CN101248164A - High viscosity synthetic ester lubricant base stock blends - Google Patents

High viscosity synthetic ester lubricant base stock blends Download PDF

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Publication number
CN101248164A
CN101248164A CNA2006800270061A CN200680027006A CN101248164A CN 101248164 A CN101248164 A CN 101248164A CN A2006800270061 A CNA2006800270061 A CN A2006800270061A CN 200680027006 A CN200680027006 A CN 200680027006A CN 101248164 A CN101248164 A CN 101248164A
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China
Prior art keywords
iso
blends
base stock
weight
polyol ester
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Chinese (zh)
Inventor
G·普西拉斯
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Lubrizol Corp
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Lubrizol Corp
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    • 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

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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

Cross blends of synthetic ester base stocks are produced from high viscosity synthetic ester base stocks having a viscosity from about iso 120 to 140 and conventional synthetic ester base stocks of varying viscosities to form base stocks having viscosities from about iso 68 to iso 220. Lubricants formed from the cross blends have sufficient miscibility with HFC refrigeration fluids with minimal use of i-C<SUB>9 </SUB>carboxylic acids to form the ester.

Description

High viscosity synthetic ester lubricant base stock blends
Background of invention
The present invention relates to synthetic polyol ester lubricant base stock, relate more specifically to be applicable to cross-blends in compressor and the refrigeration system, high viscosity synthetic ester lubricant base stock and conventional polyol ester basis oil plant.
Be well known that, before the chlorofluorocarbon as the propelling agent in the aerosol with as refrigerating fulid, but since they the disadvantageous effect of earth's ozone layer is not re-used.The effort of eliminating the use of chlorofluorocarbon has caused the exploitation of alternative fluids (they are height or complete fluorizated hydrocarbon).
Available refrigerating fulid generally includes the lubricant of minor amount.Usually, refrigerating fulid comprises about 5 to 15 or the lubricant of 20 weight parts, and surplus is a fluorocarbon.In chlorofluorocarbon systems, lubricant is generally and the abundant miscible mineral oil of chlorofluorocarbon.But, this series lubricant agent and height or complete fluorizated hydrocarbon (for example 1,1,1, the 2-Tetrafluoroethane, often be known as HFC-134a) and other free from chloride fluorocarbon unmixing, aforementioned free from chloride fluorocarbon comprises the hydrogen fluorohydrocarbon (HFC) that has 1 to 3 carbon atom, preferably has 1 to 2 carbon atom, for example methylene fluoride (HFC-32), trifluoromethane (HFC-23), pentafluoride ethane (HFC-125), 1,1,2,2-Tetrafluoroethane (HFC-134), 1,1,1-Halothane (HFC-143a) and 1,1-C2H4F2 C2H4F2 (HFC-152a).
Although HFCs and mineral oil unmixing, some carboxylicesters of polyol is also referred to as polyol ester or POEs, with height or complete fluorizated fluid complete miscibility.The polyol ester lubricant is by some polyvalent alcohol, and for example tetramethylolmethane, neopentyl glycol and trimethylammonium propyl alcohol prepare with the condensation of the straight or branched monocarboxylic acid that contains about 4 to 10 carbon atoms.In order to improve compatibility, mixture of carboxylic acids generally includes the 3,5,5 Trimethylhexanoic acid (iso-C-9) of 30-85 mole %.But the nearest current political situation has limited the property that supplies of iso-C-9.This shortage of Iso-C-9 makes that using iso-C-9 to make polyol ester is difficulty and/or expensive.
Therefore, be desirable to provide based on the cross-blends of two or more oil base stock, viscosity be ISO68 to 220, with the miscible synthetic ester lubricant oil base stock of HFCs.This adulterant is bonded into oil base stock by height and conventional polyol ester basis oil plant constitutes, described height is bonded into the condensation of oil base stock by amyl-based polyol and straight chain and branched-chain monocarboxylate and forms, and wherein almost or does not fully use iso-C-9 in mixture of carboxylic acids.Although this cross-blends is used iso-C-9 limitedly, also still miscible with HFCs, and economic oil base stock is provided when the supply of iso-C-9 is restricted.
Brief summary of the invention
The objective of the invention is in the carboxylic acid reaction mixture, seldom or not to use and make multiple and the miscible polyol ester lubricant of HFCs under the situation of iso-C-9.
Another object of the present invention provides the lubricant base stock that is used for air-conditioning and refrigeration system.
Another object of the present invention provides under the situation of limited use iso-C-9 carboxylic acid the method made from the economy of the fully miscible synthetic ester base plinth oil plant of HFC refrigeration agent.
