CN1037781C - Anti-wear additive and preparation method thereof - Google Patents

Abstract

The present invention relates to an anti-wear additive and a preparation method thereof. The anti-wear additive comprises thiophosphoamide ester having a formula (1) and partial desulphurization products thereof and is prepared by reacting dialkyl phosphorodithioic acid having a formula (2)(I) with a compound having a formula XH(II) under the existence of carbon tetrachloride and the protection of N2 gas, and X in the formula is selected from one of groups (3). The anti-wear additive of the present invention has the advantages of small odor, good anti-wear performance, good thermal stability, good hydrolytic stability, etc.

Description

A kind of wear preventive additive and preparation method thereof

The invention belongs to lubricating oil (fat) additive technology field, exactly is ashless wear preventive additive about sulfur-bearing, phosphorus, nitrogen (calling SPN in the following text) and preparation method thereof.

At present, the wear preventive additive of widely used lubricating oil (fat) mainly contains dibenzyl disulfide (T322), tritolyl phosphate (T306), sulphur phosphoric acid-formaldehyde-amine condenses (T305), the multiple fat amine salt (Huang Wenxuan such as (T307) of sulphur phosphoric acid, Han Changning compiles " lubricating oil and fuel dope handbook "), though these additives have abrasion resistance preferably, but because they at room temperature just have unpleasant stink, in addition when surface of friction produces high temperature, cause the volatilization of oil and additive to enter in the atmosphere, cause serious atmospheric pollution, therefore, uncomfortable cooperation also is not suitable for use in working at normal temperatures to the tighter occasion of lubricant smell restriction as the lubricating oil additive of this class operating mode of metal working fluid.SU 874957 has reported a kind of automobile oil that contains mineral oil and thiophosphoric acid dibasic acid esters uride, and additive therefor is to be raw material with thiophosphoryl chloride, urea element, is that solvent makes with the normal heptane, and its structural formula is , R is an aryl in the formula.US 5080813 discloses a kind of lubricating oil component that contains the sulphur phosphate amine salt, wherein the sulphur phosphate amine salt is reacted under＜100 ℃ of conditions by dialkyl dithiophosphoric acid and alkoxylamine and makes, has good abrasion resistance, can be used as the working metal solution additive, but its hydrolysis stability is poor, and unpleasant stink is arranged at normal temperatures.SU 1694630A has reported a kind of SPN of containing preparation process lubricant oil additive, and this additive is with alkylphenol, P ₂S ₅With amine be raw material, be that solvent makes with benzene, toluene.А. М. К у л и e в mentions when introducing the SPN lubricating oil additive, has The compound of structure can be used as antioxidant additive (R, R ', R " for alkyl or aryl), but do not relate to abrasion resistance (А. М. К у л и e в " Х И М И Я И Т Е Х Н О Л О Г И Я П Р И С А Д О К К М А С Л А М И Т О П Л И В А М " is P.47).

The wear preventive additive and preparation method thereof that the purpose of this invention is to provide a kind of ashless sulfur-bearing phosphorus nitrogen of low odor.

The present invention is achieved through the following technical solutions.The said anti-wear agent of the present invention is that a kind of general formula is Thio-phosphamide ester and partial desulfurization product thereof.In the formula, X is selected from

A kind of in the group, R ₁, R ₂Be identical or different C ₄～C ₂₄The alkyl of straight or branched, aryl or aralkyl, R ₃, R ₄Be C ₂～C ₈Alkyl or cycloalkyl, R ₅Have-(CH ₂) _n-structure, n=2～5 wherein, R ₆For H ,-CH ₃Or-C ₂H ₅, R ₇For H ,-CH ₃Or

, the consumption of anti-wear agent in lubricating oil (fat) is 0.1～3 heavy %.

The preparation method of the said wear preventive additive of the present invention is: with general formula be

The dialkyl phosphorodithioic acid and general formula be XH (II) compound in the presence of tetracol phenixin, at N ₂React under the gas shiled and to make.In the I formula, R ₁, R ₂Be identical or different C ₄～C ₂₄The alkyl of straight or branched, aryl or aralkyl, X is selected from the II formula A kind of in the group, R ₃, R ₄Be C ₂～C ₈Alkyl or cycloalkyl, R ₅Have-(CH ₂) _n-structure, n=2～5 wherein, R ₆For H ,-CH ₃Or-C ₂H ₅, R ₇For H ,-CH ₃Or , the mol ratio of I and II is 1: 1～2, and the mol ratio of I and tetracol phenixin is 1: 0.1～2, and used dialkyl phosphorodithioic acid (I) is according to the described method preparation of USP5080813.Reactant 0.75 ℃ of reaction 0.1～4 hour, is warming up to 100-250 ℃ earlier then, continues reaction 1～4 hour, leaves standstill, and sedimentation separates, and obtains crude product, carries out underpressure distillation then, removes moisture content, obtains the garnet oily liquids, is anti-wear agent of the present invention.

