Claims (24)
1. Postupak za proizvodnju masti za podmazivanje, koje sadrže ligninsulfonat, naznačen time, da se sastoji od
a) koraka unošenja :
- barem jednog baznog ulja,
- barem jednog kalcijevog sapuna zasićene ili nezasićene monokarboksilne kiseline s 10 do 32 ugljikova atoma, po izboru supstituirane,
- barem jednog sredstva za stvaranje kompleksa, odabranog od:
(i) alkalijske soli, s izuzetkom natrijeve soli, zemnoalkalijske soli ili aluminijeve soli zasićene ili nezasićene monokarboksilne kiseline ili hidroksikarboksilnih kiselina s 2 do 8, dikarboksilne kiseline s 2 do 16 ugljikovih atoma, od kojih je svaka po izboru supstituirana,
(ii) alkalijske i/ili zemnoalkalijske soli borne kiseline i/ili fosforne kiseline, uključivo njihovih reakcijskih produkata s LiOH i/ili Ca(OH)2 i
(ili) njihovih smjesa i
- barem jednog kalcijevog ligninsulfonata srednje molekularne mase kao prosječne mase veće od 10000 g/mol,
zagrijavanja na više od 120°C za reakciju i uz istjerivanje komponenata niskog vrelišta, za proizvodnju bazne masti i
b) koraka hlađenja i dodavanja baznog ulja i aditiva po izboru uz miješanje. 1. Process for the production of lubricating grease containing ligninsulfonate, characterized in that it consists of
a) input steps:
- at least one base oil,
- at least one calcium soap of saturated or unsaturated monocarboxylic acid with 10 to 32 carbon atoms, optionally substituted,
- at least one agent for creating a complex, selected from:
(i) alkali salts, with the exception of sodium salts, alkaline earth salts or aluminum salts of saturated or unsaturated monocarboxylic acids or hydroxycarboxylic acids with 2 to 8, dicarboxylic acids with 2 to 16 carbon atoms, each of which is optionally substituted,
(ii) alkaline and/or alkaline earth salts of boric acid and/or phosphoric acid, including their reaction products with LiOH and/or Ca(OH)2 and
(or) their mixtures and
- at least one calcium ligninsulfonate of medium molecular weight as an average mass greater than 10,000 g/mol,
heating to more than 120°C for the reaction and with the expulsion of low-boiling components, for the production of base fat and
b) steps of cooling and addition of base oil and optional additives with mixing.
2. Postupak prema patentnom zahtjevu 1, naznačen time, da se u koraku a) dodaje kalcijev hidroksid uz daljnje zemnoalkalijske hidrokside po izboru.2. The process according to patent claim 1, characterized in that in step a) calcium hydroxide is added along with further alkaline earth hydroxides of choice.
3. Postupak prema patentnom zahtjevu 1, naznačen time, da je mast za podmazivanje podešena alkalno, osobito dodatkom kalcijevog hidroksida u suvišku.3. The method according to patent claim 1, characterized in that the lubricating grease is adjusted alkaline, especially by the addition of calcium hydroxide in excess.
4. Postupak prema patentnom zahtjevu 1, naznačen time, da se zagrijavanje provodi na temperaturama koje prelaze 180°C.4. The method according to patent claim 1, characterized in that the heating is carried out at temperatures exceeding 180°C.
5. Postupak prema patentnom zahtjevu 1, naznačen time, da se uz kalcijev hidroksid u koraku a) koriste također litijev hidroksid, magnezijev hidroksid, i/ili aluminijev hidroksid, odnosno aluminijevi alkoholati i/ili aluminijevi oksoalkoholati i/ili litijevi, magnezijevi i/ili aluminijevi sapuni zasićene ili nezasićene monokarboksilne kiseline s 10 do 32 ugljikova atoma, supstituirane po izboru.5. Process according to patent claim 1, characterized in that, in addition to calcium hydroxide in step a), lithium hydroxide, magnesium hydroxide, and/or aluminum hydroxide, i.e. aluminum alcoholates and/or aluminum oxoalcoholates and/or lithium, magnesium and/or or aluminum soaps of saturated or unsaturated monocarboxylic acids with 10 to 32 carbon atoms, optionally substituted.