Another object of the present invention provides under the situation of limited use iso-C-9 carboxylic acid and the abundant miscible synthetic ester base plinth oil plant of HCF refrigeration agent, and it shows excellent resistance to abrasion and has improved compressor efficiency.
According to the present invention, provide the suitable synthetic ester lubricant cross-blends of using with multiple HFC refrigerating fulid.The applicant has been found that i) the indefinite conventional polyol ester basis oil plant of viscosity with ii) almost or the cross-blends of iso 120 to the 140 high sticking oil base stock that form without iso-C-9 fully provide miscible and show the sticking and low sticking polyol ester of the multiple height basis oil plant of excellent abrasion resistance with the HFC refrigerating fulid.
Detailed Description Of The Invention
In following explanatory and nonrestrictive description, listed detail, fully understood of the present invention to provide.But, it will be understood by those skilled in the art that the present invention can implement with other embodiment that breaks away from these details.Omitted detailed description, so that can not desalinate the description of this invention to known method, acid and manufacture method thereof.
The cross-blends material
Synthetic ester base plinth POL blending thing of the present invention comprises a), and some height is bonded into ester base oil material and b) cross-blends of conventional synthetic ester base plinth oil plant.
High sticking polyol ester
The sticking polyol ester of described height basis oil plant is to form by the condensation under the excessive situation of hydroxyl of amyl-based polyol and straight chain and branched-chain monocarboxylate's mixture, wherein almost or does not fully use iso-C-9 in mixture of carboxylic acids.United States Patent (USP) 6,744 discloses in 093 and has made the method that this class height is bonded into the ester base oil material, and this patent is incorporated herein by this reference.
In one embodiment, high sticking oil base stock is the adulterant of ester that constitutes the reaction product of two-step approach.In initial step, in the presence of the hydroxyl excessive, and in the presence of acid catalyst, make amyl-based polyol and straight chain C with 8 to 10 carbon atoms with respect to carboxyl 4-C 10Acid and/or side chain C 5-C 10The acid of acid or acid mixture reaction are to form poly-partially neopentyl polyol ester mixture.The excessive of hydroxyl is necessary for the polymerization that promotes partial ester, and the mol ratio of acid or acid mixture and polyvalent alcohol can become according to the final required viscosity of required speed of reaction, condensation level and oil base stock.After from reaction vessel, removing anticipation reaction water and having the product of required viscosity with generation, make the poly-partially neopentyl polyol ester of gained and excess acid or acid mixture (it can be similar and different with used acid mixture in the initial step) reaction, to produce the high ester products that glues.
More particularly, the sticking polyol ester of height used in the cross-blends of the present invention has the viscosity of iso 120 to 140, and according to aforesaid method with in the method described in the patent of ' 093, makes the adulterant of tetramethylolmethane and Dipentaerythritol and be selected from C 5, iso-C 5, C 7, caproic acid, iso-C 9And C 9The adulterant of one or more carboxylic acid reaction and making in the monocarboxylic acid.
In one embodiment, iso 120 to 140 high sticking polyol esters are to make 60/40 adulterant of tetramethylolmethane and Dipentaerythritol and be selected from nC 5, iso-C 5, nC 7, caproic acid and C 9In the reaction and making under the hydroxyl situation excessive of one or more carboxylic acid with respect to carboxyl.Even do not use iso-C 9A kind of as carboxylic acid, at-38 ℃ to 80 ℃, viscosity also provides sufficient compatibility with refrigerant R134a for the high-density polyol ester of iso 120 to iso 140.
Conventional polyol ester
Conventional polyol ester used herein basis oil plant is meant the synthetic ester base plinth oil plant of making by amyl-based polyol and selected straight chain and branched-chain monocarboxylate's standard condensation reaction.
Conventional ester base oil material of the present invention is the polyol ester based-lubricant of making by the conventional condensation reaction of polyvalent alcohol and carboxylic acid.Conventional polyol ester basis oil plant has the range of viscosities of iso 20 to iso 350, and can be available from many sources, comprise Castrol Industrial North America Inc.Warrenville, CPI ' s Solest trade mark, Mobil EALArctic, JEC and the Nippon Oil of IL (is trade mark with Icematic), Cognis (is trade name with Evergreen), Uniqema Corporation RL series, POEs.
Lubricating oil composition
