SU1736343A3 - Смазочный состав - Google Patents

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Publication number
SU1736343A3
SU1736343A3 SU4614702A SU4614702A SU1736343A3 SU 1736343 A3 SU1736343 A3 SU 1736343A3 SU 4614702 A SU4614702 A SU 4614702A SU 4614702 A SU4614702 A SU 4614702A SU 1736343 A3 SU1736343 A3 SU 1736343A3
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USSR - Soviet Union
Prior art keywords
tert
oil
general formula
compound
phenyl
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SU4614702A
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English (en)
Inventor
Шумахер Рольф
Ивэнс Замуэл
Дубс Паул
Original Assignee
Циба-Гейги Аг (Фирма)
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Abstract

Изобретение касаетс  смазочных составов , которые стабилизированы против окислительного разрушени . Цель- повышение антиокислительной стабильности. Смазочный состав содержит базовое масло, ароматический амин (Б) формулы RiRaNH, где RI - фенил, С4 - Cs-алкилфенил, нафтил; R2 - фенил, С4 - Са-алкилфенил, или диалкилза- мещенный фентиазин, где алкил - С4 - Се, и пространственно затрудненный амин (В) формулы (CH3)2 - СН2 - C(RsRe) - СН2С(СНз)2, где RS - Н или вместе с Re обозначает О; Re - Ci - Cs-алкиламино, Ci - С12-алкокси, Ci - С4-алкокси-С1 - С4-алкила- мино или остаток формулы R7NC(CH3)2CH2(A)CH2C(CH3)2, где А - ОСО(СН2)пСОО-, п 2 - 8, или -NH(CH2)NH,- m 5,6, R - Н, Ci - С4-алкил. Содержание смеси Б и В составл ет 0,25 - 0,75 мас.% m в расчете на базовое масло при массовом соотношении Б/В, равном 3 - 19:1. Врем  индукций при окислении увеличиваетс  в 1,5-2 раза, прирост в зкости уменьшаетс  в 5 раз. 6 табл. сл с