6. Postupak prema patentnom zahtjevu 1, naznačen time, da mast za podmazivanje sadrži neovisno jedno o drugome:
- 55 do 92 tež.%, osobito 70 do 85 tež.% baznog ulja,
- 0 do 40 tež.% , osobito 2 do 10 tež.% aditiva,
- 3 do 40 tež.%, osobito 5 do 20 tež.% kalcijevih sapuna i
- 0,6 do 10 tež.% sredstava za stvaranje kompleksa, i
- po izboru Ca(OH)2u suvišku, prvenstveno 0,01 do 2 tež.%, i
- 0,5 do 15 tež.%, a prvenstveno 4 do 8 tež.% kalcijevog ligninsulfonata, uz daljnje zemnoalkalijske ligninsulfonate po izboru,
u svakom slučaju u odnosu na ukupni sastav masti za podmazivanje.6. The method according to patent claim 1, characterized in that the lubricating grease contains independently of each other:
- 55 to 92 wt.%, especially 70 to 85 wt.% of base oil,
- 0 to 40 wt.%, especially 2 to 10 wt.% of additives,
- 3 to 40 wt.%, especially 5 to 20 wt.% of calcium soaps and
- 0.6 to 10 wt.% of complexing agents, i
- optional Ca(OH)2 in excess, preferably 0.01 to 2 wt.%, i
- 0.5 to 15 wt.%, and primarily 4 to 8 wt.% of calcium ligninsulfonate, with further alkaline earth ligninsulfonates by choice,
in any case in relation to the total composition of the lubricating grease.
7. Postupak prema patentnom zahtjevu 1, naznačen time, da se bazna mast koraka a) može proizvoditi uz primjenu
- 40 do 70 tež.%, osobito 45 do 60 tež.% baznog ulja,
- 10 do 60 tež.%, osobito 15 do 50 tež.% kalcijevih sapuna i
- 5 do 30 tež.% sredstava za stvaranje kompleksa, i
- po izboru Ca(OH)2 u suvišku, prvenstveno 0,02 do 4 tež.%, i
- 0,7 do 30 tež.% kalcijevog ligninsulfonata, uz dodatne daljnje zemnoalkalijske ligninsulfonate po izboru, u svakom slučaju u odnosu na sastav bazne masti.7. The method according to patent claim 1, characterized in that the base grease of step a) can be produced with application
- 40 to 70 wt.%, especially 45 to 60 wt.% of base oil,
- 10 to 60 wt.%, especially 15 to 50 wt.% of calcium soaps and
- 5 to 30 wt.% of means for creating complexes, i
- optional Ca(OH)2 in excess, preferably 0.02 to 4 wt.%, i
- 0.7 to 30 wt.% of calcium ligninsulfonate, with additional further alkaline earth ligninsulfonates of choice, in each case in relation to the composition of the base fat.
8. Postupak prema patentnom zahtjevu 1 ili 4, naznačen time, da mast za podmazivanje sadrži neovisno jedno o drugome 0,2 – 5 tež.% grafita i/ili nekrutog sredstva za podmazivanje ili manje od 1 tež.% krutog sredstva za podmazivanje, osobito ne MoS2.8. The method according to patent claim 1 or 4, characterized in that the lubricating grease contains, independently of each other, 0.2-5 wt.% of graphite and/or non-solid lubricant or less than 1 wt.% of solid lubricant, especially not MoS2.
9. Postupak prema patentnom zahtjevu 1, naznačen time, da je kalcijev sapun proizveden na licu mjesta kao reakcijski produkt kalcijevog hidroksida sa zasićenom ili nezasićenom monokarboksilnom kiselinom s 10 do 32 ugljikova atoma, osobito sa 16 do 20 ugljikovih atoma, po izboru supstituirane, na primjer s hidroksi, kao ester ili anhidrid. 9. The method according to patent claim 1, characterized in that the calcium soap is produced on site as a reaction product of calcium hydroxide with a saturated or unsaturated monocarboxylic acid with 10 to 32 carbon atoms, especially with 16 to 20 carbon atoms, optionally substituted, on example with hydroxy, as an ester or anhydride.
10. Postupak prema patentnom zahtjevu 1, naznačen time, da se sredstvo za stvaranje kompleksa dodaje za vrijeme koraka a) kao reakcijski produkt kalcijeve soli, osobito kalcijevog hidroksida sa zasićenom ili nezasićenom monokarboksilnom kiselinom koja ima 2 do 8, osobito 2 do 4 ugljikova atoma ili dikarboksilnom kiselinom s 2 do 16, osobito 2 do 12 ugljikovih atoma, od kojih se svaka po izboru supstituira, na primjer s hidroksi, kao ester ili anhidrid. 10. The method according to claim 1, characterized in that the complexing agent is added during step a) as a reaction product of a calcium salt, especially calcium hydroxide, with a saturated or unsaturated monocarboxylic acid having 2 to 8, especially 2 to 4 carbon atoms or a dicarboxylic acid with 2 to 16, especially 2 to 12 carbon atoms, each of which is optionally substituted, for example with hydroxy, as an ester or anhydride.
