CN101012238A - Sulfur-containing, phosphorus-containing compound, its salt, and methods thereof - Google Patents

Abstract

There is disclosed a salt of a sulfur-containing, phosphorus-containing compound. There is also disclosed a method of making the salt.

Description

Sulfur-containing, phosphorus-containing compound, its salt and method thereof

The cross reference of related application

The application requires the right of priority of the U.S. Provisional Application 60/734,757 of submission on November 9th, 2005.

Technical field

The present invention relates to sulfur-containing, phosphorus-containing compound, its salt and prepare the method for described salt.

Background technology

It is known using P contained compound in the lubricant thing.Especially, P contained compound generally includes linear alkyl chain.Yet, the problem that these compounds have be known they in the gear lubricant for preparing fully, be heat-labile at high temperature.The thermolability compound decomposes in the lubricant thing probably prematurely, and will no longer provide such as character such as resistance to abrasions for the lubricant thing.

The lubricant thing such as gear oil, experiences high temperature usually, therefore, be provided under the higher temperature not can premature decomposition the thermostability compound will be favourable.The thermostability compound therefore will in the lubricant thing, keep period of prolonging and for described binding substances be provided at prolong in the period such as character such as resistance to abrasions.Need have suitable thermostability to keep the compound of its resistance to abrasion.

Summary of the invention

According to the present invention, the compound of time formula V is disclosed:

Wherein n is 1 to 5 integer; With

R wherein ¹, R ², R ³, R ⁴, R ⁵, R ⁶, R ¹⁰And R ¹¹Be independently selected from hydrogen, cyano group and contain about 1 alkyl to about 30 carbon atoms.

On the one hand, the invention discloses the method for the salt of preparation sulfur-containing, phosphorus-containing compound, comprise sulfocompound, acid amides and P contained compound combination (combine) to form first mixture; With first mixture is combined with amine.

On the other hand, the invention discloses the method for the compound of preparation formula (II), comprise compound combination sulfocompound, acid amides and formula (I):

R wherein ¹, R ², R ³, R ⁴, R ⁵And R ⁶Be independently selected from hydrogen, cyano group and contain about 1 alkyl to about 30 carbon atoms, wherein at least one substituting group is a methyl,

Obtain the compound of formula (II):

R wherein ¹, R ², R ³, R ⁴, R ⁵And R ⁶Definition the same.

In addition, the invention discloses the method for salt of preparation sulfur-containing, phosphorus-containing compound, comprise at least a in sulfocompound, acid amides and phosphorous acid dialkyl ester and the polymer-type phosphorous acid ester is provided, to obtain sulfur-containing, phosphorus-containing compound; With provide amine to obtain the salt of sulfur-containing, phosphorus-containing compound.

Other purpose of the present invention and advantage will partly be described in the following description, and/or can know by putting into practice the present invention.Objects and advantages of the present invention will be achieved and obtain by various key elements and the combination that particularly points out in claims.

Be appreciated that above general remark and following detailed description are exemplary with illustrative, it is not construed as limiting claimed the present invention.

Description of drawings

Fig. 1 is the chart of the thermostability of the various phosphorus containg substances of explanation.

Embodiment

The present invention relates to following scheme.

The compound of scheme 1. formula V:

Wherein n is 1 to 5 integer; With

R wherein ¹, R ², R ³, R ⁴, R ⁵, R ⁶, R ¹⁰And R ¹¹Be independently selected from hydrogen, cyano group and contain about 1 alkyl to about 30 carbon atoms.

The compound of scheme 2. schemes 1, wherein R ¹And R ²It is methyl; R ³, R ⁴, R ⁵And R ⁶Be hydrogen; And R ¹⁰And R ¹¹Be to contain about 1 alkyl to about 6 carbon atoms.

The method of the salt of scheme 3. preparation sulfur-containing, phosphorus-containing compounds comprises:

With sulfocompound, acid amides and P contained compound in conjunction with forming first mixture; With

First mixture is combined with amine.

The method of scheme 4. schemes 3, wherein sulfocompound is at least a compound that comprises in free sulphur and the active sulphur.

The method of scheme 5. schemes 4, wherein sulfocompound is selected from elementary sulfur, polysulfide and olefine sulfide.

The method of scheme 6. schemes 5, wherein sulfocompound is an elementary sulfur.

The method of scheme 7. schemes 3 is wherein used and is waited molar equivalent or more substantial sulfocompound at least.

The method of scheme 8. schemes 3, wherein said method is carried out under about 90 ℃ temperature at about 23 ℃.

The method of scheme 9. schemes 3 is wherein used about 0.05 acid amides to about 2 molar equivalents.

