CA2236511A1 - Two-cycle ester based synthetic lubricating oil - Google Patents
Two-cycle ester based synthetic lubricating oil Download PDFInfo
- Publication number
- CA2236511A1 CA2236511A1 CA 2236511 CA2236511A CA2236511A1 CA 2236511 A1 CA2236511 A1 CA 2236511A1 CA 2236511 CA2236511 CA 2236511 CA 2236511 A CA2236511 A CA 2236511A CA 2236511 A1 CA2236511 A1 CA 2236511A1
- Authority
- CA
- Canada
- Prior art keywords
- oil
- cycle
- viscosity
- composition
- mixture
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Abandoned
Links
Landscapes
- Lubricants (AREA)
Abstract
A two-cycle oil which is 10-20 % of an ester of technical grade pentaerythritol with a mixture of (a) branched C8 and (b) mixed linear C8 and C10 monocarboxylic acids, having a viscosity of 6 to 8 cSt at 100 ~C, 18-30 %
of an oxo alcohol ester of a dicarboxylic acid having a viscosity of 3 to 10 cSt at 100 ~C, 30 to 40 % of a polybutene having an Mn of 300-1500, 15 to 35 %
of a normally liquid solvent having a boiling point up to 300 ~C, 0 to 5 % of other lubricating oil additives.
of an oxo alcohol ester of a dicarboxylic acid having a viscosity of 3 to 10 cSt at 100 ~C, 30 to 40 % of a polybutene having an Mn of 300-1500, 15 to 35 %
of a normally liquid solvent having a boiling point up to 300 ~C, 0 to 5 % of other lubricating oil additives.
Description
CA 02236~11 1998-0~-21 Two-Cycle Ester Based Synthetic Lubricating Oil (PT-1042) This invention relates to a lubricant composition useful as a two-cycle oil.
More particularly the invention relates to two-cycle synthetic oil which complies with certain test standards for land equipment, gasoline fuelled, two-cycle engines, such as motorcycle engines, moped engines, snowmobile 10 engines, lawn mower engines and the like. Two-stroke-cycle gasoline engines now range from small, less than 50 cc engines, to higher performance engines of 200 to 500 cc. The development of such high , -performance engines has created the need for new two-cycle oil standards - _ -and test procedures. The present composition exhibits improved detergency and reduced exhaust port blocking characteristics.
Two-cycle engines are lubricated by mixing the fuel and lubricant and allowing the mixed composition to pass through the engine. Various types of two-cycle oils, compatible with fuel, have been described in the art.
Typically, such oils contain a variety of additive components in order for the oil to pass industry standard tests to permit use in two-cycle engines.
US-A-4,994,196 (1991) discloses two-cycle engine oils comprising alpha olefin dicarboxylic ester copolymers in combination with esters of pentaerythritol and calcium phenate.
US-A-5,378,249 (1995) discloses biodegradable two-cycle engine oil compositions which comprise 20-80% of a heavy ester having a viscosity of at least 7 cSt at 100~ in combination with 10-85 weight percent of a light ester oil having a viscosity less than 6.0 cSt at 100~.
EP-A-0 572 273 discloses lubricating oil compositions for two-stroke engines comprising 30 to 70% of a polyol ester, 30 to 70% of a diester and 1 to 5% of a polybutene of molecular weight 500 to 2500 and/or 1 to 5% of a polymethylmethacrylate of molecular weight 5,000 to 40,000 and 5 to 25% of a dispersant. The compositions have good bio-degradability.
A.~ N~ T
CA 02236~11 1998-0~-21 95A02 1 - 1 a -EP-A-0 640 680 discloses two-stroke oil compositions comprising polybutenes which are very low in, or substantially free of n-butenes in order to achieve low smoke emission. Synthetic esters may be present but specific esters are not disclosed.
The present invention is based on the discovery that the use of a blend of ester basestock oils in two-cycle oil formulations provides lubricants which exhibit improvements, as measured by two-cycle engine tests, most notably in exhaust port blocking reduction and detergency.
~; ., . -CA 02236~11 1998-0~-21 Accordingly, there has been discovered a two-cycle lubricating oil composition comprising:
a) 10-20% by weight of a first synthetic ester basestock oil being an ester of pentaerythritol (technical grade) with a mixture of Cg branched and C8-C1 o linear morlocarboxylic acids, the oil having a viscosity of Pbou~
6 to 8,J~st)at 1 00~C;
b) 18-30% by weight of a second synthetic ester base st~ck oil being an oxo alcohol este~of a dicarboxylic acid, the oil having a viscosity of 3 to 1 Ol~St)at 1 00~C;
lS c) 30 to 40% by weight of a polybutene polymer being a polybutene, polyisobutylene or a mixture of polybutenes and polyisobutylenes having a number average molecular weight of ~300 to 1500;
d) 15 to 35% by weight of a normally liquid solvent having a boiling point of up to 300~C; and c~ ~l~sh po;r~
~ ~ 120~C~ ~d e) 0-5% by weight of lubricating oil additives other than a polybutene.
