PL89819B1 - - Google Patents

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Publication number
PL89819B1
PL89819B1 PL1974170920A PL17092074A PL89819B1 PL 89819 B1 PL89819 B1 PL 89819B1 PL 1974170920 A PL1974170920 A PL 1974170920A PL 17092074 A PL17092074 A PL 17092074A PL 89819 B1 PL89819 B1 PL 89819B1
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Poland
Prior art keywords
acid
amines
pattern
phenylenediamine
epoxy
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PL1974170920A
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English (en)
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    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M133/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing nitrogen
    • C10M133/02—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing nitrogen having a carbon chain of less than 30 atoms
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    • C10M2209/00—Organic macromolecular compounds containing oxygen as ingredients in lubricant compositions
    • C10M2209/10—Macromolecular compoundss obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M2209/103—Polyethers, i.e. containing di- or higher polyoxyalkylene groups
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    • C10M2209/00—Organic macromolecular compounds containing oxygen as ingredients in lubricant compositions
    • C10M2209/10—Macromolecular compoundss obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M2209/103—Polyethers, i.e. containing di- or higher polyoxyalkylene groups
    • C10M2209/109—Polyethers, i.e. containing di- or higher polyoxyalkylene groups esterified
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    • C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant Compositions
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    • C10M2215/14—Containing carbon-to-nitrogen double bounds, e.g. guanidines, hydrazones, semicarbazones
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    • C10M2219/108—Phenothiazine
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F02—COMBUSTION ENGINES; HOT-GAS OR COMBUSTION-PRODUCT ENGINE PLANTS
    • F02B—INTERNAL-COMBUSTION PISTON ENGINES; COMBUSTION ENGINES IN GENERAL
    • F02B1/00—Engines characterised by fuel-air mixture compression
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    • F02B1/04—Engines characterised by fuel-air mixture compression with positive ignition with fuel-air mixture admission into cylinder

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Organic Chemistry (AREA)
  • Lubricants (AREA)
  • Emulsifying, Dispersing, Foam-Producing Or Wetting Agents (AREA)
  • Anti-Oxidant Or Stabilizer Compositions (AREA)

