KR910001018B1 - Lubricant and new poly-fluorinated compound which can be usdas additives - Google Patents

Abstract

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Description

New polyfluorine compounds that can be used as additives

The present invention relates to novel polyfluoro compounds, and more particularly to fluorinated organic compounds bonded to lubricants to enhance the wear resistance of the lubricants.

It is known to apply some organic fluorine derivatives as additives for lubricating compositions, for example the use of salts of aliphatic amines and perhalogenated monocarboxylic acids is described in US Pat. No. 3,565,926, aromatic amines And the use of derivatives obtained by reacting fluorinated organic compounds selected from fluorinated monocarboxylic acids or fluorinated monocarboxylic acid chlorides is disclosed in French Patent No. 2,026,493. However, these carboxyl derivatives are intended for clean-dispersion due to physicochemical action which interferes with their adsorption on the surface to be lubricated, or especially due to chemical action when the clean-dispersion additive is a salt of an alkaline earth metal containing neutral or large amounts of base. It has the drawback that the wear resistance efficiency of the lubricant is lost in the presence of conventional additives such as additives.

More recently, the use of polyfluorinated chain amines or aminoalcohols has been proposed in French Patent No. 2,520,377. Although amines and aminoalcohols combined with clean-dispersion additives result in lubricating compositions with significant wear resistance friction reduction, their use is often limited because of their high volatility, which reduces the efficiency of the lubricating composition over time. do.

This drawback can be overcome by using compounds having the following general formula as wear resistant fluorinating additives:

Wherein Rf is perfluororadical, preferably straight or branched perfluoroalkyl radical having 2 to 20 carbon atoms, more preferably straight chain perfluoroalkyl radical having 6 to 16 carbon atoms; a is an integer from 0 to 10, preferably 0 to 3; b is 0 or 1, but can be 1 only when a is 0 and c is 1 at the same time; c is an integer from 1 to 4 but is 2 if a is any other number than 0; m and n are each 0 or 1; X is an optionally substituted aryl radical, preferably phenyl radical which is unsubstituted or substituted with an alkyl or alkoxy group containing 1 to 4 carbon atoms; Y is a 2-hydroxy-1-phenylethyl group; R ₁ and R ′ ₁ may be the same or different and are each hydrogen atom, alkyl radical containing 1 to 20 carbon atoms, cycloalkyl radical containing 5 or 6 carbon atoms, or optionally substituted aryl radicals; R ₂ and R ′ ₂ may be the same or different and each is a hydrogen atom or an acyl group of an aliphatic, alicyclic or aromatic carboxylic acid; If a + m + n is 0, at least one of R ₁ and R ₂ is not hydrogen or methyl radical.

By the present invention, only one compound of general formula (I) or a mixture of these compounds can be used. From an economic point of view, it is most advantageous to use mixtures of compounds having different Rf radicals.

Some compounds of formula (I) are known, for example compounds of formula (I-a) are described in French Patent Application No. 93,239 and French Patent No. 2,205,894.

Other compounds are novel products and also form part of the present invention.

In general, compounds of general formula (I) may be prepared by methods previously known (e.g., French Patents 1,532,284 and Additional Patents 93,170, 93,239, 95,059 and 2,102,753 and French Patents No. 2,205,894) can be prepared by condensation with arylamine or aminoalcohol of formula (III) from an iodine derivative of formula (II) and subsequently reacting the resulting fluoride amine of formula (IV) with epoxide If necessary, difluoride or aminoalcohol obtained during the reaction step can be esterified.

When using iodide of Rf-CH ₂ CH ₂ I type and amino alcohol (III) simultaneously, it should be noted that the condensation reaction generally produces a mixture of fluorinated amines of the general formula:

And

Where R'f is a perfluororadical having one carbon atom less than the Rf radical. However, if desired, two types of amines can be separated by gas chromatography. Saturated amines (IV-a) can optionally be prepared using excess amino alcohol (III). Similarly, unsaturated amines (IV-b) can optionally be prepared by condensing amino alcohols (III) with fluorinated olefins Rf-CH = CH ₂ by US Pat. No. 3,535,381.

까지의 온도에서 용매의 비존재하에 수행될 수 있으나, 이 축합반응은 또한 C₄내지 C₆의 지방족 알코올에서 유리하게 선택되어지는 비활성 용매중에서 환류하에 수행될 수 있다.Condensation reaction of iodide (II) with arylamine X-NH ₂ or amino alcohol (III) is 160

Although it can be carried out in the absence of solvent at temperatures up to this condensation reaction can also be carried out under reflux in an inert solvent which is advantageously chosen from aliphatic alcohols of C ₄ to C ₆ .

Non-limiting examples of epoxides include ethylene oxide, propylene oxide, 1,2-epoxybutane, 1,2-epoxyhexane, 1,2-epoxydodecane, 1,2-epoxyoctadecane and styrene oxide. May be mentioned. The reaction of the epoxide with the intermediate amine fluoride (IV) can be carried out in different ways depending on the nature of the epoxide used. If a gaseous epoxide is usually used, this reaction is preferably carried out by bubbling through or in the autoclave, whereas if it is a liquid epoxide, the reaction is a mixture of amines and epoxides. By heating only.