This invention also comprises the use of the foregoing oil in a two-cycle engine.
The first synthetic ester base oil is known in the art and is the ester of technical grade pentaerythritol with a mixture of (a) C8 branched monocarboxylic acids and (b) linear mixed C8 and C10 monocarboxylic acids. Technical grade pentaerythritol contains labout 86-90% by weight monopentaerythritol, 7-12% dipentaerythritol and 1-2% tripentaerythritol.
The acids comprise ~ 45-55 mol% of branched C8 acids, preferably 45 mol%, and 5545 mol% of a mixture of linear C8 and C10 acids, preferably 55 mol%. This acid mixture of linear octanoic and decanoic acids comprises~boutl48-58 mol% of Cg and 3642 mol% of C10, and very minor - . -_ CA 02236~11 1998-0~-21 amounts of nC:6 and nC12 acids, e.g. 3-5 mol% nC6 and 0.5-1 mol% nC12 aci~,are typically-present. The preferred ester oil has a viscosity of ~t 6.8~St)at 100~C and the preferred amount is 15% by weight.
s The second synthetic ester component is a basestock oil comprising an oxo alcohol ester of a polycarboxylic acid. Suitable oxo alcohols comprise those having Pbout 8 to 20 carbon atoms, preferably those having ~110 to 1~ carbon atoms, particularly oxo tridecyl alcohol. Such oxo alcohols are prepared by the process well known in the art which involves the catalytic reaction of olefins with carbon monoxide and hydrogen at elevated temperatures of labou~ 300 to 400~F and pressures o~500 to 4000 psig) to form particularly in the presence of cobalt catalyst aldehydes having more than 1 carbon atom than the olefin feedstock, the aldehyde then being hydrogenated to the corresponding alcohol.
Illustrative Examples of suitable dibasic acids which may be employed to synthesize the oxo diester fluid used in the present invention are oxalic acid, malonic acid~ succinic acid, glutaric acid, adipic acid, pomelic acid, suberic acid, azelaic acid and the like, generally this being ~ t 2 to 10 carbon atoms. Particularly preferred are adipic acid and alkyl adipic acids such as methyladipic acid and diethyladipic acid. ~,~c~ oxo esters synthetic base oils will have a viscosity in the range of 3 to 1OJ~cSqat 100~
for use in the present invention and they are preferably used in an amount of about 19 to 25%. Particularly preferred is a material sold by Exxon Chemical Company~as ' \listone A-30", an oxo tridecyl alcohol adipate having a viscosity of 5.3,~;S~at 1 00~C used in an amount of 20.48%.
The polybutene polymer used in this invention is typically a mixture of polybutenes, a mixture of poly-n-butenes and polyisobutylene which normally results from the polymerization of C4 olefins and generally will have a number average molecular weight of le~ 300 to 1500 with a polyisobutylene or polybutene having a number average molecular weight of ~ 400 to 1300 being particularly preferred, most preferable is a mixture of polybutene and polyisobutylene having a number average molecular weight of about 950. Number average molecular weight (Mn) is 3 5 measured by gel permeation chromatography. Polymers composed of 100% polyisobutylene or 100% poly-n-butene are also within the scope of this invention and within the meaning of the term "a polybutene polymer".
. .
CA 02236~11 1998-OS-21 A preferred polybutene polymer is a mixture of polybutenes and polyisobutylene prepared from a C4 olefin refinery stream containing pbo~
6 wt.% to 50 wt.% isobutylene with the balance a mixture of butene (cis-5 and trans-) isobutylene and less than 1 wt%. butadiene. Particularly, preferred is a polymer prepared from a C4 stream composed of 645 v~t.%
isobutylene, 25-35 wt.% saturated butenes and 15-~0 v~t.% 1- and 2-butenes. The polymer is prepared by Lewis acid catalysis. Preferably, the oils of this invention contain~bout 35 wt.% polybutene.
The solvents useful in the present invention may generally- be characterized as being normally liquid petroleum or synthetic hydrocarbon solvents having a boiling point not higher than ~bout 300~C at atmosphere pressure. The preferred amount is pbou~ 25% by weight. Such a solvent lS must also have a flash point in the range of about 60-120~C such that the flash point of the two-cycle oil of this invention is greater than 70~C.
Typical examples include kerosene, hydrotreated kerosene, middle distillate fuels, isoparaffinic and naphthenic aliphatic hydrocarbon solvents, dimers, and higher oligomers of propylene butene and similar olefins as well as paraffinic and aromatic hydrocarbon solvents and mixtures thereof.