Description

Przedmiotem wynalazku jest sposób wytwarzania dodatku do olejów smarowych, zapobiegajacego powsta¬ waniu osadów, stosowanego zwlaszcza do syntetycznych olejów smarowych, a stanowiacego produkt zawierajacy azot i który to produkt rozpuszcza sie w syntetycznych srodkach smarowych, takich jak poliglikole, estry ich mieszaniny itd.Produkt otrzymany sposobem wedlug wynalazku nadaje sie zwlaszcza do olejów stosowanych w silnikach spalinowych.Wiadomo, ze zjawisko gromadzenia wody lub osadów zdarza sie najczesciej, gdy silnik pracuje alternatyw¬ nie w wysokiej i w niskiej temperaturze, zwlaszcza w czasie zimy i przy krótkich i powtarzajacych sie przebie¬ gach.Jednym z glównych problemów, zwiazanych ze stosowaniem konwencjonalnych srodków smarowych do silników samochodowych jest obecnosc w samym srodku obcych czastek (pozostalosci po spalaniu, osadów, wody, zwiazków olowiu itd). Obecnosc wody i substancji powodujacych powstawanie osadów zalezy w znacz¬ nym stopniu od temperatury pracy srodka smarowego.Glównym celem wynalazku jest wyeliminowanie powyzszych niedogodnosci przez opracowanie sposobu wytwarzania produktu, skutecznie dyspergujacego powstajace osady.Sposób wytwarzania dodatku do olejów smarowych wedlug wynalazku polega na tym, ze stosuje sie co najmniej jeden kwas dwukarboksyIowy, w którym jedna z dwóch grup kwasowych estryfikuje sie polimerem epoksydowym lub kopolimerem epoksydowym, podczas gdy druga przeprowadza sie w grupe amidowa lub amidynowa na drodze reakcji z amoniakiem, aminami alifatyczno-aromatycznymi, aminami heterocyklicznymi badz liniowymi lub cyklicznymi pollaminami.• Jako kwasy dwukarboksylowe stosuje sie kwas szczawiowy, kwas malonowy, kwas bursztynowy, kwas glutarowy, kwas adypinowy, kwas pimelinowy, kwas suberynowy, kwas azelainowy, kwasy maleinowy i fuma¬ rowy, kwas jablkowy, kwas cytrakonowy, kwas mezakonowy, kwas itakonowy, kwas mukonowy, kwas wodoromukonowy, kwas ftalowy, kwas tereftalowy itd.Jako aminy stosuje sie metyloamine, N-metyloetyloamine, N-metylooktyloamine, dwubutyloamine,2 89819 cykloheksyloamine, aniline, dwu-p-metylofenyloamine, dodecyloamine, oktadecyloamine, o-fenylonodwu- amine, N,N-dwu-n-butylo-p-fenylenodwuamine. morfoline, indol, szesciowodoro-1,3,5-triazyne, melamine, cykloheksamine, pirolidyne, etanoloamine, dwuetanoloamine itd.Korzystnie jako zwiazki, bedace zródlem grup zawierajacych azot stosuje sie poliaminy, a zwlaszcza aminy alkilenowe, takie jak trójmetylenoaminy, czterometylenoaminy, szesciometylenoaminy, heptametylenoaminy itd, oraz aminy cykliczne, a takze wyzsze homologi wymienionych amin.Jako inne zródlo grup zawierajacych azot stosuje sie moczniki, tiomoczniki, hydrazyny, guanidyny, amidyny, amidy, tioamidy i cyjanoamidy.Grupa zawierajaca azot w produkcie wytwarzanym sposobem wedlug wynalazku charakteryzuje sie tym, ze atom azotu jest polaczony bezposrednio z grupa karboksylowa zestryfikowanego kwasu dwukarboksylowego.Wiazanie takie moze byc typu amidowego, amidynowego lub typu soli.Sposobem wedlug wynalazku w wiekszosci przypadków otrzymuje sie produkt stanowiacy mieszanine zwiazków o róznych rodzajach wiazan. Wzajemne stosunki tych wiazan nie sa znane, gdyz zaleza w znacznej mierze od rodzaju grupy zawierajacej azot i od warunków reakcji, np. temperatury.Przykladowo, w reakcji grupy kwasowej z grupa zawierajaca azot zwiazany w formie aminy, w przypadku „ zastosowania niskiej temperatury, np. nizszej niz 70°C, przewazac bedzie wiazanie typu soli o wzorze 1.W temperaturze stosunkowo wyzszej, np. wyzszej niz 80°C przewazaja wiazania typu amidowego lub amkJyno-' wego o wzorach 2 lub 3. Jednak w kazdym przypadku produkt otrzymany sposobem wedlug wynalazku, niezalez¬ nie od rodzaju i stosunków ilosciowych wystepujacych w nim wiazan, wykazuje skuteczne dzialanie jako dodatek do syntetycznych olejów i spelnia zalozone cele wynalazku.Wynalazek jest blizej wyjasniony w ponizszych przykladach wykonania, ilustrujacych zarówno sposób wedlug wynalazku jak i jego ocene jako dodatku zapobiegajacego powstawaniu osadów w syntetycznych olejach smarowych, nie mozna ich zatem uwazac za