydrogenácie od 80 °C do 200 °C. Reakcie sa môžu uskutočňovať od mierneho podtlaku až do tlaku 10 MPa, a to diskontinuálne, kontinuálne, prípadne polokontinuálne.It has been found to be advantageous to maintain the condensation temperature between 50 and 150 ° C and the hydrogenation temperature between 80 and 200 ° C. The reactions can be carried out from mild vacuum up to 10 MPa, discontinuously, continuously or semi-continuously.
Odstraňovanie vody sa uskutočňuje azeotropickou destiláciou (vynášaním vody) s použitím benzénu, toluénu, xylénu, cyklohexánu, n-hexánu, n-heptánu, n-oktánu a/alebo ich zmesi ako vynášacieho prostriedku.Water removal is accomplished by azeotropic distillation using water, benzene, toluene, xylene, cyclohexane, n-hexane, n-heptane, n-octane and / or mixtures thereof as the disintegrant.
Požadovanú kvalitu produktu je možné dosiahnuť spôsobom podľa vynálezu tak, že kondenzácia sa uskutočňuje do maximálne 90 %, výhodne 50 až 90 %, konverzie 4-aminodifenylamínu zabezpečujúcej minimálnu tvorbu vedľajších produktov. Tým sa zabezpečí vysoká čistota ketimínu po kryštalizácii aj s použitím recyklovaných materských lúhov z predchádzajúcej kondenzácie, čím množstvo vedľajších produktov v sušine reakčnej zmesi z kondenzácie neprekročí hodnotu 0,5 % hmotn., pričom 50 až 85 % filtrátu z kryštalizácie N-(l-fenyletylidén)-N'-fenyl-l,4-fenyléndiamínu sa použije v novej kondenzácii.The desired product quality can be achieved by the process according to the invention such that the condensation is carried out to a maximum of 90%, preferably 50 to 90%, of the conversion of 4-aminodiphenylamine ensuring minimal by-product formation. This ensures a high purity of the ketimine after crystallization, also using recycled mother liquors from the previous condensation, whereby the amount of by-products in the dry mass of the reaction mixture from the condensation does not exceed 0.5% by weight, while 50 to 85% of the N- (1- phenylethylidene) -N'-phenyl-1,4-phenylenediamine was used in the new condensation.
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Zistilo sa, že N-(l-fenyletyl)-N'-fenyl-1,4-fenyléndiamín sa dá použiť ako antidegradant s dlhodobým účinkom buď samostatne, alebo ako zložka do antidegradačných systémov na antioxidačnú, antiozonačnú a protiúnavovú ochranu gumových vulkanizátov v kombinácii s rýchlejšie migrujúcimi antidegradantmi.It has been found that N- (1-phenylethyl) -N'-phenyl-1,4-phenylenediamine can be used as a long-acting antidegradant either alone or as a component in anti-degradation systems for antioxidant, antiozonation and anti-fatigue protection of rubber vulcanizates in combination with faster migrating antidegradants.
Vynález je bližšie opísaný príkladmi jeho uskutočnenia, ktoré ho však týmto nijako neobmedzujú.The invention is described in more detail by the following non-limiting examples.
Príklady uskutočnenia vynálezuDETAILED DESCRIPTION OF THE INVENTION
Príklad 1Example 1
Do trojhrdlovej sulfonačnej banky vybavenej miešadlom, teplomerom a spätným chladičom so separátorom vodnej fázy sa nadávkovalo 120 g acetofenónu, 184 g 4-aminodifenylamínu (4-ADFA), 10 g katalyzátora pripraveného z bentonitu aktivovaného kyselinou chlorovodíkovou (Bieliaca hlinka) a 150 ml toluénu. Reakčná zmes sa vytemperovala na teplotu 125 °C, vznikajúca kondenzačná voda sa separovala pomocou destilačnej hlavy a toluén sa vracal naspäť rýchlosťou 1,21 1/h/kg 4-ADFA. Po štyroch hodinách reakcie sa odseparovalo 14 ml vody, čo predstavuje zhruba 80 % konverziu 4-aminodifenylaminu na N-(l-fenyletylidén)-N'-fenyl-l,4-fenyléndiamin. Po skončení reakcie sa katalyzátor nechal sedimentovať, reaktanty sa dekantovali a nechali ochladením vykryštalizovať. N-(l-Fenyletylidén)-N'-fenyl-l,4-fenyléndiamín sa oddelil filtráciou. Kryštály produktu sa analyzovali plynovou chromatografiou a obsahovali 99,7 % hmotn. N-(l-fenyletylidén)-N '-fenyl-1,4-fenyléndiaminu.A three-necked sulfonation flask equipped with a stirrer, thermometer and reflux condenser with an aqueous phase separator was charged with 120 g of acetophenone, 184 g of 4-aminodiphenylamine (4-ADFA), 10 g of catalyst prepared from hydrochloric acid-activated bentonite (bleaching clay) and 150 ml of toluene. The reaction mixture was allowed to warm to 125 ° C, the resulting condensation water was separated using a distillation head, and toluene was returned at a rate of 1.21 L / h / kg 4-ADFA. After four hours of reaction, 14 mL of water was separated, representing about 80% conversion of 4-aminodiphenylamine to N- (1-phenylethylidene) -N'-phenyl-1,4-phenylenediamine. After completion of the reaction, the catalyst was allowed to sediment, the reactants were decanted and crystallized by cooling. N- (1-Phenylethylidene) -N'-phenyl-1,4-phenylenediamine was collected by filtration. The product crystals were analyzed by gas chromatography and contained 99.7 wt. N- (1-phenylethylidene) -N'-phenyl-1,4-phenylenediamine.
