EP0283922A2 - Hydraulische Siloxan-Polyalphaolefin-Flüssigkeit - Google Patents

Hydraulische Siloxan-Polyalphaolefin-Flüssigkeit Download PDF

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Publication number
EP0283922A2
EP0283922A2 EP88104211A EP88104211A EP0283922A2 EP 0283922 A2 EP0283922 A2 EP 0283922A2 EP 88104211 A EP88104211 A EP 88104211A EP 88104211 A EP88104211 A EP 88104211A EP 0283922 A2 EP0283922 A2 EP 0283922A2
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EP
European Patent Office
Prior art keywords
weight
parts
viscosity
hydraulic
carbon atoms
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Granted
Application number
EP88104211A
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English (en)
French (fr)
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EP0283922A3 (en
EP0283922B1 (de
Inventor
Eugene Dale Groenhof
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Dow Silicones Corp
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Dow Corning Corp
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Publication of EP0283922A3 publication Critical patent/EP0283922A3/en
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Publication of EP0283922B1 publication Critical patent/EP0283922B1/de
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    • C10M111/00—Lubrication compositions characterised by the base-material being a mixture of two or more compounds covered by more than one of the main groups C10M101/00 - C10M109/00, each of these compounds being essential
    • C10M111/04—Lubrication compositions characterised by the base-material being a mixture of two or more compounds covered by more than one of the main groups C10M101/00 - C10M109/00, each of these compounds being essential at least one of them being a macromolecular organic compound
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    • C10M107/00—Lubricating compositions characterised by the base-material being a macromolecular compound
    • C10M107/02—Hydrocarbon polymers; Hydrocarbon polymers modified by oxidation
    • C10M107/18—Hydrocarbon polymers modified by oxidation
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    • C10M107/00—Lubricating compositions characterised by the base-material being a macromolecular compound
    • C10M107/50—Lubricating compositions characterised by the base-material being a macromolecular compound containing silicon
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    • C10M2205/00—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions
    • C10M2205/02—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers
    • C10M2205/028—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers containing aliphatic monomers having more than four carbon atoms
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    • C10M2205/00—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions
    • C10M2205/12—Oxidised hydrocarbons, i.e. oxidised subsequent to macromolecular formation
    • C10M2205/123—Oxidised hydrocarbons, i.e. oxidised subsequent to macromolecular formation used as base material
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    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/02—Hydroxy compounds
    • C10M2207/023—Hydroxy compounds having hydroxy groups bound to carbon atoms of six-membered aromatic rings
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    • C10M2211/00—Organic non-macromolecular compounds containing halogen as ingredients in lubricant compositions
    • C10M2211/04—Organic non-macromolecular compounds containing halogen as ingredients in lubricant compositions containing carbon, hydrogen, halogen, and oxygen
    • C10M2211/044—Acids; Salts or esters thereof
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    • C10M2229/02—Unspecified siloxanes; Silicones
    • C10M2229/025—Unspecified siloxanes; Silicones used as base material
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    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/08—Hydraulic fluids, e.g. brake-fluids