Among the preparation method of the said anti-wear agent of the present invention, when I and II react, can use mineral oil to make reaction medium.The weight ratio of I and mineral oil is 1: 0.2～2.

Among the preparation method of the said anti-wear agent of the present invention, the crude product of I and II reaction can wash with a kind of acid solution in acetic acid, sulfuric acid or the dilute hydrochloric acid of 0.5～1.0N earlier, uses NaOH, the Na of 0.5～1.0N again ₂CO ₃, NaHCO ₃In a kind of alkaline solution and water washing, dry then, promptly get anti-wear agent.

Among the preparation method of the said anti-wear agent of the present invention, the crude product of I and II reaction also can be selected NaOH, the Na of 0.5～1.0N for use ₂CO ₃, NaHCO ₃In a kind of alkaline solution and water washing, dry then, promptly get anti-wear agent.

The present invention has following characteristics:

1. wear preventive additive of the present invention and ammonium phoaphate-sulfate salt and SPN additive commonly used are compared, has low odor, the decomposition temperature height, advantages such as Heat stability is good, as the latter unpleasant stink is just arranged at normal temperatures, and the present invention is also belonging to low smelly additive below 150 ℃, can reduce the pollution to air.

2. wear preventive additive of the present invention is answered ester amine salt (T307), sulphur phosphoric acid-formaldehyde-amine condenses (T305) with sulphur phosphoric acid, molybdenum dialkyl-dithiophosphate (MoDTP) is compared has good abrasion resistance and advantages of high bearing capacity.

The following examples will the invention will be further described

Example of the present invention about " load carrying capacity of lubricant assay method " (four ball methods, GB3142-82) the main test index in:

1.P _B: last non seizure load [kilogram or newton (N)], it is illustrated in, and steel ball does not block the maximum load of stinging under the test conditions, is commonly called as P _KPoint is represented oil film strength.

2.P _D: sintering load [kilogram or newton (N)], be illustrated under the test conditions, make steel ball generation agglomerating minimum load, the maximal work ability of its expression lubricant.

3.ZMZ: integrated abrasion value is an index of the anti-extreme pressure ability of lubricant, and it equals the mathematical mean of several times correcting load. $\mathrm{ZMZ}=\frac{A+B/2}{10}=\frac{A_1+A_2+B/2}{10}$ In the formula: A: work as P _DDuring greater than 400kg, A is that 315kg reaches 9 grades of schools less than 315kg

The summation of positive carry; Work as P _DWhen being less than or equal to 400kg, A is 10 grades of corrections

The summation of load;

B: work as P _DDuring greater than 400kg, B is from 400kg, before sintering

The arithmetical av of correcting loads at different levels, work as P _DWhen being less than or equal to 400kg,

B is zero;

A ₁: P _BBefore the point, i.e. the summation of that part of correcting load on the compensation wire;

A ₂: P _BAfter the point, the summation of that part of correcting load before the 315kg.

Example 1

Take by weighing 0.5M O, O '-diisooctyl phosphorodithioic acid (is called for short sulphur phosphoric acid, make by oneself according to US5080813 example 1 method, down together), 0.5M Di-n-Butyl Amine (chemical pure, Beijing chemical reagent three factories), 0.5M tetracol phenixin (chemical pure, Tianjin chemical reagent one factory), sulphur phosphoric acid is mixed with tetracol phenixin, pour into condenser is housed, in the there-necked flask of agitator and mercurythermometer, at room temperature stir, slowly drip Di-n-Butyl Amine, after dropwising, heat up, 100-110 ℃ of reaction 3 hours, leave standstill, sedimentation, separate, the gained crude product is removed moisture content in 60-80 ℃/15 ± 5mmHg underpressure distillation, obtains the garnet liquid A ₁

Example 2

Take by weighing 0.5M O, O '-diisooctyl phosphorodithioic acid (self-control), mix, feed N with the tetracol phenixin of 0.2M ₂Gas at 0-5 ℃ of Di-n-Butyl Amine that drips 0.55M, is warmed up to 120-130 ℃ of reaction 2 hours then, leaves standstill, and sedimentation separates, and obtains crude product, uses then and the isopyknic 1N dilute sulphuric acid of crude product, and 1N NaOH and water are respectively given a baby a bath on the third day after its birth inferior, with the anhydrous MgSO of 30 grams ₄Dry 8 hours, make the garnet liquid A ₂, results of elemental analyses sees Table 1, and differential thermal analysis the results are shown in Table 2, and demulsification performance sees Table 3.

