US4954274.docx

US4954274.docx

《US4954274.docx》由会员分享，可在线阅读，更多相关《US4954274.docx（24页珍藏版）》请在冰豆网上搜索。

US4954274

UnitedStatesPatent[19]

Zaweskietal.

[!

l]

[451

PatentNumber:

DateofPatent:

4,954,274

Sep.4,1990

[21]

（22]

SULFURIZEDOLEFINEXTREME

PRESSUREADDITIVES

Inventors:

EdwardF,Zaweski,12260

BrookshireAve.,BatonRouge,La,

70815;JamesG.Jolly,5233Halls

FerryDr.,BatonRouge,La.70817

Appl.No.:

363,443

Filed:

Jun.6,1989

4,204,9695/1980Papayetal.....................·…252/45

4,225,4889/1980Horodyskyetal...........……252/45

4,240,95812/1980Braid......................一~……252/45

4,563,3021/1986Griffinetal..........................252!

45

4,645,6102/1987Bornetal............................252/45

4,710,27312/1987Okamoto.........~二~~.~~一….568/18

4︸6

尸J7

PrimaryExaminer-WilliamR.Dixon,Jr.

AssistantExaminer-JerryD.Johnson

RelatedU.S.ApplicationData

[63]ContinuationofSer.No.138,937,Dec.29,1987,aban-

doned.

玩t.C!

.5

U.S.C!

.

..…C10M135/02

252/45;252/48.8;

FieldofSearch

Re

568/18

252/45,48.8;568/18

ferencesCited

们J刀8]司

尸、︶尺曰尸、︶尸、︶

一..Ll..Ll..Ll..L

U.

2,565,493

S.PATENTDOCUMENTS

8/1951

3,410,80011/1968

3,697,49910/1972

Gardner.~~~~~~.一一一:

.~…，.252/45

Fordeta1..........................252/48.8

Myers一~~.........................252/48.8

Is}}aBS}cr

Sulfurizedolefinsareproducedbyreactingsulfur

monochloridewithamonoolefm（e.g.isobutene）inthe

presenceofminoramountsofanactiveLewisacid（e.g.

ferricchloride）toformanadduct,reactingtheadduct

withsulfurandsodiumsulfideinanaqueousalkanol

madeataratioof0.02-0.4gramatomofsulfurpergram

moleofsodiumsulfideandthenrecoveringthereaction

product.Olefinpolysulfidesobtainedbythismethod

aresolubleinbothmineralandsyntheticlubricatingoils

（includingthoseofthepolyalphaolefintype）andare

usableasextremepressureadditiveswhenincorporated

intosuchlubricatingoils.Sulfurized烯烃反应产生的硫

方法用monoolefm（例如isobutene）

较小的数量存在一个活跃的路易斯酸（例句。

氯化铁）形成一个adduct,反应adduct的

用硫和钠硫化物在水alkanol

在比例为0.02-0.4克每克的硫原子

鼹鼠的钠硫化物,然后恢复的反应

产品。

烯烃polysulfides得到这个方法

两个都是溶于油和合成润滑油矿物吗

16Claims,NoDrawings

4,954,274

1

SULFURIZEDOLEFINEXTREMEPRESSURE

ADDITIVES

ThisapplicationisacontinuationofapplicationSer.

No.138,937,filedDec.29,1987nowabandoned.

BACKGROUNDOFTHEINVENTION

Thisinventionrelatestosulfurizedolefinsand,in

2

Inaccordancewiththeinvention,thestartingolefins

arethemonoethylenicallyunsaturatedaliphatichydro-

carbonsreferredtoasaliphaticmonoolefinscontaining

3toabout6carbonatoms.Theseinclude1-butene,

52-butene,isobutene,1-pentene,2-pentene,2-methyl-l-

butene,3-methyl-l-butene,2-methyl-2-butene,1-hex-

ene,2-hexene,3-hexene,2-methyl-lpentene,2-methyl-

2-pentene,2-ethyl-2-buteneandthelikeincludingmix-

turesthereof.

particular,topolysulfurizedolefinsusedinlubricating10Preferably,theolefinsarebranched-chainolefins

oilcompositionsandtoamethodforpreparingsame.suchasisobutene,2-methyl小butene,2-methyl-2-

Sulfurizedolefinsareusedinlubricantssuchascrank-butene,2-methyl-2pentene,andthelike.Moreprefera-

caseoilandgearlubricantstoprovideextremepressurebly,theethylenicdoublebondadjoinsatertiarycarbon

properties.atomsuchasisobutylene,themostpreferredolefin

Papayetal,U.S.Pat.No.4,204,969describessucha15Thefirststagereactionispreferablyconductedby

productinwhichsulfurmonochlorideisreactedwithaddingtheolefintothesulfurmonochloride.Theolefin

analiphaticmonoolefintoobtainanintermediatewhichcanbeaddedasagasorliquid.Preferably,itisadded

isreactedwithsulfurandsodiumsulfide.beneaththesurfaceofthesulfurmonochlorideasa

Oneprobleminthefieldofsulfurizedolefinadditivesliquid.

usedforimprovingtheextremepressurepropertiesof20Inpractice,theolefinisaddeduntilthereactionwith

lubricantscontinuestobethedevelopmentofasulfu-thesulfurmonochloridestopsasindicatedbylossof

rizedpolyolefinadditivewhichissufficientlysolubleinexotherm.Anamountofabout0.45-1.5grammolesof

bothmineraloilsandsyntheticoils（particularlythoseolefinforeach0.3-0.75grammoleofsulfurmonochlo-

ofthepolyalphaolefintype）tobeusableasextremerideusuallysuffices.Apreferredamountisabout

pressureadditives.251.7-2.0grammolesofolefinpergrammoleofsulfur

ThisproblemisaddressedinBornetal,U.S.Pat.No.monochloride.