11. Postupak prema patentnom zahtjevu 1, naznačen time, da sredstvo za stvaranje kompleksa jest kalcijeva sol karboksilne kiseline i da se proizvodi na licu mjesta za vrijeme koraka a) dodavanjem zasićene ili nezasićene monokarboksilne kiseline s 2 do 8, osobito 2 do 4 ugljikova atoma ili dikarboksilne kiseline s 2 do 16, osobito 2 do 12 ugljikovih atoma, od kojih se svaka po izboru supstituira, na primjer s hidroksi, kao ester ili anhidrid.11. The method according to patent claim 1, characterized in that the agent for forming the complex is a calcium salt of a carboxylic acid and that it is produced on site during step a) by adding a saturated or unsaturated monocarboxylic acid with 2 to 8, especially 2 to 4 carbon atoms or dicarboxylic acids with 2 to 16, especially 2 to 12 carbon atoms, each of which is optionally substituted, for example with hydroxy, as an ester or anhydride.
12. Postupak prema barem jednom od patentnih zahtjeva 1 do 11, naznačen time, da se kalcijev ligninsulfonat prije dodavanja dehidrira do vrijednosti manjih od 0,5 tež.% vode, na primjer zagrijavanjem u baznom ulju na više od 95°C, osobito na više od 100°C, do na primjer 120°C.12. The method according to at least one of the patent claims 1 to 11, characterized in that the calcium ligninsulfonate is dehydrated to a value of less than 0.5% by weight of water before addition, for example by heating in the base oil to more than 95°C, especially at more than 100°C, up to for example 120°C.
13. Postupak prema barem jednom od patentnih zahtjeva 1 do 12, naznačen time, da sastav sadrži sredstvo za stvaranje kompleksa od 0,5 do 10 tež.%. 13. The method according to at least one of claims 1 to 12, characterized in that the composition contains a complexing agent from 0.5 to 10% by weight.
14. Sastav masti za podmazivanje, naznačen time, da sadrži
- 55 do 92 tež.%, osobito 70 do 85 tež.% baznog ulja,
- 0 do 40 tež.%, osobito 2 do 10 tež.% aditiva,
- 3 do 40 tež.%, osobito 5 do 20 tež.% kalcijevih sapuna zasićene ili nezasićene monokarboksilne kiseline s 10 do 32 ugljikova atoma, supstituirane po izboru,
- 0,5 do 10 tež.% sredstva za stvaranje kompleksa, odabranog od:
(i) alkalijske soli, s izuzetkom natrijeve soli, zemnoalkalijske soli ili aluminijeve soli zasićene ili nezasićene monokarboksilne kiseline ili hidroksikarboksilnih kiselina s 2 do 8, dikarboksilne kiseline s 2 do 16 ugljikovih atoma, od kojih je svaka supstituirana po izboru,
(ii) alkalijske i/ili zemnoalkalijske soli borne kiseline i/ili fosforne kiseline, uključivo njihovih reakcijskih produkata s LiOH i/ili Ca(OH)2,po izboru s Ca(OH)2 u suvišku, prvenstveno 0,01 do 2 tež.%, i
(ili) njihovih smjesa i
- 0,5 do 15 tež.%, a prvenstveno 2 do 8 tež.% kalcijevog ligninsulfonata, uz daljnje zemnoalkalijske ligninsulfonate po izboru,
u svakom slučaju u odnosu na cjelokupni sastav masti za podmazivanje,
kod čega sastav ima vrijednost penetracije konusa (Walkpenetration) od 265 do 365 mm/10 pri 25°C, određenu prema ISO 2137.14. The composition of the lubricating grease, indicated by the fact that it contains
- 55 to 92 wt.%, especially 70 to 85 wt.% of base oil,
- 0 to 40 wt.%, especially 2 to 10 wt.% of additives,
- 3 to 40 wt.%, especially 5 to 20 wt.% calcium soaps of saturated or unsaturated monocarboxylic acid with 10 to 32 carbon atoms, optionally substituted,
- 0.5 to 10% by weight of a complex forming agent selected from:
(i) alkali salts, with the exception of sodium salts, alkaline earth salts or aluminum salts of saturated or unsaturated monocarboxylic acids or hydroxycarboxylic acids with 2 to 8, dicarboxylic acids with 2 to 16 carbon atoms, each of which is optionally substituted,
(ii) alkaline and/or alkaline earth salts of boric acid and/or phosphoric acid, including their reaction products with LiOH and/or Ca(OH)2, optionally with Ca(OH)2 in excess, preferably 0.01 to 2 wt. .%, i
(or) their mixtures and
- 0.5 to 15 wt.%, and primarily 2 to 8 wt.% of calcium ligninsulfonate, with further alkaline earth ligninsulfonates by choice,
in any case in relation to the overall composition of the lubricating grease,
where the composition has a cone penetration value (Walkpenetration) of 265 to 365 mm/10 at 25°C, determined according to ISO 2137.