Such solvents may contain functional groups other than carbon and hydrogen provided such groups do not adversely affect performance of the two-cycle oil. Preferred is a naphthenic type hydrocarbon solvent having a boiling point range of about 91.1~C-113.9~C (196~-237~F) sold as "Exxsol D80" by Exxon Chemical Company.
The invention further comprises the presence of up to 5% by weighl:
of one or more special purpose conventional lubricating oil additives, and these may be any additive normally included in lubricating oils for a 30 particular purpose.
Additional conventional additives for lubricating oils which may be present in the composition of this invention include viscosity modifiers, corrosion inhibitors, oxidation inhibitors, friction modifiers, 35 dispersants, antifoaming agents, antiwear agents, pour point depressants, detergents, rust inhibitors and the like.
~ ? ~A~EP --CA 02236~11 1998-0~-21 Typical oil soluble viscosity modifying polymers will generally have weight average molecular weights of from ~l 10,000 to 1,000,000 as determined by gel permeation chromatography.
Corrosion inhibitors are illustrated by phosphosulfurized hydrocarbons and the products obtained by reacting a phosphosulfurized hydrocarbon with an alkaline earth metal oxide or hydroxide. "Cobratech 356", which is benzotrizole in propylene glycol, is preferred for use in this invention in an amount of ~boubO.03 wt.%.
Oxidation inhibitors are antioxidants exemplified by àlkaline earth metal salts of alkylphenol thioesters having preferably Cs-C12 alkyl side chain such as calcium nonylphenol sulfide, barium t-octylphenol sulfide, dioctylphenylamine as well as sulfurized or phospho sulfurized hydrocarbons. Also included are oil soluble antioxidant copper compounds such as copper salts Of C10 to C18 oil soluble fatty acids.
Friction modifiers include fatty acid esters and amides, glycerol esters of dimerized fatty acids and succinate esters or metal salts thereof.
Dispersants are well known in the lubricating oil field and include high molecùlar weight alkyl succinimides being the reaction products of oil soluble polyisobutylene succinic anhydride with ethylene amines such as tetraethylene pentamine and borated salts thereof.
Preferred for use in this invention is 2.41% of a dispersant comprising a borated Mn 950 polyisobutenyl succinimide.
Pour point depressants also known as lube oil flow improvers can lower the temperature at which the fluid will flow and typical of these additives are Cg-C18 dialkyl fumarate vinyl acetate copolymers, polymethacrylates and wax naphthalene.
Foam control can also be provided by an anti-foamant of the polysiloxane type such as silicone oil and polydimethyl siloxane.
Anti-wear agents reduce wear of metal parts and representative materials are zinc dialkyldithiophosphate and zinc diaryl diphosphate.
-- ~ P ~ FJ ~
Detergents and metal rust inhibitors include the metal salts of sulfonic acids, alkylphenols, sulfurized alkylphenols, alkyl salicylates, naphthenates and other oil soluble mono and dicarboxylic acid. Neutral or S highly basic metal salts such as highly basic alkaline earth metal sulfonates (especially calcium and magnesium salts) are frequently used as such detergents. Also useful is nonylphenol sulfide. Similar materials made by reacting an alkylphenol with commercial sulfur dichlorides. Suitable alkylphenol sulfides can also be prepared by reacting alkylphenols with lO elemental sulfur. Preferred for use in this invention is 1.5% by.weight nonylphenol sulfide.
Also suitable as detergents are neutral and basic salts of phenols, generally known as phenates, wherein the phenol is generally an alkyl l S substituted phenolic group, where the substituent is an aliphatic hydrocarbon group having ~bou~ 4 to 400 carbon atoms. Preferred for use in the invention is 0.58% by weight calcium phenate.
Also suitable are oil soluble copper carboxylates which may be 20 present in amounts of 0.2 to 2% by weight and are used as antioxidants or to improve engine performance, examples being copper oleate or copper naphthenate in amounts of 0.5 to 1.5% by weight.
The lubricating oil compositions of the present invention will mix 25 freely with the fuels used in such two-cycle engines. Admixtures of such lubricating oils with fuels comprise a further embodiment of this invention.
The fuels useful in two-cycle engines are well known to those skilled in the art and usually contain a major portion of a normally liquid fuel such as a hydrocarbonaceous petroleum distillate fuel, e.g., motor gasoline is defined 30 by ASTM specification D~39-73. Such fuels can also contain non-hydrocarbonaceous rnaterials such as alcohols, ethers, organo nitro compounds and the like, e.g., methanol, ethanol, diethyl ether, methylethyl ether, nitro methane and such fuels are within the scope of this invention as are liquid fuels derived from vegetable and mineral sources such as corn, 3s alpha shale and coal. Examples of such fuel mixtures are combinations o~
gasoline and ethanol, diesel fuel and ether, gasoline and nitro methane, etc. Particularly preferred is gasoline, that is, a mixture of hydrocarbons , , , having an ASTM boiling point of 60OC at the 10% distillation point to 205~C at the 90% distillation point.