The method of scheme 10. schemes 3 is wherein used about 0.05 amine to about 2 molar equivalents.

The method of scheme 11. schemes 3, wherein P contained compound is following formula (I) and (IV) at least a in the compound:

Wherein n be about 1 to about 5 integer and

R wherein ¹, R ², R ³, R ⁴, R ⁵, R ⁶, R ¹⁰And R ¹¹Be independently selected from hydrogen, cyano group and contain about 1 alkyl to about 30 carbon atoms.

The method of scheme 12. schemes 11, wherein in formula (IV), R ¹And R ²It is methyl; R ³, R ⁴, R ⁵And R ⁶Be hydrogen; And R ¹⁰And R ¹¹Be to contain about 1 alkyl to about 6 carbon atoms.

The method of scheme 13. schemes 3, wherein first mixture comprises following formula (II) and (V) at least a in the compound:

Wherein n be 1 to 5 integer and

R wherein ¹, R ², R ³, R ⁴, R ⁵, R ⁶, R ¹⁰And R ¹¹Be independently selected from hydrogen, cyano group and contain about 1 alkyl to about 30 carbon atoms.

The method of the compound of scheme 14. preparation formulas (II) comprising:

With the compound combination of sulfocompound, acid amides and following formula,

R wherein ¹, R ², R ³, R ⁴, R ⁵And R ⁶Be independently selected from hydrogen, cyano group and contain about 1 alkyl to about 30 carbon atoms, wherein at least one substituting group is a methyl,

Obtain the compound of formula (II):

R wherein ¹, R ², R ³, R ⁴, R ⁵And R ⁶Definition the same.

The method of scheme 15. schemes 14, wherein R ¹And R ²It is methyl; And R ³, R ⁴, R ⁵And R ⁶Be hydrogen.

The method of scheme 16. schemes 14, wherein sulfocompound is at least a compound that comprises in free sulphur and the active sulphur.

The method of scheme 17. schemes 16, wherein sulfocompound is selected from elementary sulfur, polysulfide and olefine sulfide.

The method of scheme 18. schemes 17, wherein sulfocompound is an elementary sulfur.

The method of scheme 19. schemes 14 is wherein used and is waited molar equivalent or more substantial sulfocompound at least.

The method of scheme 20. schemes 14, wherein said method is carried out under about 90 ℃ temperature at about 23 ℃.

The method of scheme 21. schemes 14 is wherein used about 0.05 acid amides to about 2 molar equivalents.

The method of scheme 22. schemes 14, wherein said method were carried out about 1 hour to about 8 hours.

The method of the salt of scheme 23. preparation sulfur-containing, phosphorus-containing compounds comprises:

With at least a combination in sulfocompound, acid amides and phosphorous acid dialkyl ester and the polymer-type phosphorous acid ester to obtain sulfur-containing, phosphorus-containing compound; With

In conjunction with amine, obtain the salt of sulfur-containing, phosphorus-containing compound.

The method of scheme 24. schemes 23, wherein amine is straight chain amine.

The method of scheme 25. schemes 24, wherein straight chain amine is the aliphatics primary aliphatic amine.

The method of scheme 26. schemes 23, wherein amine is branching amine.

The method of scheme 27. schemes 26, wherein branching amine is C _14-24The mixture of primary t-alkyl-amine.

The method of scheme 28. schemes 24 is wherein used about 0.05 amine to about 2 molar equivalents.

The method of scheme 29. schemes 24, wherein said method were carried out about 1 hour to about 8 hours.

Term used herein " hydrocarbyl substituent " or " alkyl " use with its implication commonly used, and implication commonly used is known in those skilled in the art.Particularly, it is meant and contains the carbon atom that is connected with the rest part of molecule and have the group that accounts for leading hydrocarbon characteristic.The example of alkyl comprises:

(1) hydrocarbon substituent, it is aliphatics (for example alkyl or alkenyl) substituting group, alicyclic (for example cycloalkyl, cycloalkenyl group) substituting group, with by aromatic series-, the aromatic substituents of aliphatics-and alicyclic-replace, and cyclic substituents, in described cyclic substituents, ring is finished (forming alicyclic group together as two substituting groups) by the other parts of molecule;

(2) hydrocarbon substituent of Qu Daiing, the hydrocarbon substituent of described replacement is the substituting group that contains non-alkyl, in the context of the present invention, described non-alkyl (for example halo (particularly chloro and fluoro), hydroxyl, alkoxyl group, sulfydryl, alkyl thiol, nitro, nitroso-group and sulfoxy) has not changed and has accounted for leading hydrocarbon substituent;

(3) assorted substituting group, in the context of the present invention, though described assorted substituting group is to have the substituting group that accounts for leading hydrocarbon characteristic but also contain the part (if do not contain this part except carbon, ring or chain will be made up of carbon atom) except carbon in ring or chain.Heteroatoms comprises sulphur, oxygen, nitrogen, and comprises substituting group such as pyridyl, furyl, thienyl and imidazolyl.Usually, per ten carbon atoms existence are no more than two non-hydrocarbon substituents that for example are no more than in alkyl; Usually, in alkyl, there is not non-hydrocarbon substituent.

