WO2007014337A1 - High viscosity synthetic ester lubricant base stock blends - Google Patents
High viscosity synthetic ester lubricant base stock blends Download PDFInfo
- Publication number
- WO2007014337A1 WO2007014337A1 PCT/US2006/029448 US2006029448W WO2007014337A1 WO 2007014337 A1 WO2007014337 A1 WO 2007014337A1 US 2006029448 W US2006029448 W US 2006029448W WO 2007014337 A1 WO2007014337 A1 WO 2007014337A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- iso
- base stock
- high viscosity
- viscosity
- synthetic ester
- Prior art date
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M171/00—Lubricating compositions characterised by purely physical criteria, e.g. containing as base-material, thickener or additive, ingredients which are characterised exclusively by their numerically specified physical properties, i.e. containing ingredients which are physically well-defined but for which the chemical nature is either unspecified or only very vaguely indicated
- C10M171/008—Lubricant compositions compatible with refrigerants
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M105/00—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound
- C10M105/08—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound containing oxygen
- C10M105/32—Esters
- C10M105/38—Esters of polyhydroxy compounds
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
- C10M2207/28—Esters
- C10M2207/283—Esters of polyhydroxy compounds
- C10M2207/2835—Esters of polyhydroxy compounds used as base material
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2020/00—Specified physical or chemical properties or characteristics, i.e. function, of component of lubricating compositions
- C10N2020/01—Physico-chemical properties
- C10N2020/02—Viscosity; Viscosity index
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2020/00—Specified physical or chemical properties or characteristics, i.e. function, of component of lubricating compositions
- C10N2020/09—Characteristics associated with water
- C10N2020/097—Refrigerants
- C10N2020/101—Containing Hydrofluorocarbons
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
- C10N2030/02—Pour-point; Viscosity index
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2040/00—Specified use or application for which the lubricating composition is intended
- C10N2040/30—Refrigerators lubricants or compressors lubricants
Definitions
- This invention relates to synthetic polyol ester lubricant base stocks, and more particularly to cross blends of high viscosity synthetic ester lubricant base stocks with conventional polyol ester base stocks suitable for use in compressor and refrigeration systems.
- chlorofluorocarbons previously utilized as propellants in aerosols and as refrigeration fluids are no longer used due to the adverse impact on the earth's ozone layer. Efforts to eliminate the use of chlorofluorocarbons have led to the development of alternative fluids that are highly or fully fluorinated hydrocarbons.
- Working refrigeration fluids generally include a minor amount of lubricant.
- the refrigeration fluids include between about 5 to 15 or 20 parts by weight of lubricant with the balance being the fluorocarbon.
- lubricants were traditionally mineral oils which are fully miscible with the chlorofluorocarbons.
- HFC-134a hydrofluorocarbon having 1 to 3 carbon atoms and preferably 1 to 2 carbon atoms
- HFC hydrofluorocarbon
- HFC-32 difluoromethane
- HFC-23 trifluoromethane
- pentafluoroethane HFC-125
- HFC-134 1,1 ,2,2,-tetrafluoroethane
- HFC-143a 1,1 ,1-trifluoroethane
- HFC-152a 1 ,1- difluoroethane
- HFCs are not miscible with mineral oil
- certain carboxylic esters of polyhydroxy compounds also known as polyol esters or POEs
- POEs polyol esters
- the polyol ester lubricants are prepared by the condensation of certain polyols such as pentaerythritol, neopentyl glycol and trimethylpropanol, and linear or branched monocarboxylic acids containing between about 4 to 10 carbon atoms.
- the carboxylic acid mixture typically includes 30-85 mole % 3, 5, 5 tri-methylhexanoic acid (iso-C-9).
- iso-C-9 iso-C-9
- recent events have limited the availability of iso-C-9. This shortage of iso-C-9 has made it difficult and/or expensive to manufacture polyol esters using iso-C-9.
- the blend is comprised of a high viscosity synthetic base stock formed by condensation of neopentylpolyol and linear and branched monocarboxylic acids, wherein little or no iso-C-9 is used in the carboxylic acid mix, and a conventional polyol ester base stock.
- the cross blend is miscible with HFCs notwithstanding the limited use of iso-C-9, and provides an economical base stock in times where supplies of iso-C-9 are limited.
- Another object of the present invention is to provide a lubricant base stock for air-conditioning and refrigeration systems.
- Another object of the present invention is to provide an economical process of making synthetic ester base stocks that have sufficient miscibility with HFC refrigerants with limited use of iso-C-9 carboxylic acids.
- Another object of the present invention is to provide a synthetic ester base stock that has sufficient miscibility with HFC refrigerants with limited use of iso-C-9 carboxylic acids that exhibits superior wear and increases compressor efficiency.