The lubricants of this invention are used in admixture with fuels in amounts of labe~ 20 to 250 parts by weight of fuel per 1 part by weight of lubricating oil, more typically~bout~30-100 parts by weight of fuel per 1 part by weight of oil Such admixtures and their use in two-cycle engines are further embodiments of this invention.
I0 The invention is further illustrated by the following examples which are not to be considered as limitative of its scope. Example 2 is for comparison and is not part of this invention. All percentages are by weight.
Example 1 An oil of the invention was prepared from the following:
(Trademarked components (a), (b), (c) and (h) are identified in the specification), and '~PE ester" is the preferred ester of technical grade pentaerythritol with a mixture of 45 mol% linear Cg acid and 55~m~~J0 of a mixture of n-octanoic and n-decanoic acid having a viscosity of 6.8l~St)at 1 00~C as disclosed in the specification:
Component Oil 1 (a) TPE Ester 15.00%
(b) '~istone A-30" 20.48%
(c) "Exxsol D-80" 25.00%
(d) Polyisobutylene Mn 950 35 00%
(e) Borated Mn 950 polyisobutenyl succinimide dispersant 2.41%
(f) Calcium Phenate 0.58%
(g) Nonylphenol sulfide 1.50%
(h) "Cobratech 35G" 0 03%
3 ~ 100%
AME~DE~ EET
IPrA/EP
This oil was evaluated in accordance with the JASO M345 test procedures JASO M340, M341, M342 and M343. This is an engine test established by society of Automoti\fe Engineers of Japan (JSAE) for tNo-cycle gasoline engine oils. As of July 1, 1994, oils used in two-cycle s engines are being labeled in accordance with the JASO-M345 standards as announced by the Japan Automobile Standards Organization (JASO).
JASO published the JASO M345 standards in April, 1994. "EGD
Detergency" is a refe-ence to a further modification of the normal JASO
M341 detergency test (1 hour) procedure in which the test is run for 3 10 hours. This is a more stringent standard expected to be adopted py ISO
(the International Organization for Standardization) as publislied by Committee Draft of January 5, 1995 of the Technical Committee 28. "FC" is the highest performance standard for the JASO M345 standards.
Example 2 (Comparative Example~
Oil 2 was the same as Oil 1 of the invention except that "Ketjenlube 135" a synthetic ester being a butanol ester of an alpha-olef~maleic acid copolymer used which had a Mn of 1800 and a viscosity of 35l~St)at 100~C
20 in place of the TPE Ester.
The engine test results for Oils 1 and 2 are in the Table below:
Enqine Test Results - JASO M345 & ISO-EGD
Oil 1 2Standard-FC ISO-EGD
Minimum Minimum EGD Detergency 145 122 -- 125 JASO Detergency M341 123 111 95 --JASO Lubricity M340 101 112 95 95 JASO Torque M340 99 99 98 98 JASO Blocking M343 153 93 90 90 JASO Smoke M342 125 157 85 85 , ~ _, Oil 1 of the invention shows markedly superior results in terms of detergency and exhaust port blocking while achieving passing values in all other aspects of the engine tests, when compared with another oil based on ester blends, Oil 2.
More particularly the invention relates to two-cycle synthetic oil which complies with certain test standards for land equipment, gasoline fuelled, two-cycle engines, such as motorcycle engines, moped engines, snowmobile 10 engines, lawn mower engines and the like. Two-stroke-cycle gasoline engines now range from small, less than 50 cc engines, to higher performance engines of 200 to 500 cc. The development of such high , -performance engines has created the need for new two-cycle oil standards - _ -and test procedures. The present composition exhibits improved detergency and reduced exhaust port blocking characteristics.
Two-cycle engines are lubricated by mixing the fuel and lubricant and allowing the mixed composition to pass through the engine. Various types of two-cycle oils, compatible with fuel, have been described in the art.
Typically, such oils contain a variety of additive components in order for the oil to pass industry standard tests to permit use in two-cycle engines.
US-A-4,994,196 (1991) discloses two-cycle engine oils comprising alpha olefin dicarboxylic ester copolymers in combination with esters of pentaerythritol and calcium phenate.
US-A-5,378,249 (1995) discloses biodegradable two-cycle engine oil compositions which comprise 20-80% of a heavy ester having a viscosity of at least 7 cSt at 100~ in combination with 10-85 weight percent of a light ester oil having a viscosity less than 6.0 cSt at 100~.
