CN1011781B

CN1011781B - Method for preparation of olefin polysulfides

Info

Publication number: CN1011781B
Application number: CN85104600.2A
Authority: CN
Inventors: 博恩; 布利盖; 巴克; 巴克尔
Original assignee: IFP Energies Nouvelles IFPEN
Current assignee: IFP Energies Nouvelles IFPEN
Priority date: 1984-10-10
Filing date: 1985-06-13
Publication date: 1991-02-27
Also published as: FR2571380B2; FR2571380A2; CN85104600A

Abstract

The present invention relates to a method for preparing lubricant extreme pressure additive alkene polysulfide. The method comprises the steps that (1) sulfur monochloride or sulfur dichloride and single hydrocarbon which at least contains 2 to 5 carbon atoms (usually isobutene) react to form adduct; (2) the adduct and hydrogen carbon base halide contact sulfide together; (3) the mixture is heated; after the mixture is deposited into two phases, an organic phase containing alkene polysulfide is separated; (4) when necessary, alkali is added into an obtained product. The obtained polysulfide contains a high sulfur ingredient which can be used as an extreme pressure additive of gear lubricant. Part of products can be made into the lubricant of a metal machine.

Description

Method for preparation of olefin polysulfides

The invention relates to the organosulfur additive that is exclusively used in the extreme pressure property that improves lubricant; The present invention is the method for preparing the olefin polysulfide additive about having improved especially, and the product that obtains with this method.

Prior art has partly been described the method for olefin polysulfide that many preparations can be used as the extreme-pressure additive of lubricant.

U.S.'s patent of invention has been described a kind of method 3,471, No. 404 and 3,697, No. 499, and its key step is as follows:

(1) makes sulfur monochloride and the excessive alkene, particularly iso-butylene that contain 2 to 5 carbon atoms, under 20 to 80 ℃ of temperature, react, to form a kind of adducts;

(2) adducts that first step forms and a kind of alkali metalsulphide (preferably sodium sulphite) and elementary sulfur are reacted, the ratio of metallic sulfide and sulphur is that 1.8 to 2.2 mole metal sulfide are than 1 grammeatom sulphur, in addition, the ratio of the alkali metalsulphide of every mole adducts is 0.8 to 1.2 mole; Reaction is under the situation that has alcohol or aqueous alcohol solvent to exist, under refluxing, carries out, and

(3) make resulting this kind contain the product of 1 to 3% chlorine, under refluxing, react, be lower than till 0.5% until the residual chlorine content of this product with a kind of aqueous solution of mineral alkali.

These prior art patents are pointed out, the sulphur content of resulting product can be 40 to 60%(weight), in fact, the content of sulphur is about 46%(weight usually).These products can be used as the extreme-pressure additive of lubricating oil, transmission fluid or lubricating grease, and the lubricant base oil then can be made up of mineral oil and some synthetic oil.

In addition, U.S.'s patent of invention has been described the method for polysulfide that a kind of similar preparation can be used as the extreme-pressure additive of lubricating oil for 4,204, No. 969; This method comprises following key step:

(1) under 30-100 ℃ of temperature, makes sulfur monochloride and C ₃To C ₆Aliphatic monoolefine (normally iso-butylene) react, preferably having in the presence of the promotor that contains low alcohol simultaneously, with the formation adducts;

(2) 50 ℃ to reflux temperature, make this adducts and sulphur or sodium sulphite (by for example NaOH, NaHS and/or H ₂The S preparation) to react, its ratio is that every mole of sodium sulphite in the aqueous alcohol medium has 0.1 to 0.4 mole sulphur; And, needn't be handled with alkali, just can reclaim product.

This specific example points out that prepared this product has 49%(weight) sulphur content, be 8.6mm in the viscosity of 37.8 ℃ (100) ²/ s(cSt).When needed, use the ratio of higher elementary sulfur to alkali metalsulphide and hydrogen sulfide, when the method for application prior art increases the sulphur content of additive, the product that is obtained just no longer has enough solubleness in ucon oil (for example in the polyalphaolefin class) or mineral lubricating oils, and can not be used as extreme-pressure additive.In addition, the kinematic viscosity of resultant these products all is too high usually.

The invention provides a kind of method for preparing product, this method does not have above-mentioned shortcoming, and uses higher elementary sulfur ratio simultaneously.

Another advantage of method of the present invention is this method, in the time of if desired, for example based on economically reason, can be in second step, shorten the required time of reaction medium of the adduct feeding sulfur-bearing chemical agent of alkene and the sulfur subchloride that in first step, obtains (alkali metalsulphide or sulfhydrate, and be elementary sulfur as a rule).Otherwise the kinematic viscosity of product will be too high, in addition, these products will be insoluble to synthetic oil (for example being insoluble in the polyalphaolefin) or even mineral oil in, as the situation in the method for prior art.

Accompanying drawing shows the schema of the continuity operation of part steps of the present invention.

In general, the method for preparing olefin polysulfide of the present invention may further comprise the steps:

(1) with at least a compound that is selected from sulfur monochloride and sulfur dichloride, for example under 20 to 80 ℃ of temperature, reacts with at least a aliphatic monoolefine that contains 2 to 5 carbon atoms, to form a kind of addition compound product (or adduct);

(2) with described adducts and at least a after a while with the hydrocarbyl halide that is described, with sulfide at least a sulfide, hydrogen sulphur compound and the polysulfide that is selected from basic metal, ammonium or alkaline-earth metal and generally be elementary sulfur, in a kind of medium or aqueous alcohol medium, react, when adding the various kinds chemical agent, temperature maintenance is for example between 20 to 100 ℃;

(3) with the gained mixture, for example to reflux temperature, heating, and making its sedimentation by 50 ℃, then the water of lower floor is abandoned, the organic phase from the upper strata reclaims olefin polysulfide again;

(4) in case of necessity, can handle resulting product with basic cpds such as for example mineral alkalis.

According to method of the present invention, can contain 2 to 5 carbon atoms when alkene begins, also can use separately, or mix use with other material, the most frequently used is iso-butylene, and this type of alkene also can contain the alkene (for example being diisobutylene) that surpasses 5 carbon atoms with small portion and mix use.

The usage ratio of alkene is calculated by every mole sulfur monochloride and/or sulfur dichloride, can be 1.5 to 2.5 moles, preferably 1.8 to 2.2 moles alkene.Normally 20 to 80 ℃ in the liquid sulfur monochloride that is added into and/or the alkene of sulfur dichloride, temperature are 30 to 50 ℃ specifically.

In second step of method of the present invention,, can comprise C with finishing the hydrocarbyl halide that adducts that first step obtains uses ₁To C ₁₂(C preferably ₁To C ₈) alkyl, C ₅To C ₁₂(C preferably ₆) cycloalkyl or in case of necessity, the cycloalkyl of replacement or C ₆To C ₁₂(C preferably ₇And C ₈) arylalkyl, the also arylalkyl of available replacement, muriate, bromide, iodide etc. in case of necessity.Based on actual needs, it is the most favourable using the hydrocarbyl halide of boiling point between 100 to 150 ℃.The hydrocarbyl halide that uses is a kind of monohalide basically.

What is worth mentioning, methyl, ethyl, sec.-propyl, n-propyl, the tertiary butyl, isobutyl-, normal-butyl, tert-pentyl, isopentyl, n-pentyl, n-hexyl, 2-ethylhexyl, n-octyl, cyclohexyl and benzyl muriate, bromide and iodide are arranged, and their mixture.Use isopropyl chloride, n-butyl chloride, n-butyl bromide, n-octyl chloride, cyclohexyl chloride or benzyl chloride etc., all be beneficial to.

As the characteristic of wanting finished product has significant improvement, the enough hydrocarbyl halides of necessary use.In general, in total grammeatom number of the halogen in adducts+hydrocarbyl halide molectron, the halogen of 1 to 70% grammeatom should be arranged.In general, this ratio is equivalent to the adducts of per 100 grams, 0.015 to 1.9 mole hydrocarbyl halide is arranged, especially when initial monoolefine is iso-butylene.

