JPS6040200A - Grease composition - Google Patents

Abstract

Grease compositions, wherein the grease is thickened with a metal hydroxyl-containing soap grease thickener are provided. Other essential ingredients of the compositions include borated hydrocarbyl epoxides and phosphorus and sulfur moieties.

Description

[Detailed description of the invention] The present invention relates to off 1 standard 7', 'C91σ) compositions.

More specifically, the present invention relates to a synergistic grease composition comprising a grease, a hydroxide/containing soap thickener, an Id'Ijl powder, an epoxide, and a phosphorus component and a sulfur component.

U.S. Patent No. 4.41 C1,438 - Viscous 1t17i4
Regarding 111H1i Toy Beggar;, this is Glee: <¥3
111111 Excessive amount of boric acid
, consisting of chemical evoguiside. Additionally, epoxides in the form of Karoshin θ)sen are used during (DOLIWd slubbing).

For example, US 1 A% Wi' No. 4,24.4.829 describes the use of adjunct M ester σ (epoxidized as a lubricating agent in end oil).

According to the present invention, (1) a hydroxy-containing 1 gold λ 4 soap thickener, (2) an epoxide of the following formula: C) +1 ]+2 and 3 (wherein R, R', and tt3 are hydrogen and C8 (・""3L, σ) hydrocarbon groups, and these r
l) of which at least one is a hydrocarbon) boric acid,
(11111f!! ri 1 sage monster is σ) 2〇)
Alkyl 1 tll + acid 1 position: (lt40) B(Of
-1).

(wherein, 6. Spider-
A grease composition is provided, which is produced by reacting a cell amount with a compound (I), and (3) a phosphorus component and a yellow component.

Preferably, 1+1III contains 6 or more boron atoms in the chlorination product.

The borated epoxides of the present invention can be made by reacting the epoxide with a boron compound such as boric acid oxide, fJIII acid, or an alkyl 6'll oxide salt or m2 compound thereof. Get the product! For example, the reaction between an epoxide dimer or a higher oligomer and a complex compound, which is primarily a mono(chain acid ester or ester), is equivalent to
The product J that forms the 1-111III acid ester (J-1-F, which may fall within the range of evo and nods) is 1,2-ebo-7 octane, 1,2-ebo-oxyteno J
1,2-epoxydodecane, 1,2-epoxytelatecane, 1,2-epoxypentadecane, 1,2-epoxyhexatecane, 1,2-epoxyheptatecane,
Le Lo with 1.2-evogynooctatecane, 1.2-epoxyeicosane and a mixture of such epoxides q%+, and mixtures of other epoxides. These (well, C2
□ or '3+1'-7 Finn River mixture epoxide oj: and (゛ or C28 olefin vt4 mixture σ) 4 epoxide 1 and congratulations. In addition, Octen's timer,
Also included are epoxides from dimers of decene, mixed octe/dimers with decene; 0 epoxides from decent trimers; and the like. Hydrocarbons are meant to include alkyl, aryl, cycloalkyl or cycloalkenyl groups; (for one taste, these have a number of carbon atoms of 8 to 60, preferably 10'/22 carbon atoms) Preferably the hydrocarbon is an alkyl group.

As mentioned before, the boron compound used is boric acid, filJ
II i rescue oxide or argyl l+'JI Iα salt, preferably 11.
and triethyl II.

The reaction to form the Illll 11 acid ester can be carried out at 80°C to 260°C, preferably 110°C to 180°C. The temperature chosen will often depend on the reactants of interest and whether or not a solvent is used. When this anti-L[,,woT]5, the molar ratio of the epoxide and the boron compound ITh+ is [,1. 2 7; C to 1, preferably 05 to 0.9, 1,5 vt
~ It is very difficult to choose the number of reactants. Epoxide 1 Okasashi's +1111 1; 1 reacted with Hijin and 0.1
heavyli1. Boron or 10% la LO) l+
llL&, including tr lilll l'A', :c
, t. f/L/'%j formation #-71).