ograniczenie zakresu wynalazku, poniewaz maja one tylko charakter ilustracyjny.Przyklad I. Jednoester glikolu polietylenowego o srednim ciezarze czasteczkowym 1000 poddaje sie reakcji z bezwodnikiem maleinowym w stosunku molowym 1:1, otrzymujac semiester kwasu maleinowego o liczbie wodorotlenowej wy noszacej 50 mg KOH/g. Reakcje prowadzi sie, mieszajac reagenty w ciagu 6 godzin w atmosferze azotu w temperaturze 90—100°C. Do jednego mola trójetylenoczteroaminy dodaje sie jeden mol semiestru i ogrzewa w ciagu 2 godzin w temperaturze 85-95°C, a nastepnie w ciagu 4 godzin w temperaturze 170—180°C, przepuszczajac przez mieszanine pecherzyki azotu. Po usunieciu calej wody odsacza sie produkt.Przyklad II. Jednoester glikolu polipropylenowego o srednim ciezarze czasteczkowym 2500 poddaje sie reakcji z bezwodnikiem bursztynowym w stosunku wagowym 1 :1 tak, aby otrzymac semiester kwasu bursztynowego o liczbie wodorotlenowej wynoszacej 22 mg KOH/g. Reakcje prowadzi sie, mieszajac reagenty w atmosferze azotu wciagu 8 godzin w temperaturze 120°C. Nastepnie do 1 mola semiestru dodaje sie 2 mole czteroetylenopiecioaminy i calosc ogrzewa sie wciagu 1 godziny w temperaturze 100-110°C i wciagu nastep¬ nych 6 godzin w temperaturze 170—180°C, przepuszczajac przez mieszanine pecherzyki azotu. Po usunieciu calej ilosci wody odsacza sie produkt.Przyklad III. Kopolimer poliglikolowy o stosunku tlenku etylenu do tlenku propylenu wynoszacym 9 :4, nie zeteryfikowany, o srednim ciezarze czasteczkowym 1800 poddaje sie reakcji z bezwodnikiem w stosun¬ ku wagowym 1 :2 tak, aby otrzymac semiester kwasu ftalowego o liczbie wodorotlenowej 50 mg KOH/g.Reakcje prowadzi sie, mieszajac reagenty w atmosferze azotu w ciagu 10 godzin w temperaturze 90—100°C. Do jednego mola semiestru dodaje sie 2 mole cykloheksylóaminy i ogrzewa wciagu 2 godzin w temperaturze 70—80°G i wciagu dalszych 8 godzin w temperaturze 170—190°C, przepuszczajac przez mieszanine pecherzyki azotu. Po usunieciu calej wody odsacza sie produkt.Przyklad IV. Produkt wytworzony sposobem wedlug wynalazku ocenia sie jako srodek dyspergujacy i dodatek do syntetycznych olejów smarowych zapobiegajacy powstawaniu osadów, w próbie uruchamiania i zatrzymywania na silniku Fiat 600 D. Metode te stosuje sie do oceny wlasciwosci dyspergujacych i zapobiega¬ nia powstawaniu osadów w srodkach smarowych do silników spalinowych poruszajacych sie po drogach w obrebie miast. Opiera sie ona w zasadzie na ocenie ilosci osadu powstajacego podczas prób, gromadzacego sie na filtrze odsrodkowym silnika. Próba ta polega na pracy silnika Fiat 600 D wedlug cyklu przedstawionego w tablicy I.89819 Predkosc I obr./mln 1200 ± 100 800 ±100 l 2500 ±50 4000 ±50 Woda Wlot 3& 80-85 Temperatura °C Wylot ±5 ±2 ±2 90 ±4 Olej Wylot ±2 ±2 ±2 80 ±4 Tablical Cykl próby Zuzycie paliwa kg/godz. 0,592 0.740 3,404 3,552 ,032 ,328 " Stosunek powietrza benzana *— 12/1 13/1 14/1 /1 14/1 /1 Cisnienie Kg/cm* 2-3 2-3 2-3,5 2-3,5 Czas w minutach 55 120 120 ; i Silnik zatrzymano i gwaltownie ochlodzono wode i olej'do temperatury 25°C Wyniki prób uruchamiania i zatrzymywania silnika Fiat 600 D przeprowadzonych przy uzyciu dodatku wytworzonego sposobem wedlug wynalazku podano w tablicach II i III Tablicall Próby z poliglikoJem (Lepkosc w temperaturze 100° =31,9 cSt Liczba cykli prób 9 18 27 \36 Poliglikol 12,0 24,0 36,5 56,6 Poliglikol + Anty utle¬ niacz A 12,0 ,1 26,0 34,5 Poliglikol + antyutle niacz A + 2% produktu wy¬ tworzonego w przykladzie 1 ,0 8,1 12,5 16,8 Poliglikol + antyutle niacz A + 2% produktu wy¬ tworzonego w przykladzie II 2,5 ,4 9,2 11,9 Poliglikol [ + antyutle- 1 niacz A + 1,5% produktu- f wytworzonego w przykladzie III 8,2 14,0 18,5 26,0 1 Tablica III Próby z estrem (Lepkosc w temperaturze 100°^ = 29,08 cSt) liczba Cykli prób 9 18 27 36 Ester 62,5 Osad zgromadzony w filtrze odsrodkowym (g) Ester + antyutleniacz B 45 89 Ester + antyutleniacz B+2% produktu wytworzonego w przykladzie I 9,7 16,0 23,5 27,3 Ester + antyutleniacz produktu wy¬ tworzonego w przykladzie II ,0 14,2 ,1 26,5 Ester + antyutleniacz B+1,5% produktu wytworzonego w przykladzie III 26,1 49,2 PL PL