Within the scope of the invention, might a kind ofly also contain at least a halon of the functional group of one or more heteroatomss (for example being oxygen and/or nitrogen and/or sulphur) that comprises and replace the alkyl monohalide of at least a portion with having at least.

Having in the halogenated hydrocarbon polymer of functional group at these, mainly is compound and the monobromated compound with monochlor(in)ate.They can be selected from easily:

The monohalide that contains at least one alcohol functional group, particularly:

-contain, the fontanelle compound of the aliphatic monoalcohol of 2 to 18 carbon atoms, alicyclic single alcohol, aromatic-aliphatic list alcohol etc. for example, for example ethylene chlorhydrin, ethylene bromohyrin, propylene chlorohydrin, bromopropyl alcohol, butanols, amylalcohol, hexanol, enanthol, octanol, nonyl alcohol, decyl alcohol, undecyl alcohol and dodecyl alcohol and chlorine benzyl alcohol or bromobenzyl alcohol and chlorobenzene ethyl alcohol or bromobenzene ethyl alcohol;

The halogenide of-polyvalent alcohol, for example 3-chlorine or 3-bromo-1, the 2-propylene glycol is (with its corresponding epoxy derivative; For example the 1-chloro-2,3-propylene oxide or 1-bromo-2,3-propylene oxide);

-(gathering) oxyalkylene list alcohol halogenide; For example chloro-(poly--) ethoxy ethanol, bromo-(poly--) ethoxy ethanol, (poly--) oxyethyl group propyl alcohol, (poly--) propoxy-ethanol and (poly--) propoxy-propyl alcohol;

A halogen compound that contains at least one phenol functional group, for example non-replacement or that replace (for example being replaced) chloro-phenol and bromo-phenol by alkyl;

A halogen compound that contains at least one carboxylic acid functional, for example monochloroacetic acid, bromine acetic acid, chloropropionic acid, bromo-propionic acid, chloro-butyric acid, bromo-butyric acid, chloro pentane acid, bromine valeric acid, chloro-benzoic acid, bromo-benzoic acid, chlorine succsinic acid, bromine succsinic acid etc.;

A halogen compound that contains at least one amine functional group, compound particularly aliphatic series, alicyclic or aromatics one aliphatic series, for example chlorethamin hydrochloride, chloro-N, N-dimethyl-ethamine hydrochloride, chloro-N, N-diethyl-ethamine hydrochloride, chloro-N, N-dipropyl-ethamine hydrochloride, chloro-benzylamine, bromo-benzylamine, chloro-phenylethylamine, bromo-phenylethylamine;

The monohalide that contains at least one amide functional group, for example chloro-ethanamide, bromo-ethanamide, chloro-propionic acid amide, bromo-propionic acid amide; Or

A halogen compound that contains at least one thiol functional group, for example chloro-thyroidan, bromo-thyroidan, chloro-benzenethiol, bromo-benzenethiol, chloro-benzyl sulfhydrate, bromo-benzyl sulfhydrate;

Having at these specifiablely in functionality-halogenide of different types of functional group has:

The compound that contains hydroxyl and carboxylic acid functional, for example 5-chloro-Whitfield's ointment, or 3-chloro-4-hydroxymandelic acid;

The compound that contains amine and carboxylic acid functional, for example 4-chlorophenylalanine; Or

The compound that contains hydroxyl and amine functional group.

In not leaving scope of the present invention, can be these halogenated hydrocarbon polymers and no functional hydrocarbon groups halogenide, for example above-mentioned those hydrocarbyl halides use together in any ratio.

In the following discussion, noun (an one) hydrocarbyl halide and a halogenated hydrocarbon polymer will use with exchanging, specifying used functional compound, or non-functional compound or their mixture.

In the step (2) of method of the present invention, when using above-mentioned sense one halogen compound, at at least a phase-transfer catalyst that a small amount of (for example being 0.1 to 10% weight) arranged, especially a kind of chlorination quaternary amine (for example being four butylamine chlorine), or alkyl halide phosphorus, or under the existence of kryptofix 222, be favourable to carrying out this step reaction.

Step (2) in the sulphur compound used, can be selected from sulfide, polysulfide, the sulfhydrate of basic metal (for example sodium or potassium), alkaline-earth metal (for example magnesium or calcium) or ammonium etc.The most frequently used is sodium sulphite, sodium sulfhydrate (for example under the situation that has caustic soda to exist) and sodium polysulphide etc.Used this kind sulphur compound of present method is to the ratio of whole adductss (for example being obtained at completing steps (1))+hydrocarbyl halide (as mentioned above), approximately be the halogen of every grammeatom of being contained in the molectron of adducts+hydrocarbyl halide, 0.4 to 0.8 mole sulfide is arranged.

If elementary sulfur uses with sulfide in step (2), then the mol ratio of elementary sulfur and sulfide can reach about 7/1, and this mol ratio just is equivalent to be low to moderate about 0.14/1 inverse proportion.

If wish the sulphur content not too high (the highest about 45 to 55% weight) in the product in the end, then can use up to about 4/1 the elementary sulfur and the mol ratio of sulfide.This ratio is about 0.4/1 to 3.3/1 usually in the case.So inverse proportion is at least about 0.25/1, be about 0.3/1 to 2.5/1 usually.In the case, the ratio of a used halogenated hydrocarbon does not need very high, the grammeatom percentage ratio of the halogen that the halogen grammeatom summation of 1 to the 40%(molectron that forms in " adducts " and a halogenated hydrocarbon is calculated) ratio in general be suitable.This ratio is equivalent to " adducts " of per 100 grams, and the halogen of 0.015-0.55 grammeatom is arranged, and particularly working as initial monoolefine is the words of iso-butylene.

So we just obtain to have sulphur content and generally reach 45-55%(weight) olefin polysulfide, and sulphur content can high slightly (about 60% weight) sometimes.Under 100 ℃ temperature, their kinematic viscosity changes with its sulphur content, and viscosity approximately is 4 to 20mm ²/ s; Their content of halogen (mainly being chlorine) generally all is to be lower than 1%(weight), modal is 0.6%(weight).

These products generally all are dissolved in mineral oil and the most synthetic oil with sizable solubleness, and the solubleness of some product almost is hard-core fully.Contain the product of high sulfur content, the solubleness in lubricating oil may be lower.But this dissolving is enough to make it to be used for some purposes (for example mach cutting oil additives of metal).

If in the end need to have higher sulphur content in the product (about 60 to 65% weight), but the mol ratio of application element sulphur and sulphur compound for example reaches 7/1, especially, 3.3/1 can be low to moderate 0.14/1 to 7/1(so inverse proportion, especially between 0.14/1 to 0.3/1).And then use higher proportion, and a halogenated hydrocarbon of 40 to 70% for example, (the grammeatom ratio of the halogen of representing with the grammeatom summation of the halogen of the molectron of " adducts " and halogenated hydrocarbon formation) more precisely, is about 45 to 65%.These ratios are equivalent to the halogen (more precisely, being the halogen of about 0.7-1.5 grammeatom) that per 100 " adductss " that restrain have about 0.55-1.9 grammeatom, if particularly initial monoolefine is an iso-butylene.

Therefore though might obtain some sulphur contents very high (sulphur content when cl content is lower than 1% weight is approximately 60 to 65%(weight)), (100 ℃ viscosity is 4 to 15mm to have low viscosity ²/ s) product, and these products still dissolve in the low viscosity mineral oil of application in metal processing (cutting, shaping etc.), and its solubleness is enough improved these oily extreme pressure properties.

In step (2), usually in water, and preferably in the mixture of water and a kind of low aliphatic monoalcohol (containing for example 1 to 4 carbon atom), add (or formation) sulfide, and add any elementary sulfur.

The single alcohol of specifiable lower aliphatic has: methyl alcohol, ethanol, propyl alcohol, Virahol, propyl carbinol, isopropylcarbinol and the trimethyl carbinol; The most suitable is Virahol.This used water-alcohol mixture can contain, and compares with the weight of water, for example is 2 to 60%(weight) alcohol, (and preferably 5 to 45%).

