RS49806B - Motorna ulja sa više opsega i kompozicija ulja za podmazivanje koje sadrži dodatne materije - Google Patents
Motorna ulja sa više opsega i kompozicija ulja za podmazivanje koje sadrži dodatne materijeInfo
- Publication number
- RS49806B RS49806B YUP-803/95A YU80395A RS49806B RS 49806 B RS49806 B RS 49806B YU 80395 A YU80395 A YU 80395A RS 49806 B RS49806 B RS 49806B
- Authority
- RS
- Serbia
- Prior art keywords
- component
- mass
- average molar
- molar mass
- derivative
- Prior art date
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- C10M129/02—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing oxygen having a carbon chain of less than 30 atoms
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- C10M129/02—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing oxygen having a carbon chain of less than 30 atoms
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Description
Pronalazak se odnosi na motorna ulja bez halogena, sa više opsega i kompozicije ulja za podmazivanje sa više opsega, visoke stabilnosti, koje sadrže dodatne materije i takođe imaju nizak sadržaj fosfora, a koje se sastoje iz osnovnog ulja i paketa dodatnih materija. Pronalazak se dalje odnosi na primenjeni paket dodatnih materija.
Da bi se ispunili zahtevi za trošenje kod paljenja varnicom, odnosno dizel
motora, upotrebljavaju se u motornim uljima sledeće grupe dodatnih materija:
- polimeri koji povećavaju viskozitet i indeks viskoziteta, a smanjuju tačku tečljivosti; - dispergensi bez pepela; - deterdženti koji sadrže metale; - inhibitori (inhibitori oksidacije, inhibitori korozije, inhibitori rđanja i slične materije); - inhibitori habanja;
Dodatne materije dosadašnjih ulja mogu biti u pogledu njihove funkcije i strukture klasifikovani u pet grupa. U prvu grupu spadaju dodatne materije velikih molekula (Mn = 5.000 - 2.000.000) najčešće homo- ili ko- polimerne dodatne materije koje obično imaju dejstvo povećanja viskoziteta i indeksa viskoziteta i sniženja tačke tečljivositi.
Ugradnjom polarnih bazičnih grupa u strukturu kopolimera mogu se ostvariti dodatne materije sa deterdžentno-disperzionim (u daljem tekstu DD) sporednim dejstvom, čija primena omogućuje izvesno smanjenje koncentracije DD dodatnih materija malih molekula (Mn < 2 000) u kompozicijama motornih ulja. Najpoznatiji predstavnici ovakvih dodatnih materija su poli-alkil-metakrilati (PMA) i njihovi derivati, kopolimeri etilen-propilena (OCP), kopolimeri stirol-butadiena /SBCP/ i poli-izoprena /PIP/.
Drugu grupu dodatnih materija čija se upotreba vrlo brzo širi, predstavljaju tzv. DD dodatne materije bez pepela. Njihova, u svom količinskom udelu rastuća, primena zasniva se na tome da nove konstrukcije motora stavljaju veće zahteve u pogledu dejstva - kao smanjenje obrazovanja crnog taloga, metalne emisije koja zagađuje okolinu i dejstva koje dovodi do oštećenja zaptivača - koji samo daljim razvojem DD dodatnih materija bez pepela i u njihovoj primeni u povećanoj koncentraciji mogu biti zadovoljeni. Kao DD dodatne materije bez pepela malih molekula (Mn <2000) najčešće se koriste -imid, -amid, ili ester-derivati polialkeni ćilibarnih kiselina, manih-baze sa poli-izo-buten osnovnom strukturom, poliolefin-amini i slične materije.
Treća, četvrta i peta grupa dodatnih materija formirana je od dodatnih materija sa daljim funkcijama. U te dodatne materije spada niz jedinjenja koja imaju u pogledu primene vrlo važna dejstva.
U te grupe spadaju npr. deterdženti koji sadrže metale, inhibitori oksidacije, inhibitori korozije, materije koje modifikuju trenje i inhibitori habanja, kao i sredstva za suzbijanje stvaranja pene. Niz varijanti ovih materija bez pepela koje sadrže metale je poznat i one u opšte mogu biti izabrane i primenjene takođe s obzirom na njihova uzajamna sinergetička i antagonistička dejstva na osnovu laboratorijskih ispitivanja i ispitivanja u uređaju za ispitivanje kočenja.
Tokom razvoja izvršenih za poslednjih 15 godina, sastav motornih ulja promenjen je s jedne strane primenom novih dodatnih materija povišenog dejstva koje zadovoljavaju u većoj meri nove zahteve, a s druge strane modifikovanjem strukture ranijih s uspehom primenjivanih dodatnih materija, tj. izradom dodatnih materija koje imaju pored glavnog delovanja još i dopunsko čija primena omogućuje dalje podizanje nivoa dejstva ili smanjenje do određenog nivoa potrebne koncentracije. Tako se npr. hemijskim modifikovanjem strukture dodatnih materija upotrebljenih u kompoziciji uspešno smanjuju nepoželjna uzgredna dejstva, kao što je oštećenje materijala za zaptivanje ili korozija metala ležišta. DD dejstvo se npr. povećava modifikovanjem sukcinimid dodatnih materija bez pepela organskim kiselinama (EP 0 537 386) ili optimiziranjem strukture za sintezu primenjenih polietilen-poliamina (EP 0 451 380).
Dopingovanjem dosadašnjih etilen-propilen-kopolimera sa polarnim grupama koji povećavaju viskoznost i indeks viskoziteta uspešno je usavršeno DD nusdejstvo (EP 0 400 866). Polimetakrilati sa unetim mešanim polimerima etilen-propilen-kopolimera pogodni su za stabilizovanje smeša raznih polimera koji povišavaju viskozitet i indeks viskoziteta.
Štetno dejstvo na fluor-elastomerske zaptivačke materijale dosadašnjih alkenil-sukcinimid dodatnih materija malih molekula moglo bi biti uspešno smanjeno jakim neorganskim kiselinama (US 5.114.402).
Primenom novih derivata cinkovih soli poli-izo-butenil ćilibarne kiseline moglo bi se prema EP 0 265 658, uspešno povećati otpornost uljnih kompozicija na oksidaciju pri visokim temperaturama i na formiranje taloga. Pored visokog DD dejstva i povišene stabilnosti lagerovanja moglo bi se prema EP 0 051 998 postići željeno smanjene dejstva trenja, primenom derivata estera polialkenii ćilibarne kiseline, etilen glikola i masnih kiselina.
Dodatne materije, koje pored povišenog DD dejstva poseduju i poboljšanu kompatibilnost sa zaptivačkim materijalima i nusdejstvo povišenja viskoziteta i indeksa viskoziteta, mogu se proizvesti i produženjem bočnog lanca polimera poli-izo-butenil-sukcinimida do molske mase od 5 000 i sintetizovanjem tzv. poli-izo-sukcinimid dodatnih materija (US 4 234 435, WO 90/03 359 i EP 0 271 937).
Proizvodnja ovakvih dodatnih materija sa prosečnom molskom masom od katkad više desetina hiljada omogućena je sintetizovanjem ovakvih acilirajućih sredstava koja u svojim molekulima na poliolefmskom lancu imaju vezan više od jednog anhidrida ćilibarne kiseline (BA).