As can be seen from Table 1: N of the present invention, N '-di-n-butyl, O, O '-diisooctyl dithio phosphoramidate anti-wear agent (A ₂) results of elemental analyses be consistent with calculated value.

As can be seen from Table 2: A of the present invention ₂Have good heat-resistant quality, its differential thermal analysis result is superior to molybdenum dialkyl-dithiophosphate (MoDTP) and zinc dialkyl dithiophosphate (ZDDP).

As can be seen from Table 3: anti-wear agent A of the present invention ₂Has good hydrolysis stability.

Fig. 1, the 2nd, anti-wear agent A of the present invention ₂The four-ball wear test result, use the MQ-12 four-ball tester, rotating speed 1200rpm, among the figure, the multiple ester amine salt (T307) of △-sulphur phosphoric acid, X-sulphur phosphoric acid-formaldehyde-amine condenses (T305),-molybdenum dialkyl-dithiophosphate (MoDTP) ,-A ₂

Fig. 1 contains 1 heavy %A ₂The four ball wear-load curve of whiteruss.

P be test load (newton, N); D is four ball wear diameters (mm).

Fig. 2 contains 1 heavy %A ₂Four ball frictional force-load curves of whiteruss.

P be test load (newton, N); F is a frictional coefficient.

By Fig. 1,2 as can be seen: anti-wear agent A of the present invention ₂Antifriction quality suitable with SPN additive T307, abrasion resistance is better than SPN agent T305 and T307.

In addition, measure 1 heavy %A according to GB 5096-85 method ₂+ 150SN base oil is under 100 ℃, 3 hours conditions, and steel corrosion is 16 grades.

Table 1

Element term	C	H	O	S	P	N	Amount to
								Theoretical value (heavy %)	59.88	10.81	6.65	13.31	6.44	2.91	100
Measured value (heavy %)	60.60	11.40	7.33	10.69	6.45	3.52	99.98
								Analytical procedure				SH/T0303 /92	Plasma emission spectrum

Annotate: C, H, O, N adopt West Germany Herous-Rapid C, H, N, O element branch

Analysing instrument measures.

Table 2

Additive	A 2	Molybdenum dialkyl-dithiophosphate (MoDTP)	Zinc dialkyl dithiophosphate (ZDDP)
				Decomposition temperature ℃	325	214	251
Analytical procedure	The DSC method

Table 3

Base oil and additive	Evaluation result [oil-water-emulsion-separation time (branch)]	Remarks
			Base oil (150SN)	40-40-0(5)
1 heavy %A 2	40-40-0(5)
			1 heavy %ZDDP	40-39-1(20)
1 heavy %T305	40-38-2(3)	Water is muddy
			Analytical procedure	ASTM D-1401

Example 3

With 0.2M content is that O, O '-two (dodecylphenyl) phosphorodithioic acid (self-control) of 98 heavy %, the tetracol phenixin of 0.08M, the dicyclohexyl amine (chemical pure, China Drug Co.) of 0.2M under agitation mix, 0-20 ℃, at N ₂Down reaction 3 hours of gas shiled is warmed up to 212 ℃ then, continues reaction 2 hours, leaves standstill, sedimentation, separation, thick product handle according to example 2 methods, makes 135 gram A ₃, productive rate 84.6 heavy %, results of elemental analyses sees Table 4.

Table 4

Element term	C	H	O	S	P	N	Amount to
								Theoretical value (heavy %)	72.27	10.04	4.01	8.03	3.89	1.76	100
Measured value (heavy %)	72.23	10.05	4.65	7.20	4.01	1.52	99.66

Example 4

With 0.1M content is O, O '-two (dodecylphenyl) phosphorodithioic acid (self-control) of 98 heavy % and tetracol phenixin, 55 gram mineral oil (proportion 0.8838, the V of 0.1M _{40 ℃}=131.3mm ²/ s, V _{100 ℃}=13.21mm ²/ s) mix, drip the diethylamine of 0.12M, temperature of reaction is controlled between 10-40 ℃ logical N ₂Reacted 2 hours, and then temperature was raised to 158 ℃ and continues reaction 1 hour, leave standstill, sedimentation, separation, thick product is carried out underpressure distillation, remove moisture content, obtain thick liquid A ₄114.5 gram.