In the medium that is obtained, remain on (20 to 100 ℃ of temperature) under the stirring condition, the adduct and the hydrocarbyl halide of step (1) added together this process need several minutes extremely several hours, for example 10 minutes to 3 hours.

In step (3), continue heating, for example 3 to 10 hours (temperature is between the reflux temperature at 50 ℃).

If necessary, can add step (4), comprising the resulting product of step (3) of finishing dealing with basic cpd, this kind basic cpd can be a kind of mineral alkali, the aqueous solution of caustic soda or Ke Xingjia for example, the used caustic soda and the concentration of aqueous solution of Ke Xingjia can be, for example, and 0.5 to 20%(weight).

Reaction in the step of method of the present invention (2), and processing subsequently can carry out continuously, this operation preferably according to and stream contact (rather than adverse current) charging program with multiple spot and carry out, this kind program helps the characteristic of last resultant product.

This operation can (absolute pressure can reach under 3 crust=0.3MPa) environment and carry out, and can improve temperature of reaction and speed of reaction like this, and not influence the characteristic of final product in a slight superpressure.For a more detailed description to particular case in example 43, simultaneously can be with reference to accompanying drawing.

According to the product that the inventive method is made, can be advantageously used for very much the extreme-pressure additive of lubricating oil.

First kind of purposes especially relates to preparation and is used for the lubricating oil of oilgear.

The source of base oil can be mineral or synthetic, synthetic oil especially comprises alkene oligomer, for example under the condition that Lewis acid exists, by the trimer of the prepared 1-decene of oligomerisation, tetramer, pentamer etc.Certainly, the alpha-olefin that also can use other C for example ₆To C ₁₄Alpha-olefin.

Also can use alkylbenzene, for example an alkylbenzene and dialkyl benzene, or other is by monocarboxylic acid or the synthetic ester of polycarboxylic acid (for example sebacic acid, fatty oil or the like) deutero-and monohydroxy-alcohol or polyvalent alcohol (for example 2-Ethylhexyl Alcohol, trishydroxymethyl-propane or the like).

Can use olefin polysulfide in this application, its preparation comprises the sulphur (mol ratio of sulfide/elementary sulfur for example is 1.8/1 to 2.5/1) of the relatively lower ratio of application, also available a high proportion of sulphur.Owing to be chosen in the solubleness in the lubricating oil, for the additive that can be used in the mineral oil, the mol ratio of sulfide/elementary sulfur can be low to moderate 0.4/1, and for the additive that can be used in the synthetic oil, the mol ratio of sulfide/elementary sulfur then can be low to moderate 1.5/1(or lower).

Then, can add selected alkene in the lubricating oil, its concentration can be 0.5 to 7%.

These additives can mix use, for example metal dialkyl dithio-phosphoric acid ester, metal diaryl dithio-phosphoric acid ester, phosphite and organophosphate etc. with phosphorus additive.

Also can add and enter other traditional additive, for example oxidation inhibitor, rut preventives, copper passivator, antifoams, antifriction liniment etc. are in ratio commonly used.

Second kind of purposes of the product of the inventive method preparation is the extreme-pressure additive as lubricating oil, particularly relates to the oil that preparation is used for metal processing (cutting, shaping etc.).

This purposes, comprise sulfide/elementary sulfur mol ratio that application is minimum for its preparation, for example 0.14/1 to 0.3/1 product is particularly advantageous, these products (sulphur content is very high) still fully are dissolved in the base oil that is used for the lubricant (for example 100 Neutral Solvent) that preparing metal processing uses in mineral sources unexpectedly.

On this purposes, the concentration of used additive is compared with the weight of lubricating oil, generally is 0.1 to 10%(weight), and 0.5 to 5%(weight preferably); In this purposes, also can add other conventional additive, for example be the chlorating paraffinic hydrocarbons, its ratio is compared with the weight of lubricating oil, is equivalent to 2 to 10%(weight) chlorine.

Following example explanation the present invention, but do not limit the present invention.Example 1,2,5,7,10,12,22,24 and 27 etc., the purposes of making comparisons.

Example 1(contrast)

Be heated in 10 liters of reactors of 40-45 ℃ one, add the S of 3800 grams ₂Cl ₂(28.14 moles) are then through a plunger tube, at this S that ceaselessly is stirred ₂Cl ₂The surface under, add the iso-butylenes (68.54 moles) that wherein are dissolved with 35.6 gram methyl alcohol of 3650 grams.In the process (3 hours) of whole adding iso-butylene, the temperature of reaction medium all maintains between 45 to 50 ℃.So, just obtain 7040 adducts (being called adducts again) that restrain.

In another 1 liter of reactor, add 296 gram water, 159.3 gram 60%Na in succession ₂S flocculus (1.225 moles), 19.5 gram young fine grain sulphur (0.609 grammeatom) and 31cm ³Virahol (Na ₂The S/S mol ratio is 2).This mixture heating up to 80 ℃, stirred mixture simultaneously one hour, be cooled to 45 ℃ then.

In this water medium that does not stop to stir, add the adduct that 250 grams obtain above, whole adition process takes 0.75 hour, and the temperature of reaction medium rises to 75 ℃ gradually from 45 ℃; Under total reflux (88-95 ℃) then this mixture heating up 6 hours, stirs it simultaneously fiercely.

After sedimentation, discard the water of lower floor and with 200cm ³10%(weight) caustic soda solution add in the organic phase, again the heating 6 hours under refluxing of this mixture.

The organic phase that reclaims after this sedimentation water with 200cm is cleaned three times, and under the vacuum pressure of 100 ℃ and 2666Pa dry one hour then, recycle silicon algae soil filtered.So, just obtaining the orange-yellow liquid of 189 grams, its feature is as follows:

S(% weight)=46.2

Cl(% weight)=0.37

Viscosity (mm at 100 ℃ ²/ s)=12.0

Example 2(contrast)

With example 1 identical operational condition under, 250 the gram iso-butylene/S ₂Cl ₂Adduct is with injecting the alkaline polysulfide aqueous solution in 0.2 hour.Through reaction with after handling (described) by example 1, obtain the orange-yellow viscosity product of 192.5 grams, its characteristics are as follows:

S(% weight)=45.4

Cl(% weight)=1.17

Viscosity (mm at 100 ℃ ²/ s)=30.0

Example 3

With example 1 identical operational condition under, the water of 296 grams, 159.3 grams, 60% Na ₂S solution, 15.9 gram sulphur and 31cm ³Isopropylcarbinol one after the other add (the same before following, Na ₂The mol ratio of S/S is 2).

In the water medium that does not stop to stir,, add the S that contains 225 gram examples 1 then with 0.2 hour time ₂Cl ₂/ iso-butylene adduct, and the mixture of 18.72 gram n-butyl chlorides (0.202 mole).After reaction, to handle with caustic soda, water cleans, and after drying up and filtering, obtains the orange-yellow liquid of 182.1 grams, and its characteristics are as follows:

S(% weight)=45.7

Cl(% weight)=1.08

Viscosity (mm at 100 ℃ ²/ s)=14.1

Example 4

The test of reforming example 3, injection length, Na ₂S, sulphur, isopropylcarbinol concentration (Na ₂S/S mol ratio 2) etc. condition does not all have to change, and different is the current mixture that uses, and contains the adducts and the 37.45 gram n-butyl chlorides (0.405 mole) of 200 gram examples 1.After processing, obtain the orange-yellow liquid of 181.6 grams, its characteristics are as follows:

S(% weight)=45.0

Cl(% weight)=0.68

Viscosity (mm at 100 ℃ ²/ s)=5.7

Example 5(contrast)

With example 1 identical operations condition under, use 22.4 gram sulphur (Na ₂The S/S mol ratio is 1.75).Then, with 2 hours, 250 gram iso-butylene/S ₂Cl ₂Adduct adds in the aqueous solution of alkaline polysulfide.After reaction, clean with caustic soda processing, water, after drying up again and filtering, obtain the orange-yellow liquid of 192 grams, its characteristics are as follows:

S(% weight)=47.1

Cl(% weight)=0.92

Viscosity (mm at 100 ℃ ²/ s)=19.2

Example 6

Injection length of this experiment and Na ₂Concentration (the Na of S, sulphur, isopropylcarbinol ₂The S/S mol ratio is 1.75) all identical with above-mentioned experiment; The composition of mixture comprises that the adduct and 37.45 of 200 gram examples 1 restrains n-butyl chlorides (0.405 mole).After the processing, obtain the orange-yellow liquid of 190 grams, its characteristics are as follows:

S(% weight)=45.8

Cl(% weight)=0.6

Viscosity (mm at 100 ℃ ²/ s)=4.7

Example 7(contrast)

Operational condition is identical with example 1, and different is to use 26 gram sulphur (Na ₂The S/S mol ratio is 1.5).After reaction and handling, obtain the orange-yellow product of 195 gram high viscosity, its characteristics are as follows:

S(% weight)=45.2

Cl(% weight)=1.34

Viscosity (mm at 100 ℃ ²/ s)=35.5

Example 8

Repeat example 7 with the identical operations condition, but, the current mixture that uses contains 237.5 gram iso-butylene S ₂Cl ₂Adduct and 9.4 gram n-butyl chlorides (0.102 mole).After reaction and handling, obtain the orange-yellow product of 187 grams, its characteristics are as follows:

S(% weight)=46.8

Cl(% weight)=0.95

Viscosity (mm at 100 ℃ ²/ s)=14.7

Example 9

Repeat example 7 with the identical operations condition, the current mixture that uses contains 200 gram S ₂Cl ₂/ iso-butylene adduct and 37.45 gram n-butyl chlorides (0.405 mole).Obtain 170 gram product liquids, its characteristics are as follows:

S(% weight)=46.4

Cl(% weight)=0.60

Viscosity (mm at 100 ℃ ²/ s)=4.2

Example 10(contrast)

Use 78.4 gram sulphur (Na ₂The S/S mol ratio is 0.5) repetition example 1.At 250 gram iso-butylene/S ₂Cl ₂After the adduct reaction, handled, obtain the orange-yellow product of 212 gram high viscosity, its characteristics are as follows:

S(% weight)=44.7

Cl(% weight)=1.54

Viscosity (mm at 100 ℃ ²/ s)=39.8

Example 11

Use the identical operations condition, repeat example 10, the current mixture that uses contains 200 gram iso-butylene/S ₂Cl ₂Adduct and 37.45 gram n-butyl chlorides (0.405 mole).After reaction and handling, obtain 202 gram products, its characteristics are as follows:

S(% weight)=48.1

Cl(% weight)=

Viscosity (mm at 100 ℃ ²/ s)=9.6

Example 12(contrast)

In one 1 liter reactor, add in succession: the Na of 296 gram water, 159.3 grams 60% ₂S solution, 98 gram sulphur (Na ₂S/S gram mol ratio is 0.4).After 1 hour, be cooled to 45 ℃ 80 ℃ temperature heating then, use 1.5 hours again, add 250 gram adducts of example 1.Reflux after 8 hours, organic phase is separated, handle with the method for example 1 again.Obtain 230 gram high-viscosity products, its characteristics are as follows:

S(% weight)=46.2

Cl(% weight)=2.43

Viscosity (mm at 100 ℃ ²/ s)=47.5

Example 13

Use contains the mixture of the n-butyl chloride (0.512 mole) of 187.5 gram affixtures and 47.4 grams, repeats the test of example 12.After reaction and handling, obtain 225 gram products, its characteristics are as follows:

S(% weight)=52.2

Cl(% weight)=0.74

At 100 ℃ viscosity (mm/s)=14.2

Example 14

Under the operational condition of example 13, revision test is used 120.8 gram sulphur (Na ₂The mol ratio 0.32 of S/S) and contain 187.5 the gram iso-butylene/S ₂Cl ₂The mixture of adduct and 47.4 gram n-butyl chlorides (0.512 mole).After reaction and handling, obtain 253 gram products, its characteristics are as follows:

S(% weight)=58.6

Cl(% weight)=0.61

Viscosity (mm at 100 ℃ ²/ s)=18.7

What table 1 was listed is the characteristic of the product of example 1 to 14.

Dissolubility test (it the results are shown in table 1) is by the product with example 1 to 14, presses 5%(weight) concentration add in two kinds of lubricating oil of viscosity grade SAE90, a kind of is solvent treatment mineral oil, another kind is that synthetic oil (polyalphaolefin PAO) carries out.

* Comparative Examples

The additive of * example 14 in 100 neutral solventes (Neutral Solvent), still has 1%(weight) solubleness.

This 5% concentration approaches to be generally used for preparing the concentration of automobile gear lubricating oil.These measurement results are earlier substances to be stored in-5 ℃ the cold house, and then under 20 ℃, record.In these trials, be that partly soluble product all is used as and is not dissolved under prescribed concentration.

Example 15

Repeat the test of example 4, in sodium polysulfide solution,, add 200 gram iso-butylene/S with 0.75 hour ₂Cl ₂The mixture (NaS/S mol ratio=2) of affixture and 37.45 gram n-butyl chlorides (0.405 mole).After reaction and handling, obtain 187 gram products, its characteristics are as follows:

S(% weight)=45.6

Cl(% weight)=0.51

Viscosity (mm at 100 ℃ ²/ s)=5.3

Example 16

Repeat the test of example 15, with n-butyl bromide (55.44 gram) the replacement 37.45 gram n-butyl chlorides (0.405 mole) of same molar.After under similarity condition, reacting and handling, obtain 185 gram products, its characteristics following (X represents chlorine+bromine total amount):

S(% weight)=45.4

X(% weight)=0.68

Viscosity (mm at 100 ℃ ²/ s)=5.5

Example 17

Repeat the test of example 15, with cyclohexyl chloride (47.98 gram) the replacement 37.45 gram n-butyl chlorides of same molar.After reaction and handling, obtain 187 gram products, its characteristics are as follows:

S(% weight)=45.2

Cl(% weight)=0.54

Viscosity (mm at 100 ℃ ²/ s)=4.5

Example 18

Repeat the test of example 15, with benzyl chloride (51.21 gram) the replacement 37.45 gram n-butyl chlorides of same molar.After reaction and handling, obtain 189 gram products, its characteristics are as follows:

S(% weight)=45.3

Cl(% weight)=0.72

Viscosity (mm at 100 ℃ ²/ s)=4.7

Example 19

Repeat the test of example 15, with n-octyl chloride (60.15 gram) the replacement 37.45 gram n-butyl chlorides of same molar.After reaction and handling, obtain 194 gram products, its characteristics are as follows:

S(% weight)=44.1

Cl(% weight)=0.49

Viscosity (mm at 100 ℃ ²/ s)=4.7

Example 20

Repeat the test of example 15, with isopropyl chloride (31.77 gram) the replacement 37.45 gram n-butyl chlorides of same molar.After reaction and handling, obtain 179 gram products, its characteristics are as follows:

S(% weight)=45.9

Cl(% weight)=0.53

Viscosity (mm at 100 ℃ ²/ s)=5.7

The product property of being narrated in example 15 to 20 all is listed in the table below in 2.About dissolubility test (it the results are shown in table 2) be by, with the product of example 15 to 20, under-5 ℃ of temperature, press 5%(weight) concentration, add and to carry out in the ucon oil of polyalphaolefin class of viscosity grade SAE 90.

In table 2, RX represents used hydrocarbyl halide, and X represents relevant halogen.

Example 21

Provide at one and (supply heating or refrigerative double wall, a strong agitation device (turbine class), contrary blade system (Contrablade system), an inner temperature detector, a manometer and connect in withstand voltage stainless 1 liter of response diagram of a charging volume pump tubule that is stressed adding one after the other: the Na of 159.3 grams, 60% concentration ₂The S(1.225 mole), 19.5 gram sulphur (0.609 grammeatom), 31cm ³Virahol and 296 gram water (Na ₂The mol ratio of S/S is 2).

Do not stop to use the charging volume pump in the aqueous solution of the polysulfide that stirs at this, add the S that contains 174.7 gram examples 1 ₂Cl ₂The mixture of/different propylene adduct and 30.6 gram methyl chlorides (about 0.61 mole), the material feeding time is 0.75 hour.