Reakcijom ovakvih intermedijera i poli-alkilen-poli-amina i/ili polialkohola i/ili alkanol-amina može se, i kod poliolefina sa višom prosečnom molskom masom nego kod obično primenjenih molekula (Mn = 1500 - 5000) sintetizovati dodatne materije sa velikim molarnim grupama (imid, amid ili ester) i sa visokim DD dejstvom. Struktura poznatih dodatnih materija i poznati proizvodni postupci su različiti, ali se ipak u svakoj kompoziciji koja sadrži ovakve dodatne materije može dokazati povećanje DD dejstva i takvo nusdejstvo povišenja viskoziteta i indeksa viskoziteta, koje omogućuje smanjenje količine za 10 - 30% uobičajenih polimera potrebnih za određeni stupanj viskoziteta, a time i smanjenje troškova.
Uprkos postignutim i napred opisanim uspesima u razvoju sukcinimida velikih molekula (Mn > 2000), upotreba dosadašnjih polimera koji povećavaju viskozitet i indeks viskoziteta u proizvodnji višestepenih motornih ulja postala je jedan od osnovnih uslova. Da bi se njihova primena i dalje smanjila mogu se ipak posmatrati i dalja stremljenja.
Količina polimera koju treba upotrebiti, a koji povećavaju viskozitet i indeks viskoziteta može se smanjiti npr. upotrebom osnovnih ulja dobijenih
hidrokraking procesom ili sintetičkih ulja (poliolefini, diesteri i slične materije) sa uvek većim indeksom viskoziteta. Dosadašnji polimeri koji povećavaju viskozitet i indeks viskoziteta imaju u uljima za podmazivanje povoljna dejstva, ali prilikom upotrebe kompozicija i na dejstvo hemijskih nečistoća nastalih pri primeni
kompozicije nestabilnih proizvoda raspadanja pod strogim okolnostima (kao što je visoka temperatura i mehaničko opterećenje) dovode do obrazovanja nerastvorljivih taloga sličnih smolama, a time i do prljanja motora. Usled, smanjenja molske mase zbog raspadanja, željeni viskozitet i željeni indeks
viskoziteta ulja za podmazivanje mogu se osigurati još samo u smanjenoj meri. Kvalitet motornih ulja može se dalje poboljšati upotrebom polimera povišene stabilnosti.
Tokom daljih ispitivanja došli smo do neočekivanog saznanja da se upotrebom određenih količina odgovarajućih izabranih osnovnih ulja, različitih uobičajenih dodatnih materija i jedne nove polifunkcionalne dodatne materije DD kompozicije bez pepela mogu proizvesti kompozicije motornih ulja i ulja za podmazivanje sa visokom stabilnošću, koju dosadašnji polimeri za povećanje viskoziteta ili indeksa viskoziteta sadrže u znatno smanjenoj količini, ili je uopšte ne sadrže.
Predmet pronalaska je prema tome kompozicija ulja za podmazivanje, prvenstveno kompozicija motornog ulja, koje se sastoji od motornih ulja podesnih za osnovno ulje, koja sadrži paket dodatnih materija u količini 1,5-55 mas% koji se redovno sastoji od jedne ili više dodatnih materija koje čine komponente "A", "B" i u datom slučaju "C", pri čemu pojedine komponente imaju sledeći sastav:
Komponenta " A" :
10-100 tež % polifunkcionalne deterdžentno-disperzivno delujuće dodatne kompozicije bez pepela, ili njenog uljnog rastvora, pri čemu polifunkcionalna deterdžentno-disperziono delujuća kompozicija dodatne materije sadrži takve polimerne komponente numeričke prosečne jednake ili različite molske mase, koje su proizvedene pretvaranjem jednog derivata poliolefina, prvenstveno PIB
derivata, koji je dopingovan jednom ili više dikarbonskih kiselina i/ili anhidridom dikarbonske kiseline i jednim ili više komonomera koji ne reagiraju kiselo, a ima etilensku dvostruku veza i ima prosečnu molsku masu 800, izgrađene su sa amino i/ili imino i/ili hidroksi grupom koja nosi u polimernim komponentama poliolefmski lanac od proseČno 6 - 20 kiselinskih derivata koji iznosi bar 25 mas%, pri čemu derivat može biti imid- i/ili amid- i/ili ester-amid derivat, i 0 - 90 mas% ester-amid derivat;
Komponenta " B" :
jedna ili više uobičajenih dodatnih materija, kao deterdžentno-disperziono delujućih dodatnih materija sa različitim baznim brojem i raznim sadržajem metala, antioksidansa, materija za smanjenje trenja, inhibitora habanja, inhibitora korozije, sredstva za suzbijanje stvaranja pene i materija za sniženje tačke tečljivosti;
Komponenta " C" :
jedan ili više polimera za povećanje viskoziteta, pri čemu maseni odnos komponenti "A", "B" i "C" iznosi 15-85:15-85:0-70
Dalje je predmet pronalaska da se u gornjim kompozicijama upotrebljeni paket dodatnih materija, koji se svaki put sastoji od jedne ili više dodatnih komponenti koje čine komponenta "A", "B" i eventualno "C", sadrži u napred datom sastavu.
Kao što je pomenuto paket dodatnih materija u skladu s pronalaskom, sastoji se od tri glavne komponente (A,B,C) od kojih svaka sadrži po jednu ili više dodatnih materija. Tako komponenta "A", kao glavni sastavni deo, sadrži polifunkcionalnu kompoziciju bez pepela dodatnih materija sa DD dejstvom povišenja viskoziteta ili indeksa viskoziteta iz unesenih poliolefinskih derivata, prvenstveno od derivata anhidrida poli-iso-butilen ćilibarne kiseline (u daljem tekstu polifuncionalna dodatna DD kompozicija bez pepela), komponenta "B" je smeša dodatnih materija od dosadašnjih dodatnih materija koje sadrže pepeo i/ili dodatnih materija koje ne sadrže pepeo, sa raznim dejstvima; komponenta "C" je dodatna i obična materija ili smeša dodatnih materija sa dejstvom povećanja viskoziteta ili indeksa viskoziteta. Komponenta "C" može u datom slučaju biti izostavljena.
Komponenta "A" sadrži 10-100 mas% polifunkcionalnu kompoziciju DD dodatne materije bez pepela, odnosno njen uljni rastvor, pri čemu polifunkcionalna dodatna kompozicija DD dodatnih materija bez pepela sadrži polimerne komponente, proizvedene pretvaranjem jednog poliolefinskog derivata, prvenstveno poli-iso-butilen derivata (PIB derivata) sa numeričkom prosečnom molskom masom više od 800, poželjno 1.300 - 30.000, koja je dopingovana sa jednom ili više nezasićenih dikarbonskih kiselina i/ili anhidridom ugljene kiseline, prvenstveno anhidridom maleinske kiseline i sa jednim ili više nekiselinskih komonomera sa etilenskom dvostrukom vezom ili kopolimerima ovakvih komonomera (i/ili homopolimerima anhidrida maleinske kiseline), sa jednim jedinjenjem koje sadrži amino- i/ili imino- i/ili hidroksi- grupu, pri čemu polimerne komponente pokazuju istu ili različitu numeričku prosečnu molsku masu i u kojima je poliolefinski lanac čija je numerička prosečna molska masa poželjno ista sa molskom masom polazne materije, i prosečno nosi 6-20 derivata kiseline pri čemu je količina molekula sa više od jednog derivata kiseline veća od 25 mas%, a derivat može biti imid- i/ili amid- i/ili ester-amid derivat.
