JPH01172396A - Reaction product of dialkyl or trialkylphosphide and elemental sulfur and production thereof - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to the reaction products of dialkyl and trialkyl phosphites with elemental sulfur, the reaction of the resulting products with epoxides, olefins, and amines, and the use of lubricating products. Concerning use in oil formulations.

U.S. Pat.
The use of O-dialkyl phosphorous acids with esters to make dialkylthiophosphates is disclosed.

U.S. Pat. No. 4,242,511 discloses the reaction of 1) 0°S-dialkylthiophosphate esters by partial dealkylation of thiophosphates to form salts of dealkylated products by treatment with amines. are doing.

Although dithiophosphate products are known lubricant additives, their manufacture involves steps that result in toxic and undesirable by-products such as hydrogen sulfide and chloride-containing M waste streams.

The present invention is a method for producing a first reaction product suitable for use as an additive to lubricating oils, comprising: a molar ratio of sulfur to phosphite of 0.8 to 1; a temperature of 2.75 to 110°C; It consists of reacting a dialkyl or trialkyl phosphite with elemental sulfur in the absence of any catalytic material added to promote the reaction of both reactants.

The invention further comprises reacting the first reaction product with the amine, olefin or alkylene oxide at a molar ratio of amine, olefin or alkylene oxide to phosphite of 0.9 to 1.2 and a temperature of 10 to 90°C. Also provided is a method of producing a second reaction product suitable for use as an additive to lubricating oils.

The present invention further provides a second product with P2O5 and 1:3 p2O.
A method of making a third reaction product suitable for use as a lubricating oil additive is also provided, comprising reacting a molar ratio of the products: .

The invention also provides a lubricant composition comprising a lubricating oil and 0.1 to 10% by weight of the total composition of first, second and third products.

According to the invention, a dialkyl or trialkyl phosphite of the following general formula: (Rho)2POR2 in which Rr is a C4-C18 hydrocarbon radical and R2 is hydrogen or a C4-C18 hydrocarbon radical; The first product is obtained by reacting 18 hydrocarbon groups) with elemental sulfur in the presence of powdered sulfur in the absence of a catalyst at elevated temperatures. Useful dialkyl or trialkyl phosphites include oleyl, phenyl, nonylphenyl,
Includes octylphenyl, 2-ethylhexyl, 1,3-dimethylbutyl, tridecyl, isodecyl, octyl and butyl phosphites and mixtures thereof. Non-reactive organic solvents can be used if desired. Preferably the organic solvent is selected from benzene, toluene, xylene, and mixed alkyl and aromatic petroleum distillates. The powdered sulfur is conveniently less than 1 mm, preferably 0.01 mm.
The average particle size should be less than a millimeter, which reduces reaction time. A reaction temperature of 75 to 110'C is preferred and a molar ratio of sulfur to phosphite of 0.
8 to 1.2 is preferred. The reaction is preferably carried out under a blanket of nitrogen or other non-reactive gas.

At the end of the reaction period, the reaction mixture is allowed to cool to room temperature. The desired product can then be spun under vacuum to remove solvent and volatile by-products and then filtered or decanted from the reaction vessel.

This first reaction product thus obtained may then be further reacted with an amine, olefin or alkylene oxide. The molar ratio of one of these reactants to react with 1 mole of phosphite in the reaction product is between 0.9 and 1.2.
It is. This second reaction involves mixing the reactants and approximately 1
The reaction is carried out at a temperature of 0 to about 90°C (optionally with heating). The resulting second product can then be separated and purified by filtration and decantation. This second product is suitable for use in lubricating oil and grease formulations.

The amine compound to be reacted with the first product formed by the alkyl phosphite and sulfur can be primary, secondary or tertiary. A preferred amine is Primene 81
R1 benzotriazole, tolu) +Jazole, including amine-containing polymeric succinimides and aromatic amines such as dialkyldiphenylamine and (alkylated) phenylnaphthylamine.

If olefins are used, they can be selected from vinyl ethers, vinyl esters, vinylamides and other active olefins.

