公开(公告)号：US2917457A

公开(公告)日：1959-12-15

申请号：US60619056

申请日：1956-08-27

Applicant: SHELL DEV

Inventor： PREISS DONALD M

CPC classification number: C10M7/00 ,  C10M5/00 ,  C10M2201/062 ,  C10M2201/063 ,  C10M2201/065 ,  C10M2201/066 ,  C10M2201/08 ,  C10M2201/081 ,  C10M2201/082 ,  C10M2201/084 ,  C10M2201/085 ,  C10M2201/102 ,  C10M2201/103 ,  C10M2201/105 ,  C10M2201/14 ,  C10M2203/10 ,  C10M2207/282 ,  C10M2207/34 ,  C10M2211/02 ,  C10M2215/22 ,  C10M2215/221 ,  C10M2215/225 ,  C10M2215/226 ,  C10M2215/30 ,  C10M2217/028 ,  C10M2217/044 ,  C10M2217/045 ,  C10M2217/06 ,  C10M2223/04 ,  C10M2223/041 ,  C10M2223/042 ,  C10M2227/02 ,  C10M2229/02 ,  C10M2229/04 ,  C10M2229/041 ,  C10M2229/043 ,  C10M2229/044 ,  C10M2229/05 ,  C10M2229/051 ,  C10N2210/02 ,  C10N2220/02 ,  C10N2230/08 ,  C10N2240/02 ,  C10N2240/12 ,  C10N2240/121 ,  C10N2250/10 ,  C10N2270/00