Can in cross-blends, add multiple additives, to make the refrigeration lubricant of complete fusion.These additives comprise: antioxidant, antiwear additive and metal deactivator.
Antioxidant
The refrigeration lubricant of fusion can contain about 0.01 weight % to 1 weight % or about 0.05 weight % to 0.5 weight % or about 0.10 weight % one or more antioxidants to about 0.20 weight % fully.
Antioxidant has reduced the in use rotten possibility of lubricating oil.This going bad can increase by oil viscosity, show by oxidation products (for example acid, sludge and the lacquer deposit on the metallic surface).In one embodiment, use 0.10 weight %BHT.
Anti-wear agent
Fully the refrigeration lubricant of fusion can also contain about 0.0075 weight % to 3 weight % or about 0.01 weight % one or more anti-wear agents to about 2 weight % or about 0.06 weight % to about 1 weight %.
Anti-wear agent has reduced the wearing and tearing of metal parts shown in their title.Comprise can be available from the Vanlube 672 of RT Vanderbilt for anti-wear agent commonly used in the refrigeration lubricant, and Tritolyl Phosphate (TCP) wear preventive additive.
Metal deactivator
Fully the refrigeration lubricant of fusion can also contain about 0.001 weight % to 0.1 weight % or about 0.0075 weight % one or more metal deactivators to about 0.05 weight %, for example Methylbenzotriazole (can available from Ciba Specialty Chemicals, trade(brand)name Irgamet TTZ) and sebacic acid inhibiter.In one embodiment, use the Methylbenzotriazole (TTZ) of 0.01 weight %.
Other additive
Other additive comprises sour blocker, for example Texaco ' s Cadura E-10.The fusion condition
By being that sticking polyol ester of height and the viscosity grade of iso 120 to iso 140 is the conventional polyol ester fusion of iso 20 to iso 350 with viscosity, realize required final viscosity, thereby make cross-blends of the present invention.Sticking and conventional polyol ester of described height and selected additive (if any) in the stainless steel still of steam jacket about 24 hours 120 ℃ to 180 ℃ temperature range fusion.
By according to the fusion of following cross-blends chart, realize the required viscosity grade of cross-blends.
Cross-blends
Iso 32 cross-blends Iso 68 cross-blends Iso 120 cross-blends Iso 220 cross-blends
High sticking POE 15 weight % iso 120 73 weight % iso 120 100 weight % iso 120 60 weight % iso 120
Conventional POE 85 weight % iso 20 27 weight % iso 20 ---- 40 weight % iso 350
Embodiment
Embodiment only is exemplary, rather than will limit the scope of the invention.
The high-density polyol ester that example I and 134a are miscible
The following example shows to have only some high sticking polyol ester of making according to ' 093 patent just miscible with R134a.
The composition that uses ' 093 to make
Polyvalent alcohol, MOL% 100％ 100％ 100％ 100％ 100％ 100％
Acid MOL%
nC5 100％ 50％ 56％ 5％ 66％
nC6
nC7 20％
nC9
nC8
3 methylvaleric acids 10% 10％
iso-C5 34％ 34％
Caproic acid 10％
2-EH 70％ 95％
iso-C9 50％
Other additive
BHT％ 0.10％ 0.10％ 0.10％ 0.10％ 0.10％ 0.10％
Physical/chemical
Reaction back viscosity 220 220 232 139 196 120-139
40C 220 220 232 139 196 120
R134a compatibility at room temperature No No No -38 No -39
Data show, having only range of viscosities is that the sticking polyol ester of height of is0 120 to iso 140 is just miscible with R134a.Therefore, should make cross-blends with the sticking polyol ester of the height in this scope.
The example II cross-blends
Figure S2006800270061D00071
VG120=can be high sticking grade available from the iso120 of Hatco Corporation
SW20=can be available from iso 20 POE of Castrol Industrial North America
SW68=can be available from iso 68 POE of Castrol Industrial North America
SW220=can be available from iso 220 POE of Castrol Industrial North America
SW350=can be available from iso 350 POE of Castrol Industrial North America
The EXAMPLE III wear data
Abrasive nature according to ASTM D2670 Falex Pin and Vee Blocky experimental test cross-blends.Falex Pin﹠amp; The extreme pressure character or the wearing character of lubricant evaluated and tested in Vee Block test.This machine makes test pin rotate with 290rpm with respect to two immobilized Vee pieces., and sample is immersed in the cross-blends lubricant Vee piece applied load by ratchet mechanism, in lubricant, blasts the R-134a refrigeration agent simultaneously.Apply 250lb load initial 5 minute run-in period, applies 400lb load at 30 minutes duration of test.Measure wearing and tearing and be expressed as ratchet mechanism and between at the trial, keep specified permanent load and the progressive number of teeth.The results are shown in the Table III of cross-blends.
The Falex Pin and the Vee Block wear data mean value of three operations of Table III
The wear data that records of gram number with loss
The cross-blends sample number The number of teeth Pin Vee Block1 Vee Block2
1 7 0.0016 -0.0007 0.0002
2
3 15 2 0.014 2 0.0005 2 0.0002 2
4 13.75 1 0.0132 1 0.0007 1 0.0002 1
5
6
Conventional POEs
Icematic SW 68 23.5 1 0.0196 1 0.0007 1 0.00085 1
Fn 1The mean value of 4 operations
Fn 2The mean value of 3 operations