Useful alkylene oxides include ethylene oxide and propylene oxide. The resulting primary and secondary products, which are useful as lubricating oil additives, contain phosphorus pentoxide, h
05, can be reacted in a molar ratio of about 1 mole of P2O5 to about 3 moles of the thiophosphate product to form a third product of improved performance. It is used with grease in a range of about 0.1 to about 10% by weight of the total composition. Additionally, other additives such as detergents, antioxidants, anti-wear agents may be present.

These include phenates, sulfonates, succinimides, zinc dialkyldithiophosphates, polymers, calcium and magnesium salts of phenates and sulfonates, overbased salts thereof, and the like.

Lubricants contemplated for use with the esters of the present invention include mineral-based and synthetic hydrocarbon oils of lubricating viscosity, mixtures of mineral and synthetic oils, and greases therefrom, and mixtures thereof. Synthetic hydrocarbon oils include long chain alkanes such as cetane and olefin polymers such as oligomers of hexene, octene, decene, and dodecene.

These vicinal diols are particularly effective in synthetic oils that are formulated using a mixture of synthetic hydrocarbon olefin oligomers and smaller amounts of hydrocarbyl carboxylate ester fluids. Other synthetic oils that can be used alone with the compounds of the present invention or mixed with mineral oils or synthetic hydrocarbon oils include fully esterified ester oils containing no free hydroxyl groups, e.g. (2) to 20 monocarboxylic acids, trimethylolpropane esters of C2 to C20 monocarboxylic acids, (2J polyacetals, and (3) siloxane fluids. Particularly useful synthetic esters include polycarbonate More preferably, pentaerythritol, or this mixture of di- and tripentaerythritol, is prepared from an aliphatic monocarboxylic acid having 1 to 20 carbon atoms or such an acid. It is an ester fluid made by complete esterification of a mixture of

A wide variety of thickeners can be used in the greases of this invention. These thickeners include alkali and alkaline earth metal soaps of fatty acids and fatty substances having from 12 to 30 carbon atoms per molecule. Metals) Representative examples include IJum, lithium, calcium, and barium. Fatty substances are exemplified by stearic acid, hydroxystearic acid, stearin, cottonseed oil powder, oleic acid, palmitic acid, myristic acid and hydrogenated fish oil.

Other thickeners include salts and salt-soap complexes such as calcium stearate-acetate (U.S. Pat. No. 2,197).
．． 263), barium stearate acetate (No. 2,654,561), calcium stearate-caprylate-acetate complex (No. 2,999.06)
No. 5), calcium caprylate-acetate (No. 2)
, 999,066), and calcium salts of low, medium, and high molecular weight acids and nut oil acids and soaps.

Other groups of thickeners include substituted ureas, phthalocyanines, indathrene, pigments such as perylimide, pyromellidiimide, and ammeline.

Preferred thickening gelling agents for use in the present grease compositions are primarily hydrophobic clays. Such thickeners are clays that are initially hydrophilic in nature, but can be modified to contain, e.g. It can be made from clays that have been converted to a hydrophobic state by pretreatment with organic cationic surfactants. Representative onium compounds include tetraalkylammonium chlorides, such as dimethyldioctadecylammonium chloride, dimethyldibenzylammonium chloride, and mixtures thereof. This method of transformation is well known to those skilled in the art and is believed to require no further explanation and does not form part of the present invention. More particularly, clays useful as starting materials in forming the thickeners for use in the present grease compositions can include natural, chemically unmodified clays.

These clays are crystalline complex silicates and their exact composition cannot be precisely described as they vary widely from one natural source to another. In addition to the silicate lattice, these clays contain various cation exchange groups (e.g.)
It can be described as a complex inorganic silicate containing IJium, such as aluminum silicate, magnesium heptasilicate, barium silicate, etc. Hydrophilic clays particularly useful for conversion into the desired thickeners include montmorillonite clays such as bentonite, attapulgite, hectorite, illite, saponite, sepiolite, pyrotite, vermiculite, zeolite clays, and the like.

Thickeners are used at about 0.5 to about 30%, preferably 3 to 15% by weight of the total grease composition.

Having described the invention in general terms, the following examples are given by way of specific illustration. Parts are by weight.