Although large pressure relief is generally preferred, ALs may be able to conduct the reaction at 1 to 5 atmospheres. Furthermore, if conditions permit, a propellant may be used. Generally, relatively non-polar and non-reactive acids are used, including benzene, toluene, xylene and 1,4-dioxane. Sen's hydrocarbon solvents and alcoholic solvents including propatool and butanol! River can. Mixtures of alcoholic solvents and hydrocarbon solvents can also be used.

114'j is not critical during the reaction. Thus, our method σ
) Can be carried out in any concavity in 1 to 20 hours.

A narrow group of thickeners are preferred for making the greases of this invention. Hydroxy-containing fat alkali and alkaline hand soaps containing at least -615 fatty esters of 1 (14-bar glycerides, 121 to about 60 sigma per mole) carbon atoms ) are included among the preferred thickening agents. Kanabashi is sodium,
Represented by lithium, calcium and barium. Lithium is 91% preferable. Among these alcohols and fatty substances η, preferred σ) are 12-hydroxystearic acid and glycerides containing 12-hydroxystearic acid++a′v.

It is not necessary that all of the thickeners be derived from the preferred ingredients. The important 1.14 points can be achieved by using only about 15 IjK fractions (all 1, 11σ). Replenishment h1 (for example, 85 cities), Section 1 to σ] A wide range of glue adhesives can be used in the grease of the present invention. Sen σ) Useful”・t1
The sticky agent is methyl-12-hyaloxystearate 1-1C4
12 Jib J Rubon Nrin O) Nester, and Tarsin Sangetsu Vr Rib NR's Alkali F Puko contains Alkali-1 Noryohi 1>S' 21 Soap. carbon atom 1
Meat containing 2 or 0 (other alkaline earths that do not contain 1 hydroxyl group are alkaline 10), Megane Kaedeha V ribs 1 or 2 can be used. These include stearic and oleic soaps.

The thickener is calcium stearate-acetate (
United States 4jJ'jx"F"Seven loli? ,1shi/,,,'
, barium stearate-acetate (U.S. Patent No. 2,564,561), calcium stearin removal ~
Caprylate-acetate complex (U.S. Pat. No. 2,999,0
65), calcium caprylate-acetate (U.S. Pat. No. 2,999.066), and calcium salts and low
Includes soap-like salts and salt-soap complexes of medium and high molecular weight acids and nutty oil acids.

Other groups of thickeners include substituted ureas; phthalocyamines; indanthrene; pigments such as perylimide, pyromellidiimide and ammeline; and certain hydrophobic clays. It can be made from clay, which is initially hydrophilic, but used as a component of grease compositions.
By introducing long σ1 hydrocarbon groups on the surface, the clay has been converted to a hydrophobic state and can be pretreated with organic cationic surfactants such as onium compounds. 〕・I↓・ヱTake it, Uko, L
will be held. Representative onium compounds are tetraalkylammonium chlorides, such as dimethyldioctadecylammonium chloride, dimethyldibenzylammonium chloride, and mixtures thereof.

This inversion method is well known to those skilled in the art and is believed to require no further discussion.

The third component of the grease composition (θ) of the present invention is a phosphorus component and a bright yellow component. Both of these components are expressed by the following formula = (where 1(5
is a hydrocarbon group containing from 1 to 18 carbon atoms,
M is a metal or non-gold stock, II is a valence of 4, and X is oxygen or (l+ii, yellow) present in the same molecule, such as in a metal or non-metal phosphorodithioate. You may.

In this compound, ■ is preferably an alkyl group, but may also be a propyl, butyl, pentyl, hexynopeoctyl, decinopetetradecyl or oftatecyl group. : Nibutanol, 4-methyl-2-pentanol, 2-ethylhexanol, oleyl alcohol, Oyori Oyori derived from mixtures thereof. Furthermore, σ) alkaryl groups such as butylphenol, octerphenol, nonylphenol, and dodecylphenol are included. Gold 1 (Ha is Zhou Shun 1 Ritsui IA, 11Δ, 1113 and ~Ill
i&' cy) Contains gold 11 and 13. Also σ) that may be mentioned are lithium, sodium, calcium, 114+ lead, cadmium, silver, and gold. Non-metallic ions include vinyl esters such as vinyl acetate, vinyl ethers such as bunal vinyl ether, and propylene oxide. L is derived from an epoxide such as 1,2-evogydodecane.