EP-A-0 572 273 discloses lubricating oil compositions for two-stroke engines comprising 30 to 70% of a polyol ester, 30 to 70% of a diester and 1 to 5% of a polybutene of molecular weight 500 to 2500 and/or 1 to 5% of a polymethylmethacrylate of molecular weight 5,000 to 40,000 and 5 to 25% of a dispersant. The compositions have good bio-degradability.
A.~ N~ T
CA 02236~11 1998-0~-21 95A02 1 - 1 a -EP-A-0 640 680 discloses two-stroke oil compositions comprising polybutenes which are very low in, or substantially free of n-butenes in order to achieve low smoke emission. Synthetic esters may be present but specific esters are not disclosed.
The present invention is based on the discovery that the use of a blend of ester basestock oils in two-cycle oil formulations provides lubricants which exhibit improvements, as measured by two-cycle engine tests, most notably in exhaust port blocking reduction and detergency.
~; ., . -CA 02236~11 1998-0~-21 Accordingly, there has been discovered a two-cycle lubricating oil composition comprising:
a) 10-20% by weight of a first synthetic ester basestock oil being an ester of pentaerythritol (technical grade) with a mixture of Cg branched and C8-C1 o linear morlocarboxylic acids, the oil having a viscosity of Pbou~
6 to 8,J~st)at 1 00~C;
b) 18-30% by weight of a second synthetic ester base st~ck oil being an oxo alcohol este~of a dicarboxylic acid, the oil having a viscosity of 3 to 1 Ol~St)at 1 00~C;
lS c) 30 to 40% by weight of a polybutene polymer being a polybutene, polyisobutylene or a mixture of polybutenes and polyisobutylenes having a number average molecular weight of ~300 to 1500;
d) 15 to 35% by weight of a normally liquid solvent having a boiling point of up to 300~C; and c~ ~l~sh po;r~
~ ~ 120~C~ ~d e) 0-5% by weight of lubricating oil additives other than a polybutene.
This invention also comprises the use of the foregoing oil in a two-cycle engine.
The first synthetic ester base oil is known in the art and is the ester of technical grade pentaerythritol with a mixture of (a) C8 branched monocarboxylic acids and (b) linear mixed C8 and C10 monocarboxylic acids. Technical grade pentaerythritol contains labout 86-90% by weight monopentaerythritol, 7-12% dipentaerythritol and 1-2% tripentaerythritol.
The acids comprise ~ 45-55 mol% of branched C8 acids, preferably 45 mol%, and 5545 mol% of a mixture of linear C8 and C10 acids, preferably 55 mol%. This acid mixture of linear octanoic and decanoic acids comprises~boutl48-58 mol% of Cg and 3642 mol% of C10, and very minor - . -_ CA 02236~11 1998-0~-21 amounts of nC:6 and nC12 acids, e.g. 3-5 mol% nC6 and 0.5-1 mol% nC12 aci~,are typically-present. The preferred ester oil has a viscosity of ~t 6.8~St)at 100~C and the preferred amount is 15% by weight.
s The second synthetic ester component is a basestock oil comprising an oxo alcohol ester of a polycarboxylic acid. Suitable oxo alcohols comprise those having Pbout 8 to 20 carbon atoms, preferably those having ~110 to 1~ carbon atoms, particularly oxo tridecyl alcohol. Such oxo alcohols are prepared by the process well known in the art which involves the catalytic reaction of olefins with carbon monoxide and hydrogen at elevated temperatures of labou~ 300 to 400~F and pressures o~500 to 4000 psig) to form particularly in the presence of cobalt catalyst aldehydes having more than 1 carbon atom than the olefin feedstock, the aldehyde then being hydrogenated to the corresponding alcohol.
Illustrative Examples of suitable dibasic acids which may be employed to synthesize the oxo diester fluid used in the present invention are oxalic acid, malonic acid~ succinic acid, glutaric acid, adipic acid, pomelic acid, suberic acid, azelaic acid and the like, generally this being ~ t 2 to 10 carbon atoms. Particularly preferred are adipic acid and alkyl adipic acids such as methyladipic acid and diethyladipic acid. ~,~c~ oxo esters synthetic base oils will have a viscosity in the range of 3 to 1OJ~cSqat 100~
for use in the present invention and they are preferably used in an amount of about 19 to 25%. Particularly preferred is a material sold by Exxon Chemical Company~as ' \listone A-30", an oxo tridecyl alcohol adipate having a viscosity of 5.3,~;S~at 1 00~C used in an amount of 20.48%.
The polybutene polymer used in this invention is typically a mixture of polybutenes, a mixture of poly-n-butenes and polyisobutylene which normally results from the polymerization of C4 olefins and generally will have a number average molecular weight of le~ 300 to 1500 with a polyisobutylene or polybutene having a number average molecular weight of ~ 400 to 1300 being particularly preferred, most preferable is a mixture of polybutene and polyisobutylene having a number average molecular weight of about 950. Number average molecular weight (Mn) is 3 5 measured by gel permeation chromatography. Polymers composed of 100% polyisobutylene or 100% poly-n-butene are also within the scope of this invention and within the meaning of the term "a polybutene polymer".