Abstract: A lubricating grease comprises a lubricating oil gelled with an inorganic gelling agent and a minor proportion of a polymerized lactam of a monoaminomonocarboxylic acid having a chain of at least five carbon atoms between carboxyl and amino groups, which polymer acts as a water-repellent. The oil may be mineral oil such as a refined, semi-refined or unrefined paraffinic, naphthenic or asphaltic based oil with a viscosity of 50-4000 s.u.s. at 100 DEG F. or a blend of such oils, or a synthetic oil such as an aliphatic diester of a dicarboxylic acid, e.g. dioctylphthalate, bis-(2-ethylhexyl) sebacate, or bis-(3,5,5-trimethylhexyl) sebacate, an ester of phosphoric or silicic acid, e.g. tritolyl phosphate or tetrakis-(2-ethylhexyl) silicate, a halocarbon oil, e.g. a fluorocarbon oil distilling above 200 DEG C. or a silicone oil, e.g. one produced by the hydrolysis of a compound of the formula R2SiX2, where R is lower alkyl and X halogen or alkoxy which may be mixed with up to 25 mol. per cent of RSiX3 or RSiX3 and R3SiX; a list of suitable compounds and mixtures is given. The silicone oil used may have a viscosity of 25-3000 s.u.s. at 100 DEG F., examples being dimethylsilicone polymer, phenylmethylsilicone polymer and chlorophenylmethylsilicone polymer. The gelling agent is an inorganic colloid of amorphous or crystalline structure preferably as an aerogel, e.g. silica, alumina, magnesia, ferric oxide, nickel sulphide and mixtures thereof or a clay such as Georgia clay, attapulgite, Wyoming bentonite or hectorite. The colloid may alternatively be incorporated by solvent transfer from water either directly using a surface-active agent or indirectly by first displacing the water with acetone or an alcohol and then displacing this with the oil. Amounts of 2-20 per cent by weight of the whole composition of the gelling agent may be used. Clays are preferably acidtreated with 2-10 per cent by weight of the clay of phosphoric, nitric or sulphuric acid. The lactam is added as a monomer to the gelling agent at any stage before or after incorporation in the oil and polymerized by heating the composition to 100-500 DEG F. for 1-48 hours to give a polymer of molecular weight no less than 500. Suitable lactams include cyclohexanone isoxime, the products of conversion or rearrangement of 2-, 3- or 4-methylcyclohexanone oxime or of 2-methylcycloheptanone isoxime, cycloheptanone isoxime, 2 - ethylcyclohexanone isoxime, cyclo-octanone isoxime, epsilon-caprolactam and the homologous eight-membered ring lactams such as suberone isoxime. Amounts of 5-250 per cent by weight of the gelling agent may be used.ALSO:A composition used as a lubricating grease comprises a lubricating oil gelled to a grease consistency with an inorganic gelling agent and a minor proportion of a polymerized lactam of a monoamino-monocarboxylic acid having a chain of at least 5 carbon atoms between the amino and carboxyl groups. The lactam is added to the gelling agent at any convenient stage before or after incorporation in the oil and is polymerized by heating the composition to 100-500 DEG F. for 1-48 hours to give a polymer of molecular weight not less than 500. Suitable lactams include cyclohexanone isoxime, the products of rearrangement or conversion of 2-, 3- or 4-methylcyclohexanone oxime, cycloheptanone isoxime, the products of rearrangement of 2-methylcycloheptanone isoxime, 2-ethylcycloheptanone oxime, cyclooctanone isoxime, epsilon-caprolactam and the homologous eight - membered lactams such as suberone isoxime. Preferably the ring contains no more than 14 members. Amounts of 5-250 per cent by weight of the gelling agent may be used. The gelling agent, used in amounts of 2-20 per cent by weight of the whole composition, may be colloidal, silica, alumina, magnesia, ferric oxide or nickel sulphide or a clay, which may be acid treated. Oils specified are silicone oils, mineral oils, aliphatic diesters of dicarboxylic acids, esters of phosphoric or silicic acid and halocarbon oils. The silicone oils suitable for use are those obtained by the hydrolysis and condensation of compounds of the formula R2SiX2, where R is lower alkyl and X is a hydrolysable halogen or alkoxy group or a mixture of alkylated silicon compounds containing at least 75 mol. per cent of the above dialkyl compounds with monoalkyl compounds of the formula RSiX3 or a mixture of monoalkyl and trialkyl compounds (R3SiX), generally the mixture having a composition corresponding to R4-zSiXz, where z is between 2.25 and 1.5. Suitable dialkyl silicon compounds include dimethyl-, methyl ethyl-, diethyl- and methyl propyl-silicon dichlorides, dimethyl- and diethyl-silicon dibromides, dimethyl-dimethoxy-silicon and diethyl- and dimethyl-diethoxy-silicons. The products preferably have between 1.75 and 4 carbon atoms per silicon atom, they should be high boiling liquids having a viscosity at 100 DEG F. of 25-3500 s.s.u. Chlorinated and fluorinated silicones can also be used. Particularly useful polymers are dimethyl-, phenylmethyl- and chlorophenylmethyl-silicones.

公开(公告)号：US2886524A

公开(公告)日：1959-05-12

申请号：US56192256

申请日：1956-01-27

Applicant: SHELL DEV

Inventor： ARMSTRONG JACK W ,  PREISS DONALD M

IPC: B01J19/06 ,  C04B33/13

CPC classification number: C04B33/1305 ,  C04B33/13 ,  C10M5/00 ,  C10M7/00 ,  C10M2201/08 ,  C10M2201/081 ,  C10M2201/082 ,  C10M2201/084 ,  C10M2201/085 ,  C10M2201/14 ,  C10M2205/00 ,  C10M2207/282 ,  C10M2207/34 ,  C10M2211/02 ,  C10M2211/06 ,  C10M2213/02 ,  C10M2213/062 ,  C10M2215/06 ,  C10M2215/062 ,  C10M2215/064 ,  C10M2215/066 ,  C10M2215/068 ,  C10M2215/086 ,  C10M2215/14 ,  C10M2215/22 ,  C10M2215/221 ,  C10M2215/225 ,  C10M2215/226 ,  C10M2215/28 ,  C10M2215/30 ,  C10M2217/00 ,  C10M2217/02 ,  C10M2217/04 ,  C10M2223/04 ,  C10M2223/041 ,  C10M2223/042 ,  C10M2227/02 ,  C10M2229/02 ,  C10M2229/04 ,  C10M2229/041 ,  C10M2229/043 ,  C10M2229/044 ,  C10M2229/05 ,  C10N2220/02 ,  C10N2230/08 ,  C10N2240/02 ,  C10N2240/12 ,  C10N2240/121 ,  C10N2250/10 ,  C10N2270/00 ,  C10N2270/02