Phosphorus and (11!il ftII are also two σ) separately σ
) compound σ) can be supplied from i11 combination, +
911 For example, (1) Dipidrocarbyl phosphisomer or phosphite known mixtures having 2 to 10 carbon atoms in each hydrocarbon, and valent isobutylene, dibenzyl dibenzyl, valorized terpene, two phosphoric acid phosphants, etc. It is a combination of sulfides such as rhodithionyl and 111L Jojoba oil. Phosphites include dibutyl, dihexyl, dioctyl, didecyl and similar (υσ) phosphites. Acid esters containing 4 to 20 carbon atoms in each hydrocarbon group, such as tributyl phosphate, tridecyl phosphate, tricresyl phosphate, and mixtures of such phosphates may also be used.

In summary, in the practice of the present invention, it is critical to incorporate all six components mentioned above into the composition to obtain a highly improved droplet, #5 ff grease.

Thus: First, for the manufacture of greases, the Jl+ viscous must contain at least about 15% by weight zero metal or non-group hydroxyl-containing soap.

Second, add 001 car silk% 11 to 10 tochichi to the grease.
Preferably, 01 to 2 i+1ill 11i di+H grade epoxide should be added. Here, the borated epoxide is reacted with at least equimorphic boron. Third, the composition is a compound containing phosphorus and 'IpiL yellow, or Ll'-J'1. j component and 11i1 yellow component are separately supplied.
01i↓ amount or about 1011 eyebrows, preferably 0.2M
': D: %Putanishii2. ．． 4 (, , j, t must be included. When using separate compounds, use the mixture described above (corresponding to the I target water system, 1 + σ) to make equimolar fi + 7) '4' r and supply sulfur.

In general, Ki Kaiaki's reaction product 1 Jk thing 11, F's degree of 1 base friction reduction, 1 control dissipation activity, surface j 1) 1 and 1 activation 1/
However, in many applications, borate epoxides and/or j: IJ'1-containing compound (rejuvenation) is the entire composition - h'σ) 0.02 1 to 2 + 1 ill
Iij: Preferably 02% to 4% of the total silk is used too much.

The grease of the present invention can be mineral oil, 1 ton or 1 ton of oil, or mixtures thereof. In general, both mineral oil, paraffin oil and O. The /11! compound is any suitable nV'P'R viscosity 1 (.12), for example 1oo-F and 4
5 to 6 ot) IjSSU, and 50 to 250S S Ll at θ1 or 210-F
(2, shi) and. These elements 11 may have a viscosity index in the range of 4.1 [10] or above JL1.

70 to 950) Viscosity index is high. The average molecular weight of these oils may be between 2,501 Z and 800 ff). When producing a grease, the grease is generally added to the grease formulation to include the desired thickening agent and the additive. After that, use the entire grease composition in balance 4) with sufficient odor.

Synthetic oil is preferable to mineral oil. It is important to use this λl compound for success). Typical synthesis vehicles; ↓ polyisobutylene, bolybdenum, hydrogenated polydecene, polypropylene glycol, polyethylene kligol, +=)) tyrolpropane esters neopentyl and pentaerythritol esters, di(2-
ethylhexyl) sebacate, di(2-ethylhexyl) adipate, dibutyl tucrate, fluorocarbon, /licade nisdel, 7 run, phosphorus-containing faf2o) nisdel, liquid urea, ferrocene conductor, hydrogenated synthetic oil,
Polyphenyls, siloxanes and silicones (polysiloxanes), alkyl-substituted diphenyl ethers, reportedly butyl lid-bearing I bis(p-phenogyne phenyl) ethers, and phenoxy-7 phenyl ethers.

Example 1 f+:IIl 1,2-Evoxohexatecan chloride Approximately 1440 M 1,2-epoxyhexatecan (obtained commercially from Union Carbide), 5001 M toluene and 500 g l' 1lIIJj crotch heating +1
j41 teP (pump and condenser
+ift 5 liters of glass anti-L1.1 was loaded into the container. Stir the contents for 14 minutes until the moisture stops forming.
Heat beni to 4℃.