. .
CA 02236~11 1998-OS-21 A preferred polybutene polymer is a mixture of polybutenes and polyisobutylene prepared from a C4 olefin refinery stream containing pbo~
6 wt.% to 50 wt.% isobutylene with the balance a mixture of butene (cis-5 and trans-) isobutylene and less than 1 wt%. butadiene. Particularly, preferred is a polymer prepared from a C4 stream composed of 645 v~t.%
isobutylene, 25-35 wt.% saturated butenes and 15-~0 v~t.% 1- and 2-butenes. The polymer is prepared by Lewis acid catalysis. Preferably, the oils of this invention contain~bout 35 wt.% polybutene.
The solvents useful in the present invention may generally- be characterized as being normally liquid petroleum or synthetic hydrocarbon solvents having a boiling point not higher than ~bout 300~C at atmosphere pressure. The preferred amount is pbou~ 25% by weight. Such a solvent lS must also have a flash point in the range of about 60-120~C such that the flash point of the two-cycle oil of this invention is greater than 70~C.
Typical examples include kerosene, hydrotreated kerosene, middle distillate fuels, isoparaffinic and naphthenic aliphatic hydrocarbon solvents, dimers, and higher oligomers of propylene butene and similar olefins as well as paraffinic and aromatic hydrocarbon solvents and mixtures thereof.
Such solvents may contain functional groups other than carbon and hydrogen provided such groups do not adversely affect performance of the two-cycle oil. Preferred is a naphthenic type hydrocarbon solvent having a boiling point range of about 91.1~C-113.9~C (196~-237~F) sold as "Exxsol D80" by Exxon Chemical Company.
The invention further comprises the presence of up to 5% by weighl:
of one or more special purpose conventional lubricating oil additives, and these may be any additive normally included in lubricating oils for a 30 particular purpose.
Additional conventional additives for lubricating oils which may be present in the composition of this invention include viscosity modifiers, corrosion inhibitors, oxidation inhibitors, friction modifiers, 35 dispersants, antifoaming agents, antiwear agents, pour point depressants, detergents, rust inhibitors and the like.
~ ? ~A~EP --CA 02236~11 1998-0~-21 Typical oil soluble viscosity modifying polymers will generally have weight average molecular weights of from ~l 10,000 to 1,000,000 as determined by gel permeation chromatography.
Corrosion inhibitors are illustrated by phosphosulfurized hydrocarbons and the products obtained by reacting a phosphosulfurized hydrocarbon with an alkaline earth metal oxide or hydroxide. "Cobratech 356", which is benzotrizole in propylene glycol, is preferred for use in this invention in an amount of ~boubO.03 wt.%.
Oxidation inhibitors are antioxidants exemplified by àlkaline earth metal salts of alkylphenol thioesters having preferably Cs-C12 alkyl side chain such as calcium nonylphenol sulfide, barium t-octylphenol sulfide, dioctylphenylamine as well as sulfurized or phospho sulfurized hydrocarbons. Also included are oil soluble antioxidant copper compounds such as copper salts Of C10 to C18 oil soluble fatty acids.
Friction modifiers include fatty acid esters and amides, glycerol esters of dimerized fatty acids and succinate esters or metal salts thereof.
Dispersants are well known in the lubricating oil field and include high molecùlar weight alkyl succinimides being the reaction products of oil soluble polyisobutylene succinic anhydride with ethylene amines such as tetraethylene pentamine and borated salts thereof.
Preferred for use in this invention is 2.41% of a dispersant comprising a borated Mn 950 polyisobutenyl succinimide.
Pour point depressants also known as lube oil flow improvers can lower the temperature at which the fluid will flow and typical of these additives are Cg-C18 dialkyl fumarate vinyl acetate copolymers, polymethacrylates and wax naphthalene.
Foam control can also be provided by an anti-foamant of the polysiloxane type such as silicone oil and polydimethyl siloxane.
Anti-wear agents reduce wear of metal parts and representative materials are zinc dialkyldithiophosphate and zinc diaryl diphosphate.
-- ~ P ~ FJ ~
Detergents and metal rust inhibitors include the metal salts of sulfonic acids, alkylphenols, sulfurized alkylphenols, alkyl salicylates, naphthenates and other oil soluble mono and dicarboxylic acid. Neutral or S highly basic metal salts such as highly basic alkaline earth metal sulfonates (especially calcium and magnesium salts) are frequently used as such detergents. Also useful is nonylphenol sulfide. Similar materials made by reacting an alkylphenol with commercial sulfur dichlorides. Suitable alkylphenol sulfides can also be prepared by reacting alkylphenols with lO elemental sulfur. Preferred for use in this invention is 1.5% by.weight nonylphenol sulfide.