Unless clearly explanation in addition, otherwise term used herein " weight percent " is meant the per-cent of the whole binding substances weight of described ingredients constitute.

On the one hand, the invention provides resistance to abrasion with improvement and at least a compound that improves character in the thermostability.Described compound can be to comprise the sterically hindered sulfur-containing, phosphorus-containing compound, and described steric hindrance makes compound decomposition at high temperature minimize and/or prevent compound decomposition at high temperature.Compound disclosed herein can show the thermostability of improvement and therefore in the lubricant thing than not comprising the longer period of sterically hindered binding substances reservation.Steric hindrance can exist in any form, as branching, the side chain hydrocarbyl chain forms such as (dependent hydrocarblychains) of hydrocarbyl chain.

P contained compound such as phosphorous acid ester or phosphoric acid ester can be used in the method disclosed herein.It is known preparing the two method of phosphorous acid ester and phosphoric acid ester.For example, can be by making phosphorous acid or different phosphorous acid ester and various pure prepared in reaction phosphorous acid esters.Other synthesis method comprises makes phosphorus trichloride and excessive alcohol reaction.In addition, cyclic phosphites can be carried out the transesterification reaction preparation by phosphorous acid ester and glycol, can obtain monomer and polymer-type mixture of products.Referring to Oswald, Alexis A., " Synthesis of Cyclic Phosphorous Acid Esters byTransesterification, " Can.J.Chem., 37:1498-1504 (1 959); And Said, people's such as Musa A. " and Reactivity of Cyclic Arsenites and Phosphites:X-raystructures of bis (5,5-dimethyl-1; 3,2 ,-diosarsenan-2-yl) ether andbis (2; 4,8,10-tetra-tert-butyl-12H-dibenzo[d; g] [1; 3,2] dioxarsenocin-6-yl) ether, " J.Chem.Soc, 22:2945-51 (1995) describedly openly incorporates this paper into as a reference.Preparing cycloalkyl hydroperoxide also is known for the method for thiophosphite (hydrogen thiophosphite), as by ring-type chloro phosphorous acid ester and hydrogen sulfide are reacted in the presence of pyridine.Referring to Zwierzak, A., " Cyclic organophosphorus compounds.I.Synthesis and infrared spectral studies of cyclic hydrogen phosphitesand thiophosphites; Can.J.Chem.; 45:2501-12 (1967) describedly openly incorporates this paper into as a reference.

On the one hand, phosphorous acid ester can be two or a trialkyl ester of phosphorous acid.Each alkyl can have about 1 to about 24 carbon atoms, or 1 to about 18 carbon atoms, or about 2 to about 8 carbon atoms.Each alkyl can be alkyl, thiazolinyl, aryl and composition thereof independently.When alkyl was aryl, it can contain at least about 6 carbon atoms; Or about 6 to about 18 carbon atoms.The non-limitative example of alkyl or alkenyl comprises propyl group, butyl, hexyl, heptyl, octyl group, oil base (oleyl), inferior oil base (linoleyl), stearyl or the like.The non-limitative example of aryl comprises phenyl, naphthyl, heptylphenol etc.On the one hand, each alkyl can be methyl, propyl group, butyl, amyl group, hexyl, heptyl, oil base or phenyl independently, for example methyl, butyl, oil base or phenyl, and further example is methyl, butyl, oil base or phenyl.

The non-limitative example of available phosphorous acid ester comprise hydrogen for aminophon (dibutylhydrogen phosphonate), hydrogen for phosphonic acids diisobutyl ester, hydrogen for phosphonic acids two oil base esters, hydrogen for phosphonic acids two (C14-18) ester, triphenyl phosphite, all phosphorous acid dialkyl esters suc as formula (I) compound, with all polymer-type phosphorous acid esters suc as formula (IV) compound, the compound of formula (I) and formula (IV) is as follows:

With

Wherein n is about 1 to about 5 integer; With

R wherein ¹, R ², R ³, R ⁴, R ⁵, R ⁶, R ¹⁰And R ¹¹Be independently selected from hydrogen, cyano group and contain about 1 alkyl, for example contain about 1 and arrive the alkyl of about 20 carbon atoms and for example contain about 1 alkyl to about 10 carbon atoms to about 30 carbon atoms.On the one hand,, be not limited to any particular theory, it is believed that repeating unit can complete cure if n is the integer greater than about 5.