- cross blends of synthetic ester lubricants suitable for use with a wide range of HFC refrigeration fluids are provided.
- Applicants have discovered that cross blends of i) conventional polyol ester base stocks of varying viscosities; and ii) iso 120 to 140 high viscosity base stock, formed with little or no iso-C-9, provides a range of high and low viscosity polyol ester base stocks that are miscible with HFC refrigeration fluids and exhibit superior protection against wear.
- the synthetic ester base stock blend of the present invention comprises a cross blend of a) certain high viscosity synthetic ester base stocks and b) conventional synthetic ester base stocks.
- the high viscosity polyol ester base stock is formed by condensation of neopentylpolyol and a mix of linear and branched monocarboxylic acids in an excess of hydroxyl groups, wherein little or no iso-C-9 is used in the carboxylic acid mix.
- the method of making such a high viscosity synthetic ester base stock is disclosed in U.S. Patent No. 6,744,093 which is incorporated herein by reference.
- the high viscosity base stock is a blend of esters which form the reaction product of a two step process.
- a neopentyl polyol having from 8 to 10 carbon atoms is reacted with an acid or acid mixture of linear C 4 - C 10 acids and/or branched C 5 - C 10 acids in the presence of an excess of hydroxyl groups to carboxyl groups in the presence of an acid catalyst to form a partial polyneopentylpolyol ester mixture.
- the excess of hydroxyl groups is necessary to promote the polymerization of the partial esters and the molar ratio of acid or acid mixture to the polyol can be varied depending on the desired rate of reaction, degree of condensation and the ultimate desired viscosity of the base stock.
- the resulting partial polyneopentylpolyol ester is then reacted with an excess of an acid or acid mixture that can vary or be the same acid mixture used in the initial step to yield the high viscosity ester product.
- the high viscosity polyol ester used in the cross blend of the present invention has a viscosity of iso 120 to 140 and is made in accordance with the method described above and in the ' 093 patent using a blend of pentaerythritol and dipentaerythritol reacted with a blend of carboxylic acids selected from one or more of C 5 , iso-C 5 , C 7 , hexanoic, iso-Cg and Cg monocarboxylic acids.
- the iso 120 to 140 high viscosity polyol ester is made using a 60/40 blend of pentaerythritol and dipentaerythritol reacted with carboxylic acids selected from one or more of nC 5 , iso-C 5 , nC 7 , hexanoic and C 9 in the presence of an excess of hydroxyl groups to carboxyl groups. The reaction continues until it yields a product of the desired viscosity.
- a high density polyol ester having a viscosity between iso 120 and iso 140 provides sufficient miscibility with refrigerant R134a from -38°C to 8O 0 C even without the use of iso-Cg as one of the carboxylic acids.
- polyol ester base stocks as used herein, is intended to mean synthetic ester base stocks prepared by standard condensation reaction of neopentylpolyol and a selection of linear and branched monocarboxylic acids.
- the conventional ester base stocks of the present invention are polyol ester based lubricants made by a conventional condensation reaction of polyols and carboxylic acids.
- the conventional polyol ester base stocks have a viscosity range from iso 20 to iso 350 and are available from a number of sources including Castrol Industrial North America Inc. Warrenville, IL under the lcematic brand, Cognis (under the Evergreen brand name), Uniqema Corporation RL series, CPI's Solest brand of POEs, Mobil EAL Arctic, JEC.and Nippon Oil. Lubricating Oil Composition
- a variety of additives may be added to the cross-blends to make the fully- blended refrigeration lubricant. These additives include: anti-oxidants, anti-wear additives and metal deactifiers. Anti-oxidants A fully-blended refrigeration lubricant may contain from about 0.01 % to 1 % by weight, alternatively from about 0.05% to 0.5% by weight, alternatively from about alternatively from about 0.10 % to about 0.20% by weight, of one or more antioxidants.
- Anti-oxidants reduce the tendency of lubricating oils to deteriorate in service. This deterioration can be evidenced by increased oil viscosity and by the products of oxidation such as acids, sludge and varnish-like deposits on the metal surfaces. In one embodiment 0.10wt% BHT is used. Anti-wear agent
- a fully blended refrigeration lubricant may also contain from about 0.0075% to 3% by weight, alternatively from about 0.01 % to about 2% by weight, alternatively from about 0.06% to about 1 % by weight, of one or more anti-wear agents.
- Anti-wear agents as their name implies, reduce wear of metal parts.
- Anti- wear agents commonly used in refrigeration lubricants include Vanlube 672 which is available from RT Vanderbilt and tricresyl phosphate (TCP) antiwear additives.
- Metal Deactifier is available from RT Vanderbilt and tricresyl phosphate (TCP) antiwear additives.