This was about 1011 eyebrows 111 nephews. Vacuum at about 160°C? The solvent was removed by distillation and the product was filtered through a diatom filter at about 120 DEG C. to obtain the clear amber γ+iL form as an amber waxy fluid.

Example 2 Approximately 177'G and O in a closed contactor approximately 110 ps
i! At the final strength of 12%, lithium monohydrate (2,5%) was added to water in 11 vehicles (approximately 76%).
Hydroxystearin l'& (8%) and glycerides (
A lithium hydroxystearate grease thickener was produced by saponifying 9th). All percentages are percentages of total adhesive.

Example 6 After dehydrating the thickener in an open oven, 1 liter of 1.4 square meter
The 1111 elementary ester was added into the grease concentrate.

1440 F-01,2-epoxy-hexadecane, 5
D OM-σ) Heat toluene and 50[JP flll acid;
The elementary-containing id [stell was prepared iθ. #l fluorodistillation σ) The reaction mixture was heated to 144° C. until the evolution of water ceased as a result. Remove the solvent by vacuum distillation and remove the phase full
The acid ester was mixed with diatomaceous earth to form a clear amber fluid that became waxy after cooling.

After introducing the boron-loaded Jl 1j into the grease concentrate thickener, it was heated to 31 degrees and then added with enough oil to give a thickening and cutting content of about 9.0%. Result 111
I11 raw material machining content 'f80: reduced to 1%. The resulting grease θ)llllll elemental content is approximately 0.04 N
It was 4M%. 99° CIL (after conversion, the dialkyl group is converted from a mixture of C3 nitrod, L and c6 tertiary alcohol σ) containing a curved dialkyl fluorodithioate, 1llllI'#1'
+ machining, extremely 1 top machining and O・nii・t 14ty #I=
74i11 additive was added to the grease. ASTM
I) 2265-78 grease MM+ point test (4f results are shown in JJFo): Table 1 I) 226b,'l. 1. Let's try it (
"G') Heath grease: dehydrated grease J+;!+viscosity g11 1
99°C Example 1: Dehydrated grease thickening cutting +t43j1.
257°C14; %11[Chlorinated epoxide Example 2: Dehydrated grease thickener +1.0, lj',
307°Q%1lIII-grade chlorinated epoxide -8 selected mineral oil + additive package (amine anti-tanning agent, phenolic 1611 clarification agent, gold salt, hydrithiophosphate,
Tsukuda C or I 1 gold] Debari l Zhan Qi 11 and nitrogen containing:
Base greases that are fully formulated or without boron additives: 193'C Dehydrated Grease Thickener + Diluted Mineral Oil + 1 Additive Package (Amine Antioxidants, Phenols) IZ-forming agent, Kanahashi dithiophosphate, yellow-containing Kinba 1 (activating agent, and nitrogen-containing surface resistance 1 (including 11 additive) It!III
Is I' = The disadvantage of a dehydrated thickener without epoxide is 1.
It was 99°C. When flII11 acid chlorinated epoxide was added to the thickener, the M point increased to 257°C. 1 to 4 after adding the fleece additive package to obtain the J′IC end crease. -] womasara V
One drop at 307°C. Kinkaede dithiophosphe =
Similar O containing 1 but not containing 1ν cut iy chlorinated epoxide
) 7i, '4i, l1 of well-blended final grease
li is 196 "C".