On the one hand, in the compound of formula (I), R ³, R ⁴, R ⁵And R ⁶Can be hydrogen; R ¹And R ²It can be methyl.This chemical combination is commonly called phosphorous acid DOPCP (NPGP) and the registration number in chemical abstracts is CAS#4090-60-2 (5,5-dimethyl-1,3,2-dioxaphosphorinane (dioxaphosphorinan)-2-ketone).On the one hand, in the compound of formula (IV), R ¹And R ²It can be methyl; R ³, R ⁴, R ⁵And R ⁶Can be hydrogen; And R ¹⁰And R ¹¹Can be to contain about 1 alkyl to about 6 carbon atoms.This compound is the polymer-type by product that produces in the process of preparation phosphorous acid DOPCP.

P contained compound can also be at least a in the reaction product of phosphoric acid ester or its salt, phosphorous acid or phosphorous anhydride and unsaturated compound, or its two or more mixture.

The phosphorodithioic acid metal-salt can be by making metal base and at least a thiophosphorous acid (it can be single thiophosphorous acid or dithio phosphorous acid) prepared in reaction.

Phosphorous acid or phosphorous anhydride can react with unsaturated compound, and described unsaturated compound includes but not limited to acid amides, ester, acid, acid anhydrides and ethers.

On the one hand, P contained compound as phosphorous acid ester, can comprise the steric hindrance of the described compound of various increases and therefore increase the functional group that described compound is resisted the thermolysis ability.On the one hand, the β position branching of the Sauerstoffatom that P contained compound can be in hydrocarbyl chain it is believed that branching at this beta carbon can change the thermostability of P contained compound in the lubricant thing as described in (as improving).

In addition, P contained compound can use those sterically hindered component that increases the compound that is generated preparations.For example, the alcohol that is used to prepare as phosphorous acid ester can be β-branching alcohol.The non-limitative example of β-branching alcohol comprises isopropylcarbinol, 2-Ethylhexyl Alcohol, neopentyl glycol, neopentyl alcohol, Cetorhinus maximus alkanol (pristanol) and methyl isobutyl carbinol (MIBC).

P contained compound disclosed herein can be used as parent material to obtain sulfur-containing, phosphorus-containing compound.On the one hand, the method for preparing sulfur-containing, phosphorus-containing compound can comprise provides such as above-mentioned P contained compound, sulfocompound and nitrogenous compound to obtain sulfur-containing, phosphorus-containing compound.Sulfur-containing, phosphorus-containing compound is compared the resistance to abrasion that can have improvement with non-sulfur-containing, phosphorus-containing compound.Binding substances disclosed herein can comprise the reaction product of P contained compound, sulfocompound and nitrogenous compound such as acid amides.

Sulfocompound can be any compound that comprises free sulphur and/or active sulphur.The non-limitative example of sulfocompound comprises sulfurized animal or plant fat or oily, sulfurized animal or plant fatty acid ester, the complete esterification of phosphorated trivalent or pentahydric acid or the ester of partial esterification, olefine sulfide, the dialkyl polysulfide, sulfurized diels-Alder reaction affixture, the sulfurized Dicyclopentadiene (DCPD), the sulfuration of fatty acid ester and single unsaturated olefin or covulcanization mixture, lipid acid, the covulcanization blend of fatty acid ester and alpha-olefin, the dialkyl polysulfide that functional group replaces, thioaldehydes, (for example acid of thioketones and derivative thereof, ester, imines or lactone), episulfide compounds, the acetal derivant of sulfur-bearing, the covulcanization blend of terpenes and non-cyclic olefin, polysulfide olefin product, and elementary sulfur.

On the one hand, sulfocompound can be by making the preparation of alkene such as iso-butylene and reaction of Salmon-Saxl.The sulphur content that product such as sulfide isobutene or sulfuration polyisobutene have usually is 10 to 55 weight %, for example 30 to 50 weight %.Can use various other alkene or unsaturated hydrocarbons for example isobutene dimer or trimer are used to form this sulfocompound.

In yet another aspect, polysulfide by one or more by formula R ²⁰-S _x-R ²¹The compound of expression is formed, wherein R ²⁰And R ²¹Can be can contain separately to have an appointment 3 to the alkyl of about 18 carbon atoms, x can be for about 2 to about 8, for example about 2 in about 5 scope, and can further be 3.Alkyl can be various types of alkyl, as alkyl, cycloalkyl, thiazolinyl, aryl or aralkyl.Can use tertiary alkyl polysulfide such as di-t-butyl trisulphide and comprise the di-t-butyl trisulphide mixture (for example mainly by or fully by three, four and the mixture formed of pentasulfide).The example of the dialkyl polysulfide that other is useful comprises diamyl polysulfide, dinonyl polysulfide and two (dodecyl) polysulfide and dibenzyl polysulfide.