- a fully blended refrigeration lubricant may also contain from about 0.001 % to %0.1 by weight, alternatively from about 0.0075% to about 0.05% by weight, of one or more metal deactifier such as tolutriazole (available from Ciba Specialty Chemiclas under the trade name lrgamet TTZ) and sebacic acid corrosion inhibitors. In one embodiment 0.01 % by weight of tolutriazole (TTZ) is used.
- Other additives include acid blockers such as Texaco's Cadura E-10. Blending Conditions
- the cross blends of the present invention are made by blending high viscosity polyol ester having a viscosity in the range of iso 120 to iso 140 with conventional polyol esters of viscosity grade iso 20 to iso 350 to achieve the desired final viscosity.
- the high viscosity and conventional polyol esters along with a selection of additives, if any, are blended in a steam-jacketed stainless kettle at a temperature range of 120 0 C to 180 0 C for around 24 hours.
- cross Blends The desired viscosity grade of the cross blends is achieved by blending in accordance with the following cross blend chart.
- Example I High Density Polvol Esters Miscible with 134a
- the following example illustrates that only certain high viscosity polyol esters made in accordance with the x 093 patent are miscible with R 134a.
- Example III Wear Data The wear properties of the cross blends were tested in accordance with ASTM
- the Falex Pin & Vee Block Test evaluates the extreme pressure properties or wear characteristics of a lubricant.
- the machine rotates a test pin against two stationery Vee Blocks at 290 rpm. Load is applied to the Vee blocks through a ratchet mechanism and the test specimen is immersed in the cross blend lubricant while R-134a refrigerant is bubbled up through the lubricant.
- a 250 Ib load was applied for the first 5 minute break-in period and a 400 Ib load was applied for the 30 minute duration of the test. Wear is measured and reported as the number of teeth the ratchet mechanism advances in order to maintain constant load during the prescribed test time.
- the results for the cross blends are in Table III. Table III Falex Pin and Vee Block Wear Data average of three runs
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Emergency Medicine (AREA)
- Lubricants (AREA)
Abstract
Description
Claims
Priority Applications (5)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP06800459A EP1941010A1 (en) | 2005-07-27 | 2006-07-27 | High viscosity synthetic ester lubricant base stock blends |
BRPI0614172A BRPI0614172B1 (en) | 2005-07-27 | 2006-07-27 | polyol ester lubricant base material |
AU2006272507A AU2006272507B2 (en) | 2005-07-27 | 2006-07-27 | High viscosity synthetic ester lubricant base stock blends |
CA2615286A CA2615286C (en) | 2005-07-27 | 2006-07-27 | Hydrofluorocarbon miscible synthetic ester lubricant base stock blends |
US11/996,614 US20080214418A1 (en) | 2005-07-27 | 2006-07-27 | High Viscosity Synthetic Ester Lubricant Base Stock Blends |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US70290605P | 2005-07-27 | 2005-07-27 | |
US60/702,906 | 2005-07-27 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2007014337A1 true WO2007014337A1 (en) | 2007-02-01 |
Family
ID=37440842
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/US2006/029448 WO2007014337A1 (en) | 2005-07-27 | 2006-07-27 | High viscosity synthetic ester lubricant base stock blends |
Country Status (7)
Country | Link |
---|---|
US (1) | US20080214418A1 (en) |
EP (1) | EP1941010A1 (en) |
CN (2) | CN101248164A (en) |
AU (1) | AU2006272507B2 (en) |
BR (1) | BRPI0614172B1 (en) |
CA (1) | CA2615286C (en) |
WO (1) | WO2007014337A1 (en) |
Families Citing this family (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US8476210B2 (en) * | 2008-09-09 | 2013-07-02 | Glenn Short | Composition for compressor working fluid for applications with soluble gas or gas condensates |
CN105132088A (en) * | 2015-07-08 | 2015-12-09 | 新疆福克油品股份有限公司 | Synthetic ester refrigerator oil composition |
CN112552977A (en) * | 2020-12-30 | 2021-03-26 | 南京威尔药业集团股份有限公司 | Method for preparing synthetic ester base oil through step-by-step reaction |
Citations (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0430657A1 (en) * | 1989-11-29 | 1991-06-05 | Asahi Denka Kogyo Kabushiki Kaisha | Lubricant for refrigerators |