'f'jt'a'F m if: u people Mobil-Oil Corporation (4 others) Continued from page 1

Claims (1)

[Claims] 1) Full of main arsenal amount of grease and less (both 15)
Chukochi's hydroxyl group-containing soap thickener, (zt DJ lower σ)
Formula; (In the formula, R1It', 2, t3 is hydrogen or a hydrocarbon group containing 8 to 0 carbon atoms, at least one of which is a hydrocarbon group) σ) Epoxide, boric acid, boric acid oxide, and σ) Formula: ′ (R40) B(01,-1). (wherein X is 1 to 6, y is 0 to 2, and 7 it et al.) The sum is 7)) prepared by reacting with at least a molar compound of an alkyl borate selected from the group consisting of 0. D
1 > ii to 10% by weight - 1ii: reaction product, and (3) from about 001% to about 10% by weight of phosphorus and phosphorus compounds, or similar amounts of phosphorus and titanium; A grease composition consisting of a mixture of a phosphorus compound that provides yellow color and a compound containing IIf. i fl
Y's alkali metal stone 1 ken or alkaline earth gold? = Soap, aliphatic glyceride, or a fatty acid ester containing 12 to 0 carbon atoms, Bamboo 8'
(The composition according to claim 1. 3) The composition according to claim 2, wherein gold is thorium, lithium, calcium, or barium. 4 ) A thickener derived from 12-hydroxystearin r'i't7), +114Jc'1 Claim σ) Range σ: lN. ll composition. 5) Epoxide is 1,2-epoxyoctane, 1.2
-Epoxydecane, 1.2-epoxydodecane, 1.2
- Epoxytetradecane, 1,2-epoxypentadecane, 1,2-epoxyhexadeca/, 1,2-epoxyoctadecane, 1,2-epoxycheicozan, C22 to C3o olefin σ) Epoxide of mixture, C to C28 olefin 4. The composition according to claim 1, which is a poxide, an epoxide consisting of a decentrimer, or a dimer of octene; a dimer of decene; a dimer of mixed octene and decene; and a blank epoxide. thing. 6) The phosphorus component and the sulfur component are determined by the following formula = (where It
``is a hydrocarbon group containing 6 to 18 carbon atoms, M is a metal or a nonmetal, n is an atom of M, and X is a phosphorothio of 72 rvtt, supplied by Gy, %;iL
+Claim Q) The composition according to Range 1. 7) R5 is an alkyl group, Q'J'f'F Claim 6X, @ σ) J, IJv, +1. el
. 8) R55t, -j lobil, butyl, pentyl, hexyl, octyl, dodecyl, butrabucyl, octadecyl, or axo-oleyl group or a mixture thereof q71,! 1.11♂1 σ) Composition according to claim 7. 9) R5, Improper tool, furinol, imbutanol, sec-butanol, 4-methyl-2-pentanol, 2-ethylhexanol are mixtures thereof, the patent claim slj'H,' j , iJj♂, 8J
*The composition described in *. 10) M is a metal from Group 1A, 11A, +113 or 4 of the Round Table 1. Particular feature a'1: The composition according to claim 6. 11) Gold is lithium, sodium, calcium, zinc, cadmium or gold, Claim 10
1111 in Jl'i. 12) A composition according to claim 6, wherein M is derived from vinyl acetate, butyl vinyl ether, propylene oxide or 1,2-epoxydodecane. 16) The phosphorus component and the sulfur component are 11) dihydrocarbyl diphosphates having 2 to 6 carbon atoms in each hydrocarbon group, mixtures of phosphites of this Jfli, or 4 to 20 carbon atoms in each hydrocarbon group. a phosphoric acid ester having a carbon atom; bow l1
σ) Composition as described in box 91, paragraph 1, of the ``1 month'' request, which is supplied by a combined proboscis. 14)! tf1 phosphate, dibutyl, dihexyl, dioctyl or didecyl σ) phosphite or mixtures thereof; 4) Claim 15. σ written in ra)
Composition. 15) 4'! j "f'2 Nisder is tributyl,
1+ composition according to claim 16, which is a phosphate ester of tritesyl or tricresyl or a mixture thereof. 16) Eboxide is 1,2-evogysihexadecane, 6111:+=” the compound is boric acid, and the compound containing phosphorus and (l+n is zinc dialkyl phosphorodithionate), Here, this alkyl group is C3 (alcohol), C6 (alcohol),
Claim 16, 3, which can be removed from the mixture.
The composition listed in No. 1. 17) The grease vehicle is mineral oil, synthetic oil or a mixture thereof. The composition according to Item 1 of IJ Box.