The amount of the sulfocompound that uses can be equimolar or bigger with respect to every normal P contained compound at least.On the one hand, can use about 1 sulfocompound to about 1.5 molar equivalents.

Nitrogenous compound can be any nitrogenous compound, as by structure R ³CON ⁴R ⁵Shown acid amides, wherein R ³, R ⁴And R ⁵Can be independently of one another for hydrogen or contain about 1 alkyl, or by the ethoxylation acid amides shown in the following structure to about 30 carbon atoms:

Wherein the summation of x and y can be about 1 to about 50, for example about 1 to about 20, further is for example about 1 to about 10.On the one hand, work as R ³, R ⁴And R ⁵When being alkyl, they contain has an appointment 1 to about 18 carbon atoms, for example contains and has an appointment 1 to about 6 carbon atoms.

Work as R ³Be hydrogen and R ⁴And R ⁵During for alkyl, nitrogenous compound is the dialkyl methane amide.The non-limitative example of applicable dialkyl methane amide comprises dimethyl formamide, diethylformamide, dipropyl methane amide, the methylethyl methane amide, dibutyl formamide, methyl butyl methane amide, ethyl-butyl methane amide, two oil base methane amides, the distearyl methane amide, didecyl methane amide, two (tridecyl) methane amide, decyl tridecyl methane amide, decyl oil base methane amide and tridecyl oil base methane amide etc.

Work as R ³Be alkyl and R ⁴And R ⁵When all being hydrogen, nitrogenous compound is uncle's hydrocarbyl amide.The non-limitative example of uncle's hydrocarbyl amide comprises ethanamide, propionic acid amide, butyramide, valeramide, laurylamide, myristic amide and palmitic amide.Some commercially available simple fatty acid amides can be available from Armak Company: coconut fatty amide, stearylamide, h-tallow fatty amide, oleylamide and 13-docosenoic acid acid amides (13-docosenamide).

Work as R ³And R ⁴All be alkyl and R ⁵During for hydrogen, nitrogenous compound is the acid amides that N-replaces.The non-limitative example of the acid amides that N-replaces comprises N-methylacetamide, N-ethyl acetamide, N-methylpent acid amides, N-propyl group laurylamide, N-methyl oleylamide and N-butyl stearylamide.

Work as R ³, R ⁴And R ⁵When all being alkyl, nitrogenous compound is N, the N-disubstituded amide.N, the non-limitative example of N-disubstituded amide comprise N,N-dimethylacetamide, N-methyl-N-ethyl acetamide, N, N-diethyl propionic acid amide, N, N-dibutyl valeramide, N, N-dimethyl stearylamide and N, N-dimethyl oleylamide.

Other non-limitative example of nitrogenous compound comprises N, two (2-hydroxyethyl) the dodecane acid amides of N-, N, two (2-hydroxyethyl) the coconut fatty acid acid amides of N-, N, two (2-hydroxyethyl) oleylamide of N-, N-2-hydroxyethyl coconut oleoyl amine (N-2-hydroxyethylcocamide) and N-2-hydroxyethyl stearylamide.

Nitrogenous compound can any promotion P contained compound the amount of sulfuration exist.On the one hand, the amount of nitrogenous compound can be for about 0.05 to about 2 molar equivalents, and for example about 1 to about 1.5 molar equivalents.

On the one hand, sulfur-containing, phosphorus-containing compound can be formula (II) and (V) at least a in the compound:

Wherein n is 1 to 5 integer; With

R wherein ¹, R ², R ³, R ⁴, R ⁵, R ⁶, R ¹⁰And R ¹¹Be independently selected from hydrogen, cyano group and contain about 1, for example contain about 1 to the alkyl of about 20 carbon atoms with contain about 1 alkyl that arrives about 10 carbon atoms to the alkyl of about 30 carbon atoms.

On the one hand, in formula (II), R ¹And R ²It can be methyl; And R ³, R ⁴, R ⁵And R ⁶Can be hydrogen.On the other hand, in formula V, R ¹And R ²It can be methyl; R ³, R ⁴, R ⁵And R ⁶Can be hydrogen; And R ¹⁰And R ¹¹Can be to contain about 1 alkyl to about 6 carbon atoms.

