FI95592B - Siloksaanipohjainen jäähdytysöljy ja menetelmä sen valmistamiseksi - Google Patents
Siloksaanipohjainen jäähdytysöljy ja menetelmä sen valmistamiseksi Download PDFInfo
- Publication number
- FI95592B FI95592B FI895519A FI895519A FI95592B FI 95592 B FI95592 B FI 95592B FI 895519 A FI895519 A FI 895519A FI 895519 A FI895519 A FI 895519A FI 95592 B FI95592 B FI 95592B
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- Prior art keywords
- weight
- mixture
- cooling oils
- siloxane
- mixtures
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- C10M107/00—Lubricating compositions characterised by the base-material being a macromolecular compound
- C10M107/50—Lubricating compositions characterised by the base-material being a macromolecular compound containing silicon
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- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
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- C09K5/00—Heat-transfer, heat-exchange or heat-storage materials, e.g. refrigerants; Materials for the production of heat or cold by chemical reactions other than by combustion
- C09K5/08—Materials not undergoing a change of physical state when used
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- C10M111/00—Lubrication compositions characterised by the base-material being a mixture of two or more compounds covered by more than one of the main groups C10M101/00 - C10M109/00, each of these compounds being essential
- C10M111/04—Lubrication compositions characterised by the base-material being a mixture of two or more compounds covered by more than one of the main groups C10M101/00 - C10M109/00, each of these compounds being essential at least one of them being a macromolecular organic compound
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- C10M169/00—Lubricating compositions characterised by containing as components a mixture of at least two types of ingredient selected from base-materials, thickeners or additives, covered by the preceding groups, each of these compounds being essential
- C10M169/04—Mixtures of base-materials and additives
- C10M169/044—Mixtures of base-materials and additives the additives being a mixture of non-macromolecular and macromolecular compounds
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- C10M2227/02—Esters of silicic acids
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Description
1 95592
Siloksaanipohjainen jäähdytysöljy ja menetelmä sen valmistamiseksi Tämä patenttihakemus koskee jäähdytysöljyä, joka koostuu siloksaaneista ja soveltuu käytettäväksi matalissa 5 lämpötiloissa lämpötilaan - 140°C asti. On tunnettua, että silikoniöljyjä voidaan käyttää kylmäseoksiin, kun käyte- 2 -1 tään öljyjä, joiden viskositeetti on 5 - 20 mm . s mitattuna lämpötilassa 20°C /W. Simmler, G-I-T Fachzeits-chrift fur das Laboratorium 6 (1962) 101, 189, 278/. Kos-10 ka käyttö on luonteeltaan staattista, ei mainitussa yhteydessä ole merkitystä sillä, että viskositeetti on matalissa lämpötiloissa jo suhteellisen korkea.
Tähän asti on viskositeetiltaan alhaisina jäähdy-tysaineina matalissa lämpötiloissa käytetty toisaalta itse 15 kylmäkoneen kierrossa olevia jäähdytysaineita (halogeeni- hiili- ja halogeenihiilivety-yhdisteitä, kuten esimerkiksi 11 12 22 502 yhdisteitä R , R , R ja R ) ja toisaalta kulloisenkin lämpötila-alueen mukaan alkoholien (metanolin ja ety-leeni- ja propyleeniglykolin) ja suolojen (kalsiumklori-20 din, natriumkarbonaatin jne.) vesiliuoksia. Näiden jäähdy-tysaineiden haittapuolet ovat kyllin tunnettuja: alemmat alkoholit vaativat matalan leimahduspisteen vuoksi työläitä turvatoimenpiteitä ja ovat osittain myrkyllisiä, ja suolojen vesiliuokset ovat voimakkaasti syövyttäviä 25 ja niillä on matalissa lämpötiloissa liian korkea viskositeetti. Lopuksi mainittakoon, että halogeenihiili- ja halogeenihiilivety-yhdisteet aiheuttavat otsonikerroksen fotokemiallista hajoamista ja ovat osittain myös myrkyllisiä. Siksi esimerkiksi JP-hakemusjulkaisussa 50/43 500 30 esitetyt silikoniöljyjen ja halogeenihiilivety-yhdisteiden seokset ovat heikkoja kompromisseja.