Gornja polifunkcionalna kompozicija DD dodatne materije bez pepela sadrži prvenstveno najmanje dve polimerne komponente sa različitom, jednom nižom (Mnl) i jednom višom (Mnll) numeričkom prosečnom molskom masom, pri čemu je prosečna molska masa polimerne komponente sa nižom numeričkom prosečnom molskom masom manja od šestoslruke prosečne molske mase izlaznog poliolefina a njen maseni odnos prema polimernoj komponenti sa većom numeričkom prosečnom molskom masom iznosi 0,01-5:1.
Odnos numeričkih prosečnih molskih masa pomerne komponente sa većom i manjom prosečnom molskom masom je: Mnll/Mnl = 3-50, prvenstveno 10-20.
Pri proizvodnji polifunkcionalne kompozicije DD dodatne materije bez
pepela najpre se prvenstveno proizvodi acilizaciono sredstvo, pri čemu se na jedan poliolefin, prvenstveno PIB sa numeričkom prosečnom molskom masom najmanje 800, a prvenstveno najmanje 1300, dopinguje polarni kopolimerni bočni lanac od anhidrida maleinske kiseline i jednog anhidrida polarnog, ili apolarnog, nekiselinskog komonomera sa etilenskom dvojnom vezom ili mešavine takvih komonomera. Komonomer može biti posebno uneto jedinjenje ili (u radnom
procesu češće primenjeni) inicijator ili jedno jedinjenje koje kontroliše ugradnju, ili nezasićeni produkt razlaganja osnovne poliolefmske materije, ili nezasićena komponenta iz degradacije poliolefina (EP 0 658 572). Dopingovanje se može izvesti postupnim sprezanjem anhidrida maleinske kiseline i komonomera na poliolefinski molekul i/ili dodavanjem poliolefinu kopolimerskog lanca prethodno načinjenog od anhidrida maleinske kiseline i jednog ili više komonomera ili delova ovih. Kod proizvodnje acilizacionog sredstva gradi se pored anhidrida maleinske kiseline (komonomer) poliolefin molskog odnosa od 1,2 - 5,5:0,01-3,5:1 u prisustvu ili odsustvu rastvaračkog sredstva i u prisustvu 5-25 mas% (u odnosu na anhidrid maleinske kiseline) jednog radikalnog inicijatora i 0,1-5 mas% jedinjenja koje kontroliše odnos ugradnje monomera, kod pritiska između 100-1500 kPa u inertnoj atmosferi i/ili atmosferi ugljovodonikapri temperaturi između 80-180°C. Intermedijer se u datom slučaju razređuje osnovnim uljem i posle izbistravanja čisti filtriranjem. Dobijeno acilizaciono sredstvo čisti se 2-15 časova ili na poznati način modifikuje pomoću jednog ili više, najmanje bifunkcionalnih jedinjenja sa amino i/ili imino- i/ili hidroksi grupom pri molarnom odnosu acilizaciono sredstvo (amin i/ili alkohol) od 0,7 - 5,5:1 pri temperaturi od između 120-235°C, u prisustvu ili odsustvu katalizatora; po potrebi se razredi osnovnim uljem, pročisti i modifikuje na poznat način.
Dobijeni intermedijer koji se sastoji od jednog dugog apolarnog poliolefmskog lanca i priključenog jako polarnog kopolimerskog lanca sa statističkom ili promenljivom strukturom, vrlo je podesan za proizvodnju imid-i/ili ester- i/ili amid- i/ili esteramid- derivata sa visokim disperzionim dejstvom, pri čemu grupe priključene na isti poliolefinski lanac mogu biti iste ili različite. Kod ovih osnovnih materija, omogućuju nastale polifunkcionalne grupe, koje najčešće stoje na kraju, uglavnom sastavljene od velikog broja karboksilnih grupa, da se kod aciliranja uz primenu odgovarajućih, najmanje bifunkcionalnih baznih reagenasa stvore takve polimerne strukture koje korisno modificiraju reološka svojstva mazivnih ulja. Otkriveno je, naime, da se prilikom primene poli-iso-butilena sa numeričkom prosečnom molskom masom preko 800, a prvenstveno više od 2000, mogu dobiti dodatne materije koje pored povoljnog DD dejstva imaju dejstvo povećanja viskoziteta i indeksa viskoziteta koje je veće nego kod poli-izo-butilenskih osnovnih materija sa visokim sadržajem alfa-olefina (iznad 70 mas%) i naročito su podesne za proizvodnju takvih polimernih komponenti.
Može se uočiti činjenica od naročite prednosti da poli-iso-butileni pomoću pronalaska mogu biti upotrebljeni kao dodatne materije kako u pogledu toplog viskoziteta, tako i hladnog.
Prema našim eksperimentalnim iskustvima polifunkcionalna kompozicija DD dodatne materije bez pepela ima bolju termičku i oksidacionu stabilnost nego dosadašnje dodatne materije, a time se povećava indeks stabilnosti i time se stabilnost kompozicija motornog ulja povećava u neočekivanoj meri.
Komponenta "A" sadrži pored gore opisanog glavnog sastavnog dela po potrebi 0-90 mas% dosadašnjih i komercijalno uobičajenih derivata malih molekula alkenil-ćilibarne kiseline, kao estere, esteramide, poli-iso-butilen-sukcinimide, ili njihove mešavine. Naročito su preporučljivi proizvodi načinjeni prema HU 197 936 i 205 778.
Kao komponenta "B" primenjuju se u kompoziciji prema pronalasku takve dalje dodatne materije sa poznatim delovanjem koje su praktički neizbežne u proizvodnji modernih kompozicija modernih ulja visokog dejstva. Ovde se primenjuju prvenstvena jedna ili više takvih DD dodatnih materija sa različitim sadržajem metala i različitog broja baza (TBN) kao bazni i hiperbazni kalcijum- i magnezijum- sulfonati, fenati i salicilati, antioksidansi, kao cink-dialkil-ditiofosfati i ditiokarbamati, prostorno ograničeni fenoli, krezoli, aromatični amini i njihovi derivati; dodatne materije koje umanjuju trenje i habanje kao alifatični amini, amidi i esteri, esteramidi, fosfati, tiofosfati, sulfidi, polisulfidi i njihovi derivati; inhibitori korozije kao alkiltriazoli, merkapto-benz-triazoli, monokarbonske kiseline, dikarbon-kiseline i njihovi derivati, sredstva za suzbijanje pene, kao dialkil-siHkon-polimeri, dodatne materije za smanjenje tačke tečljivosti, kao poliakilmetakrilati, poliakil-akrilati, etilen-vinil kopolimeri, dialkilfumarat kopolimeri i slične materije.