Abstract: A process for the preparation of grease-forming compositions comprises adding an aniline compound to a fluid clay hydrogel, mechanically separating water, displacing the remaining water with a water-soluble organic liquid, adding a lubricating oil to the resultant organogel in a proportion sufficient to prevent collapse of the gel structure but insufficient to form a grease, evaporating the water-soluble organic liquid, and heating the mixture in an oxidizing atmosphere to oxidize the aniline compound. The lubricating oil may be a refined, unrefined or semi-refined paraffinic, naphthenic or asphaltic base mineral oil (50 to 4000 SUS/100 DEG F.) or blend thereof or a synthetic oil such as the esters of phosphorus- and/or silicon-containing and aliphatic dicarboxylic acids, e.g. tritolyl phosphate, tetrakis-(2-ethylhexyl)-silicate, dioctyl phthalate, and bis-(2-ethylhexyl) and bis-(3,5,5 - trimethylhexyl) - sebacates, halocarbon oils, e.g. fluorocarbons, and liquid organosilicone polymers, e.g. dimethyl and methyl phenyl silicone polymers which are extensively described and exemplified. The aniline compounds include aniline itself and nuclear amino, methyl and hydroxyl substitution products thereof, e.g. the phenylene diamines, amino phenols, toluidines and xylidenes. When heated in the oxidizing atmosphere, i.e. air with or without added oxygen, the ultimate oxidation product of aniline is aniline black, and although intermediate products such as emeraldine, nigraniline, and pernigraniline are effective it is preferred that at least 50% of the aniline be completely oxidized. The clays are preferably high-based exchange clays such as Wyoming bentonite or hectorite, though low-base exchange clays, e.g. Georgia clay, attapulgite, may be used. The clay hydrogel is preferably treated with a mineral acid, e.g. H2SO4, HCl, H3PO4. Suitable water-soluble organic liquids include alcohols, ketones and esters, e.g. methyl, ethyl and isopropyl alcohols, acetone, methylethyl ketone and ethyl acetate. The oil used to prepare greases from these concentrates is preferably the same as that already incorporated therein. Examples comprise hectorite clay treated with 85% H3PO4, aniline, alcohol as volatile solvent, and a silicone oil. The compositions were heated in a forced draught oven at 300 DEG F. for 2 days and then milled with more silicone oil to form greases. Specification 736,270 is referred to.ALSO:A process for the preparation of greaseforming compositions (see Group III) comprises adding an aniline compound to a fluid clay hydrogel, mechanically separating water, displacing the water from the remaining concentrated clay hydrogel with a water-soluble organic liquid, adding a lubricating oil to the organogel in amount sufficient to preserve the gel structure during subsequent evaporation of the organic liquid but insufficient to form a grease structure, evaporating the water-soluble organic liquid and heating in an oxidizing atmosphere to oxidize the aniline compound. A silicone oil may subsequently be added to form a grease containing 1 to 8% wt. of clay. In an example 1 kg. of 2% wt. Hectorite clay in an aqueous slurry is acidified with 1.4 g. 85% H3PO4. 40 g. aniline are added, the water removed by filtration, and the filter coke washed with ethanol. The aniline coated clay is then dispersed in 1000 ml. ethanol and 100 g. commercial silicone oil and the alcohol evaporated off. The composition is then heated in a forced draught oven at 300 DEG F. for 2 days to oxidize to aniline. On milling the resulting composition with 100 g. silicone oil a smooth black grease is obtained. Specification 736,270, [Group III], is referred to.