This mixture was heated 8 hours down at 105 ℃; Can see that pressure along with the time descends gradually, makes reactor cooling to envrionment temperature, then open reactor, remove aqueous phase substance again.

As in last example, the organic product that obtains under about 95 ℃ temperature, is used 10%(weight) caustic soda handled 6 hours, water cleans again, dries up, and filters then.

Obtain the orange-yellow product of 155 grams, its characteristics are as follows:

S(% weight)=46.5

Cl(% weight)=0.5

Viscosity (mm at 100 ℃ ²/ s)=5.2

5%(weight in the time of-5 ℃) solvability:

In mineral oil: dissolving

In polyalphaolefin: dissolving

Example 22(contrast)

In 1 liter of reactor, add 145 gram sulfur dichloride (SCl ₂) (1.407 moles), again through a plunger tube, at this SCl that is ceaselessly stirred ₂The surface under, add the iso-butylenes (3.43 moles) that wherein are dissolved with 1.78 gram methyl alcohol of 178 grams.In the time (0.5 hour) of whole adding iso-butylene, temperature of reaction is maintained between 45 ℃ to 50 ℃, then, obtain the adduct of 301.5 grams.

In second 1 liter of reactor, one after the other put into 296 gram water, 159.3 gram 60%Na ₂S flocculus (1.225 moles), 39.2 the gram Powdered sulphur (1.225 grammeatom), with and 31cm ³Virahol (Na ₂The S/S mol ratio is 1).Under 80 ℃,, then temperature is reduced to 45 ℃ mixture heating up 1 hour.

In this medium that does not stop to stir, add the adduct that 214.2 grams obtain above, whole adition process takes 0.5 hour.The temperature of reaction medium rises to 75 ℃ by 45 ℃ gradually; Then, on one side strong agitation, (88-95 ℃) heated 6 hours under total reflux on one side.After sedimentation, remove the aqueous phase substance of lower floor, and with 200 ³Cm 10%(weight) the caustic soda aqueous solution adds this organic phase.Mixture was refluxed 6 hours.

The organic phase water that reclaims after the sedimentation is cleaned three times, and under the vacuum pressure of 2666Pa and 100 ℃ of temperature dry one hour, recycle silicon algae soil filtered, and obtains the orange-yellow product of 180 gram high viscosity, and its characteristics are as follows:

S(% weight)=44.1

Cl(% weight)=1.59

Viscosity (mm at 100 ℃ ²/ s)=47.3

Example 23

With example 22 identical operational conditions under, restraining iso-butylene/SCl by 37.45 gram n-butyl chlorides (0.405 mole) and 171.3 ₂The mixture of adduct with 0.5 hour, adds sodium polysulphide (Na ₂The S/S=1 mole) in the aqueous solution.After the processing, obtain the orange-yellow liquid of 182 grams, its characteristics are as follows:

S(% weight)=45.8

Cl(% weight)=0.64

Viscosity (mm at 100 ℃ ²/ s)=7.2

The characteristic of example 22 and 23 described products is all listed in the table 3, as above example, dissolubility test is by the product with example 22 and 23, press 5%(weight) concentration, add and to carry out in the SAE90 lubricating oil (synthetic oil of a kind of mineral oil and a kind of polyalphaolefin class).

Table 3

The real product characteristics of product in SAE90,5% weight solvability

Routine number at 100 ℃ of S Cl-mineral oil polyalphaolefins

20 ℃-5 ℃ 20 ℃-5 ℃ of viscosity (% weight) (% weight)

（cm ²/s）

22 47.3 44.1 1.59 do not dissolve insoluble separating does not dissolve insoluble separating

23 7.2 45.8 0.64 dissolving dissolving dissolving dissolvings

* Comparative Examples

Example 24(contrast)

In one 1 liter reactor, adding 162 gram 32%(weight) the NaHS aqueous solution, 74 restrains the 50% caustic soda aqueous solution, 79.65 gram Virahols, 14.8 restrain Powdered sulphur (the NaHS/S mol ratio is 2).Mixture was stirred 5 minutes, add 99cm ³Water, reheat to 75 ℃.

In the aqueous solution of this sodium polysulphide, add the iso-butylene/S of 250 gram examples, 1 preparation ₂Cl ₂Adduct, 75 ℃ of temperature, this adds operation and takes two hours.Then,, then Virahol is distilled under 90 ℃ and barometric point, place again subsequently the 2666Pa vacuum pressure under and distill mixture heating 4 hours under refluxing.

After sedimentation, use 125cm ³Water and 100cm ³Benzene cleans organic phase.Make organic phase sedimentation once again, and then clean with the water and the benzene of above-mentioned same amount.Organic phase reflux heating 0.5 hour, make its cooling and sedimentation again.Under 2666Pa vacuum pressure and 100 ℃ of temperature, with the organic phase evaporation of reclaiming to drive away benzene.Behind diatomite filtration, obtain the orange-yellow product of 201.1 grams, its characteristics are as follows:

S(% weight)=48.6

Cl(% weight)=0.75

Viscosity (mm at 100 ℃ ²/ s)=6.1

Example 25

Use is by 237.5 gram S ₂Cl ₂The mixture that/iso-butylene adduct and 9.4 gram n-butyl chlorides (0.102 mole) are formed repeats the test of example 24.After reaction and handling, obtain 190 gram product liquids, its characteristics are as follows:

S(% weight)=47.4

Cl(% weight)=0.62

Viscosity (mm at 100 ℃ ²/ s)=5.7

Example 26

Use is by 200 gram iso-butylene/S ₂Cl ₂The mixture that adduct and 37.45 gram n-butyl chlorides (0.405 mole) are formed repeats the test of example 24.After reaction and handling, obtain 176.1 gram products, its characteristics are as follows:

S(% weight)=46.8

Cl(% weight)=0.59

Viscosity (mm at 100 ℃ ²/ s)=4.3

Example 27(contrast)

Use 59.25 gram sulphur (the NaHS/S mol ratio is 0.5), repeat the test of example 24.At 250 gram iso-butylene/S ₂Cl ₂After adduct reaction and the processing, obtain the orange-yellow product of 253 grams, its characteristics are as follows:

S(% weight)=55.4

Cl(% weight)=0.93

Viscosity (mm at 100 ℃ ²/ s)=14.1

Example 28

Use is by 200 gram S ₂Cl ₂The mixture that/iso-butylene adduct and 37.45 gram n-butyl chlorides (0.405 mole) are formed repeats the test of example 27.After reaction and handling, obtain 214 gram products, its characteristics are as follows:

S(% weight)=55.0

Cl(% weight)=0.54

Viscosity (mm at 100 ℃ ²/ s)=8.0

The characteristic of the product of being narrated in the example 24 to 28 is all listed in the table 4.

As above-mentioned example, dissolubility test is by the product with example 21 to 25, presses 5%(weight) concentration, add in the SAE90 lubricating oil (a kind of is mineral oil, and another kind is the synthetic oil of polyalphaolefin class) and carry out.

Example 29

In 1 liter of reactor, one after the other add 214.4 gram 32%(weight) the NaHS aqueous solution, 74 grams, 50% aqueous solution, the 78.4 Powdered sulphur of gram and 79.65 gram Virahols (NaHS/S mol ratio 0.5).Mixture was stirred 5 minutes, add 99cm ³Water 80 ℃ of heating down, is cooled to 45 ℃ then.

Table 4

The characteristics of adduct product are 5%(weight in SAE90) solvability

Real (NaHS)/(S) n-butyl chloride S of product ₂Cl ₂/ different S Cl viscosity mineral oil polyalphaolefin

100 ℃ of example number (mole) (gram) butylene (gram) (% weight) (% weight)

（mm ²/g） 20℃ -5℃ 20℃ -5℃

Insoluble separating dissolved in 24 20 250 48.6 0.75 6.1 dissolvings

25 2 9.4 237.5 47.1 0.62 5.7 dissolving dissolvings are dissolved

26 2 37.45 200 46.8 0.59 4.3 dissolving dissolving dissolving dissolvings

27 0.5 0 250 55.