15. Sastav prema patentnom zahtjevu 14, naznačen time, da sastav ima vrijednost penetracije konusa (Walkpenetration) od 285 do 355 mm/10, određenu prema ISO 2137.15. Composition according to patent claim 14, characterized in that the composition has a cone penetration value (Walkpenetration) of 285 to 355 mm/10, determined according to ISO 2137.
16. Sastav prema barem jednom od patentnih zahtjeva 14 ili15, naznačen time, da bazno ulje ima kinematički viskozitet od 20 do 2500 mm2/s, prvenstveno od 40 do 500 mm2/s pri 40°C. 16. Composition according to at least one of patent claims 14 or 15, characterized in that the base oil has a kinematic viscosity of 20 to 2500 mm2/s, preferably from 40 to 500 mm2/s at 40°C.
17. Sastav prema barem jednom od patentnih zahtjeva 14 do16, naznačen time, da se sredstvo za stvaranje kompleksa sastoji od:
- alkalijske soli, prvenstveno litijeve soli, zemnoalkalijske soli, prvenstveno kalcijevih soli, ili aluminijeve soli zasićene ili nezasićene monokarboksilne kiseline s 2 do 8, osobito 2 do 4 ugljikova atoma ili dikarboksilne kiseline s 2 do 16, osobito 2 do 12 ugljikovih atoma, od kojih je svaka supstituirana po izboru.17. The composition according to at least one of the patent claims 14 to 16, characterized in that the agent for forming the complex consists of:
- alkali salts, primarily lithium salts, alkaline earth salts, primarily calcium salts, or aluminum salts of saturated or unsaturated monocarboxylic acids with 2 to 8, especially 2 to 4 carbon atoms or dicarboxylic acids with 2 to 16, especially 2 to 12 carbon atoms, from each of which is substituted by choice.
18. Sastav prema barem jednom od patentnih zahtjeva 14 do17, naznačen time, da aditiv obuhvaća jedan ili više članova odabranih iz sljedeće skupine:
- aminski spojevi, fenolni spojevi, antioksidansi koji sadrže sumpor, cinkov ditiokarbamat ili cinkov ditiofosfat, kao antioksidacijska sredstva;
- organski klorni spojevi, sumpor, fosfor ili kalcijev borat, cinkov ditiofosfat, organski bizmutovi spojevi, kao aditivi za visoki pritisak;
- C2 do C6 polioli, masne kiseline, esteri masnih kiselina ili ulja životinjskog ili biljnog podrijetla;
- petrolej sulfonat, dinonilnaftalon sulfonat ili sorbitan ester, kao antikorozivna sredstva;
- benzotriazol ili natrijev nitrit, kao deaktivatori metala;
- polimetakrilat, poliizobutilen, oligo-Dec-1-en i polistireni za poboljšanje viskoziteta;
- molibden dialkilditiokarbamat ili molibden sulfid dialkilditiokarbamat ili aromatski amini, kao aditivi protiv habanja;
- funkcionalni polimeri kao na pr. oleilamidi, organski spojevi na bazi polietera i amida ili molibden ditiokarbamat, kao sredstva za smanjivanje trenja; i
- polimerni praškovi kao poliamidi, poliimidi, ili PTFE, grafit, metalni oksidi, borov nitrid, metalni sulfidi, kao na pr. molibdenov disulfid, volframov disulfid ili miješani sulfidi na bazi volframa, molibdena, bizmuta, kositra i cinka, anorganske soli alkalijskih i zemnoalkalijskih metala, kao na pr. kalcijev karbonat, natrijevi i kalcijevi fosfati, kao kruta sredstva za podmazivanje.18. Composition according to at least one of patent claims 14 to 17, characterized in that the additive comprises one or more members selected from the following group:
- amine compounds, phenolic compounds, antioxidants containing sulfur, zinc dithiocarbamate or zinc dithiophosphate, as antioxidants;
- organic chlorine compounds, sulfur, phosphorus or calcium borate, zinc dithiophosphate, organic bismuth compounds, as additives for high pressure;
- C2 to C6 polyols, fatty acids, fatty acid esters or oils of animal or vegetable origin;
- petroleum sulfonate, dinonylnaphthalene sulfonate or sorbitan ester, as anticorrosive agents;
- benzotriazole or sodium nitrite, as metal deactivators;
- polymethacrylate, polyisobutylene, oligo-Dec-1-ene and polystyrenes to improve viscosity;
- molybdenum dialkyldithiocarbamate or molybdenum sulfide dialkyldithiocarbamate or aromatic amines, as anti-wear additives;
- functional polymers such as oleylamides, organic compounds based on polyether and amide or molybdenum dithiocarbamate, as means to reduce friction; and
- polymer powders such as polyamides, polyimides, or PTFE, graphite, metal oxides, boron nitride, metal sulfides, such as e.g. molybdenum disulfide, tungsten disulfide or mixed sulfides based on tungsten, molybdenum, bismuth, tin and zinc, inorganic salts of alkali and alkaline earth metals, such as e.g. calcium carbonate, sodium and calcium phosphates, as solid lubricants.