Definitions

  • the present invention relates to hydraulic fluid compositions which may be used over a wide temperature range and yet exhibit relatively high flash points. More particularly, the fluids of this invention consist essentially of a dimethylsiloxane/alkylmethylsiloxane copolymer blended with a synthetic hydrogenated polyalpha­olefin. This invention further relates to a method of employing said compositions in a hydraulic system.
  • silicone fluids are known for their superior resistance to shear, thermal and oxidative degradation. Moreover, unlike typical hydrocarbon lubricating oils or hydraulic fluid, they maintain a relatively flat viscosity-temperature profile. On the other hand, these silicones generally do not possess the high degree of lubricity in steel-to-steel contact that is exemplified by hydrocarbons such as mineral oil, a property vital in many hydraulic applications. This problem can be resolved to some extent by the incorporation of certain lubricity additives in the silicone "base fluid.”
  • compositions comprising mineral oil and, as a viscosity index improver therefor, a homopolymeric diorganopolysiloxane in which the majority of the organo groups are methyl groups.
  • the remaining organo groups may be selected from alkyl, alkaryl or aralkyl groups having from 6 to 30 carbon atoms in amount sufficient to render them soluble in the mineral oil.
  • a major contribution to the art asserted by this disclosure is the dissolution of high viscosity polydimethylsiloxane in the hydrocarbon oil to provide a lubricating composition having improved viscosity-­temperature properties in which the siloxane component does not separate from the mixture at low temperatures.
  • EP-A-0 177 825 published April 16, 1986, describes lubricating oil preparations comprising silicone copolymers containing organomethylsiloxane units wherein the organo group is selected from alkyl groups having 1 to 7 carbon atoms or the phenyl radical and alkylmethylsiloxane units wherein the alkyl group can have from 6 to 16 carbon atoms.
  • copolymers have the further restrictions in that they must have a pour point below -15°C. and must be miscible with mineral oil, synthetic lubricating oils and the lubricity additives commonly employed in such oils.
  • This invention therefore, relates to a homogeneous hydraulic fluid composition, consisting essentially of: (A) about 40 to 90 parts by weight of a dimethylsiloxane/alkyl­methylsiloxane copolymer represented by the average formula wherein Me denotes the methyl group, R ⁇ is independently selected from alkyl radicals having 1 to 10 carbon atoms, R denotes an alkyl group having from 4 to 10 carbon atoms, x has an average value of about 5 to 15.
  • y has a value of about 0.5 to 4 and the ratio y/x is at most 0.3; and (B) about 10 to 60 parts by weight of a synthetic hydrogenated polyalpha­olefin represented by the formula said blend having a total of 100 parts by weight of said components (A) and (B).
  • component (B) is represented by the formula
  • component (B) is selected from the dimer, trimer or tetramer of decene-1, and said homogeneous hydraulic fluid has a viscosity of at most 2500 cS at -54°C., a viscosity of at least 3.5 cS at 100°C. and an open cup flash point of at least 163°C.
  • This invention also relates to a process for transmitting force in a hydraulic system, the improvement comprising using the above-described compositions as a hydraulic fluid in said system.
  • the present invention relates to hydraulic fluid compositions consisting essentially of a homogeneous blend of (A) a dimethylsiloxane/alkylmethylsiloxane copolymer and (B) a synthetic hydrogenated polyalphaolefin.
  • Component (A) of the present invention is a copolymer which may be represented by the average formula wherein Me denotes the methyl radical and R is a linear or branched alkyl group having 4 to 10 carbon atoms, such as n-­ pentyl, isopentyl, n-hexyl, n-heptyl, n-octyl, diisobutyl, n-nonyl or n-decyl. Straight chain alkyl groups are preferred over branched structures. It is further preferred that R is selected from the n-hexyl or n-octyl radicals.
  • the R ⁇ groups on the terminal silicon atoms are identical or different short chain alkyl groups having from one to 10 carbon atoms, such as methyl, ethyl, propyl, butyl, hexyl, octyl or decyl, with methyl being preferred.
  • x in the above formula may range from about 5 to 15, preferably from 6 to 12.
  • the value of y may correspondingly range from about 0.5 to 4, preferably from 0.5 to 3.