Description

Изобретение относитс  к составам смазочных материалов, которые стабилизированы против окислительного разрушени .
Известно и общеприн то к смазочным материалам на основе минеральных масел или синтетических масел добавл ть присадки дл  улучшени  их эксплуатационных свойств. Особое значение имеют добавки против окислительного разрушени  смазочных материалов, так называемых антиокси- дантов. Окислительное разрушение смазочных материалов, так называемых ан- тиоксидантов. Окислительное разрушение смазочных материалов играет большую роль прежде всего в случае моторных масел, так как в камере сгорани  моторов господствуют высокие температуры и нар ду с кислородом имеютс  оксиды азота (NOx), которые действуют как катализаторы окислени 
В качестве антиоксидантов дл  смазочных материалов примен ют амин, алкили- рованные фенотиазины 1.
Известно также применение ароматических аминов в комбинации с другими антиоксидантами, как, например, с триарил- фосфитами, тиодипропионатами или феноль- ными антиоксидантами 2.
Известен также смазочный состав на основе базового масла, содержащий в качестве антиокислительной присадки диарила- мины, замещенные алкилами 3.
VI GJ О
К
00
со
Однако известные присадки не обеспечивают достаточно высокие антиокислительные свойства.
Целью изобретени   вл етс  повышение антиокислительной стабильности.
Поставленна  цель достигаетс  тем, что смазочный состав, содержащий базовое масло и ароматический амин (Б), в качестве последнего содержит соединение общей формулы...
Л
- -vr-- -
- /IiRТ
кГ ъ
rp,eRi-фенил, С4-Св-алкилфенил, наф- тил;
R2 - фенил, С4 - Св-алкилфенил, или соединение общей формулы где Нз и R4 - независимо друг от друга С4 - Ce-алкил, и состав дополнительно содержит пространственно затрудненный амин (В) общей фор- %ДК5
У
Vifh mi,
° Щ
где RS - водород или вместе с Re обозначает О,
Рб-Ст-Сб-алкиламино, С1 С12-алкок- си,
Ci - С4-алкокси-С1 - С4-алкиламино или остаток общей формулы flu
A-Q- 
СН3 СН5
гдеА--ОСО(СН2)пСОО-, J
п 2 - 8,
или-МН(СН2)тМН-,
т 5,6;
R - водород, Ci - С4-алкил, и содержание смеси Б и В составл ет 0,25 - 0,75 мас.% в расчете на базовое масло при массовом соотношении компонентов Б/В, равном 3 - 19:1.
Примерами ароматического амина  вл ютс  следующие соединени : дифениламин, N-аллилдифениламин, 4-изопропоксидифе- ниламин, 1М-фенил-1-нафтиламин, М-фенил-2- нафтиламин, ди-4-метоксифениламин, (1,3-диметилбутил)-фенил амин, (1,1,3,3-тетраметилбутил)-фенил амин, трет- октилированный Ы-фенил-1-нафтиламин, технические смеси, полученные путем взаи0
5
0
0
5
о
5
0
5
модействи  дифениламина с диизобутиле- ном (моно-,ди- и триалкилированные трет- бутил- и трет-октилдифениламины), фенотиазин, N-аллилфенотиазин, 3,7-ди- трет-октил-фенотиазин, технические смеси, полученные путем взаимодействи  феноти- азина с диизобутиленом.
Особенно предпочтительно в качестве компоненты Бпримен ть4,4-ди-трет-октилди- фениламин или 3,7-ди-трет-октилфенотиазин, ил и техническую смесь, полученную путем взаимодействи  дифениламина с диизобутиленом , в особенности такую смесь, котора  содержит максимально 5 мас.% дифениламина , 8-15 мас.% 4-трет-бутилдифениламина, 24 - 32 мас.% 4-трет-октилдифениламина, 4,4 -ди-трет-бутилдифениламина и 2,4,4- три-трет-бутилдифениламина,23-34мас.% 4-трет-€утил -тоет)1аУ1лдифениламина, 2,2- и 3,3- ди-трет-октилдифениламина и 2,4-ди-трет-бутил-4, - трет-октилдифениламина, 21-34 мас.% 4,4-ди-третчжтилдифениламина и 2,4-ди-трет-ок- тил-4 -трет-бутилдифениламина.
Количество добавки (Б) и (В) к базовому маслу (А) выбираетс  в зависимости от рода базового масла и от желательной степени стабилизации. В общем, сумма Б и В составл ет 0,25 - 0,75 мас.% в расчете на А. Соотношение Б и Вможет измен тьс  в широких пределах, в общем, Б в количественном отношении - преобладающа  компонента. Предпочтительно соотношение составл ет Б/В 3-5:1.
В качестве базового масла может быть использовано минеральное или синтетическое масло, которое обычно используетс  дл  приготовлени  смазочных материалов.
Смазочный материал дополнительно может содержать присадки, как, например, другие антиоксиданты, пассиваторы металлов , ингибиторы ржавчины, улучшающие индекс в зкости вещества, снижающие температуру застывани  вещества, диспергато- ры, поверхностно-активные вещества или противоизносные присадки.,
Отдельные добавки раствор ютс  в -L масле. Дл  ускорени  процесса растворе- ни  масло подогревают или раствор ют предварительно добавки в растворителе.
Пример1.С помощью дифференциально-сканирующего калориметра (термоанализатор 1090 фирмы Дюпон) измер ют врем  индукции окислени  проб масла воздухом , который содержит 400 ррт N02, в изометрических услови х. Измерение осуществл ют при 170°С под давлением 8 бар. В качестве базового масла примен ют стандартное минеральное масло (Aral 136), к которому добавл ют 1 об.% 1-децена дл  повышени  чувствительности к кислороду. К
маслу добавл ют следующие аминные стабилизаторы .
Ароматические амины:
А-1 -техническа  смесь, полученна  путем реакции дифениламина с диизобути- леном, содержаща  3 мас.% дифениламина, 14 мас.% 4-трет-бутилди- фениламина, 30 мас.% 4-трет-октилдифе- ниламина, 4,4-ди-трет-бутилдифениламина и 2,4,4 -три-трет-бутилдифениламина, 29 мас,% 4-трет-бутил-4 -трет-октилдифениламина, 2,2- и 3,3 -ди-трет-октилдифениламина и 2,4-ди- трет-бутил-4 -трет-октилдиф ениламина, 18 мас.% 4,4 -ди-трет-октилдифениламина, 6 мае.% 2,4-ди-трет-октил-4 -трет-бутилдифе- ниламина;
- 3,7-ди-(трет-октил)-фенотиазин.
Пространственно затрудненные амины:
Н-1-ди-(2,2,6,6-тетраметилпиперидин- 4-ил)-себацинат;
Н-2 - 2,2,6,6-тетраметил-4-пиперидон;
Н-3 - ди-(2,2,6,6-тетраметилпиперидин- 4-ил)-сукцинат;
Н-4 - ди-(1,2,2,6,6-пентаметилпипери- дин-4-ил)-себацинат;
Н-5 - 2,3,6-триметил-2,6-диэтил-4-пипе- ридон;
Н-6 - 2,2,6,6-тетраметил-4-бутиламино- пиперидин.
В табл.1 указано врем  индукции: чем выше врем  индукции, тем выше антиокислительное действие стабилизирующей добавки .
П р и м е р 2. При окислении углеводородов образуютс  кислородсодержащие группы, как, например, гидроксильные, карбоксильные или сложноэфирные группы, Путем ИК-спекТроскопии можно хорошо измер ть количество таких групп и из этого измерени  определ ть активность антиок- сидантов. Дл  этой цели пробы стандартного минерального масла (Aral R 136), к которому примешивают дл  повышени  чувствительности к кислороду 1 об.% 1-де- цена, в изотермических услови х нагревают в атмосфере воздуха, к которому примешиваетс  400 ррт N02 под давление 8 бар в течение 12 ч. Затем измер ют ИК-абсорб- цию при 1730 и 1630 . Чем ниже эти величины, тем выше активность стабилизаторов Таблицы 2а и 26 показывают результаты при различных температурах.
КО- -СНгСНгШСндак
TOST-методу (turbine Oxidation Stabilitg test) согласно ASTMD-943. Дл  этой цели 300 мл минерального масла (Mobile TOC К 305) смешивают с 60 мл воды и в присутствии железной и медной проволоки при пропускании кислорода нагревают 1000 ч при 95°С. Измер етс  образование кислот путем определени  числа нейтрализации TAN (мг КОН/г масла), а также образовавшегос  количества осадка.
В качестве стабилизатора примен ют амин А-1 индивидуально и в смеси с затрудненным амином Н-7(2,2,6,6-тетраметил-4- додецилоксипиперидин), причем обща 
концентраци  стабилизаторов всегда 0,25% в расчете на масло (см.табл.З),
П р и м е р 4. Аналогично примеру 1 измер ют врем  индукции окислени  при 170°С. При этом примен ют следующие затрудненные амины: Н-8 - N, N -бис-(2,2,6,6- тетраметилпиперидин-4-ил)-гексаметилен диамин;
Н-9 - N, -бис(2,2,6,6-тетраметилпипе- ридин-4-ил)-пентаметилендиамин;
Н-10 - 4-(3-метоксипропиламино)- 2,2,6,6-тетраметилпиперидин (см.табл.4).
П р и м е р 5. Аналогично примеру 1 измер ют врем  индукции окислени  при 170°С. При этом примен ют в качестве ароматического амина (А-3) (п-октилфенил)-1- нафтиламин (см.табл.5).
П р и м е р 6. Скорость окислени  может измер тьс  также путем измерени  прироста в зкости при обработке кислородом при
повышенной температуре.
Дл  этого через масло в течение 70 ч при 150°С пропускают ток кислорода (1 л/ч). Масло предварительно сенсибилизировано с помощью каталитического количества
нафтената меди. В зкость масла измер ют до и после с помощью вискозиметра Убел- лоде (см.табл.6).
45