19. Sastav prema barem jednom od patentnih zahtjeva 14 do 18, naznačen time, da je mast za podmazivanje otporna na vodu, i to
a) u skladu s ispitivanjem prema DIN 51807-1 stupnja vrednovanja 1-90 i/ili
b) u skladu s ispitivanjem prema DIN 51807-2 stupnja vrednovanja 1-80. 19. Composition according to at least one of patent claims 14 to 18, characterized in that the lubricating grease is resistant to water, and
a) in accordance with the test according to DIN 51807-1 evaluation level 1-90 and/or
b) in accordance with the test according to DIN 51807-2 evaluation level 1-80.
20. Sastav prema barem jednom od patentnih zahtjeva 14 do 19, naznačen time, da kalcijev ligninsulfonat ima srednju molekularnu masu (prosječnu masu) veću od 10000, osobito veću od 12000 ili čak veću od 15000 g/mol, koji nezavisno od toga sadrži 2 do 12 tež.%, osobito 4 do 10 tež.% sumpora (računatog kao elementarni sumpor) i/ili dalje nezavisno sadrži 5 do 10 tež.%, osobito 8 do 15 tež.% kalcija.20. Composition according to at least one of claims 14 to 19, characterized in that the calcium ligninsulfonate has an average molecular weight (average weight) greater than 10,000, especially greater than 12,000 or even greater than 15,000 g/mol, which independently contains 2 up to 12 wt.%, especially 4 to 10 wt.% of sulfur (calculated as elemental sulfur) and/or further independently contains 5 to 10 wt.%, especially 8 to 15 wt.% of calcium.
21. Sastav prema barem jednom od patentnih zahtjeva 14 do 20, naznačen time, da mast za podmazivanje sadrži bazno ulje na bazi sirovina iz obnovljivih izvora i/ili je formirana udjelom većim od 95% na bazi sirovina iz obnovljivih izvora.21. Composition according to at least one of patent claims 14 to 20, characterized in that the lubricating grease contains a base oil based on raw materials from renewable sources and/or is formed in a proportion greater than 95% based on raw materials from renewable sources.
22. Sastav prema barem jednom od patentnih zahtjeva 14 do 20, naznačen time, da sastav ima točku kapanja višu od 2000C prema DIN ISO 2176. 22. Composition according to at least one of patent claims 14 to 20, characterized in that the composition has a dripping point higher than 2000C according to DIN ISO 2176.
23. Primjena sastava prema barem jednom od patentnih zahtjeva 14 do 22, naznačena time, da sastav jest za podmazivanje barem jednog zupčastog prenosnog mehanizma.23. Application of the composition according to at least one of patent claims 14 to 22, characterized in that the composition is for lubrication of at least one toothed transmission mechanism.
24. Primjena sastava prema barem jednom od patentnih zahtjeva 14 do 22, naznačena time, da sastav jest za podmazivanje mjesta podmazivanja u homokinetičkim zglobovima s nabranom kapom za zglob, izrađenom od termoplastičnih poliestera, kao materijala za izradu nabrane kape za zglob.24. Application of the composition according to at least one of patent claims 14 to 22, characterized in that the composition is for lubrication of the lubrication point in homokinetic joints with a pleated joint cap, made of thermoplastic polyester, as a material for making a pleated joint cap.