Claims (5)

1. Zastrzezenia patentowe 1. Sposób wytwarzania dodatku do olejów smarowych, stanowiacego produkt zawierajacy azot, zna¬ mienny tym, ze w co najmniej jednym kwasie dwukarboksylowym jedna z dwóch grup kwasowych estryfikuje sie polimerem epoksydowym lub kopolimerem epoksydowym, a nastepnie druga przeprowadza sie w grupe amidowa lub amidynowa na drodze reakcji z amoniakiem, aminami alifatyczno-aromatycznymi, aminami heterocyklicznymi badz liniowymi lub cyklicznymi poliaminami.
2. Sposób wedlug zastrz. 1,znamienny tym, ze jako zwiazki epoksydowe stosuje sie tlenek etylenu, tlenek propylenu lub tlenek butylenu.
3. Sposób wedlug zastrz. 1, znamienny tym, ze jako dwukarboksylowy kwas stosuje sie kwas4 89819 szczawiowy, kwas malonowy, kwas bursztynowy, kwas glutarowy, kwas adypinowy, kwas pimelinowy, kwas suberynowy, kwas azelainowy, kwas maleinowy, kwas fumarowy, kwas jablkowy, kwas cytrakonowy, kwas mezakonowy, kwas itakonowy, kwas mukonowy, kwas wodoromukonowy, kwas ftalowy lub kwas tereftalowy.
4. Sposób wedlug zastrz. 1,znamienny tym, ze jako amine stosuje sie metyloamine, N-metyloety- loamine, N-metyloktyloamine, dwubutyloamine, cykloheksyloamine aniline, dwu-p-metylofenyloamine dode- cyloamine, oktadecyloamine, o-fenylenodwuamine, N,N-dwu-n-butylo-p-fenylenodwuamine, morfoline, indol, szesciowodoro-1,3,5-triazyne, melamine cykloheksamine, pirolidyne lub etanoloamine.
5. Sposób wedlug zastrz. 1, znamienny tym, ze jako aminy stosuj^sie trójmetylenoaminy, czterometylenoaminy, szesciometylenoaminy, siedmioetylenoaminy, cykliczne i wyzlfe homologi tych amin, moczniki, tiomoczniki, hydrazyny, guanidyny, amidyny, amidy, tioamidy lub cyjanoamidy. o II (-) tt (^C-0) HN (- Wzór 1 0 II (-C-N( ) Wzór N- II (-C -N( ) Wzór 3 Prac. Poligraf. UP PRL naklad 120+18 Cena 10 zl PL PL
PL1974170920A 1973-05-09 1974-05-08 PL89819B1 (pl)

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IT987220B (it) 1975-02-20
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