Preporučljivi sastavni delovi komponente "B" su kao DD dodatne materije koje sadrže metale, bazni i hiperbazni kalcijum i magnezijum-sulfonati, fenati i salicilati, kao inhibitori cink-dialkil-tiofosfati, ditio-karbamati bez pepela, prostorno ograničeni fenoli i aromatični amini, kao materije koje smanjuju trenje-derivati masnih kiselina i fosforne kiseline i polialkisiloksani kao i inhibitori habanja ditiokarbamti sumporisani derivati biljnog ulja i kao materije koje snižavanju tačku očvršćavanja poliakril-metakrilati, kao i smeše gornjih materija.
Kao komponenta "B" primenljive, komercijalno uobičajene dodatne materije može obrazovani stručnjak lako izabrati na osnovu ranijeg iskustva i rezultata tehnički primenljivih prethodnih ispitivanja.
Komponenta "C" je neki poznati polimer koji uvećava viskozitet i indeks viskoziteta ili odgovarajući izabrana mešavina takvih polimera. Za kompozicije sa više opsega motornih ulja preporučuju se polialkilmetakrilati, etilen-propilen kopolimeri, stirol-diolifenkopolimeri, kao i njihovi derivati koji sadrže azot.
Odnos dodatnih materija koje se upotrebljavaju u komponentama "A", "B" i "C" unutar komponenti kao i odnos pojedinih komponenti između sebe određenje raznim parametrima. Kao primer za ove parametre mogu biti pomenuti stepen viskoznosti i efekta komponente koju treba proizvesti osobine primenjenog osnovnog ulja kao i dejstvo zavisno od koncentracije dodatne materije.
Za proizvodnju kompozicija ulja za podmazivanje i kompozicija ulja sa osobinama visokog delovanja i povoljnih osobina mogu biti izabrane koncentracije dopunskih materija u pojedinim komponentama (A,B,C) primenjenih dodatnih materija prvenstveno u okvirima područja navedenih u tabeli 1.
U slučajevima kompozicija za više opsega motornog ulja, količina pojedinih komponenti prvenstveno se podešava prema opsezima navedenim u tabeli 2.
Značajno je da se mogu upotrebiti takve komponente koje mogu imati istovremeno više funkcija, pri čemu njihova dejstva mogu povećavati ili smanjivati jedno drugo. Njihova koncentracija se, dakle, određuje uzimajući u obzir njihovo uzajamno dejstvo.
Paket dodatnih materija u skladu sa pronalaskom, može se primeniti i kao
koncentrat. U takvim slučajevima se paket dodatnih materija prvenstveno razredi u 0-85 mas% sredstvu za razređivanje, kako bi se olakšalo rukovanje. Kao sredstvo za razređivanje mogu se npr. upotrebiti osnovna ulja manjeg viskoziteta, VK ispod 15 mm/s.
U kompoziciji prema pronalasku kao osnovno ulje mogu se upotrebiti takva uobičajena osnovna ulja na bazi mineralnih ulja koja se mogu proizvesti rafiniranjem rastvaračkog sredstva i/ili rafiniranjem hidriranja i/ili katalitičkim oslobađanjem parafina i/ili rafiniranjem aktivne gline i/ili završnim rafiniranjem hidriranja i/ili hidrokraking procesom, a po potrebi pročišćena naknadnim oslobađanjem sredstvom za rastvaranje - i/ili katalitičkim oslobađanjem parafina, pri čemu se sastav ovih osnovnih ulja prilagođava prvenstveno mešanjem komercijalno uobičajenih osnovnih ulja različitih viskoziteta s obzirom na željeni stepen viskoziteta i dejstvo. Isto tako su prvenstveno podesna i sintetička ulja, kao poli-alfa-olefmi, ester dikarbonske kiseline ili poliester kao i biljna ulja i/ili njihovi derivati čije proporcije treba podesiti odgovarajućim potrebama primene. Pri primeni paketa dodatne materije u skladu s pronalaskom ocenjuju se kao naročito povoljne različite mešavine osnovnih ulja, proizvedene iz parafmskih sirovih ulja kombinacijom rafiniranja rastvaračkog sredstva i/ili hidrirajućim rafiniranjem sa poli-alfa-olefinima i esterima dikarbonske kiseline, pri čemu se podešavaju proporcije u pogledu željenog viskoziteta.
Korišćenjem paketa dodatnih materija u skladu s pronalaskom, mogu se proizvesti kompozicije motornih ulja koje odgovaraju poznatim stepenima dejstva. Tako se može npr. prema API klasifikaciji (ASTM D 4485) postići stepen SG i SH ili prema CCMC klasifikaciji (predavanje G.H. Cahilll-a: Evolucija mašinskih podmazujući sekvenci na CEC III-ćeg internacionalnog simpozijuma evolucije performansi automazivnih goriva i sredstava za podmazivanje, 13 april 1989) postići stepen PD-2 i GL-5/.
Paket dodatnih materija prema pronalasku može se osim u smesama motornih ulja primenjivati takođe i u drugim kompozicijama ulja za podmazivanje kao u menjačkom ulju, hidrauličnoj tečnosti, ulju za automatske menjače (ATF), uljima za hlađenje i mašinskim uljima, kao i u drugim kompozicijama, kao u uljima za kočnice, uljima za dovođenje toplote i uljima za otvrdnjavanje - kaljenje i motornim pogonskim uljima, radi poboljšanja osobina ovih. Prvenstvena oblast primene je ipak proizvodnja kompozicija motornih ulja sa višenamenskim dodatnim materijama.
Izrada kompozicija vrši se običnim mešanjem. Tu se može tako postupiti da se dodatne materije upotrebljene u komponentama pojedinačno dodaju osnovnom ulju i celokupna kompozicija temeljito izmeša. Druga mogućnost je da se načini prethodno paket dodatnih materija pri čemu su dodatne materije izmešane u željenim količinama, zatim se viskozitet, radi olakšanja daljeg rada podesi viskozitet na željeni nivo proizvoljnim osnovnim uljem prvenstveno onim primenjenim u kompoziciju. Tako dobijeni koncentrat obradi se sa željenim osnovnim uljem pomešan u kompoziciju.
Prilikom izrade kompozicije, treba redosled dovođenja dodatnih materija da bude određen s obzirom na moguće hemijske reakcije. Razne komponente dodatne materije prvenstveno se umešaju takvim redom u osnovno ulje kojim se svodi na minimum verovatnoća reakcije između jedinjenja raznih hemijskih struktura i mogućnosti reagovanja. Da bi se izbeglo termičko raspadanje, treba raditi na temperaturi između 40 i 80°C.
Karakteristična prednost pronalaska da se osnovni materijal PIB velikih molekula, upotrebljen za dodatnu materiju bez pepela i halogena koja omogućuje izradu DD dodatne materije sa povišenim dejstvom koja primenjena sa odgovarajućim količinama daljih uobičajenih dodatnih materija, samo u maloj meri oštećuje elastomerne materijale za zaptivanje, ili ih čak štiti. Štaviše ona poseduje povišeni stabilitet na smicanje, dejstvo povećanja viskoziteta i indeksa viskoziteta, kao i dopunsko nusdejstvo inhibicije habanja i na taj način omogućava smanjenje ili izostavljanje polimera ili inhibitora habanja koji sadrže fosfor i time izradu kompozicija visoke stabilnosti i pogodnih za okolinu.
Pronalazak će biti na osnovu sledećih primera bliže razjašnjen bez ograničenja zaštite na primere. U primerima biće prikazane kompozicije motornih ulja koje imaju stepen SG prema najrasprostranjenijoj API klasifikaciji.