Example 1 209.3 grams of Tris-2 in a 1 liter flask
- Ethylhexyl phosphite and 16 grams of sulfur were fed under a nitrogen atmosphere. The initial reaction raised the temperature to 109°C. Temperature drops (when you start, heat up to 100
The temperature was maintained for 8 hours.

Analysis showed the product to contain 6.7 percent phosphorus and 7.5 percent sulfur.

A product was made from 208 grams of triinopropyl phosphite and 32 grams of sulfur according to the method of Example 1. Analysis revealed that the product contained 6.57 percent phosphorus and 1
It was found to contain 1.6 percent sulfur.

64F (2.0 moles) of sulfur was added to 288F (2.0 moles) of dibutyl hydrogen phosphite. The temperature was raised to 100° C. under nitrogen atmosphere with stirring and held for 8 hours. The resulting reaction mixture was cooled to ambient temperature and the desired reaction product was recovered.

Example 4 Sulfur (3°C) was added while increasing the temperature from ambient to 100°C
2r,, 1.0 mol) and bis-(2-ethylhexyl)
Hydrogen phosphite (306r, 1.0 mol) was stirred under nitrogen atmosphere. Products were also made from di-oleyl hydrogen phosphite and dilauryl hydrogen phosphite according to the Example 40 procedure.

EXAMPLE 5 645' (2.0 mol) of sulfur was added to 388r (2.0 mol) of diptyl hydrogen phosphite. The temperature was raised to 100° C. with stirring under a nitrogen atmosphere and held for 8 hours.

The reaction mixture was cooled to ambient temperature and kept in a water bath while propylene oxide (204r, 3.5 mol) was added over 1.5 hours. The temperature was raised to reflux excess propylene oxide (pot temperature 90°C). 2
After a period of time, excess propylene oxide was distilled off to the condenser. Heptane (100m) was added and reflux was continued for a further 3 hours. The solvent was distilled off and the product was
Vacuum distillation was performed at Hgs100°C.

The product was cooled to 50°C and filtered through diatomaceous earth.

Example 6 Phosphorous pentoxide (9,5?, 0.066 mol) was added little by little to 4
The product of Example 5 (113,6
r, 0.2 mol) was stirred at 50° C. under nitrogen. The temperature was raised to 75°C and held for 2 hours. The product was then filtered.

The product, the collected lachrymal fluid, was stirred at 50° C. while Primen 81R (2), 7F) was added dropwise for 20 minutes. Primen 81R is a mixed CI2 to Cu K trialkyl primary amine manufactured and sold by Rom & Hass. The final product was stirred for an additional hour at 50°C.

Following the procedures of Examples 1 and 20, products were made from dilauryl hydrogen phosphite, bis-2-ethylhexyl hydrogen phosphite, and dioleyl hydrogen phosphite.

Example 7 Sulfur (3
22,1.0 mol) and bis-(2-ethylhexyl)water'R phosphite (306r, 1.0 mol) were stirred under nitrogen. Primen 81R (191 grams) was added dropwise over 20 minutes at 100'C. After addition, 10
Stirring was continued for an additional hour at 0°C. The temperature was lowered to 50°C and the product was filtered through diatomaceous earth.

Following the Example 70 procedure, products were also made from dibutyl hydrogen phosphite, di-oleyl hydrogen phosphite, and dilauryl hydrogen phosphite.

Product Evaluation The products described in Examples 1 and 2 were mixed with mineral oil and subjected to shell four-ball abrasion testing. The results in Table 1 demonstrate the anti-wear protection provided by these products.

Table 1 172 inch ball, 52) 00 stay base stock 1,02 1.92 4.12 3.85 Example 1 0,57 0,75 0,82 0.87
Example 2 0.65 0.50 0.70 0.
70 The product of Example 1 was placed at 0.6 weight percent in a fully formulated hydraulic oil and tested in the Vickers 1o4c pump wear test (ASTM D2882) with a similar formulation using 0.7 weight percent commercially available zinc dithiophosphate. compared. The results were as follows and demonstrated the anti-wear performance of the products of the invention.

Table 2 Zinc ditheophosphate 27 Products of Example 1 22 The products described in Examples 5.6 and 7 were compounded with mineral oil and shell four-ball abrasion tested.