Mainitut epäkohdat voitetaan tämän keksinnön mukaisilla jäähdytysaineilla. Kyse on suolattomista, alkoholittomista ja halogeenihiilivety- ja halogeenihiiliyhdistei-35 tä sisältämättömistä jäähdytysöljyistä, joilla on alhainen 2 95592 viskositeetti matalissa lämpötiloissa ja joille on tunnusmerkillistä, että ne koostuvat heksametyylidisiloksaanin ja/tai oktametyylitrisiloksaanin ja/tai lineaarisen deka-metyylitetrasiloksaanin ja/tai oktametyylisyklotetrasi-5 loksaanin ja/tai dekametyylisyklopentasiloksaanin seoksista .
Seuraavassa käytetään yksinkertaisuuden vuoksi silikonien kohdalla nomenklaturiaa, jota kuvataan esimerkiksi teoksessa W. Noll, Chemie und Technologien der 10 Silicone, 2. p., 1968, s. 3 Sen mukaisesti lineaaristen siloksaanien kohdalla käytetään oktametyylitrisilok-saanille nimitystä ja dekametyylitetrasiloksaanille nimitystä M2D2 vastaaviHe korkeammille homologeille yleisnimitystä M2Dn· Syklisistä siloksaaneista käytetään 15 oktametyylisyklotetrasiloksaanille ja dekametyylisyklo- pentasiloksaanille lyhenteitä ja ja korkeammille homologisille syklosiloksaaneille lyhenteitä Dg, D? jne.
Näitä lyhytketjuisia ja syklisiä siloksaaneja saa-... daan esimerkiksi happamissa olosuhteissa tapahtuvalla 20 tasapainoreaktiolla M2:n (heksametyylidisiloksaanin) ja dimetyylidikloorisilaanin hydrolyysin kautta muodostetun silikoniöljyn (A-öljyn) välillä, jossa käytetään paino-suhdetta 1:1 ja yleensä hapanta ioninvaihdinta, kuten esimerkiksi hapolla aktivoitua bentoniittia. Jos tällaista *: 25 reaktiotuotetta kuumennetaan, kun katalysaattori on ero tettu suodattamalla, saadaan viskositeetiltaan alhainen siloksaaniseos, kuten esimerkiksi Baysilone-öljy (kaupallinen tuote, Bayer AG, Leverkusen). GC-analyysillä tehty karakterisointi ja luettelo vastaavista kiehumispis-30 teistä esitetään taulukossa 1. Jos tällaiselle tuoteseok-·[ selle tehdään jakotislaus, voidaan yksittäiset siloksaanit erottaa toisistaan tai keksinnön mukainen ja toivottu siloksaaniseos voidaan saada aikaan käyttämällä vastaavaa tislausjaetta.
35 Näistä yksittäisistä siloksaaneista näyttää M2D2 ensin olevan tuote, jolla on parhaat tunnusarvot jäähdy- il IMI lii II In t M 1 3 95592 tysöljyn kannalta, koska sillä on alhainen viskositeetti lämpötilassa -40°C ja sen leimahduspiste on yli 55°c. viimeksi mainittu ominaisuus on merkittävä siksi, että vahin-komääräysten mukaan M2D2:a ei enää pidetä "syttyvänä" eikä 5 siksi tarvita kalliita työturvallisuustoimenpiteitä. Puhtaan M2D2:n kiteytymispiste on kuitenkin -76°C (katso taulukko 2), mikä rajoittaa voimakkaasti käyttöä jäähdytysai-neena.
Nyt on yllättävästi havaittu, että M2D:n ja/tai 10 D4:n ja/tai D5:n lisääminen alentaa voimakkaasti M2D2:n jähmettymispistettä. M2D2:n ja M2D:n seos, jossa M2D:n osuus on korkeintaan 20 paino-%, muodostaa järjestelmän, jonka viskositeetti on alhainen lämpötilassa -40°C ja leimahduspiste yli 55°C. Jos joukkoon sekoitetaan enemmän 15 M2D:tä tai M2:a, alenevat viskositeetti ja jähmettymispis-te, mutta samalla myös leimahduspiste; seos saattaisi kuitenkin olla kiinnostava tiettyihin teollisuuden käyttötarkoituksiin. Jähmettymispiste (standardin DIN 51 556 mukainen) on yleensä 3 - 5°C matalampi kuin vastaava standardin 20 DIN ISO 3 016 mukaisesti määritetty jähmettymispiste (pour point).
Keksinnön mukaisille jäähdytysöljyille on tunnusomaista, että ne koostuvat seoksista, joissa on 5 - 95 paino-% suoraketjuista dekametyylitetrasiloksaania (M2D2) ja 25 vähintään yhtä seuraavista komponenteista: 0,1 - 23 paino-% heksametyylidisiloksaania (M2), 0,1 - 20 paino-% oktametyylitrisiloksaania (M2D), 0,1 - 15 paino-% oktametyylisyklotetrasiloksaania (D4), 0-50 paino-% dekametyylisyklopentasiloksaania (Dg), 30 sekä mahdollisesti väriaineita, jolloin seoksen komponenttien summa on 100 %.