Primer 1
Parametri proizvodnje i karakteristike intermedijera za poli-iso-butilen-poli-sukcinimid derivata koji se primenjuju u komponenti "A" kao polifunkcionalna kompozicija DD dodatne materije bez pepela, obuhvaćeni su u tabeli 3, a karakteristike iz ovih sintetizovanih krajnjeg produkta obuhvaćena su u tabeli 4. PIBPOBAO-KA, PIBPOBAO-KB: Uljni rastvor intermedijera PIB anhidrida ćilibarne kiseline.
Primer 2
Proizvode se sledeće kompozicije motornih ulja uz primenu polifunkcionalnih DD dodatnih kompozicija bez pepela prema primeru 1 (PIBPSI-1, PIBPSI-2). Test kompozicije motornih ulja K-l do K-14 proizvode se kako sledi: U uređaj koji raspolaže grejnim ogrtačem do 120°C, odnosno ogrtačkim hlađenjem i unutrašnjim mešačem, uvode se najpre uljna komponenta u kompoziciju sa najmanjim viskozitetom (uključujući sintetičke komponente) na temperaturi okoline. Zatim se pri zagrevanju i stalnom mešanju uljne komponente u redu po porastu viskoziteta uvode pri temperaturi okoline. Smeša ulja zagreje se na temperaturu od 70°C i u odgovarajućoj količini mogu se radi lakšeg postupka primešati u datom slučaju do 60°C zagrejane materije koje snižavaju tačku tečljivosti (P.P.D.) razne dodatne materije za povećanje indeksa viskoziteta (V.I.I.-1, 2, 3 i 4) kao i zajedno sa ovima primenjeni dispergensi bez pepela.
Mešavina gornjih materija mesa se tada 1 sat, a zatim se na temperaturu od oko 60°C ohlađenoj smeši doda željena količina cink-ditiofosfata, deterdžentne smeše i antioksidansa. Posle mešanja od 1 sat hladi se smeša na temperaturu okoline. Sastav tako dobijenih 14 test kompozicija sa nivoom dejstva od SG/CD po API obuhvaćen je u tabeli 5.
Najvažnije karakteristike kvaliteta materija primenjenih kod test-kompozicija su: Rafinati mineralnih ulja SN-80, SN-150 i SN-350 su frakcije bez parafina sa N-metil-pirolidonom kao sredstvom za rastvaranje rafiniranih i hidriranih frakcija destilata priređenih iz mađarskog mineralnog ulja. Njihov kinematički viskozitet iznosi kod 100°C: 3,42 mm<2>/s, 5,40 mm<2>/s i 8,62 mm<2>/s, a njihov indeks viskoziteta iznosi 102, 106 i 95, sadržaj aromata iznosi, prema vrsti 4,9%, 4,6% i 7,7%, tačka tečenja iznosi
-18, -18 i -15°C. Osnovno ulje SAE 10/95H je rafinirano ulje bez parafina koje se proizvodi lakim hidrokrakig procesom i potom redistiliranjem. Ulja SAE 10-95H
pokazuje kinematski viskozitet kod 100°C i 40°C od 5,29 i 31,7 mm<2>/s indeks viskoziteta 100, sadržaj aromata po Brades-u 7,7%, sadržaj sumpora 0,04%, tačku tečenja -18°C. Komponente PAO-4 i PAO-6 su komercijalni poli-alfa-olefini.
Materija koja snižava tačku tečenja PPD je polimetakrilat.
Od četiri materije koje modifikuju indeks viskoziteta su V.I.I.-l uobičajeno primenjeni u motornim uljima, polimetakrilat V.I.L-2, rastvor stirol-izopren-kopolimera u osnovnom ulju SN-150, V.I.I.-3 poli-izopren koji modifikuje indeks viskoziteta, V.I.L-4 rastvor olefin kopolimera u osnovnom ulju SN-150. Osnovno ulje SN-150 koje se primenjuje kod V.I.L-2,3,4 pokazuje kod osnovnih ulja navedene karakteristike kvaliteta.
Komponenta ZDDP je cink-dialkil izofosfat čija je primena rasprostranjena kao dodatna materija kompozicija motornih ulja za dizel- i benzinske motore i proizvodi se i sa primešanim primarnim i sekundarnim alkoholima. On pokazuje sadržaj cinka od 9,2 mas% i sadržinu fosfora 8,4 mas% i sadrži derivate difenil-amina kao antioksidans (AO).
Komponenta DET je deterdžent iz smeše baznih kalcijum- i magnezijum-salicilata, ona pokazuje CA sadržinu 4,9 mas% sadržaj Mg 2,6 mas% i bazni broj od 2,53 mk KOH/g prema ASTMD 2896.
Primer 3
Dejstva pronalaska koja čine njegove prednosti pokazuju se na osnovu kompozicija K-l do K-14.
Kompatibilitet sa materijalom za zaptivanje
Poznati nedostatak običnih sukcinimod-deterdgencija je, osobito u koncentracijama preko 3-4 mas% neželjeno oštećenje materijala za zaptivanje upotrebljenog u motorima. Dobra kompatibilnost pronalaska sa materijalima za zaptivanje dokazuje se na osnovi kompozicija motornih ulja K-6, K-7, K-8 i K-3. Kao referentna uljna kompozicija dati su podaci na kompoziciju K-5 koja sadrži obični sukcinimid (Komad 301). Kompozicije se, pored testova CEC izvedenih sa četiri elastomera, ispituju i pomoću i pomoću testiranja VW-3344 jednog fluornog elastomera, ali pod strožijim okolnostima. Rezultati su dati u tabeli 6
Delimično sintetičke kompozicije K-5, K-6, K-7 i K-8 koje odgovaraju SAE stepenu viskoziteta 10W-40 pokazuju, sa izuzetkom sukcinimida, isti sastav (kompozicija K-8 sadrži PAO-6, druge tri kompozicije sadrže PAO-4). Kompozicija K-3 se zasniva na mineralnim uljima, sadrži rafinat mineralnih ulja koji se proizvodi lakim hidrokraking procesom i pokazuje stepen viskoziteta SAE od 15W-40.
U tabeli 6 date su dobre i vrlo dobre procene koje kompozicije K-3, K-6, K-7 i K-8 pokazuju prednost predmetnog pronalaska u poređenju sa lošim rezultatima kompozicije K-51.
Inhibiraiuće dejstvo habanja
Prema podacima u tabeli 7 nove izrade pokazuju pod određenim uslovima inhibirajuće dejstvo habanja.
Kompozicija K-9 koja je načinjena pomoću uobičajenih dispergenata i kompozicija K-10 koja je načinjena pomoću paketa dodatnih materija u skladu s pronalaskom u Timken uređaju OK opterećenje (ASTM D 2782) na isti način 45 lb (22 kg). Posle tročasovnog testa habanja pri opterećenju 40 lb (19,5 kg) pokazuje ipak kompozicija K-l 1 za 60% manje habanje.
Dejstvo modifikacije viskoziteta. zamena polimera za modifikaciju viskoziteta
Jedna od najvećih prednosti novih kompozicija prema pronalasku sastoji se u povećanom dejstvu viskoziteta i indeksa viskoziteta.