Example 5

O, O '-two (dodecylphenyl) phosphorodithioic acid (self-control) of 0.2M and tetracol phenixin, 100 gram mineral oil and the 0.2M Di-n-Butyl Amine of 0.2M are mixed logical N under 10～20 ℃ ₂Reacted 0.5 hour, and be warmed up to 145 ℃ then, continue reaction 1.5 hours, leave standstill, sedimentation, separation, thick product is carried out underpressure distillation, remove moisture content, obtain 208.0 gram brownish black thick liquid A ₅, productive rate 91.2 heavy %.

Example 6

O, O '-two (dodecyl) phosphorodithioic acid (self-control) of 0.15M 98 heavy % is under agitation mixed with the tetracol phenixin of 0.225M, in 0.5 hour, divide and add 0.165M piperidines (chemical pure for 4 times, commercially available), after adding, holding temperature stirred 10 minutes at 70 ℃, was warming up to 135-136 ℃ of reaction 3 hours then, left standstill, sedimentation, separation, underpressure distillation gets 93.34 gram A ₆, productive rate 86.51 heavy %.

Example 7

With A ₂, A ₃, A ₄, A ₆Be added to respectively in the 650SN base oil, be mixed with the lubricating oil that contains additive concentration 1 heavy %.Measure its anti-supporting capacity, and compare, the results are shown in Table 5 with T307, T405 to four balls.

As can be seen from Table 5, anti-wear agent A of the present invention ₂, A ₃, A ₄, A ₆Compare with the multiple ester amine salt (T307) of sulphur phosphoric acid, sulfurized olefin cotton oil (T405), have supporting capacity preferably.

Table 5

Additive		Four ball-joint loading capabilities, 1500rpm
			Title	Concentration	P B
A 2	1 heavy %	785N(80kg)
			A 3	981N(100kg)
A 4		785N(80kg)
			A 6	785N(80kg)
T307		735N(75kg)
			T405	530N(54kg)

Annotate: T307: the multiple ester amine salt of sulphur phosphoric acid

T405: sulfurized olefin cotton oil

Claims (5)

1. the wear preventive additive of a lubricating oil, fat is characterized in that it is that a kind of general formula is

The thio-phosphamide ester, X is selected from the formula A kind of in the group, R ₁, R ₂Be identical or different C ₄～C ₂₄The alkyl of straight or branched, aryl or aralkyl, R ₃, R ₄Be C ₂～C ₈Alkyl or cycloalkyl, R ₅Have-(CH ₂) _n-structure, n=2～5 wherein, R ₆For H ,-CH ₃Or-C ₂H ₅, R ₇For H ,-CH ₃Or

, the consumption of anti-wear agent in lubricating oil, fat is 0.1～3 heavy %.

2. the preparation method of a lubricating oil, fat anti-wear agent is characterized in that it is to be by general formula

Dialkyl dithiophosphoric acid and general formula be XH (II) compound in the presence of tetracol phenixin, at N ₂React under the gas shiled and make, in the I formula, R ₁, R ₂Be identical or different C ₄～C ₂₄The alkyl of straight or branched, aryl or aralkyl, X is selected from the II formula A kind of in the group, R ₃, R ₄Be C ₂～C ₈Alkyl or cycloalkyl, R ₅Have-(CH ₂) _n-structure, n=2～5 wherein, R ₆For H ,-CH ₃Or-C ₂H ₅, R ₇For H ,-CH ₃Or

I and II mol ratio are 1: 1～2, I and tetracol phenixin mol ratio are 1: 0.1～2, and reactant 0～75 ℃ of reaction 0.1～4 hour, is warming up to 100～250 ℃ earlier then, continue reaction 1～4 hour, leave standstill, sedimentation, separation, obtain crude product, carry out underpressure distillation then, remove moisture content, make anti-wear agent.

3. according to the said preparation method of claim 2, when it is characterized in that I and II reaction, can use mineral oil to make reaction medium, I and mineral oil weight ratio are 1: 0.2～2.

4. according to the said preparation method of claim 2, the thick product that it is characterized in that I and II reaction washs with the acid solution of one of acetic acid, sulfuric acid or dilute hydrochloric acid of 0.5～1.0N earlier, uses NaOH, the Na of 0.5～1.0N again ₂CO ₃, NaHCO ₃One of alkaline solution and water wash, drying promptly gets anti-wear agent of the present invention.

5. according to the said preparation method of claim 2, it is characterized in that the crude product of I and II reaction can be directly with 0.5～1.0N NaOH, Na ₂CO ₃, NaHCO ₃In a kind of alkaline solution and water wash, drying, promptly get anti-wear agent of the present invention.

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