The method for preparing salt is also disclosed.Particularly, can provide additional nitrogenous compound to obtain salt to sulfur-containing, phosphorus-containing compound.Additional nitrogenous compound can be different with the above-mentioned nitrogenous compound of being discussed during sulfur-containing, phosphorus-containing compound about preparation.The salt of sulfur-containing, phosphorus-containing compound is compared the resistance to abrasion that can have improvement with sulfur-containing, phosphorus-containing compound with non-sulfur-containing, phosphorus-containing compound.On the one hand, the invention discloses the lubricant thing of the reaction product of the additional nitrogenous compound (as amine) that comprises sulfocompound, P contained compound, nitrogenous compound (as acid amides) and choose wantonly.

Method disclosed herein can comprise the use solvent.Solvent can be that at least a in the reactant dissolves in wherein or product dissolves in wherein any inert fluid material.The non-limitative example of solvent comprises benzene,toluene,xylene, normal hexane, hexanaphthene, petroleum naphtha, Anaesthetie Ether Trivalin SF, dibutyl ether dioxane, chlorobenzene, oil of mirbane, tetracol phenixin, chloroform, base oil such as poly-alpha olefins and solution-air oil (gas-to-liquid oil) and process oil.

Additional nitrogenous compound can help any acid that neutralizes.Can use any nitrogenous compound, as long as it dissolves in the lubricant thing for preparing fully, described lubricant thing can comprise base oil.The non-limitative example of additional nitrogenous compound comprises acid amides, amine and contains the heterogeneous ring compound such as the pyridine of basic nitrogen.On the one hand, additional nitrogenous compound is an amine, and it can be primary amine, secondary amine or tertiary amine.

On the one hand, alkylamine can be to contain the about 4 uncle's alkylamines to about 30 carbon atoms in alkyl, for example contains about 8 to about 20 carbon atoms in alkyl.Alkyl can be saturated or undersaturated.The typical example of saturated primary amine is known as the aliphatics primary aliphatic amine those.Typical aliphatic amide comprises alkylamine such as n-hexyl amine, n-octylamine, positive decyl amine, dodecyl amine, n-tetradecane base amine, Pentadecane base amine, n-hexadecyl amine, Octadecane base amine (stearylamine) etc.These primary amine obtain with distillation level or technical grade.The distillation level can provide purer reaction product, and the amine of technical grade can form acid amides and imide in reaction.The blended aliphatic amide also is suitable.

On the one hand, the amine salt of disclosed compound can get and have in the comfortable alkyl at least about those of uncle's Armeen of 4 carbon atoms.For major part, they can derive from has the alkylamine that is lower than about 30 carbon atoms in alkyl altogether.

Usually, uncle's Armeen is the monoamine that is expressed from the next:

R wherein ¹, R ²And R ³Can be identical or different and can be to contain about 1 alkyl to about 30 carbon atoms.The illustrative example of this amine is tert-butylamine, uncle's hexyl primary amine, 1-methyl isophthalic acid-amino-hexanaphthene, uncle's octyl group primary amine, uncle's decyl primary amine, uncle's dodecyl primary amine, uncle's tetradecyl primary amine, uncle's hexadecyl primary amine, uncle's octadecyl primary amine, uncle's tetracosyl primary amine, uncle's octacosyl primary amine.

The mixture of amine also can be used for purpose of the present disclosure.The illustrative example of the mixture of such amine can be C ₈-C ₁₆The mixture of primary t-alkyl-amine and similar C ₁₄-C ₂₄The mixture of primary t-alkyl-amine.Primary t-alkyl-amine and preparation method thereof is known to a person of ordinary skill in the art, therefore there is no need further discussion.The primary t-alkyl-amine and preparation method thereof that is used for disclosure purpose is at United States Patent (USP) 2,945, describes in 749, and this patent is incorporated this paper into as a reference.

Wherein hydrocarbon chain comprises that the primary amine of olefinic degree of unsaturation is also very useful.Therefore, the R group can contain at least one olefinic degree of unsaturation according to the length of chain, and usually per 10 carbon atoms comprise and are no more than a two key.Typical amine is laurylene base amine, Semen Myristicae oil base amine (myristoleylamine), palm oil base amine (palmitoleylamine), oil base amine and inferior oil base amine.

Secondary amine comprises the dialkylamine that has in the abovementioned alkyl two, comprise fatty primary secondary amine, also comprise the blended dialkylamine, wherein R ' can be an aliphatic amide, R " can be that as methyl, ethyl, n-propyl, sec.-propyl, butyl etc., perhaps R " can be to have other alkyl nonactive or polar substituent (CN, alkyl, carbalkoxy, acid amides, ether, thioether, halo, sulfoxide, sulfone) to low alkyl group (1-9 carbon atom).That the fat polyamine diamines can comprise is single-or symmetry or asymmetric quadrol, propylene diamine (1,2 or 1,3) or the above-mentioned polyamine analogs of dialkyl group.Suitable fat polyamine comprises N-cocoyl (coco)-1,3-diaminopropanes, N-soya alkyl trimethylene diamines, N-tallow (tallow)-1,3-diaminopropanes and N-oil base-1,3-diaminopropanes.