Ovo dejstvo prikazano je pomoću podataka navedenih u tabeli 8 i pokazuje podatke triju kompozicija kod kojih je ispitana uobičajena dodatna materija Komad-301 i polifunkcionalna prema pronalasku, DD kompozicija dodatnih materija bez pepela u kompozicijama na bazi mineralnih ulja i SAE stepena 15W-40 u delimično sintetičkim kompozicijama SAE stepena 10W-40, kao i u sintetičkim kompozicijama SAE stepena 5 W-50, pri čemu kompozicije u pogledu daljih sastojaka pokazuju isti sastav. Najvažniji reološki podaci navedeni su tabelama 8 i 9. Kompozicije se podešavaju unutar pojedinih stepena viskoziteta menjanjem viskoziteta osnovnog ulja i količina polimera za modifikaciju na približno isti nivo.
Od ovih, prema pronalasku, polifunkcionalnih DD kompozicija dodatnih materija bez pepela, pokazuje PIBPSI-1 manje dejstvo povišenja viskoziteta, ali i
to ipak omogućuje smanjenje količine polimera koji modifikuje viskozitet za jednu trećinu kod SAE stepena 15 W-50 u poređenju sa količinom koja se primenjuje kod DD referentne dodatne materije Komad-301. Kod SAE stepena 10W-40 smanjenje sadržine polimera, tj. ušteda je oko 25%, a kod stepena 5W-50 oko 15%.
Kompozicija dodatne materije PIBPSI-2, koja ima veće dejstvo modifikovanja viskoziteta, omogućuje u kompozicijama K-4 i K-6 kod DD-koncentracije potrebne za API stepena SG, zamenu ukupne količine polimera koji modifikuje viskozitet za SAE stepene 15W-40 i 10W-40; u kompozicijama stepena 5W-50 bila je potrebna usled njene primene samo trećina količine polimera za modifikaciju viskoziteta u poređenju sa DD referentnom kompozicijom. Kako se vidi iz viskoziteta u hladnom i toplom, koji su po stepenima približno isti, i iz sličnih viskoziteta osnovnih ulja, ne povećavaju u paketu dodatnih materija prema pronalasku primenjene DD dodatne materije kao polimeri koji modifikuju viskozitet, viskozitet ulja u hladnom, više nego obični polimeri. (Videti tabelu 8)
Stabilnost na smicanje
Prema podacima prikazanim u tabeli 9 stabilnosti na smicanje, proizlazi da Bosch-injektorska stabilnost na smicanje (ASTM D 3934) kompozicije motornog ulja K-7, K-13 i K-14 koje i delimično ili potpuno sadrže sukcinimide kao dodatnu materiju za modifikovanje viskoziteta, slična stabilnosti na smicanje kompozicije K-12 motornog ulja, koja sadrži referentni sukcinimid (Komad-301) i V.I.I.-l na bazi polimer akrilata.
Deterdžentno- disperziono dejstvo, efekt na uređaju za ispitivanje kočenja.
Ispitivanja na uređaju za ispitivanje kočenja, jedna od odlučujućih
karakteristika za kvalifikovanje kompozicija motornog ulja obuhvaćena je u tabeli 10. Uljne kompozicije K-2 i K-3 ispitivane su na ispitnim uređajima kočenja Petter W-l, Ml02 E, sekvenca IIIE i PV 1431. Brojevi zagađenosti motora ispitivanja na uređaju za ispitivanje kočenja M 102 E i sekvence III E pokazuju izrazito disperziono dejstvo i vrednosti brojeva čistoće klipa na redaju za ispitivanje sekvence IIIE i PV 1431 dokazuju odgovarajuće deterdžentno dejstvo dodatnih materija upotrebijenih materija u uljnim kompozicijama. Povoljni sastav kompozicija koji ima prema pronalasku dalje je utvrđenje dobrim svojstvima
habanja izmerenim na uređaju za ispitivanje kočenja Petter M 102 E, a pogotovu na uređaju za ispitivanje kočenja - sekvenca IIIE, i vrlo malom istrošenošcu ležajeva izmerenom na probnom stolu s kočnicom Petter W-l.
Primer4
Sastav paketa koncentrata dodatne materije prema pronalasku i iz njega razređene kompozicije motornog ulja, prikazani su u tabeli 11.
Claims (18)
1. Motorna ulja sa više opsega i kompozicija ulja za podmazivanje koja sadrži dodatne materije, koja se sastoji od motornog ulja podesnog za osnovna ulja,naznačena time,što sadrži 1,5-55 mas% paketa od jedne ili više dodatnih materija koje se sastoje od komponenti "A", "B" i u datom slučaju "C", pri čemu pojedine komponente pokazuju sledeći sastav: komponenta "A": 10-100 mas% polifunkcionalne deterdžentno-disperziono delujuće kompozicije dodatne materije bez pepela ili njihovog uljnog rastvora, pri čemu polifunkcionalna deterdžento disperziono delujuća kompozicija dodatnih materija bez pepela sadrži takve iste ili različite polimlerne komponente koje imaju iste ili različite numeričke molske mase, koje pretvaranjem jednog poliolefinskog derivata- prvenstveno PIB derivata, koji sa jednom ili više dikarbonskih kiselina i/ili anhidrida dikarbonskih kiselina i sa jednim ili više nekiselinskih komonomera dopingovanih etilenskom dvojnom vezom i ima numeričku prosečnu molsku masu od najmanje 800, a proizvedena je sa jednom amino i/ili imino i/ili hidroksi-grupom koja je sadržana u spoju i koja u polimernim kompoentama nosi poliolefinski lanac sa prosečno 6 - 20 derivata kiselina i količinu molekula sa više od jednog derivata kiseline, najmanje 25 mas%, pri čemu derivat može biti imid- i/ili amid- i/ili ester-amid derivat i 0-90 mas% običnog derivata alkenil-ćilibarne kiseline, kao imid- i/ili ester i/ili ester-amid derivat; - Komponenta "B": jednu ili više običnih dodatnih materija, kao deterdžentno-disperziono delujuće dopunske materije sa raznim brojem baza i različitim sadržajem metala, antioksidansa, materija za smanjenje trenja, inhibitora habanja, inhibitora korozije, sredstva za suzbijanje stvaranja pene, i materije za sniženje tačke tečljivosti; komponente "C": jedan ili više uobičajenih polimera za povišenje viskoziteta i indeksa viskoziteta, pri čemu maseni odnos komponenti "A", "B" i "C" iznosi 15-85:15-85:0-70.
2. Kompozicija motornog ulja prema zahtevu 1,naznačena timešto sadrži komponentu "A" takvih polimernih komponenti koje su dopingovane anhidridom maleinske kiseline.
3. Kompozicija motornog ulja prema zahtevima 1 i 2,naznačena timešto sadrži komponentu "A" sa takvim polimernim komponentama koje su proizvedene pretvaranjem poli-iso-butilena sa numeričkom prosečnom molskom masom od 1300 - 30000, kao poliolefin.