Claims (4)

1. polyol ester lubricant base stock, comprising viscosity is the cross-blends of the sticking polyol ester of height basis oil plant with the conventional polyol ester basis oil plant with particular viscosity of about iso 120 to iso 140, and the ratio of sticking polyol ester basis oil plant of described height and conventional polyol ester basis oil plant can be realized required cross-blends viscosity.
2. the polyol ester of claim 1 basis oil plant, the wherein iso 20 conventional oil base stock fusion of the sticking oil base stock of the height of 15 weight % and 85 weight %, acquisition viscosity is the cross-blends of iso 32.
3. the polyol ester of claim 1 basis oil plant, the wherein iso 20 conventional oil base stock fusion of the sticking oil base stock of the height of 73 weight % and 27 weight %, acquisition viscosity is the cross-blends of iso 68.
4. the polyol ester of claim 1 basis oil plant, the wherein iso 350 conventional oil base stock fusion of the sticking oil base stock of the height of 60 weight % and 40 weight %, acquisition viscosity is the cross-blends of iso 220.
CNA2006800270061A 2005-07-27 2006-07-27 High viscosity synthetic ester lubricant base stock blends Pending CN101248164A (en)

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EP (1) EP1941010A1 (en)
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BR (1) BRPI0614172B1 (en)
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US20080214418A1 (en) 2008-09-04
BRPI0614172A2 (en) 2011-03-15
CA2615286A1 (en) 2007-02-01
BRPI0614172B1 (en) 2016-04-26
AU2006272507A1 (en) 2007-02-01
CA2615286C (en) 2014-02-25
AU2006272507B2 (en) 2011-08-25
WO2007014337A1 (en) 2007-02-01
EP1941010A1 (en) 2008-07-09

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