Do not dissolve insoluble separating 0.93 14.1 do not dissolve insoluble separating

28 0.5 37.45 200 55.0 0.54 8.0 dissolving dissolvings are dissolved

* Comparative Examples

In the medium that this ceaselessly stirs,, add the 200 gram iso-butylene/S that obtain in the example 1 with 0.75 hour ₂Cl ₂The mixture of adduct and 37.45 gram n-butyl chlorides (0.405 mole).Refluxed 6 hours, and allowed the liquid sedimentation, discard the aqueous alcohol phase, use 200cm ³10% caustic soda solution is handled this organic phase 6 hours.

After the sedimentation, reclaim this organic phase, use 200cm ³Water cleans 3 times, under 100 ℃ and 2666Pa vacuum pressure dry one hour, uses diatomite filtration then.So just obtain the orange-yellow product of 197 grams, test shows that it is in the mineral base oil (at 20 ℃ and-5 ℃) of SAE90, in 5%(weight) minimum concentration under be can dissolved, its characteristics are as follows:

S(% weight)=51.7

Cl(% weight)=0.47

Viscosity (mm at 100 ℃ ²/ s)=9.27

Example 30

Repeat the test of example 11, use 159.3 gram 60%Na ₂S flocculus, 218 gram water, the pulverous sulphur of 78.4 grams, 79.65 gram isopropylcarbinol (Na ₂The S/S mol ratio is 0.5); Then mixture is heated down at 75 ℃.

Under the operational condition of example 24, continue test, with 2 hours in the alkaline polysulfide solution of gained, add by 200 and restrain iso-butylene/S ₂Cl ₂The mixture that adduct and 37.45 gram n-butyl chlorides (0.305 mole) are formed.After reaction and handling, obtain the orange-yellow product of 195 grams, it is in the mineral oil (20 ℃ and-5 ℃) of SAE90, in 5%(weight) minimum concentration under be dissolved, the characteristics of resulting this product are as follows:

S(% weight)=53.1

Cl(% weight)=0.54

Viscosity (mm at 100 ℃ ²/ s)=8.92

Example 31: the corrodibility of measuring product of the present invention

According to ASTM D-130(NF M 07-015) standard, use and to contain 5%(weight) the SAE Thera Bath of additive, carry out the corrosion test of copper sheet.Tested some additive for preparing in the previous example.

The results are shown in table 5.Use a numeral (1 to 4) to grade, after this numeral, add the corrosion progression that an English alphabet is indicated copper sheet.

Table 5

S is 3 hours in the product instance number additive

100 ℃ 121 ℃ of ratios (% weight)

45.0 1a 1b

8 46.8 2a 1b

9 46.4 1b 2a

11 48.1 2c 3b

13 52.2 3a 4a

26 46.8 3b 3c

28 55.0 4c 4c

In order to prepare automobile gear lubricating oil, need select for use progression to be less than or equal to 3(especially at 121 ℃), for example example 4,8,9 and 11 product.In addition, during preparing metal processing usefulness oily, can use any product of making according to the inventive method, but, preferably select the product of high corrosion progression for use, for example those products of example 13,26,28 are particularly useful for ferrous metal.

Example 32: to the evaluation of extreme-pressure additive characteristic of the present invention

Carried out to show the test of the extreme pressure property of additive in the gear lubrication oil formula that example 4,9 and 11 is prepared.

A. the first cover test, with Timken (TIMKEN) frictional testing machines, according to the testing sequence of ASTM D 2782-71, the concentration of product in the SAE Thera Bath in example 4,9 and 11 is 3%(weight) condition under, they are tested; Measured result is listed in table 6.

Table 6

Added additive heavy burden (pound) * indenture area

Instance number " qualified " " defective " (mm ²)

There is not additive 69 9.1

4 30 35 19.5

9 40 45 20.8

11 40 45 20.8

* 1 pound=0.4536 kgf

These results show, utilize additive of the present invention, and what can increase lubricated metallic surface very for certain ankyloses heavy burden (seizing load).

B. the second cover test, with 4-ball machine (4-ball machine), test procedure according to ASTM D 2783 and ASTM D 2266, the concentration of additive in the SAE Thera Bath in example 4,9 and 11 is 1.5%(weight) condition under, their extreme pressure property is tested; Measured result is listed in table 7.

Table 7

Added the additive heavy burden-

Connect-generation of heavy burden 40kgf dynamics

The diameter of ball impression trace of instance number abrasion index (kilogram)

(millimeter)

Do not have 22.2 60 0.80

4 64.4 400 0.64

9 62.9 400 0.61

11 65.6 500 0.69

These results show, use additive of the present invention, can make heavy burden/abrasion index and ball bonding meet-bear a heavy burden (ball weld-load) and heighten.

Example 33

In 1 liter of reactor, add 296 gram water, 159.3 gram 60%Na in succession ₂S flocculus (1.225 moles), 152.3 gram pulverous sulphur (4.75 grammeatom), 31cm ³Virahol, Na ₂The S/S mol ratio is 0.258.This was heated one hour at 80 ℃, and stir simultaneously, and then temperature is reduced to 45 ℃.

Then in the water medium that constantly stirs, add the mixture of 125 grams by example 1 described adduct that obtains (approximately being the chlorine of 1.01 grammeatom) and 93.4 gram n-butyl chlorides (1.01 moles), whole adition process takes 1.5 hours, and the temperature of reaction medium rises to 75 ℃ by 45 ℃ gradually; Then, 75 ℃ of heating 6 hours, heating (80-85 ℃) 2 hours to reaction was finished under total reflux then mixture.

After sedimentation, remove aqueous phase substance, 200cm ³4%(weight) caustic soda liquor adds in the organic phase, and this mixture reheat was refluxed 6 hours.

After the organic phase sedimentation of reclaiming, clean three times with 200cm water; Under 100 ℃ and 2666Pa vacuum pressure dry one hour then, recycle silicon algae soil filtered.So, just obtaining the orange-yellow liquid of 276 grams, its characteristics are as follows:

S(% weight)=60.0

Cl(% weight)=0.86

At 100 ℃ viscosity (mm/s)=5.7

Example 34

Repeat the test of example 32, use 159.3 gram 60%Na ₂The S(1.225 mole), 163.4 gram sulphur (5.096 grammeatom), Na ₂The S/S mol ratio is 0.24, and 125 gram S ₂Cl ₂The mixture of/iso-butylene adduct and 93.4 gram n-butyl chlorides (1.01 moles).

After processing, obtain 286.3 gram products, its characteristics are as follows:

S(% weight)=61.7

Cl(% weight)=0.9

Viscosity (mm 100% ²/ s)=6.2

Example is as 35

Repeat the test of example 33, use 159.3 gram 60%Na ₂The S(1.225 mole), 196.05 gram (6.115 grammeatom) sulphur (Na ₂The S/S mol ratio is 0.2), with and 93.65 the gram S ₂Cl ₂The mixture of/iso-butylene adduct and 116.8 gram n-butyl chlorides (1.263 moles).

After the processing, obtain 252.7 gram products, its characteristics are as follows:

S(% weight)=63.0

Cl(% weight)=0.54

Viscosity (mm at 100 ℃ ²/ s)=5.23

Under two kinds of different temperature and in the mineral oil of two kinds of heterogeneities, measure the solvability of the additive of pressing example 33,34 and 35 described preparations, these two kinds of mineral oil are;

-100 neutral solvent mineral oil

-cycloalkyl spindle oil

Gained the results are shown in following table 8.

Table 8

Solvability after 15 days

Additives amount 100 neutral solventes have been added

Instance number %(weight) mineral oil cycloalkyl spindle oil

20℃ -5℃ 20℃ -5℃

2 limpid muddinesses are limpid

4 limpid muddinesses are limpid

33 7 half is muddy limpid

10 muddinesses-limpid

20--limpid

2 limpid half is muddy limpid

4 half muddy half is muddy limpid

34 7 half is muddy limpid

10 muddinesses-limpid

20--limpid

2 limpid muddinesses are limpid

4 muddinesses-limpid

35 7--limpid

10--limpid

20--limpid

Example 36: to the evaluation of the extreme pressure property of additive

According to ASTM D 2783 programs, use a 4-ball machine, measure the extreme pressure property of additive in metal processing machining oil prescription according to example 33,34 and 35 preparations.