4. Kompozicija motornog ulja prema jednom od zahteva 1-3,naznačena timešto sadrži komponentu "A" sa najmanje dve takve polimerne komponenta koje imaju različite - jednu nižu /Mnl/ i jednu višu /Mnll/ numeričku prosečnu molsku masu, pri čemu je numerička prosečna molska masa polimerne komponente sa nižom prosečnom molskom masom manja od šestostruke molske prosečen mase izlaznog poliolefina, i što je odnos prosečne molske mase polimerne komponenta sa nižom prosečnom molskom masom prema polimernoj komponenti sa višom prosečnom molskom masom 3-50:1, prvenstveno 10-20:1, a odnos mase polimerne komponente sa nižom numeričkom prosečnom molskom masom prema komponenti sa višom prosečnom molskom masom 0,01 -5:1.
5. Kompozicija motornog ulja prema jednom od zahteva 1 - 4,naznačena timešto sadrži komponentu "B" od anorgaskih kalcijumovih ili magnezijumovih soli, kao -sulfonata, -fenata, -salicilata, ili njihovu mešavinu kao deterdžentno-disperzionu delujuću dodatnu materiju sa različitim baznim brojem i različitim sadržajem metala.
6. Kompozicija motornog ulja prema jednom od zahteva 1-5,naznačena timešto sadrži 0,6-26 mas% komponente "A", 0,3-18,6 mas% komponente "B" i 0-25 mas% komponente "C".
7. Kompozicija ulja za podmazivanje koja se sastoji od osnovnog ulja podesnog za ulje za podmazivanje i dodatnih materija,naznačena timešto ima sadržaj od 1,5-55 mas% paketa dodatne materije od kojih svaki sadrži jednu ili više dodatnih materija koje se sastoje od komponenti "A", "B" i datom slučaju"C", pri čemu komponente pokazuju sledeći sastav: -Komponenta "A": 10-100 mas% polifunkcionalne deterdžentno-disperziono delujuće kompozicije dodatne materije bez pepela ili njenog uljnog rastvora, pri čemu polifunkcionalna deterdžentno-disperziono delujuća kompozicija sadrži dodatne takve polimerne komponente koje pokazuju jednake ili razne prosečne molske mase i koje su dopingovane pretvaranjem jednog poliolefinskog derivata, prvenstveno PIB derivata koji je jednom ili više dikarbonskih kiselina, i/ili anhidridom dikarbonskih kiselina i jednim ili više nekiselinskim komonomerom sa eltilenskom dvostrukom vezom dopingovan i ima numeričku prosečnu molsku masu od najmanje 800, a proizvedena sa jednim ili više spojeva koji sadrže amino-i/ili imino- i/ili hidroksi grupu i nosi u polimernim komponentama poiolefinski lanac prosečno 6-20 kiselinskih derivata, a količina molekula sa više od jednog kiselinskog derivata iznosi najmanje 25 mas% pri čemu derivat može biti imid-i/ili amid i/ili ester-amid derivat i 0-90 mas%i običnog derivata alkenil-ćilibarne kiseline, kao imid- i/ili ester- i/ili ester-amid derivat; -komponenta "B": jednu ili više dodatnih materija sa raznim baznim brojevima i različitim sadržajem metala, antioksidansa, materija za smanjenje trenja, inhibitora habanja, inhibitora korozije, sredstva za suzbijanje pene i materija za sniženje tačke tečljivosti; -komponenta "C": jedan ili više polimera koji povećavaju viskozitet i indeks viskoziteta, pri čemu maseni odnos komponenti "A", "B" i "C" iznosi: 15-85:15-85:0-70.
8. Kompozicija ulja za podmazivanje prema zahtevu 7,naznačena timešto ima sadržaj komponete "A" takvih polimera koji su dopingovani anhidridom maleinske kiseline.
9. Kompozicija ulja za podmazivanje prema zahtevu 7 i 8,naznačena timešto sadržina komponente "A" ima takve polimerne komponente koje su proizvedene pretvaranjem poli-iso-butilena sa numeričkom prosečnom molskom masom od 1300 - 30000, kao poliolefin.
10. Kompozicija ulja za podmazivanje prema jednom od zahteva 7-9,naznačena time,što ima sadržaj komponente "A" od najmanje dve polimerne komponente, koje imaju -jedna nižu /Mnl/ i jedna višu /Mnll/ nemaričku prosečnu molsku masu polimernih komponenti, pri čemu je numerička prosečna molska masa manja od šestostruke prosečne molske mase izlaznog poliolefina; stoje odnos prosečne molske mase polimerne komponente sa nižom numeričkom molskom masom prema polimernoj komponenti sa višom numeričkom prosečnom molskom masom 3-50:1, prvenstveno 10-20:1 i što maseni odnos polimerne komponente sa nižom numeričkom prosečnom molskom masom iznosi 0,01-5:1.
11. Kompozicija ulja za podmazivanje, prema bilo kom od zahteva 7-10,naznačena time,što ima sadržaj komponente "B" od organskih kalcijumovih ili magnezijumovih soli, kao sulfonati, penati, salicilati ili njihova mešavina deterdžentno-disperziono delujuću dodatnu materiju sa različitim baznim brojem i različitim metalnim sadržajem.
12. Kompozicija ulja za podmazivanje prema jednom od zahteva 7-11,naznačena time,što ima sadržaj od 0,6-26 mas% komponente "A", 0,3-18,6 mas% komponente "B" i 0-25 mas% komponente "C".
13. Paket dodatne materije koji je podesan za kompozicije ulja za podmazivanje, prevenstveno za kompozicije motornog ulja,naznačen timešto sadrži 15-100 mas% komponenti "A", "B" i datom slučaju "C" od kojih se svaka sastoji od jedne ili više dodatnih materija i 0-85 mas% sredstva za razređivanje, pri čemu komponente pokazuju sledeći sastav: - komponenta "A": 10-100 mas% polifunkcionalne deterdžentno-disperziono delujuće dodatne kompozicije bez pepela ili njenog uljnog rastvora pri čemu poli funkcionalna deterdžentno-disperziono delujuća kompozicija dodatne materije bez pepela sadrži takve polimerne komponente koje imaju iste ili različite numeričke molske prosečne mase koje su pretvaranjem jednog polimernog derivata poliolefina, prvenstveno PIB derivata, koji je dopingovan jednom ili više dikarbonskih kiselina i/ili anhidridima dikarbonskih kiselina i jednim ili više nekiselinskih komonomera sa etilenskom dvostrukom vezom i ima prosečnu molsku masu od najmanje 800; i proizveden je jedinjenjem koje ima jednu amino i/ili imino- i/ili hidroksi-grupu i koja sadrži u polimernim komponentama poliolefinski lanac od prosečno 6-20 kiselinskih derivata, kao i količinu molekula sa više od jednog kiselinskog derivata, koja iznosi najmanje 25 mas%, pri čemu derivat može biti imid- i/ili amid- i/ili ester-amid derivat 0-90 mas% uobičajenog derivata alkenil-ćilibarne kiseline, kao imid- i/ili ester-amid derivat; - komponenta "B": jedna ili više običnih dodatnih materija, kao deterdžentno-disperziono delujuće dodatne materije različitih baznih brojeva i različitog sadržaja metala, antioksidansa, materija za smanjenje trenja, inhibitora habanja, inhibitora korozije, sredstava za suzbijanje pene i materija za sniženje tačke tečljivosti; -komponenta "C": - jedan ili više uobičajenih polimera za povišenje viskoziteta ili indeksa viskoziteta, pri čemu je maseni odons komponenata "A", "B" i "C" 15-85:15-85-0-70.