  • the value of y is, however, restricted such that the ratio y/x is at most 0.3.
  • x and y are chosen such that the viscosity of the copolymer fluid ranges from about 5 to 50 centistokes (cS) at 25°C.
  • the viscosity is about 10 - 20 cS.
  • R is n-hexyl, R ⁇ is methyl, x is about 6 and y is about 1 or when R is n-octyl, R ⁇ is methyl, x is about 8 and y is about 0.5.
  • the copolymers of the present invention may be prepared by methods which are well known in the art. For example, they may be synthesized by the cohydrolysis, and subsequent condensation, of the appropriate diorganodialkoxy­silanes or diorganodichlorosilanes. In this approach, a desired quantity of an end-capping reactant, (R ⁇ )3SiZ, is included in the reaction mixture to regulate the molecular weight of the product (i.e., more end-capping reactant yields a lower molecular weight product).
  • the R ⁇ groups of said end-capping reactant are the same as those set forth above for component (A).
  • the Z group is a hydrolyzable species such as halide (e.g., chlorine, fluorine or bromine) or alkoxy (e.g., methoxy, ethoxy).
  • Another procedure which may be followed in the synthesis of the subject copolymers is the acid or base catalyzed equilibration of diorganocyclosiloxanes in the presence of the aforementioned end-capping reactant.
  • Yet another, and preferred, method comprises the steps of preparing an SiH-functional copolymer intermediate of the general formula wherein Me represents the methyl radical and R ⁇ has been previously defined.
  • These intermediates are well known in the art and may be prepared by the acid equilibration of a commercially available polymethylhydrogensiloxane with cyclic dimethylsiloxanes in various ratios. Molecular weight of the intermediate may be controlled by incorporating the proper level of an endcapping monomer, such as hexamethyldisiloxane.
  • the SiH-functional intermediate is then reacted with about a 25% excess of the desired alkene to chemically add the latter to the SiH groups of the former. This addition reaction is catalyzed by platinum complexes known in the art.
  • Component (B) of the present invention is at least one synthetic hydrogenated polyalphaolefin (PAO) selected from the dimer, trimer or tetramer of decene-1, which may be represented by the following formulae:
  • PAO synthetic hydrogenated polyalphaolefin
  • component (B) is the PAO trimer. It is, however, possible to achieve the high flash point and viscosity-temperature profile needed to meet the requirements of the Low-Temperature MIL-H-83282 target by blending component (A) with mixtures of the above dimer, trimer and tetramer. as may be determined by routine experimentation.
  • PAO fluids are well known in the art and can be prepared from the monomer decene-1 by catalytic polymerization and hydrogenation.
  • the interested reader is directed, for example, to methods outlined by Cupples et al. in the October 1981 government report number AFWAL-TR-81-4109 (Materials Laboratory, Air Force Wright Aeronautical Laboratories, Wright-Patterson Air Force Base). These fluids are commercially available from the Gulf Oil Chemicals Co., Houston, Texas, under the trade name SYNFLUID.
  • compositions of the present invention may be prepared by simply blending components (A) and (B) to form a homogeneous mixture therebetween.
  • the method of mixing is not critical and any of the commonly employed methods known in the art may be used.
  • the blend so formed is referred to as a "base fluid" in that it is ordinarily combined with lubricity additives and other adjuvants, described infra, to form a fully formulated hydraulic fluid.
  • component (B) is the decene trimer
  • component (A) is the decene trimer
  • from about 40 to 90 parts by weight of component (A) is blended with about 60 to 10 parts of component (B) to form 100 parts of the compositions of the present invention. It is preferred, however, that from about 40 to 60 parts by weight of component (A) is blended with about 60 to 40 parts of the decene trimer.
  • equal weights of the decene trimer and the dimethylsiloxane/alkylmethylsiloxane copolymer fluid of component (A) are employed wherein the dimethyl­siloxane/alkylmethylsiloxane copolymer component is delineated by the preferred ranges described above.
  • component (B) is the decene tetramer
  • component (A) is blended with about 20 to 10 parts of component (B) to form 100 parts of the compositions of the present invention.
  • compositions of the present invention may be defined in terms of the key physical properties required by the Low-Temperature MIL-H-83282 target.