Nitrogenous compound can any promotion method disclosed herein be finished necessary amount and is provided, that is, and if there is no enough nitrogenous compounds, then P contained compound incomplete vulcanization.On the one hand, nitrogenous compound can be provided with about 0.05 to about 2 molar equivalent with respect to every normal P contained compound, for example provides about 1 nitrogenous compound to about 1.5 molar equivalents with respect to every normal P contained compound.

Method disclosed herein can be carried out under about room temperature (23 ℃) or higher temperature, is for example carrying out at least about 50 ℃, and is for example carrying out in about 90 ℃ scope at about 50 ℃.Usually, at room temperature mix about 1 minute just enough to about 8 hours period.

The method for preparing this salt is known and reports in the literature, for example referring to United States Patent (USP) 2,063,629; 2,224,695; 2,447,288; 2,616,905; 3,984,448; 4,431,552; 5,354,484; People's such as Pesin Zhurnal Obshchei Khimii, 31 (8): 2508～2515 (1961); With the open WO87/07638 of PCT international application, the disclosure of described document is incorporated this paper into as a reference.

May be separately formed the salt of sulfur-containing, phosphorus-containing compound, then it is added in lubricated or the functional fluid binding substances.Perhaps, when salt as described in P contained compound (as phosphorous acid ester disclosed herein) and other component blend form when forming lubricated or functional lubricated binding substances.Yet, very important if the original place forms salt to the restriction that is present in the acid (as antirust component) in the binding substances, because the formation of sulfuration and salt can be reacted and end to acid with nitrogenous compound.

The salt of sulfur-containing, phosphorus-containing compound can be oil-soluble, that is, the hydrocarbyl chain of salt can sufficiently long, as has six carbon atom at least, makes the compound that generates dissolve in the binding substances for preparing.The introducing hydrophobic grouping can be increased in the solubleness in the nonpolar medium.The non-limitative example of the salt of sulfur-containing, phosphorus-containing compound comprises diisobutyl thiophosphoric acid C _8-16Primary t-alkyl-amine salt, two-2-ethylhexyl-thiophosphoric acid C _8-16Primary t-alkyl-amine salt and neopentyl glycol thiophosphoric acid C _8-16Primary t-alkyl-amine salt.On the one hand, considered the salt of phosphorodithioic acid.In yet another aspect, the salt of sulfur-containing, phosphorus-containing compound can be formula (III) shown below and (VI) at least a in the compound:

Wherein n is 1 to 5 integer; With

R wherein ¹, R ², R ³, R ⁴, R ⁵, R ⁶, R ⁷, R ⁸, R ⁹, R ¹⁰And R ¹¹Be independently selected from hydrogen, cyano group and contain about 1 alkyl, for example contain about 1 and arrive the alkyl of about 20 carbon atoms and for example contain about 1 alkyl to about 10 carbon atoms to about 30 carbon atoms.On the one hand, in formula (VI), R ¹And R ²It can be methyl; R ³, R ⁴, R ⁵, R ⁶, R ⁷And R ⁸Can be hydrogen; R ⁹Can be uncle C _12-14Alkyl; And R ¹⁰And R ¹¹Can be to contain about 1 alkyl to about 6 carbon atoms.On the one hand, in formula (III), R ³, R ⁴, R ⁵, R ⁶, R ⁷And R ⁸Can be hydrogen; R ¹And R ²It can be methyl; And R ⁹Can be uncle C _12-14Alkyl.

Embodiment

Embodiment 1-prepares sulfur-containing, phosphorus-containing compound

1 L reactor can be equipped and all press feed hopper, described funnel can pack into sulphur (26.7,0.83mol), ETHOMID ^(487.5g is 0.83mol) with 4Cst PAO (188.56g) for O/17.Then feed hopper can pack into liquid neopentyl glycol phosphite (NPGP) (125.0g, 0.83mol).NPGP under standard conditions be solid and have about 60 ℃ to about 65 ℃ fusing point.The heating feed hopper is avoided solidifying.

Stir and nitrogen protection atmosphere under, NPGP can be added in the reactor and also keep the temperature (mass temperature) of reactive material to be about 60 ℃ to about 90 ℃ simultaneously.Can control the ability control feed rate of heat release by reaction system.This process can be heat release; Therefore, between charge period, may need reactive material is cooled off.Behind reinforced finishing, reaction mixture can exhaust up to all sulphur by about 6 hours to about 90 ℃ of stir abouts 2 about 70.