公开(公告)号：US2829100A

公开(公告)日：1958-04-01

申请号：US55227155

申请日：1955-12-12

Applicant: SHELL DEV

Inventor： ARMSTRONG JACK W ,  PREISS DONALD M ,  EDGAR JOHN A

IPC: C04B33/13

CPC classification number: C04B33/1305 ,  C04B33/13 ,  C10M5/00 ,  C10M7/00 ,  C10M2201/08 ,  C10M2201/081 ,  C10M2201/082 ,  C10M2201/084 ,  C10M2201/085 ,  C10M2201/103 ,  C10M2201/14 ,  C10M2207/282 ,  C10M2207/34 ,  C10M2209/101 ,  C10M2211/02 ,  C10M2211/022 ,  C10M2211/024 ,  C10M2211/06 ,  C10M2213/00 ,  C10M2213/02 ,  C10M2213/04 ,  C10M2213/06 ,  C10M2213/062 ,  C10M2215/04 ,  C10M2215/06 ,  C10M2215/10 ,  C10M2215/102 ,  C10M2215/16 ,  C10M2215/22 ,  C10M2215/221 ,  C10M2215/222 ,  C10M2215/225 ,  C10M2215/226 ,  C10M2215/26 ,  C10M2215/30 ,  C10M2217/022 ,  C10M2217/042 ,  C10M2217/043 ,  C10M2217/046 ,  C10M2217/06 ,  C10M2219/044 ,  C10M2219/064 ,  C10M2221/02 ,  C10M2223/04 ,  C10M2223/041 ,  C10M2223/042 ,  C10M2227/02 ,  C10M2229/02 ,  C10M2229/04 ,  C10M2229/041 ,  C10M2229/043 ,  C10M2229/044 ,  C10M2229/05 ,  C10M2229/051 ,  C10N2220/02 ,  C10N2230/08 ,  C10N2240/02 ,  C10N2240/12 ,  C10N2240/121 ,  C10N2250/10 ,  C10N2270/00