4,645,610whichteachesthatthesolubilityofsuchole-Asstatedhereinabove,thereactionoftheolefinand

finpolysulfideadditivesinbothmineralandsyntheticthesulfurmonochlorideiscarriedoutinthepresenceof

oilsisinverselyproportionaltothesulfurcontentoftheminoramountsofanactiveLewisacid.TheLewisacid

additive.Thatis,asthesulfurcontentoftheadditive30canbeaddedtothesulfurmonochlorideinitially,added

increasesthesolubilityoftheadditiveinbothmineraltothereactionmixturecontinuouslyorperiodically

andsyntheticoils（particularlythoseofthepolyal-duringthecourseoftheolefinaddition,oritcanbe

phaolefintype）decreases.Reportedly,olefinpolysul-mixedwiththeolefinandaddedtogetherwiththeole-

fideadditivesofhighsulfurcontenthavingenhancedfm.Thepreferredmodeofadditionistoaddtheentire

solubilityinbothmineralandsyntheticoilscanbeob-35amountinitiallytothesulfurmonochlorideandthen

tamedaccordingtoBornetalbycontactinganadditionaddtheolefin.

productproducedbythereactionofatleastoneali-ThetermactiveLewisacidreferstoanyLewisacid

phaticmonoolefincontaining2to5carbonatomsandorelectronacceptorwhichwhenutilizedinaccordance

sulfurmonochlorideordichloridewithahydrocarbylwiththeteachingssetforthhereinproducesanadduct

halideandatleastonesulfurcompoundselectedfrom40which,aftersulfurization,affordsalubricantadditive

sulfides,hydrosulfidesandpolysulfidesofalkalimetals,possessingsufficientsolubilityineithermineralorsyn-

ammoniumoralkaline-earthmetalsandusuallyelemen-theticoils（especiallythoseofthepolyalphaolefintype）

talsulfurinanaqueousoraqueousalcoholicmediumattofunctionasanextremepressureadditiveinsuchoils.

certainreactionconditions.ExamplesofLewisacidswhichcanbeusedintheprac-

Griffinetal,U.S.Pat.No.4,563,302alsoreportsthat45ticeoftheinventionincludealuminumbromide,alumi-

sulfurizedolefinshavingimprovedsolubilityinlubri-numfluoride,borontrifluoride,borontrichloride,stan-

Gatingoils（especiallyinalpha-olefinoligomersyntheticnicchloride,titaniumtetrachloride,ferricchloride,

oils）canbeobtainedbyreactinganalkylmercaptan,ferricbromide,aluminumchloride,andthelike.Ferric

sulfur,sodiumsulfideand,optionally,sodiumhydrosul-chlorideisthepreferredLewisacidforuseintheprac-

fideinanaqueousalcoholmediumwithanadductpre-50ticeofthepresentinventionandisreadilyavailable

paredbyreactingamonoolefinwithsulfurmonochlo-commercially.

rideorsulfurdichloride.TheamountofLewisacidusedinthepracticeofthe

___________________________inventionisanamountwhichwillproduceolefinpolv-

一一~一~-----一----一一一’--一’sutnaesofsutnctentsomouttymmmeratanasyntneuc

Unexpectedly,ithasnowbeendiscoveredthatsulfu-55oilsthattheycanbeusedinsuchoilsaseffectiveex-

rizedolefiniccompoundswhicharesolubleinbothtremepressureadditives.Theamountmayvarywith

mineralandsyntheticoilsoflubricatingviscosityatthespecificLewisacidused.Theamountrequiredis

concentrationssufficienttoimprovetheextremepres-readilydeterminedexperimentallybyaddingthepartic-

surepropertiesofsuchoils（includingthoseofthepp-ularLewisacidselectedforuseinthepreparationofthe

lyalphaolefintype）canbeobtainedbyreactingsulfur60adducttothereactionmixtureofsulfurmonochloride

monochloridewithaliphaticmonoolefininthepresenceandmonoolefinuntilanadductisproduced,which,as

ofminoramountsofanactiveLewisacidandthereafterindicatedpreviously,aftersulfurizationaffordsanaddi-

reactingtheadductsoproducedwithsulfurandsodiumtivepossessingthedesiredsolubilityandextremepres-

sulfideinaqueousalkanol.Theadduct,producedinthissurepropertiesbothinmineralandsyntheticoils.

fashion,aftersulfurizationaffordsalubricantadditive65Ingeneral,minoramountswhichcanvaryfrom

sufficientlysolubleinbothmineralandsyntheticoilstoabout0.025percenttoabout5.0percentbyweightof

beusableasanextremepressureadditiveineithertypeLewisacidbasedontheweightofsulfurmonochloride

oflubricant.areusedintheinvention.Apreferredamountisfrom

3

4,954,274

4

about0.05percenttoabout3.0percentbyweight.The

mostpreferredisabout0.1percentbyweight.

Thefirststagereactioncanbeconductedatanytem-

peraturehighenoughtocausethereactiontoproceed,

butnotsohighastocausedecompositionofthereac-

tamsorproducts.Ausefulrangeisabout300-1000C.A

morepreferredrangeisabout400-750C.andamost

preferredrangeisabout500-600C.

Thefirststagereactionshouldbeconductedfora

timesufficienttocompletethereactionbetweenthe

sulfurmonochlorideandolefin.Thisisusuallylimited

byheatremoval.Olefinfeedrateispreferablycon-

trolledtoholdthetemperaturewithinthedesired

range.Whenthesulfurmonochloridehasbeencon-

sumed,thetemperaturewilldrop.Externalheatmaybe

addedtocontinuethereactionforafurthertime,but

thisdoesnotappeartobenecessary.Theoverallti