The results summarized in Table 3 demonstrate the anti-wear protection provided by these products. The mineral oil blend was further evaluated for EP properties using a four-ball weld test.

The results are listed in Table 4.

Table 3 1/2 inch ball, 52) 00 Steel 5 Butyl 93 (200) 0.5
3 0.8199 (390) 0.8 0.755
2-ethylhexyl 93 (200) 0.5
5 0.5199 (390) 1.6 1.6 5 Lauryl 93 (200) 0.
55 0.5199 (390) 1.4 1.9 5 Oleil 93 (200) 0
．． 6 1.6199 (390) 1.4 1.7 6 Butyl 93 (200) 0
．． 5 0.7199 (390) 1.2 1.7 6 2-Ethylhexyl 93 (200) 6 Lauryl 93 (200) 6 Oleyl
93 (200) 0.5 0.819
9(390) 1.7 1.87 Butyl
93 (200) 0.5 0.519
9 (390) 1.1 1.87 2-ethylhexyl 93 (200) 0.55 0.7519
9 (390) 0.55 1.757 Lauryl 93 (200) 0.5 1.5
199 (390) 0.8 1.77 Oreil 93 (200) 0.4 0
．． 6199 (390) 1.4 1.7 Pace stock 126 26.
95 Butyl 200 4
6.65 2-ethylhexyl 160
37.15 Lauryl 160
34.45 Oreil 160
41.16 Butyl 2
00 40.96 2-ethylhexyl 6 lauryl 6 oleyl 200 4
0.67 Butyl 200
46.37 2-ethylhexyl 200
43.67 Lauryl 2
00 48.47 Oreil
200 41.2 (4 others)

Claims (11)

[Claims] (1) di- or tri-hydrocarbyl (substituted or unsubstituted) phosphite and elemental sulfur in the absence of a catalyst at a molar ratio of sulfur to phosphite of 0.8 to 1.2 and 75°C to 110°C. A method of producing a reaction product suitable for use as a lubricating oil additive, comprising reacting at temperature. (2) combining said product with another reactant that is an aliphatic or aromatic amine or a basic heterocyclic compound containing at least one ring nitrogen atom; an olefinic compound; or an alkylene oxide; and phosphite molar ratio of 0.9 to 1.2 and 10°C to 90°C
2. A process according to claim 1, wherein further reaction is carried out at a temperature of . (3) reacting said further product with P_2O_5;
A method according to claim 2. 4. The method of claim 3, wherein the molar ratio of P_2O_5 and reaction product is about 1 mole of P_2O_5 to 3 moles of said further product. (5) The phosphite has the formula (R_1O)_2POR_
2 (wherein R_1 represents a C_4 to C_1_8 alkyl group or a C_6 to C_1_8 aryl group,
_2 is a hydrogen atom, a C_4 to C_1_8 alkyl group, or a C_6 to C_1_8 aryl group, and R_1
(which may be the same or different), the method according to any one of claims 1 to 4. (6) The di- or tri-hydrocarbyl phosphites are the same or different selected from oleyl, phenyl, nonylphenyl, octylphenyl, 2-ethylhexyl, 1,3-dimethylbutyl, tridecyl, isodecyl, octyl, butyl or mixtures thereof. Claim 1 has one or more substituents that may be present.
The method described in any one of Items 1 to 5. (7) The other reactants mentioned above are (C_1_2 to C_1
_4 tertiary alkyl) primary amines or mixtures thereof;
benzotriazole; or toltriazole;
A method according to claim 2, 3, 4, 5 or 6. (8) Claims 2 and 3, wherein the other reactant is an amine-containing polymeric succinimide or an aromatic amine.
, 4, 5, or 6. (9) Claim 2, wherein said other reactant consists of a vinyl ether, vinyl ester or vinyl amide;
The method according to item 3, 4, 5 or 6. (10) Claims 2, 3, 4, wherein the other reactant is ethylene oxide or propylene oxide;
The method according to item 5 or 6. (11) The method according to any one of claims 1 to 10, further comprising the step of separating the products obtained in each step.