Následne sa produkt zriedil toluénom v hmotnostnom pomere 1:1, pridalo sa 1,5 % hmotn. na násadu hydrogenačného katalyzátora Pd/C (obsahujúceho 3 % hmotn. Pd) a reakčná zmes sa hydrogenovala vodíkom pri teplote 160 °C a tlaku 5MPa. Po ukončení odberu vodíka sa odfiltroval katalyzátor, oddelilo rozpúšťadlo a tavenina produktu sa spastilkovala.Subsequently, the product was diluted with toluene in a weight ratio of 1: 1, 1.5 wt. and the reaction mixture was hydrogenated with hydrogen at 160 ° C and 5MPa. Upon completion of the hydrogen uptake, the catalyst was filtered off, the solvent was separated and the product melt was distilled.
Produkt obsahoval 96,3 % hmotn. N-(l-fenyletyl)-N'-fenyl-l,4-fenyléndiamínu.The product contained 96.3 wt. N- (l-phenylethyl) -N'-phenyl-l, 4-phenylenediamine.
Príklad 2Example 2
Do aparatúry ako v príklade 1 sa k východiskovým reaktantom a použitému kondenzačnému katalyzátoru z príkladu 1 pridalo 50 ml toluénu a 100 ml filtrátu z kondenzácie z príkladu 1 a 5g Bieliacej hlinky. Po odseparovaní 14,2 ml vody z kondezácie rýchlosťou 0,5 1/h/kg 4-ADFA sa reakčná zmes dekantovala a N-(l-fenyletylidén)-N'-fenyl-l,4-fenyléndiamín sa nechal vykryštalizovať. Obsahoval 99,8 % hmotn. účinnej látky.To the apparatus as in Example 1, 50 ml of toluene and 100 ml of the condensation filtrate of Example 1 and 5g of Bleaching earth were added to the starting reactants and the condensation catalyst of Example 1 used. After separating 14.2 ml of condensation water at a rate of 0.5 L / h / kg of 4-ADFA, the reaction mixture was decanted and N- (1-phenylethylidene) -N'-phenyl-1,4-phenylenediamine was crystallized. It contained 99.8 wt. of the active substance.
Kryštály sa rozpustili v toluéne a nasadili do hydrogenačného reaktora s prídavkom 1,0 % hmotn. hydrogenačného Adkinsovho meďnatochromitého katalyzátora s obsahom železa. Po ukončení spotreby vodíka a oddelení toluénu destiláciou produkt vo forme lámanej taveniny obsahoval 97,8 % hmotn. N-(l-fenyletyl)-N '-fenyl-1,4-fenyléndiamínu.The crystals were dissolved in toluene and charged to a hydrogenation reactor with 1.0 wt. hydrogenation of an Adkins copper-chromium catalyst containing iron. Upon completion of hydrogen uptake and removal of toluene by distillation, the fractured melt product contained 97.8 wt. N- (1-phenylethyl) -N'-phenyl-1,4-phenylenediamine.