  • 100 parts by weight of the blend consists of about 10 to 90 parts by weight of component (A) and about 90 to 10 parts by weight of at least one synthetic hydrogenated polyalphaolefin selected from the dimer, trimer or tetramer of decene-1, such that the homogeneous blend has a viscosity of at most 2500 cS at -54°C., a viscosity of at least 3.5 cS at 100°C. and an open cup flash point of at least 163°C.
  • about 40 to 60 parts by weight of component (A) is blended with about 60 to 40 parts of component (B).
  • additives are generally incorporated into the base fluids of this invention to prepare completely formulated hydraulic fluids.
  • Antiwear, or lubricity, additives such as tricresyl phosphate, dibutyl­chlorendate and antimony dialkyl-dithiocarbamate are preferably incorporated at about 1 to 10 percent by weight.
  • Rubber swell additives such as di(2-ethylhexyl) sebecate or tributyl phosphate, may be incorporated at about 1 to 5% by weight. These are typically employed with polydimethylsiloxanes since these base fluids tend to shrink rubber components by leaching out plasticizers from the latter. Generally, less swell additive is needed as alkyl content, or size of the alkyl group, of component (A) is increased or a greater amount of component (B) is utilized.
  • Antioxidants such as p, p ⁇ dioctyldiphenylamine and butylated hydroxytoluene at concentrations of about 0.1 to 0.5% by weight are generally required to protect the alkyl groups from oxidation at elevated operating temperatures. Dyes may also be incorporated at low levels, mainly for identification purposes.
  • non-essential additives such as fire retardants, defoamers and corrosion inhibitors may also find utility in combination with the base fluids of the present invention.
  • component (A) Increasing the alkylmethylsiloxane content of component (A) towards 100% resulted in polymers which were unsatisfactory in that these base fluids could not be formulated to conform to the viscosity requirements of the Low-Temperature MIL-H-83282 target. Furthermore, as alkyl content is increased, swell of any rubber components in the hydraulic system also increases, an undesirable consequence in some systems.
  • This invention also relates to an improved process for transmitting hydraulic force (pressure) in a hydraulic system, wherein the hydraulic fluid consists essentially of one of the siloxane copolymer-PAO blends described above.
  • the fluid-containing portions of the hydraulic components of said hydraulic system are filled with the compositions of this invention, as disclosed above.
  • hydraulic components envisioned herein include pumps, fluid coupling devices, such as diaphragms, hydraulic line means, valves and hydraulic actuating means, such as hydraulic motors, pistons and servo-valves.
  • the hydraulic systems which benefit most from the use of the hydraulic base fluids of this invention are those which are required to operate between the temperature extremes of -54°C. and 135°C. and simultaneously require improved fire resistance over systems using mineral oil as the hydraulic fluid.
  • the process of the present invention is, therefore, most appropriately employed in conjunction with military aircraft hydraulic systems.
  • Other hydraulic systems wherein the process of the present invention may be advantageously employed include those of civilian aircraft, military transport and combat vehicles for land and sea, space vehicles and machinery for use in arctic regions or other cold environments.
  • a homogeneous blend was prepared by mixing equal portions of the fluid prepared in Example 2 and a 4 cS SYNFLUID (Gulf Oil Chemicals Co., Houston, TX). The latter fluid is described as a trimer of decene having the formula The blend was subjected to measurements of viscosity at various temperatures as well as open-cup flash point and fire point, the results being reported in Table 1, below.
  • a siloxane copolymer having the average structure was prepared according to the method described in Example 1, above. This fluid was blended in equal amount with 4 cS SYNFLUID as in Example 3 and the blend viscosity and flash point determined. These results also appear in Table 1.
  • This homopolymer had a viscosity of 14.1 cS at 25°C. and a calculated average structure
  • This fluid was blended with an equal amount of the decene trimer (4 cS SYNFLUID), as described in Example 3, above. Viscosity and flash point test results for this blend are also reported in Table 1.