The lubricant formula of being studied comprises 100 neutral solvent oil of 3% chlorine (with the form of clorafin) and 1% sulphur (with the form of the sulfur additives of example 33,34 and 35), and gained the results are shown in following table 9.

These results show, use additive of the present invention, can strengthen the welding-heavy burden (ball weld-load) of ball in a large number.

Table 9

Chlorination is added sulphur and is added 100NS in 100NS oil 4-ball test(ing)

The solvability that the paraffin agent is real in adding in the agent oil welding of loading/ankylose

In the weight % example number add heavy burden before the wearing and tearing

Sulphur heavily adds the agent index and bears a heavy burden

Amount % 20 ℃ of % of weight 0 ℃ (kgf)

Do not have----21.4 50 126

4.62 do not have--limpid 38.1 80 200

Do not have 33 60 1.67 limpid half muddy 42.8 80 315

4.62 33 60 1.67 limpid 93.8 100 620

4.62 34 61.7 1.62 limpid 97.2 100 620

4.62 35 63 1.59 limpid 101.0 100 620

Example 37

In 1 liter of container, add 159.3 gram 60%Na ₂The S(1.225 mole), 22.4 gram flowers of sulfur (0.7 grammeatom), 28.35 gram caustic soda pills, 296cm ³Water and 3 gram TBAC tetrabutylammonium chloride (Na ₂The S/S mol ratio is 1.75), this mixture was heated one hour down at 80 ℃, and stir simultaneously, and then temperature is reduced to 45 ℃.Then, solution is transferred in the separating funnel, and heating outside, make temperature maintenance at about 45 ℃.

In second 1 liter of reactor, add 162.5 gram S ₂Cl ₂/ iso-butylene adduct, and 67 gram monochloroacetic acids (0.709 mole) then, heat mixture down at 50-55 ℃, and stir simultaneously, make mixture even.

Use this warmed-up separating funnel, little by little sodium polysulphide was added in this chlorinated mixture, temperature of reaction is maintained between 55 to 60 ℃ with two hours.

Then mixture reflux under (100-103 ℃) temperature is cooled to 75 ℃ after 8 hours again, adds 150cm ³Benzene stops to stir, and allows the reaction mixture sedimentation.

The aqueous phase substance of the sodium salt that contains residue sodium polysulphide and formed polythio diethyl alkyd is removed.

With this organic phase and 200 ³The 10%(weight of cm) caustic soda solution, heating is three hours under refluxing, and thoroughly stirs simultaneously.Again temperature is reduced to 75 ℃, add 10 gram sodium-chlor to assist sedimentation; Remove aqueous phase substance then.

The organic phase of this recovery, under constantly stirring, use 120cm ³The 6N HCl aqueous solution was handled one hour down for 70 ℃ in temperature, makes the solution sedimentation, and the aqueous solution is discarded; Use 150cm ³Water cleans organic phase twice, is placed on Na ₂SO ₄Top drying refilters, and then at vacuum (2.7 * 10Pa ³, 100 ℃) and evaporation down.

So, obtain the orange-yellow organic product of 125 grams, its acid number (I _A) be equivalent to about 1650 molar weight; In addition, the infrared spectra of this compound shows the carbonyl group existence.

The characteristic of resultant carbonyl acid sulphur compound is as follows:

S(% weight)=40.1

Cl(% weight)=0.94

Viscosity (mm at 100 ℃ ²/ S)=31.5

I _A＝34.0

Example 38

In 1 liter of reactor, one after the other add 159.3 gram 60%Na ₂S, 22.4 gram sulphur, 296 gram water, 31cm ³Virahol and 3 gram tetrabutylammonium chlorine.This mixture was heated 1 hour down at 80 ℃, and stir simultaneously, be cooled to 45 ℃ then.

With two hours, in this solution that constantly stirs, add 162.5 gram S ₂Cl ₂The mixture of/iso-butylene adduct and 67 gram 1-chlorine 2-propyl alcohol (0.709 mole), simultaneously the temperature maintenance of this mixture at approximately 79-80 ℃.Then, heated 8 hours down at total reflux (90-95 ℃).

Then, stop to stir, make mixture 75 ℃ of sedimentations; The aqueous phase substance that contains excessive sodium polysulphide and formed poly-sulfo-dipropylene glycol is discarded.

Use 200cm ³10%(weight) the caustic soda aqueous solution is handled this organic phase three hours under reflux (about 95 ℃).Make it be cooled to 75 ℃ then, add 100cm ³Benzene, stop to stir, make its sedimentation.

Use 150cm ³Water cleans twice with the organic phase that is reclaimed, and is placed on Na ₂SO ₄Top drying is filtered the back 100 ℃ and decompression (2.7 * 10 ³Pa) evaporation down, so, 130 gram deep yellow organic products obtained, its hydroxy number (I _OH) be equal to 603 molecular weight; In addition, the infrared spectra of this compound shows the oh group existence.

The characteristic of resulting hydroxyl sulphur compound is as follows:

S(% weight)=40.7

Cl(% weight)=0.01

At 100 ℃ viscosity (mm/s)=5.2

I _OH＝93

Example 39

Use 162.5 gram S ₂Cl ₂The mixture of/iso-butylene adduct and 57.1 gram ethylene chlorhydrins (0.709 mole); Repeat the test of example 38.

After processing, obtain 134 gram deep yellow organic products, its hydroxy number (I _OH) be equivalent to 1600 molecular weight; In addition, the infrared spectra of this compound shows the oh group existence.

The characteristic of resultant hydroxyl sulphur compound is as follows:

S(% weight)=41.6

Cl(% weight)=0.7

Viscosity (mm at 100 ℃ ³/ s)=7.72

I _OH＝35

Example 40

In 1 liter of reactor, add 187.5 gram S ₂Cl ₂/ iso-butylene adduct and 65 gram 4-chlorophenols 50-55 ℃ of heating, make this mixture it even.

Use remains on 45 ℃ separating funnel from the temperature of indirect heating, in the reactor that constantly stirs, adds 159.3 gram Na ₂S, 22.4 gram sulphur, 31cm ³The solution of Virahol, 296 gram water and 3 gram tetrabutylammonium chlorine remains on temperature between 50 to 60 ℃ simultaneously.

Under refluxing with this mixture heating up 8 hours.

Material in sedimentation and after removing water is used 200cm ³10% caustic soda liquor solution-treated organic phase, and then add 82cm ³6N HCl handle, and 70 ℃ of heating 1 hour down.

Behind sedimentation, cleaning, drying, filtration and reduction vaporization, obtain 126 gram tawny organic products, its infrared spectra shows the phenolic group group and exists.

The characteristics of resulting phenol sulfides are as follows:

S(% weight)=38.2

Cl(% weight)=0.95

Viscosity (mm at 100 ℃ ²/ s)=13.6

I _OH＝23

Example 41

Use contains 200 gram S ₂Cl ₂/ iso-butylene adduct, 18.5 gram n-butyl chlorides and 53.6 gram 4-chloromethyls 2, the mixture of 6-two uncle's sulfo-butylphenols repeats the test of example 38.

After 8 hours, with caustic soda processing, cleaning, dry and filtration, obtain the orange-yellow product of 200 grams in reflux (85-90 ℃), its infrared spectra shows the existence of hindered phenol group.

The characteristic of this phenol sulfides is as follows:

S(% weight)=37.4

Cl(% weight)=0.95

Viscosity (mm at 100 ℃ ²/ s)=7.1

Example 42

In 1 liter of reactor, one after the other add 144.8 gram 60%Na ₂S, 20.4 gram sulphur, 222cm ³Water, 31cm ³Virahol and 3 gram tetrabutylammonium chlorine.This mixture was heated 1 hour down at 80 ℃, and stir simultaneously, then temperature is reduced to 45 ℃.

In this solution that constantly stirs,, add 162.5 gram S then with 2 hours time ₂Cl ₂/ iso-butylene adduct and 65.5 gram 1-chlorine 2, the mixture of 3-propylene oxide, and keep temperature of reaction simultaneously between 50 to 55 ℃.