EP0498152A1 (en) * | 1991-01-17 | 1992-08-12 | Cpi Engineering Services, Inc. | Lubricant composition for fluorinated refrigerants |
EP0572198A1 (en) * | 1992-05-25 | 1993-12-01 | Nippon Oil Co. Ltd. | Lubricating oil composition for food processing machinery |
WO1993024585A1 (en) * | 1992-06-03 | 1993-12-09 | Henkel Corporation | Polyol ester lubricants for refrigerant heat transfer fluids |
EP0730020A2 (en) * | 1995-03-01 | 1996-09-04 | Mitsubishi Gas Chemical Company, Inc. | Polyol ester-based lubricant and process for the production thereof |
EP0801129A2 (en) * | 1996-04-09 | 1997-10-15 | Mitsubishi Gas Chemical Company, Inc. | Polyol ester based-lubricant |
US5820777A (en) * | 1993-03-10 | 1998-10-13 | Henkel Corporation | Blended polyol ester lubricants for refrigerant heat transfer fluids |
US20030125218A1 (en) * | 2001-10-10 | 2003-07-03 | Cardis Angeline Baird | Biodegradable non-toxic gear oil |
Family Cites Families (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
KR950005694B1 (en) * | 1989-07-05 | 1995-05-29 | 가부시끼가이샤 교오세끼 세이힝기주쓰 겡뀨쇼 | Refrigeration lubricants |
ZA928934B (en) * | 1991-12-06 | 1994-05-19 | Exxon Chemical Patents Inc | Refrigeration working fluid compositions |
US6183662B1 (en) * | 1992-06-03 | 2001-02-06 | Henkel Corporation | Polyol ester lubricants, especially those compatible with mineral oils, for refrigerating compressors operating at high temperatures |
US20010019120A1 (en) * | 1999-06-09 | 2001-09-06 | Nicolas E. Schnur | Method of improving performance of refrigerant systems |
EP1339815B1 (en) * | 2000-10-25 | 2009-08-26 | The Lubrizol Corporation | Pib/poe/mineral oil blend lubricants for high temperature chain applications |
BR0214272A (en) * | 2001-11-19 | 2004-12-14 | Lubrizol Corp | Service fluid in a compression cooling system |
US6774093B2 (en) * | 2002-07-12 | 2004-08-10 | Hatco Corporation | High viscosity synthetic ester lubricant base stock |
US20070232506A1 (en) * | 2006-03-28 | 2007-10-04 | Gao Jason Z | Blends of lubricant basestocks with polyol esters |
-
2006
- 2006-07-27 CA CA2615286A patent/CA2615286C/en active Active
- 2006-07-27 EP EP06800459A patent/EP1941010A1/en not_active Withdrawn
- 2006-07-27 WO PCT/US2006/029448 patent/WO2007014337A1/en active Application Filing
- 2006-07-27 CN CNA2006800270061A patent/CN101248164A/en active Pending
- 2006-07-27 BR BRPI0614172A patent/BRPI0614172B1/en active IP Right Grant
- 2006-07-27 US US11/996,614 patent/US20080214418A1/en not_active Abandoned
- 2006-07-27 AU AU2006272507A patent/AU2006272507B2/en active Active
- 2006-07-27 CN CN2011102251551A patent/CN102304410A/en active Pending
Patent Citations (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0430657A1 (en) * | 1989-11-29 | 1991-06-05 | Asahi Denka Kogyo Kabushiki Kaisha | Lubricant for refrigerators |
EP0498152A1 (en) * | 1991-01-17 | 1992-08-12 | Cpi Engineering Services, Inc. | Lubricant composition for fluorinated refrigerants |
EP0572198A1 (en) * | 1992-05-25 | 1993-12-01 | Nippon Oil Co. Ltd. | Lubricating oil composition for food processing machinery |
WO1993024585A1 (en) * | 1992-06-03 | 1993-12-09 | Henkel Corporation | Polyol ester lubricants for refrigerant heat transfer fluids |
US5820777A (en) * | 1993-03-10 | 1998-10-13 | Henkel Corporation | Blended polyol ester lubricants for refrigerant heat transfer fluids |
EP0730020A2 (en) * | 1995-03-01 | 1996-09-04 | Mitsubishi Gas Chemical Company, Inc. | Polyol ester-based lubricant and process for the production thereof |
EP0801129A2 (en) * | 1996-04-09 | 1997-10-15 | Mitsubishi Gas Chemical Company, Inc. | Polyol ester based-lubricant |
US20030125218A1 (en) * | 2001-10-10 | 2003-07-03 | Cardis Angeline Baird | Biodegradable non-toxic gear oil |
Non-Patent Citations (1)
Title |
---|
See also references of EP1941010A1 * |
Also Published As
Publication number | Publication date |
---|---|
CA2615286C (en) | 2014-02-25 |
US20080214418A1 (en) | 2008-09-04 |
AU2006272507B2 (en) | 2011-08-25 |
EP1941010A1 (en) | 2008-07-09 |
BRPI0614172A2 (en) | 2011-03-15 |
CN102304410A (en) | 2012-01-04 |
CA2615286A1 (en) | 2007-02-01 |
AU2006272507A1 (en) | 2007-02-01 |
CN101248164A (en) | 2008-08-20 |
BRPI0614172B1 (en) | 2016-04-26 |
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