Príklad 3Example 3
Produkt z príkladu 2 sa po rozomletí použil ako antidegradant do gumových zmesí na báze prírodného kaučuku a syntetického kaučuku a jeho ochranné účinky sa porovnávali s účinkami klasických antidegradantov na báze p-fenyléndiamínu ako N-(l,3-dimetylbutyl)-N'-fenyll,4-fenyléndiamín (6PPD) alebo N-izopropyl-N'-fenyl-1,4-fenyléndiamín (IPPD).The product of Example 2, after grinding, was used as an antidegradant into natural rubber-synthetic rubber based rubber compositions and its protective effects were compared to those of classical p-phenylenediamine-based antidegradants such as N- (1,3-dimethylbutyl) -N'-phenyll , 4-phenylenediamine (6PPD) or N-isopropyl-N'-phenyl-1,4-phenylenediamine (IPPD).
Okrem vlastného ochranného účinku N-(l-fenyletyl-N '-fenyl- 1,4-fenyléndiamínu sa významné zvýšenie ochranného účinku (antiozonačný, antioxidačný a protiúnavový) dosiahlo najmä v zmesiach s uvedenými derivátmi p-fenyléndiamínu, a to najmä po predstamutí vulkanizátov pri zvýšených teplotách, ako aj po ich vypieraní v okyslenej vode.In addition to the intrinsic protective effect of N- (1-phenylethyl-N'-phenyl-1,4-phenylenediamine), a significant increase in the protective effect (antiozonation, antioxidant and anti-fatigue) was achieved especially in mixtures with said p-phenylenediamine derivatives, especially after pre-vulcanization at elevated temperatures, as well as after scrubbing in acidified water.
Príklad 4Example 4
Do aparatúry ako v príklade 1 s objemom sulfonačnej banky 4 litre sa k východiskovému 4-aminodifenylamínu pridalo 1200 ml acetofenónu a 35,0 g meďnatochromitého katalyzátora s obsahom železa ako aj 100 ml toluénu a 500 ml filtrátu so zložením ako mal filtrát z kondenzácie z príkladu 1. Po vytemperovaní na kondenzačná teplotu sa oddestilovalo 14,8 ml vody rýchlosťou 3 Vh/kg 4-ADFA. Následne sa oddestiloval nezreagovaný acetofenón a N-(l-fenyletylidén)-N'-fenyl-l,4-fenyléndiamín sa nechal po vychladnutí na teplotu 30 °C vykryštalizovať. Obsahoval 99,5 % hmotn. N-(l-fenyletylidén)-N'-fenyl-l,4-fenyléndiamínu.To the apparatus as in Example 1 with a 4 liter sulfonation flask volume, 1200 ml of acetophenone and 35.0 g of a copper-chromium catalyst containing 100 ml of toluene and 500 ml of a filtrate having the composition of the condensation filtrate of Example 1 were added to the starting 4-aminodiphenylamine. 1. After warming to the condensation temperature, 14.8 mL of water was distilled off at a rate of 3 Vh / kg of 4-ADFA. Subsequently, unreacted acetophenone was distilled off and N- (1-phenylethylidene) -N'-phenyl-1,4-phenylenediamine was allowed to crystallize after cooling to 30 ° C. It contained 99.5 wt. N- (l-phenylethylidene) -N'-phenyl-l, 4-phenylenediamine.
Hydrogenácia sa ďalej robila v n-heptáne pri teplote 150 °C pri tlaku 3 MPa s hydrogenačným katalyzátorom Raney nikel v množstve 25 % hmotn. vzhľadom na nasadený N-(l-fenyletylidén)-N'-fenyl-l,4-fenyléndiamín. Po odseparovaní katalyzátora a n-heptánu sa získala tavenina obsahujúca 96,1 % hmotn. N-(l-fenyletyl)-N '-fenyl-1,4-fenyléndiamínu.Hydrogenation was further carried out in n-heptane at 150 ° C at 3 MPa with Raney Nickel Hydrogenation Catalyst in an amount of 25% by weight. based on N- (1-phenylethylidene) -N'-phenyl-1,4-phenylenediamine employed. After separation of the catalyst and n-heptane, a melt containing 96.1 wt. N- (1-phenylethyl) -N'-phenyl-1,4-phenylenediamine.