Then, mixture heating up is refluxed (94-96 ℃) 15 hours then, adds 150cm again ³Toluene.Stop heating and stirring then, allow sedimentation carry out.

Use 200cm ³10% caustic soda solution, under refluxing, handled 3 hours, use 200cm again ³Water cleans twice, is placed on Na ₂SO ₄Top drying is after the filtration, at 100 ℃ and 2.7 * 10 ³The Pa vacuum pressure is evaporation down.

Thereby the dark organic product of 120 grams that obtain; Its infrared spectra shows oh group and exists.

The characteristic of resulting this kind hydroxylation sulfide is as follows:

S(% weight)=41.4

Cl(% weight)=0.8

Viscosity (mm at 100 ℃ ²/ s)=16.3

I _OH＝76

Example 43

In this example, identical relative proportion in the application example 6 is proceeded operation.

About the description of this example please referring to accompanying drawing.

Enter this reactor R1 that ceaselessly stirs simultaneously, have flow to be 123 volumetrical S per hour ₂Cl ₂The fontanel mixture of/iso-butylene adduct and n-butyl chloride (pipeline 1, volume pump P1), flow is 248 volumetrical sodium polysulphide aqueous alcohol solutions (pipeline 2, volume pump P2) per hour; The temperature maintenance of reactor R1 is at 60 to 65 ℃, and absolute pressure is 0.203MPa.

Average retention time is after two hours in R1,371 volumetrical effluent liquid per hour, and in upflow tube (pipeline 3) flowed into ceaselessly stirred reactor R2, R2 constantly stirred with this reaction, and remained under 105 ℃ and the 0.203MPa absolute pressure.

After 8 hours, this effluent liquid flows to separator S1 through upflow tube 4 in average reservation.In this separator S1, be deposited in 80 ℃ of temperature mutually and in 0.5 hour mean time, carry out (absolute pressure is 0.203MPa).Per hour the upper strata sulphur organic phase fluid of 371 volumetric flow rates flows among the pressure reducer G1 of " GROVE back-pressure " type through pipeline 5, and wherein pressure is reduced to barometric point by desired value (0.203MPa), and then, organic phase is inflow reactor R3 again.

Lower floor's water among the separator S1 is through pipeline 6, volume pump P3 and and the pressure reducer G2 removing of the same type with G1.

ceaselessly stirring and remain among the reactor R3 under 95-100 ℃ and the barometric point, add inbound traffics simultaneously and be 116 volumetrical 10%(weight per hour for per hour 371 volumetrical organosulfur phases (pipeline 5) and flow) caustic soda solution (pipeline 7, volume pump P4).After 6 hours, flow is 221 volumetrical mixtures per hour at average contact time, flow into separator S2 through upflow tube (pipeline 8, volume pump P5), and in this separator S2, settlement action takes place in half an hour and under 60 ℃ of temperature.

Per hour the upper strata organosulfur phase of 100 volumetric flow rates (through manage 9, volume pump P6) among the inflow reactor R4, and useless caustic soda stream is then removed in the bottom of separator S2 (pipeline 10, volume pump P7).

In the reactor R4 that is ceaselessly stirring, add the organosulfur phase of per hour 100 volumetric flow rates of coming from S2 simultaneously, and the water of the cleaning usefulness of 115 volumetric flow rates (pipeline 11, volume pump P8) per hour.

Under 60 ℃, after half an hour, mixture flows among the slurry tank S3 through overflow line 12 in average retention time, in this slurry tank S3, is separated 60 ℃ of temperature and carries out in 0.5 hour.

This supernatant water flows into mixing tank M1 through upflow tube (pipeline 13), in this mixing tank, feeds dense caustic soda by pipeline 14 simultaneously, and feeds make up water by pipeline 15, to prepare 10% caustic soda solution.

With the organosulfur phase of 100 volumetric flow rates per hour, be collected in separator S3 bottom (pipeline 16, volume pump P9), and flow into film continuous evaporator (2.7 * 10 ³Pa/100 ℃), pass through strainer then, arrive storage tank at last.

The physics-chem characteristic of resulting additive is as follows:

S(% weight)=46.1

Cl(% weight)=0.52

Viscosity (mm at 100 ℃ ²/ s)=6.1

Claims

1, a kind of method for preparing olefin polysulfide is characterized in that this method comprises the following steps:

(1) with at least a compound that is selected from sulfur monochloride or sulfur dichloride, under 20 to 80 ℃ temperature, in every mole of sulfur monochloride and (or) sulfur dichloride has the ratio of 1.5 to 2.5 moles monoolefine, react with at least a monoolefine that contains 2 to 5 carbon atoms, to form adduct or adducts;

(2) in a kind of medium of mixture of moisture or water and aliphatic monohydric alcohol, under 20 to 100 ℃ temperature, with described adducts and at least a C that is selected from ₁To C ₁₂Alkyl, C ₅To C ₁₂Cycloalkyl or substituted cycloalkyl and C ₆To C ₁₂The muriate of arylalkyl or substituted aryl alkyl, the hydrocarbyl halide contact of bromide and iodide, the ratio of described hydrocarbyl halide is that per 100 gram adductss have 0.015 to 1.9 mole hydrocarbyl halide, with with at least a basic metal that is selected from, the sulfide of ammonium or alkaline-earth metal, the sulfide of sulfhydrate and polysulfide, the ratio of used sulfide is that the halogen of every grammeatom of being contained in the molectron that forms of described adducts and hydrocarbyl halide has 0.4 to 0.8 mole sulfide, and every mole described sulfide has the elementary sulfur of 0 to 7 grammeatom ratio to contact; And

(3) with resulting mixture, heat to reflux temperature at 50 ℃, after being divided into two-phase, from organic phase, obtain olefin polysulfide again.

2, a kind of method according to claim 1 is characterized in that used aliphatic monoolefine is the mixture of iso-butylene or iso-butylene and a small amount of diisobutylene in step (1).

3, a kind of method according to claim 1 is characterized in that this hydrocarbyl halide is muriate, bromide or the iodide that are selected from methyl, ethyl, sec.-propyl, n-propyl, the tertiary butyl, isobutyl-, normal-butyl, tert-pentyl, isopentyl, n-pentyl, n-hexyl, 2-ethylhexyl, n-octyl, cyclohexyl, benzyl.

4, a kind of method according to claim 1 is characterized in that described hydrocarbyl halide comprises at least a single halogenated hydrocarbon that is selected from alcohol, phenol, carboxylic acid, amine, acid amides, thiol functional group of having of at least a portion.

5, a kind of method according to any one claim in the claim 1 to 4 is characterized in that described sulphur compound is to be selected from sodium sulphite, Sodium sulfhydrate and polysulfide.

6, a kind of method according to any one claim in the claim 1 to 4, the ratio that it is characterized in that elementary sulfur is the elementary sulfur that every mole of sulfide has 0.4 to 7 grammeatom.

7, a kind of according to any one the claim method in the claim 1 to 4, it is characterized in that also comprising step (4) in this method, wherein handle the product that makes by step (3) with a kind of basic cpd.

8, a kind of method according to any one claim in the claim 1 to 4 is characterized in that carrying out operate continuously from step (2), with used chemical agent in the step (2), according to repeatedly the contact method, with and stream mode contact.

9, a kind of method according to claim 1, the ratio that it is characterized in that hydrocarbyl halide used in the step (2) are that per 100 gram adductss have 0.015 to 0.55 mole hydrocarbyl halide.

10, a kind of method according to claim 9, the ratio that it is characterized in that elementary sulfur used in step (2) are the elementary sulfurs that every mole sulfide has 0.4 to 3.3 grammeatom.

11, a kind of method according to claim 1, the ratio that it is characterized in that hydrocarbyl halide used in step (2) are that per 100 gram adductss have 0.55 to 1.9 mole hydrocarbyl halide.

12, a kind of method according to claim 11, the ratio that it is characterized in that elementary sulfur used in step (2) are the elementary sulfurs that every mole sulfide has 3.3 to 7 grammeatom.