Keksinnön mukaiset jäähydytsöljyt valmistetaan siten, että heksametyylidisiloksaanin ja hydrolysoimalla saadun A-öljyn välisessä tasapainoreaktiossa syntyneestä ly-35 hytketjuisten ot,c<>-bis-(trimetyylisiloksi)dimetyylisiloksaa- nien ja syklisten dimetyylisiloksaanien seoksesta poistetaan osa heksametyylidisiloksaanista tislaamalla ja muodostetaan haluttu siloksaaniseos jakotislauksella ja mahdollisesti lisäämällä lisäksi puhtaita komponentteja.
4 95592
Jos M2D2:een tai M2D2:n ja M2D:n seokseen sekoitetaan M2:a ja/tai syklisiä siloksaaneja D4 ja/tai Dg, ei lisättävä määrä saisi D4:n kohdalla olla yli 30 paino-% ja D5:n kohdalla yli 50 paino-%, jotta vältetään erottuminen 5 ja kiteytymissameneminen matalissa lämpötiloissa. D4:ä lisätään edullisesti 5-15 paino-% ja Dg:ä 5 - 20 paino-%, jolloin D5 on D4:ä edullisempi paremman jähmettymispistettä alentavan vaikutuksensa vuoksi. Näitä neljää siloksaania voidaan keksinnön mukaisesti sekoittaa, kuten taulukoiden 2 10 ja 3 esimerkit osoittavat, siten, että viskositeetti on 2 -1 lämpötilassa -40°C alle 10 mm . s , edullisesti mahdollisimman alhainen, ja leimahduspiste on yli 43°C, edullisesti yli 55°c. Jos keksinnön mukaisten yksittäisten siloksaanien sijasta käytetään vastaavia tilastollisia M2:n ja korkeam-15 pien M_D -tyyppien seoksia (taulukon 4 esimerkit), viskosi- « Π teetti kohoaa ja leimahduspiste alenee, niin että tällainen jäähdytysöljy on yleensä vähemmän arvokasta. Sellaisissa erityiskäyttötapauksissa, joissa matalalla leimahduspis-teellä ei ole merkitystä, saattavat myös tilastolliset 20 seokset, joissa jakautuma on sangen kapea, kuten esimerk- • · < kien 17 ja 19 mukaiset seokset, olla kiintoisia. Mainittujen esimerkkien mukaisesti voidaan siloksaanien M2D ja M2D2 ja D4 ja/tai Dg seokseen lisätä M2:a pitoisuuteen 23 paino-% asti, ilman että leimahduspiste alenee arvon 21°C alapuo-25 lelle. Tällaista seosta pidetään "syttyvänä", jolloin turva 11 isuuskustannukset ovat pienemmät kuin "helposti sytty- ♦ vien" aineiden tai aineseosten (leimahduspiste alle 21°C) ollessa kyseessä.
Siten valmistettuja jäähdytysöljyjä voidaan käyttää 30 lämmönsiirtoon lämpötilaan -140°C asti. Edullisia käyttötarkoituksia ovat siten pakastamot, kylmäkalusteet ja pa-.· kastearkut, mutta myös maaperään sijoitettavissa silmukois sa käytettävät ja muut lämmönsiirtonesteet, jotka ovat yhteydessä lämpöpumppuihin ja jotka tunnetusti voivat jäähtyä 35 huomattavasti lämpöpumpun haihdutinpuolella tapahtuneen lämmön kulumisen jälkeen. Tällaisissa niin kutsutuissa au-rinkojärjestelmissä, joita on tähän asti valmistettu veden ja etyleeniglykolin seoksiin perustuvina, ei saavuteta matalia lämpötiloja.
5 95592
Keksinnön mukaisilla jäähdytysöljyillä on tässä käyttötapauksessa se etu, etteivät ne vaikuta syövyttävästi ja että ne ovat toksikologisesti haitattomia. Koska esimerkiksi esimerkin 5 mukainen M2D2:n ja Dg:n seos muuttuu 5 kiinteäksivastalämpötilan -130°C alapuolella ja toisaalta yksittäiset komponentit kiehuvat normaaliolosuhteissa vasta lämpötiloissa 194 ja 210°C, voidaan ajatella myös käyttöaluetta, jolla lämpötilakuormitukset ovat äärimmäisiä, kuten esimerkiksi autojen jäähdytysnesteinä tai muuntamoöl-10 jyinä ilmastovyöhykkeillä, joissa lämpötilavaihtelut ovat voimakkaita.