Abstract: A process for the preparation of lubricating grease compositions comprises adding an aminoplast-forming amino compound or hexamethylenetetramine to a fluid clay hydrogel, mechanically separating a substantial proportion of water from the hydrogel, displacing the remaining water by a volatile water-miscible organic liquid, adding a water-insoluble lubricating oil and evaporating the water-miscible organic liquid. The lubricating oil may be a paraffinic, naphthenic or asphaltic base lubricating oil or blend thereof or a synthetic oil such as the esters of phosphorus or silicon-containing acids and esters of aliphatic dicarboxylic acids with monohydric alcohols, e.g. tritolyl phosphate, dioctyl phthalate, bis-(2-ethyl hexyl) and bis-(3,5,5-trimethylhexyl) sebacates and tetrakis (2-ethyl hexyl) silicate. Suitable base oils for high temperature greases are the halocarbon oils such as the fluorocarbons and the organisilicone liquids such as polymers of dimethyl silicone which are extensively described and exemplified. The clay is preferably a high base exchange clay such as Wyoming bentonite or hectorite, though low base exchange clays such as Georgia clay and attapulgite may be used. Suitable amino compounds include those with at least 2 amino groups per molecule, each being attached to an unsaturated carbon atom, e.g. urea, thio-urea, guanidine, melamine, and dicyandiamide and the compounds obtained by replacing one hydrogen atom in such compounds by an alkyl group, e.g. methyl, ethyl and propyl urea, thioureas and guanidines; aryl primary amines, e.g. aniline and its alkyl derivatives; and alkyl sulphonamides, e.g. benzene, toluene, and other alkaryl sulphonamides. In all these compounds at least one amino group is attached to an unsaturated carbon or sulphur atom. Volatile water-miscible organic liquids are those which are more volatile than the lubricating oil and preferably have a relatively low boiling point such as alcohols and ketones, e.g. methanol, ethanol, isopropyl alcohol, acetone and methyl ethyl ketone, esters, e.g. ethyl acetate, and mixtures of the above. An optional feature of the invention is to treat the clay hydrogel with a mineral acid, e.g. phosphoric (which is preferred), hydrochloric or sulphuric, preferably before adding the amino compound. A further optional feature of the invention is to use the process to prepare the aminoplast-coated clay greases of Specification 793,092 by subsequently adding an aldehyde, preferably with the lubricating oil, to react with the amine already present. Suitable aldehydes include saturated and unsaturated aliphatic aldehydes or cyclic derivatives thereof, e.g. formaldehyde, acrolein, furfural, crotonaldehyde and acetaldehyde. When hexamethylene tetramine is used, it may be decomposed to formaldehyde by heating the clay hydrogel and a phenoplast resin formed by adding a phenol, e.g. phenol, resorcinol, the cresols and alkyl phenols such as t-butyl phenol and t-amyl phenol. Alternatively the amino compound added initially may not, or may only partially be used, to form the resin, which may be formed by subsequently adding an aldehyde and an amine or phenol, e.g. with the lubricating oil. In several examples, the amino compounds used are aniline, melamine, hexamethylene tetramine, and benzidine and the oil in each is a dimethyl silicone fluid, the aldehydes used are paraformaldehyde and furfural and, where hexamethylene tetramine is decomposed, phenol is used to form a phenoplast resin. Specification 736,270 also is referred to.ALSO:A process for the preparation of lubricating grease compositions (see Group III), comprises adding an aminoplast-forming amino compound or hexamethylene tetramine to a fluid clay hydrogel, mechanically separating a substantial proportion of water from the hydrogel, displacing the remaining water by a volatile water-miscible organic liquid, adding a water-insoluble lubricating oil and evaporating the water-miscible organic liquid. An optional feature of the invention is to use the process to prepare the aminoplast coated clay greases of Specification 793,092 by subsequently adding an aldehyde, preferably with the lubricating oil, to react with the amine and form an aminoplast resin in situ on the clay. The clay is preferably a high base exchange clay such as Wyoming bentonite or Hectorite, though low base exchange clays such as Georgia clay and Attapulgite may be used. The clay may be treated with a mineral acid, e.g. phosphoric, hydrochloric or sulphuric before adding the amino compound. Suitable amino compounds include those with at least two amino groups per molecule, each being attached to an unsaturated carbon atom, e.g. urea, thiourea, guanidine, melamine and dicyandiamide and the compounds obtained by replacing an hydrogen atom in such compounds by an alkyl group, e.g. methyl, ethyl and propyl urea, thioureas and guanidines; aryl primary amines, e.g. aniline, its alkyl derivatives and benzidine; and alkyl sulphonamides, e.g. benzene and toluene and other alkaryl sulphonamides. In all these compounds at least one amino group is attached to an unsaturated carbon or sulphur atom. Aldehydes which may be added to form the aminoplast resin include saturated and unsaturated aliphatic aldehydes or cyclic derivatives thereof, e.g. formaldehyde, acrolein, furfural, crotonaldehyde and acetaldehyde. When hexamethylene tetramine is used it may be decomposed to formaldehyde by heating the clay hydrogel and a phenoplast resin formed in situ by adding a phenol, e.g. phenol, resorcinol, the cresols, and alkyl phenols such as t-butyl phenol and t-amyl phenol. The lubricating oil used as the basis for the greases may be paraffinic, naphthenic, asphaltic, halocarbon (e.g. fluorocarbon), synthetic (e.g. tritolyl phosphate, tetrakis (2-ethyl hexyl) silicate, dioctylphthalate, bis(2-ethyl hexyl) sebacate, bis(3,5,5-trimethylhexyl) sebacate); or silicones which may be prepared by the hydrolysis and condensation of compounds of the average formula R4-zSiXz wherein 2.25 \sF z \s0 1.5, R is a lower alkyl radical and X is a hydrolysable halogen or alkoxy group. In the examples, the oil is a dimethyl silicone fluid and the clay is Hectorite in a 2 per cent slurry acidified with H3PO4; the resins are as follows, the amines being added first: (1) and (2) aniline-paraformaldehyde, (3) aniline-formalin, (4) anilinemelamine-paraformaldehyde, (5) hexamethylene tetramine-phenol-paraformaldehyde, (6) hexamethylene tetramine-phenol, (7) aniline-furfural, (8) melamine-paraformaldehyde, and (9) benzidine-paraformaldehyde. Specification 736,270, [Group III], also is referred to.