Also suitable as detergents are neutral and basic salts of phenols, generally known as phenates, wherein the phenol is generally an alkyl l S substituted phenolic group, where the substituent is an aliphatic hydrocarbon group having ~bou~ 4 to 400 carbon atoms. Preferred for use in the invention is 0.58% by weight calcium phenate.
Also suitable are oil soluble copper carboxylates which may be 20 present in amounts of 0.2 to 2% by weight and are used as antioxidants or to improve engine performance, examples being copper oleate or copper naphthenate in amounts of 0.5 to 1.5% by weight.
The lubricating oil compositions of the present invention will mix 25 freely with the fuels used in such two-cycle engines. Admixtures of such lubricating oils with fuels comprise a further embodiment of this invention.
The fuels useful in two-cycle engines are well known to those skilled in the art and usually contain a major portion of a normally liquid fuel such as a hydrocarbonaceous petroleum distillate fuel, e.g., motor gasoline is defined 30 by ASTM specification D~39-73. Such fuels can also contain non-hydrocarbonaceous rnaterials such as alcohols, ethers, organo nitro compounds and the like, e.g., methanol, ethanol, diethyl ether, methylethyl ether, nitro methane and such fuels are within the scope of this invention as are liquid fuels derived from vegetable and mineral sources such as corn, 3s alpha shale and coal. Examples of such fuel mixtures are combinations o~
gasoline and ethanol, diesel fuel and ether, gasoline and nitro methane, etc. Particularly preferred is gasoline, that is, a mixture of hydrocarbons , , , having an ASTM boiling point of 60OC at the 10% distillation point to 205~C at the 90% distillation point.
The lubricants of this invention are used in admixture with fuels in amounts of labe~ 20 to 250 parts by weight of fuel per 1 part by weight of lubricating oil, more typically~bout~30-100 parts by weight of fuel per 1 part by weight of oil Such admixtures and their use in two-cycle engines are further embodiments of this invention.
I0 The invention is further illustrated by the following examples which are not to be considered as limitative of its scope. Example 2 is for comparison and is not part of this invention. All percentages are by weight.
Example 1 An oil of the invention was prepared from the following:
(Trademarked components (a), (b), (c) and (h) are identified in the specification), and '~PE ester" is the preferred ester of technical grade pentaerythritol with a mixture of 45 mol% linear Cg acid and 55~m~~J0 of a mixture of n-octanoic and n-decanoic acid having a viscosity of 6.8l~St)at 1 00~C as disclosed in the specification:
Component Oil 1 (a) TPE Ester 15.00%
(b) '~istone A-30" 20.48%
(c) "Exxsol D-80" 25.00%
(d) Polyisobutylene Mn 950 35 00%
(e) Borated Mn 950 polyisobutenyl succinimide dispersant 2.41%
(f) Calcium Phenate 0.58%
(g) Nonylphenol sulfide 1.50%
(h) "Cobratech 35G" 0 03%
3 ~ 100%
AME~DE~ EET
IPrA/EP
This oil was evaluated in accordance with the JASO M345 test procedures JASO M340, M341, M342 and M343. This is an engine test established by society of Automoti\fe Engineers of Japan (JSAE) for tNo-cycle gasoline engine oils. As of July 1, 1994, oils used in two-cycle s engines are being labeled in accordance with the JASO-M345 standards as announced by the Japan Automobile Standards Organization (JASO).
JASO published the JASO M345 standards in April, 1994. "EGD
Detergency" is a refe-ence to a further modification of the normal JASO
M341 detergency test (1 hour) procedure in which the test is run for 3 10 hours. This is a more stringent standard expected to be adopted py ISO
(the International Organization for Standardization) as publislied by Committee Draft of January 5, 1995 of the Technical Committee 28. "FC" is the highest performance standard for the JASO M345 standards.
Example 2 (Comparative Example~
Oil 2 was the same as Oil 1 of the invention except that "Ketjenlube 135" a synthetic ester being a butanol ester of an alpha-olef~maleic acid copolymer used which had a Mn of 1800 and a viscosity of 35l~St)at 100~C
20 in place of the TPE Ester.
The engine test results for Oils 1 and 2 are in the Table below:
Enqine Test Results - JASO M345 & ISO-EGD
Oil 1 2Standard-FC ISO-EGD
Minimum Minimum EGD Detergency 145 122 -- 125 JASO Detergency M341 123 111 95 --JASO Lubricity M340 101 112 95 95 JASO Torque M340 99 99 98 98 JASO Blocking M343 153 93 90 90 JASO Smoke M342 125 157 85 85 , ~ _, Oil 1 of the invention shows markedly superior results in terms of detergency and exhaust port blocking while achieving passing values in all other aspects of the engine tests, when compared with another oil based on ester blends, Oil 2.