Keksinnön mukaiset siloksaaniseokset voidaan värjätä mahdollisten vuotojen saamiseksi näkyviin. Niinpä joukkoon voidaan sekoittaa huoneen lämpötilassa kulloinkin 15 0,01 paino-% seuraavia antrakinonivärlaineita: antrakinoni 1-aminoantrakinoni 1.4- bis-isobutyyliaminoantrakinoni 1-(4-dimetyyliaminopropyyliamino)-4-metyyliaminoantrakinoni 20 1-(4-metyylitenyyliamino)-antrakinoni • 4 1.4- bis-(2,6-dietyyli-4-metyylifenyyliamino)-antrakinoni 1.4- bis(4-t-butyylifenyyliamino)-antrakinoni l-metyyliamino-4-(3-metyylifenyyliamino)-antrakinoni l-metyyliamino-4-(4-metyylifenyyliamino)-antrakinoni 25 1-(3-dimetyyliaminopropyyliamino)-4-(4-metyylifenyyliami- .· no)-antrakinoni.
Lisäksi voidäan värjäämiseen käyttää korkeintaan noin 0,002 paino-% seuraavia luonnonväriaineita:
Ceresrot 7 B 30 Ceresgelb CRN
Cochni Harot Ceresblau GN.
Taulukoiden 2 ja 3 esimerkit havainnollistavat tätä keksintöä. Taulukossa 2 esitetään lisäksi vastaavien 35 puhtaiden aineiden tunnusarvoja. Taulukon 4 siloksaanit ovat tilastollisten siloksaanien seoksia, ja niillä on joko korkeampi viskositeetti matalissa lämpötiloissa tai alhaisempi leimahduspiste kuin vastaavilla keksinnön mukaisilla yksittäisten siloksaanien seoksilla.
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Claims (3)
1. Suolavapaita, alkoholivapaita ja halogeenihiili-vetyvapaita jäähdytysöljyjä, joilla on alhainen viskosi-5 teetti matalissa lämpötiloissa, tunnetut siitä, että ne koostuvat seoksista, joissa on 5 - 95 paino-% suo-raketjuista dekametyylitetrasiloksaania (M2D2) ja vähintään yhtä seuraavista komponenteista: 0,1 - 23 paino-% heksametyylidisiloksaania (M2) , 10 0,1 - 20 paino-% oktametyylitrisiloksaania (M2D) , 0,1 - 15 paino-% oktametyylisyklotetrasiloksaania (D4) , 0-50 paino-% dekametyylisyklopentasiloksaania (Ds) , sekä mahdollisesti väriaineita, jolloin seoksen komponenttien summa on 100 %.
2. Menetelmä patenttivaatimusten 1 mukaisten jääh- dytysöljyjen valmistamiseksi, tunnettu siitä, että heksametyylidisiloksaanin ja hydrolysoimalla saadun A-öljyn välisessä tasapainoreaktiossa syntyneestä lyhyt-. ketjuisten α,ω-bis-(trimetyylisiloksi)dimetyylisiloksaa- 20 nien ja syklisten dimetyylisiloksaanien seoksesta poiste taan osa heksametyylidisiloksaanista tislaamalla ja muodostetaan haluttu siloksaaniseos jakotislauksella ja mahdollisesti lisäämällä lisäksi puhtaita komponentteja.
3. Patenttivaatimuksen 1 tai 2 mukaisten jäähdytys-25 Öljyjen käyttö, tunnettu siitä, että niitä käyte- tään lämmönsiirtoon lämpötilaan -140 °C asti. u 9559?