Embodiment 2-adds additional nitrogenous compound to form salt

Add additional nitrogenous compound such as branching amine then in the sulfur-containing, phosphorus-containing compound that can in embodiment 1, prepare (as PRIMENE ^81R) (153.6g, 0.83mol).Mixture can stir 30 minutes at 60 ℃.

The resistance to abrasion that embodiment 3-improves

Wear-resistant validity level can obtain by measuring the phosphorus substance time length at high temperature.The gear for preparing fully places the heating bath that is under about 325  with fluid.The gear for preparing fully of aliquot is taken a sample and mensuration with fixed time interval with fluid ³¹P nucleus magnetic resonance (NMR) spectrum.Observe ³¹Phosphorus substance in the PNMR spectrum is also drawn to time and thermolysis.Generated the figure of phosphorus resistance to abrasion material.The rate of decomposition of phosphorus substance or decomposition amount change according to the difference of the chemical structure of alkyl chain.The example of phosphorus resistance to abrasion component is dialkyl group-thiophosphoric acid amine salt.Alkyl-branched change has changed the thermolysis speed of dialkyl group thiophosphoric acid amine salt in 325  heating baths.When the beta carbon of phosphorus-to-oxygen bonds was alkyl-branched with methyl-branched or high homology, thermostability was the highest.The example of the stability that increases illustrates by gradually low (shallower) slope among Fig. 1.

The purpose that is used for this specification sheets and claim, except as otherwise noted, the numeral of all expression quantity, per-cent or ratios and other numerical value that in specification sheets and claim, uses, can be regarded as is to be modified by term " about " in all cases.Therefore, unless different explanations are arranged, be can be according to the approximation that changes by the open required character of attempting to obtain of the present invention in the digital parameters described in following specification sheets and the claim.At least and not attempt the application with the principle of claim scope equivalence is construed as limiting, each digital parameters should make an explanation according to the remarkable numeral of being reported or by using the common technology of rounding off at least.

It should be noted that as this specification sheets and claim and use that singulative " " and " described " comprise plural form, are meant one unless clearly and clearly be limited to.Therefore, for example about " antioxidant ", it comprises the antioxidant that two or more are different.As used herein, term " comprises " and phraseological variant is nonrestrictive, makes the project of enumerating under this term not get rid of other and can be replaced or add to similar item in the Listed Items.

Although described concrete scheme, application person or others skilled in the art can recognize at present not prediction or may present unforeseen alternative, change, variant, improvement, substantial Equivalent.Therefore, submit to the claim that also can make amendment to attempt to comprise these all alternatives, modification, variant, improvement and substantial Equivalent.

Claims (6)

1. the compound of formula V:

Wherein n is 1 to 5 integer; With

R wherein ¹, R ², R ³, R ⁴, R ⁵, R ⁶, R ¹⁰And R ¹¹Be independently selected from hydrogen, cyano group and contain about 1 alkyl to about 30 carbon atoms.

2. prepare the method for the salt of sulfur-containing, phosphorus-containing compound, comprising:

With sulfocompound, acid amides and P contained compound in conjunction with forming first mixture; With

First mixture is combined with amine.

3. the method for claim 2, wherein P contained compound is following formula (I) and (IV) at least a in the compound:

Wherein n be about 1 to about 5 integer and

R wherein ¹, R ², R ³, R ⁴, R ⁵, R ⁶, R ¹⁰And R ¹¹Be independently selected from hydrogen, cyano group and contain about 1 alkyl to about 30 carbon atoms.

4. the method for claim 2, wherein first mixture comprises following formula (II) and (V) at least a in the compound:

Wherein n be 1 to 5 integer and

R wherein ¹, R ², R ³, R ⁴, R ⁵, R ⁶, R ¹⁰And R ¹¹Be independently selected from hydrogen, cyano group and contain about 1 alkyl to about 30 carbon atoms.

5. the method for the compound of preparation formula (II) comprising:

With the compound combination of sulfocompound, acid amides and following formula,

R wherein ¹, R ², R ³, R ⁴, R ⁵And R ⁶Be independently selected from hydrogen, cyano group and contain about 1 alkyl to about 30 carbon atoms, wherein at least one substituting group is a methyl,

Obtain the compound of formula (II):

R wherein ¹, R ², R ³, R ⁴, R ⁵And R ⁶Definition the same.

6. prepare the method for the salt of sulfur-containing, phosphorus-containing compound, comprising:

With at least a combination in sulfocompound, acid amides and phosphorous acid dialkyl ester and the polymer-type phosphorous acid ester to obtain sulfur-containing, phosphorus-containing compound; With

In conjunction with amine, obtain the salt of sulfur-containing, phosphorus-containing compound.

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