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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)
  • Lubricants (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
EP88104211A 1987-03-23 1988-03-17 Hydraulische Siloxan-Polyalphaolefin-Flüssigkeit Expired - Lifetime EP0283922B1 (de)

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US2895087A 1987-03-23 1987-03-23
US28950 1987-03-23

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GB2506975A (en) * 2012-08-14 2014-04-16 Dow Corning Lubricant compositions
WO2015181358A1 (fr) 2014-05-30 2015-12-03 Total Marketing Services Polyoléfines lubrifiantes de basse viscosité
FR3037949A1 (fr) * 2015-06-29 2016-12-30 Total Marketing Services Polyolefines lubrifiantes de basse viscosite
FR3037968A1 (fr) * 2015-06-29 2016-12-30 Total Marketing Services Polyolefines comme fluide special
FR3037969A1 (fr) * 2015-06-29 2016-12-30 Total Marketing Services Polyolefines lubrifiantes de basse viscosite
WO2018236591A1 (en) * 2017-06-22 2018-12-27 Exxonmobil Research And Engineering Company LOW VISCOSITY LUBRICANTS BASED ON HYDROCARBON FLUIDS CONTAINING METHYLPARAFFIN

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DE4204200A1 (de) * 1992-02-13 1993-08-19 Daimler Benz Ag Fluessigkeit und deren verwendung
JP3341318B2 (ja) * 1992-10-21 2002-11-05 エヌオーケー株式会社 低温作動油
JP3344852B2 (ja) * 1994-10-28 2002-11-18 東レ・ダウコーニング・シリコーン株式会社 液状組成物
US10420531B2 (en) 2012-12-28 2019-09-24 Volcano Corporation Synthetic aperture image reconstruction system in a patient interface module (PIM)
FR3021665B1 (fr) * 2014-05-30 2018-02-16 Total Marketing Services Procede de preparation de polyolefines lubrifiantes de basse viscosite
CN105754692A (zh) * 2016-04-14 2016-07-13 上海禾泰特种润滑科技股份有限公司 一种空气压缩机油组合物及其制备方法

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US3445390A (en) * 1964-12-23 1969-05-20 Mobil Oil Corp Method of high temperature lubrication and fluid operation
US3957664A (en) * 1972-07-24 1976-05-18 Gulf Research & Development Company Lubricant and hydraulic fluid compositions
US4244831A (en) * 1976-04-07 1981-01-13 Union Carbide Corporation Silicone-hydrocarbon compositions
DE3436164A1 (de) * 1984-10-03 1986-04-10 Bayer Ag, 5090 Leverkusen Schmieroelzubereitungen
US4640792A (en) * 1985-11-25 1987-02-03 Dow Corning Corporation Silicone brake fluid having reduced air solubility

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GB2506975A (en) * 2012-08-14 2014-04-16 Dow Corning Lubricant compositions
WO2015181358A1 (fr) 2014-05-30 2015-12-03 Total Marketing Services Polyoléfines lubrifiantes de basse viscosité
FR3021664A1 (fr) * 2014-05-30 2015-12-04 Total Marketing Services Polyolefines lubrifiantes de basse viscosite
WO2017001487A1 (fr) * 2015-06-29 2017-01-05 Total Marketing Services Polyoléfines comme fluide spécial
FR3037968A1 (fr) * 2015-06-29 2016-12-30 Total Marketing Services Polyolefines comme fluide special
FR3037969A1 (fr) * 2015-06-29 2016-12-30 Total Marketing Services Polyolefines lubrifiantes de basse viscosite
FR3037949A1 (fr) * 2015-06-29 2016-12-30 Total Marketing Services Polyolefines lubrifiantes de basse viscosite
WO2017001442A1 (fr) * 2015-06-29 2017-01-05 Total Marketing Services Polyoléfines lubrifiantes de basse viscosité
WO2017001458A1 (fr) * 2015-06-29 2017-01-05 Total Marketing Services Polyoléfines lubrifiantes de basse viscosité
CN107849474A (zh) * 2015-06-29 2018-03-27 道达尔销售服务公司 低粘度润滑聚烯烃
CN107922866A (zh) * 2015-06-29 2018-04-17 道达尔销售服务公司 低粘度润滑聚烯烃
US10377960B2 (en) 2015-06-29 2019-08-13 Total Marketing Services Low viscosity lubricating polyolefins
WO2018236591A1 (en) * 2017-06-22 2018-12-27 Exxonmobil Research And Engineering Company LOW VISCOSITY LUBRICANTS BASED ON HYDROCARBON FLUIDS CONTAINING METHYLPARAFFIN

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JPS63254161A (ja) 1988-10-20
DE3861601D1 (de) 1991-02-28
EP0283922A3 (en) 1988-10-26
JPH0563509B2 (de) 1993-09-10
AU597804B2 (en) 1990-06-07
AU1337588A (en) 1988-09-22
EP0283922B1 (de) 1991-01-23
CA1334966C (en) 1995-03-28

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