Claims (9)
1. A two-cycle oil composition which comprises:
(a) 10-20% of a first synthetic ester base stock oil being an ester of technical grade pentaerythritol with a mixture of (a) branched C8 and (b) mixed linear C8 and C10 monocarboxylic acids, the oil having a viscosity of 6 to mm2/S 8(cSt)at 100°C., (b) 18-30% of a second synthetic ester base stock oil being an oxo alcohol ester of a dicarboxylic acid, the oil having a viscosity of 3 to 10mm2/s(cSt)at 100°C., (c) 30 to 40% of a polybutene having an Mn of 300-1500, (d) 15 to 35% of a normally liquid solvent having a boiling point up to 300°C, and having a flesh point of 60° to 120°C,and (e) 0 to 5% of other lubricating oil additives.
(a) 10-20% of a first synthetic ester base stock oil being an ester of technical grade pentaerythritol with a mixture of (a) branched C8 and (b) mixed linear C8 and C10 monocarboxylic acids, the oil having a viscosity of 6 to mm2/S 8(cSt)at 100°C., (b) 18-30% of a second synthetic ester base stock oil being an oxo alcohol ester of a dicarboxylic acid, the oil having a viscosity of 3 to 10mm2/s(cSt)at 100°C., (c) 30 to 40% of a polybutene having an Mn of 300-1500, (d) 15 to 35% of a normally liquid solvent having a boiling point up to 300°C, and having a flesh point of 60° to 120°C,and (e) 0 to 5% of other lubricating oil additives.
2. The composition of claim 1 wherein said (a) amount is 15%, said (b) amount is 19-25%, said (c) amount is 35% and said (d) amount is 25%.
3. The composition of claims 1 or 2 wherein (b) is oxo tridecyl adipate having a viscosity of mm2/s 5.3 (cSt)at 100°C.
4. The composition of claims 1 or 2 wherein (c) polybutene has an Mn of 950.
5. The composition of claims 1 or 2 wherein (d) is a naphthenic solvent having a boiling point range of 91.1°C-113.9°C.
6. A fuel lubricant mixture for two-cycle engines which exhibits improved detergency and reduced exhaust port blocking upon combustion which comprises 20 to 250 parts by weight, fuel per 1 part by weight of the oil of claims 1 or 2.
7. The mixture of claim 8 wherein the range is 30-100 parts of fuel per part of oil.
8. The use of the oil of claim 1 in a two-cycle engine.
9. The use of the fuel lubricant mixture of claim 8 in a two-cycle engine.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GBGB9523916.6A GB9523916D0 (en) | 1995-11-22 | 1995-11-22 | Two-cycle ester based synthetic lubricating oil (pt-1041) |
| GB9523916.6 | 1995-11-22 | ||
| PCT/EP1996/005115 WO1997019154A1 (en) | 1995-11-22 | 1996-11-20 | Two-cycle ester based synthetic lubricating oil |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2236511A1 true CA2236511A1 (en) | 1997-05-29 |
Family
ID=29403942
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA 2236511 Abandoned CA2236511A1 (en) | 1995-11-22 | 1996-11-20 | Two-cycle ester based synthetic lubricating oil |
Country Status (1)
| Country | Link |
|---|---|
| CA (1) | CA2236511A1 (en) |
-
1996
- 1996-11-20 CA CA 2236511 patent/CA2236511A1/en not_active Abandoned
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US5965498A (en) | Two-cycle synthetic lubricating oil | |
| EP0876447B1 (en) | Two-cycle ester based synthetic lubricating oil | |
| US4088589A (en) | Dual pour depressant combination for viscosity index improved waxy multigrade lubricants | |
| US4992183A (en) | Multigrade hydrogenated decene-1 oligomer engine oils | |
| CA2550562C (en) | Low ash or ashless two-cycle lubricating oil with reduced smoke generation | |
| US5888948A (en) | Two-cycle lubricating oil | |
| US6610634B1 (en) | Two-cycle lubricating oil | |
| US6455477B1 (en) | Two-cycle lubricating oil with reduced smoke generation | |
| CA2349459C (en) | Two-cycle lubricating oil | |
| EP0552554B1 (en) | Lubricating oil compositions | |
| CA2236511A1 (en) | Two-cycle ester based synthetic lubricating oil | |
| CA2343058C (en) | Lubricating oil compositions and fuels for two-cycle engines | |
| JP3981999B2 (en) | Lubricating oil composition for two-cycle engines | |
| EP0288777A2 (en) | Synthetic hydrocarbon engine oils | |
| CA2236509A1 (en) | Two-cycle synthetic lubricating oil |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| FZDE | Dead |