14. Paket dodatnih materija prema zahtevu 13,naznačen time,što sadrži komponentu "A" u takvim polimernim komponentama koje su dopingovane anhidridom maleinske kiseline.
15. Paket dodatnih materija prema zahtevu 13 ili 14,naznačen timešto sadrži komponentu "A" sa takvim polimernim komponentama, koje su dobijene pretvaranjem poli-iso-butilena sa numeričkom prosečnom molskom masom od 1300-30000, kao poliolefm.
16. Paket dodatne matrije prema jednom od zahteva 13-15,naznačen timešto sadrži komponentu "A" od najmanje dve takve polimerne komponente koje imaju jedna nižu /Mnl/ i jedna višu /Mnll/ numeričku prosečnu molsku masu pri čemu je numerička prosečna molska masa polimerne komponente sa nižom numeričkom molskom masom manja od šestostruke prosečne molske mase prema polimernoj komponenti sa višom numeričkom prosečnom molskom masom 3-50:1, prvenstveno iznosi 10-20:1, a maseni odnos polimerne komponente sa nižom numeričkom prosečnom molskom masom prema komponenti sa višom numeričkom prosečnom molskom masom iznosi 0,01-5:1.
17. Paket dodatne materije prema jednom od zahteva 13-16,naznačen timešto mu je sadržaj komponente "B" organskih kalcijumovih ili magnezijumovih soli, kao sulfonati, fenati, salicilati ili njihova mešavina kao deterdžentno-disperziono delujuće dodatne materije sa raznim baznim brojevima i različitim sadržajem metala.
18. Paket dodatne materije prema jednom od zahteva 13-17,naznačen timešto ima sadržaj 0,6-26 mas% komponente "A", 0.3-18.6 mas% komponente "B" 0-25 mas% komponente "C".
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| HU9502797A HU213255B (en) | 1995-09-25 | 1995-09-25 | Multiple- stage engineoil and lubricant composition and additive-pocket |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| YU80395A YU80395A (sh) | 1998-07-10 |
| RS49806B true RS49806B (sr) | 2008-08-07 |
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| Application Number | Title | Priority Date | Filing Date |
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| YUP-803/95A RS49806B (sr) | 1995-09-25 | 1995-12-26 | Motorna ulja sa više opsega i kompozicija ulja za podmazivanje koje sadrži dodatne materije |
Country Status (14)
| Country | Link |
|---|---|
| EP (1) | EP0789069B1 (sr) |
| AT (1) | ATE365202T1 (sr) |
| CZ (1) | CZ294327B6 (sr) |
| DE (1) | DE59511080D1 (sr) |
| EE (1) | EE9500079A (sr) |
| ES (1) | ES2289741T3 (sr) |
| HR (1) | HRP950611B1 (sr) |
| HU (1) | HU213255B (sr) |
| PL (1) | PL179150B1 (sr) |
| RO (1) | RO119233B1 (sr) |
| RS (1) | RS49806B (sr) |
| RU (1) | RU2161179C2 (sr) |
| SK (1) | SK284909B6 (sr) |
| UA (1) | UA43339C2 (sr) |
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| WO2022005486A1 (en) | 2020-07-02 | 2022-01-06 | Halliburton Energy Services, Inc. | Seal bag for seal of an electric submersible pump |
| US11708838B2 (en) | 2020-07-02 | 2023-07-25 | Halliburton Energy Services, Inc. | Chemical sequestration of wellbore fluids in electric submersible pump systems |
| RU2769603C1 (ru) * | 2021-03-17 | 2022-04-04 | Федеральное государственное бюджетное образовательное учреждение высшего образования «Тамбовский государственный технический университет» (ФГБОУ ВО «ТГТУ») | Невысыхающий состав для защиты стальных изделий |
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| US4767551A (en) * | 1985-12-02 | 1988-08-30 | Amoco Corporation | Metal-containing lubricant compositions |
| US5167848A (en) * | 1989-05-30 | 1992-12-01 | Exxon Chemical Patents Inc. | Grafted viscosity index improver |
| FR2706469B1 (fr) * | 1993-06-16 | 1995-10-13 | Inst Francais Du Petrole | Polyisobutènes polyfonctionnels, leur préparation, leur formulation et leur utilisation. |
| JP3001385B2 (ja) * | 1993-12-13 | 2000-01-24 | シェブロン ケミカル カンパニー | ポリマー分散剤 |
| HU211439B (en) * | 1993-12-16 | 1996-02-28 | Veszpremi Egyetem | Ash-free detergent-dispergant polymer type additive composition and process for preparing thereof |
| HU214008B (hu) * | 1994-04-15 | 1998-04-28 | MOL Magyar Olaj- és Gázipari Rt. | Detergens-diszpergens adalékok belső égésű motorok kenőolajaihoz és előállítási eljárásuk |
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1995
- 1995-09-25 HU HU9502797A patent/HU213255B/hu not_active IP Right Cessation
- 1995-12-07 AT AT95119299T patent/ATE365202T1/de not_active IP Right Cessation
- 1995-12-07 ES ES95119299T patent/ES2289741T3/es not_active Expired - Lifetime
- 1995-12-07 EP EP95119299A patent/EP0789069B1/de not_active Expired - Lifetime
- 1995-12-07 DE DE59511080T patent/DE59511080D1/de not_active Expired - Lifetime
- 1995-12-20 CZ CZ19953410A patent/CZ294327B6/cs not_active IP Right Cessation
- 1995-12-21 SK SK1629-95A patent/SK284909B6/sk not_active IP Right Cessation
- 1995-12-21 HR HR950611A patent/HRP950611B1/xx not_active IP Right Cessation
- 1995-12-25 UA UA95125473A patent/UA43339C2/uk unknown
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- 1995-12-28 RU RU95122599/04A patent/RU2161179C2/ru not_active IP Right Cessation
- 1995-12-29 PL PL95312098A patent/PL179150B1/pl not_active IP Right Cessation
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Also Published As
| Publication number | Publication date |
|---|---|
| SK162995A3 (en) | 1997-07-09 |
| ES2289741T3 (es) | 2008-02-01 |
| SK284909B6 (sk) | 2006-02-02 |
| HU9502797D0 (en) | 1995-11-28 |
| UA43339C2 (uk) | 2001-12-17 |
| PL312098A1 (en) | 1997-04-01 |
| YU80395A (sh) | 1998-07-10 |
| HRP950611A2 (en) | 1998-02-28 |
| ATE365202T1 (de) | 2007-07-15 |
| EP0789069A3 (de) | 1998-05-13 |
| HRP950611B1 (en) | 2008-08-31 |
| RU2161179C2 (ru) | 2000-12-27 |
| EE9500079A (et) | 1997-04-15 |
| CZ341095A3 (cs) | 1998-04-15 |
| HU213255B (en) | 1997-05-28 |
| RO119233B1 (ro) | 2004-06-30 |
| EP0789069B1 (de) | 2007-06-20 |
| DE59511080D1 (de) | 2007-08-02 |
| PL179150B1 (pl) | 2000-07-31 |
| CZ294327B6 (cs) | 2004-11-10 |
| EP0789069A2 (de) | 1997-08-13 |
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