SK 286712 Β6SK 286712 Β6
Príklad 5Example 5
Do aparatúry ako v príklade 1 sa k východiskovým reaktantom, toluénu a použitému kondenzačnému katalyzátoru z príkladu 2, pridalo 6 g katalyzátora Jeltar 300 pripraveného z bentonitu aktivovaného kyselinou sírovou. Po vytemperovaní na pracovnú teplotu 120 °C a odseparovaní 11,5 ml vody z kondenzácie rýchlosťou 2,1 1 toluénu/h/kg 4-ADFA sa reakčná zmes dekantovala a N-(l-fenyletylidén)-N'-fenyl-l,4-fenyléndiamín nechal vykryštalizovať.To the apparatus of Example 1, 6 g of Jeltar 300 catalyst prepared from sulfuric acid activated bentonite was added to the starting reactants, toluene and the condensation catalyst used in Example 2. After warming to a working temperature of 120 ° C and separating 11.5 ml of water from the condensation at a rate of 2.1 L toluene / h / kg 4-ADFA, the reaction mixture was decanted and N- (1-phenylethylidene) -N'-phenyl-1, 4-Phenylenediamine crystallized.
Produkt kondenzácie obsahujúci 99,4 % hmota. N-(l-fenyletylidén)-N'-fenyl-1,4-fenyléndiamínu sa následne rozpustil v toluéne a zhydrogenoval na N-(l-fenyletyl)-N'-fenyl-1,4-fenyléndiamín s použitím 1,5 % hmota, katalyzátora obsahujúceho 25 % hmota, medi nanesenej na hydrotalcite. Produktom hydrogenácie a finalizácie boli pastilky obsahujúce 97,1 % hmota. N-(l-fenyletyl)-N-fenyl-1,4-fenyléndiamínu.A condensation product containing 99.4% by weight. N- (1-phenylethylidene) -N'-phenyl-1,4-phenylenediamine was subsequently dissolved in toluene and hydrogenated to N- (1-phenylethyl) -N'-phenyl-1,4-phenylenediamine using 1.5% %, a catalyst comprising 25% by weight, of copper deposited on hydrotalcite. The products of hydrogenation and finalization were pastilles containing 97.1% by weight. N- (l-phenylethyl) -N-phenyl-1,4-phenylenediamine.
Príklad 6Example 6
Do aparatúry ako v príklade 1 sa k východiskovým reaktantom, toluénu a použitému kondenzačnému katalyzátoru z príkladu 4 pridalo 8 g katalyzátora, ktorým bol prírodný práškový zeolit (Zeocem Bystré). Po vytemperovaní na pracovnú teplotu 120 °C a odseparovaní 13,0 ml vody z kondenzácie rýchlosťou 2,1 1 toluénu/h/kg 4-ADFA sa reakčná zmes dekantovala a N-(l-fenyletylidén)-N'-fenyl-l,4-fenyléndiamín nechal vykryštalizovať.To the apparatus of Example 1, to the starting reactants, toluene and the condensation catalyst of Example 4 used, 8 g of a catalyst which was a natural zeolite powder (Zeocem Bystré) was added. After warming to 120 ° C and separating 13.0 ml of water from the condensation at a rate of 2.1 L of toluene / h / kg of 4-ADFA, the reaction mixture was decanted and N- (1-phenylethylidene) -N'-phenyl-1, 4-Phenylenediamine crystallized.
Obsahoval 99,6 % hmota. N-(l-fenyletylidén)-N'-fenyl-1,4-fenyléndiamínu. Produkt kondenzácie sa následne rozpustil v toluéne a zhydrogenoval na N-(l-fenyletyl)-N'-fenyl-l,4-fenyléndiamín s použitím medi na kremeline (Cherox 4611) ako hydrogenačného katalyzátora.It contained 99.6% by weight. N- (l-phenylethylidene) -N'-phenyl-1,4-phenylenediamine. The condensation product was then dissolved in toluene and hydrogenated to N- (1-phenylethyl) -N'-phenyl-1,4-phenylenediamine using copper on silica (Cherox 4611) as the hydrogenation catalyst.
PATENTOVÉ NÁROKYPATENT CLAIMS
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| SK1454-2003A SK286712B6 (en) | 2003-11-25 | 2003-11-25 | Method of preparation of N-(1-phenylethyl)- N'-phenyl-1,4- phenylenediamine |
| PCT/SK2004/000014 WO2005051886A1 (en) | 2003-11-25 | 2004-11-25 | Method of preparation of n-(1-phenylethyl)-n'-phenyl-1,4-phenylenediamine and use thereof |
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| Application Number | Priority Date | Filing Date | Title |
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| SK1454-2003A SK286712B6 (en) | 2003-11-25 | 2003-11-25 | Method of preparation of N-(1-phenylethyl)- N'-phenyl-1,4- phenylenediamine |
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