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE3839333 | 1988-11-22 | ||
DE3839333A DE3839333A1 (de) | 1988-11-22 | 1988-11-22 | Kaeltetraegeroel auf siloxanbasis |
Publications (3)
Publication Number | Publication Date |
---|---|
FI895519A0 FI895519A0 (fi) | 1989-11-20 |
FI95592B true FI95592B (fi) | 1995-11-15 |
FI95592C FI95592C (fi) | 1996-02-26 |
Family
ID=6367589
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
FI895519A FI95592C (fi) | 1988-11-22 | 1989-11-20 | Siloksaanipohjainen jäähdytysöljy ja menetelmä sen valmistamiseksi |
Country Status (13)
Country | Link |
---|---|
EP (1) | EP0370316B1 (fi) |
JP (1) | JP2839162B2 (fi) |
KR (1) | KR0135280B1 (fi) |
AT (1) | ATE116673T1 (fi) |
AU (1) | AU624443B2 (fi) |
CA (1) | CA2003332A1 (fi) |
DE (2) | DE3839333A1 (fi) |
DK (1) | DK171442B1 (fi) |
ES (1) | ES2067516T3 (fi) |
FI (1) | FI95592C (fi) |
GR (1) | GR3015666T3 (fi) |
NO (1) | NO177354C (fi) |
ZA (1) | ZA898859B (fi) |
Families Citing this family (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE4309070A1 (de) * | 1993-03-20 | 1994-09-22 | Licentia Gmbh | Hochtemperaturbatterie |
JP4493007B2 (ja) * | 2003-04-28 | 2010-06-30 | 信越化学工業株式会社 | ジメチルポリシロキサン組成物 |
DE102012211258A1 (de) * | 2012-06-29 | 2014-01-02 | Wacker Chemie Ag | Siloxan-Mischungen |
JP6339442B2 (ja) * | 2014-08-01 | 2018-06-06 | シーシーアイ株式会社 | 着色冷却液組成物 |
Family Cites Families (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2468869A (en) * | 1946-02-15 | 1949-05-03 | Corning Glass Works | Organosilicon compositions and methods of making them |
IT1087577B (it) * | 1976-12-09 | 1985-06-04 | Dow Corning | Sistema per la raccolta dell'energia solare utilizzante un fluido migliorato per il trasferimento del calore |
-
1988
- 1988-11-22 DE DE3839333A patent/DE3839333A1/de not_active Withdrawn
-
1989
- 1989-11-08 NO NO894446A patent/NO177354C/no not_active IP Right Cessation
- 1989-11-09 DE DE58908854T patent/DE58908854D1/de not_active Expired - Lifetime
- 1989-11-09 AT AT89120762T patent/ATE116673T1/de not_active IP Right Cessation
- 1989-11-09 ES ES89120762T patent/ES2067516T3/es not_active Expired - Lifetime
- 1989-11-09 EP EP89120762A patent/EP0370316B1/de not_active Expired - Lifetime
- 1989-11-17 JP JP1297768A patent/JP2839162B2/ja not_active Expired - Lifetime
- 1989-11-17 AU AU44773/89A patent/AU624443B2/en not_active Ceased
- 1989-11-20 FI FI895519A patent/FI95592C/fi active IP Right Grant
- 1989-11-20 CA CA002003332A patent/CA2003332A1/en not_active Abandoned
- 1989-11-21 ZA ZA898859A patent/ZA898859B/xx unknown
- 1989-11-21 DK DK584289A patent/DK171442B1/da not_active IP Right Cessation
- 1989-11-21 KR KR1019890016880A patent/KR0135280B1/ko not_active IP Right Cessation
-
1995
- 1995-04-03 GR GR950400810T patent/GR3015666T3/el unknown
Also Published As
Publication number | Publication date |
---|---|
AU624443B2 (en) | 1992-06-11 |
EP0370316B1 (de) | 1995-01-04 |
DE3839333A1 (de) | 1990-05-23 |
ATE116673T1 (de) | 1995-01-15 |
NO894446D0 (no) | 1989-11-08 |
JP2839162B2 (ja) | 1998-12-16 |
ZA898859B (en) | 1990-08-29 |
FI95592C (fi) | 1996-02-26 |
ES2067516T3 (es) | 1995-04-01 |
DK584289A (da) | 1990-05-23 |
KR0135280B1 (ko) | 1998-04-22 |
NO177354B (no) | 1995-05-22 |
FI895519A0 (fi) | 1989-11-20 |
CA2003332A1 (en) | 1990-05-22 |
AU4477389A (en) | 1990-05-31 |
DE58908854D1 (de) | 1995-02-16 |
NO177354C (no) | 1995-09-06 |
KR900008003A (ko) | 1990-06-02 |
GR3015666T3 (en) | 1995-07-31 |
JPH02242878A (ja) | 1990-09-27 |
DK171442B1 (da) | 1996-10-28 |
DK584289D0 (da) | 1989-11-21 |
NO894446L (no) | 1990-05-23 |
EP0370316A1 (de) | 1990-05-30 |
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Legal Events
Date | Code | Title | Description |
---|---|---|---|
BB | Publication of examined application | ||
PC | Transfer of assignment of patent |
Owner name: GE BAYER SILICONES GMBH & CO.KG. |
|
FG | Patent granted |
Owner name: GE BAYER SILICONES GMBH & CO. KG |