Claims (1)

  1. Формула изобретени 
    Смазочный состав, содержащий базовое масло и ароматический амин, отличающийс  тем, что, с целью повышени  антиокислительной стабильности, состав в качестве ароматического амина (Б) содержит соединение общей формулы
    ООССНгСКг-/ 5-ОК
    П р и м е р 3. Поведение при окислении стабилизированных согласно изобретению смазочных масел испытываетс  также по
    RR,
    ЙЬА|
    где RI -фенил, С4-Св-алкилфенил, наф- тил;
    R2 - фенил, Сл - Са-алкилфенил, или соединение общей формулы
    где Нз и R4 - независимо друг от друга СА - Сз-алкил,
    и состав дополнительно содержит пространственно затрудненный амин (В) общей формулы
    Ч
    h
    где RS - водород или вместе с Re обозначает О; R - Ci - Cs-алкиламино, Ci - С12-алкокси,С1-С4-алкокси-С1-С4-алкила- мино или остаток общей формулы
    SA
    KjHtT
    СН3
    где (СН2)пСОО-, - 8,
    ИЛИ-МН(СН2)тМН-,
    т 5,6;
    R - водород. Ci - С4-алкил, и содержание смеси Б и В составл ет 0,25 - 0,75 мае. % в расчете на базовое масло при массовом соотношении Б/В, равном 3 - 19:1,
    Л
    Таблица 1
    Т аб л и ц а 2
    Соединение формулы
    173634310
    Продолжение таблицы 2
    Таблица 3
    Таблица 4
    Таблица 5
    Таблица б
SU4614702A 1988-07-18 1989-07-17 Смазочный состав SU1736343A3 (ru)

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EP0356677B1 (de) 1993-06-09
EP0356677A1 (de) 1990-03-07
US5073278A (en) 1991-12-17
MX169536B (es) 1993-07-09
CA1334532C (en) 1995-02-21
BR8903526A (pt) 1990-03-13
CN1020748C (zh) 1993-05-19
JPH0273894A (ja) 1990-03-13
AU3817489A (en) 1990-01-18
KR910003078A (ko) 1991-02-26
CN1041610A (zh) 1990-04-25
AU621910B2 (en) 1992-03-26
ES2055762T3 (es) 1994-09-01
JP2832541B2 (ja) 1998-12-09
DE58904610D1 (de) 1993-07-15
ZA895408B (en) 1990-03-28
KR970007781B1 (en) 1997-05-16

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