온도에서 카르복실산 또는 하기식의 유도체를 사용하여 수행될 수 있다:Any esterification of fluorinated diols or aminoalcohols to yield compounds of formula (I) in which R ₂ and / or R ₂ ′ represents acyl residues is from 0 to 100

At a temperature using a carboxylic acid or a derivative of the formula:

Wherein Z is an OH group, a chlorine atom or an alkoxy group containing 1 to 5 carbon atoms, R ₃ is a straight or immediate chain saturated or unsaturated chain having 1 to 30 carbon atoms, preferably 4 to 22 carbon atoms Aliphatic radicals, cycloaliphatic radicals or aromatic radicals.

When acid (Z = OH) is used, the reaction is carried out in the presence of a dehydrating agent such as sulfuric acid or molecular sieves. The water formed can be removed by azeotropic distillation using an inert solvent, preferably an aromatic solvent such as, for example, benzene, toluene, or xylene.

If carboxylic acid esters (Z = alkoxy) are used, this reaction is carried out in the presence of a transesterification catalyst such as, for example, sulfuric acid, p-toluenesulfonic acid or aluminum alcoholate. Excess ester R ₃ COZ can be used as the reaction solvent.

When the esterification reaction is carried out using an acid chloride (Z = Cl), this reaction is a tertiary amine containing 3 to 20 carbon atoms and preferably trimethylamine, triethylamine, tripropylamine, tributylamine, It is carried out in the presence of a hydrogen acid trapping agent such as a compound which may be selected from triphenylamine and pyridine. Esterification reactions of this kind are generally aliphatic ethers (ethyl, propyl, isopropyl, butyl, isobutyl or amyl ether, methyl t-butyl ether, methyl t-amyl ether) or halogenated aliphatic hydrocarbons such as methylene chloride and chloroform It is carried out in a solvent consisting of.

Examples of acid chlorides that can be used include butyryl, caproyl, capryloyl, isovaleryl, lauroyl, linoleyl, heptanoyl, oleyl, palmitoyl, pelagonyl, phenylacetyl, pivaloyl, More particular mention may be made of stearoyl, undecenoyl, benzoyl, 2-methylbenzoyl, 4-t-butylbenzoyl or cinnamoyl chloride.

Most of the iodine derivatives of formula (II) are for example by RNHaszeldine (JCS 2856-2861 (1949) and JCS 3761 (1953) and Tiers (GVDTiers; JACS 75, 5978 (1953)). The products and methods for their preparation are known from French Patent No. 2,211,430 and "Phosphorus and Sulfur 20, 197 (1984)".

Among the compounds of the general formula (I) according to the present invention, the compounds of the general formula (I-a) and the compounds of the following general formulas are most preferred.

In the above formula, the sum of (b + c) is 2, R ₁ "is a hydrogen atom or methyl radical, and R ₁ '" represents an alkyl radical containing 2 to 16 even carbon atoms.

The amount of the additive of the general formula (I) added to the lubricating oil to obtain the optimum efficiency is at least 0.01% or more, preferably 0.05 to 0.5% based on the weight of the lubricating oil. The additive according to the present invention is preferably composed of an industrial product having a ratio of the compound of the general formula (I) having b = 0 by 10% by weight or more.

Lubricating oils may be mineral oils, synthetic hydrocarbons, synthetic oils belonging to other classes below, but are not limited to these examples. Glycols, glycol ethers, glycol esters, polyoxyalkylene glycols, ethers and esters thereof, monocarboxylic or polycarboxylic acids and esters of monoalcohols or polyalcohols.

When crude oil fractions for the production of engine oils such as "neutral solvents" are used as the basis for lubricating bases, they are seen as ashless dispersants such as conventional clean-dispersion additives or succinic acid derivatives such as calcium alkylarylsulfonates or barium alkylphenates. It is advantageous to combine with the organofluorinated derivatives of the invention. Clean dispersant additives enhance the degree of dissolution of the fluoride additive in oil without affecting the wear resistance of the fluoride additive and without reducing its strength.

When the fluorinated derivative according to the present invention is added to a formed oil that already contains an additive such as zinc alkyldithiophosphate, the oil is not affected by other additives, such as dispersibility, cleanliness and corrosion inhibitory properties. Not only does it substantially increase their wear resistance, but it also increases their charge capacity.

In the oils for internal combustion engines, replacement of all or part of the zinc dithiophosphate used as the antiwear agent with 0.1 to 0.2% of the organofluorine compound according to the present invention has the same or greater wear resistance as that achieved with conventional additives.

Thus, the fluorinating additive according to the present invention can be used as a substitute for zinc alkyldithiophosphate in lubricating oils for gasoline engines or diesel engines or as an auxiliary additive for such lubricating oils.

The following examples and tests illustrate the invention without limiting its application. Unless otherwise indicated, percentages are expressed in weight.

Example 1

에서 2시간 동안 가열해준다. 냉각한 후, 트리에틸아민 히드로클로라이드를 여과하고 에테르로 세척한 다음, 진공하에 증발시켜 용매를 제거한다. 잔류물을 IR 분광법으로 분석하여 (3400cm^-1에서 알코올 흡수띠 및 1730cm^-1에서 에스테르 흡수띠), 하기의 일반식을 갖는 에스테르와 상응함을 알 수 있다:With continued stirring at ambient temperature, 5.84 g of heptanoyl chloride was added to 100 g of diisopropyl ether with aminodiol fluoride C ₈ F ₁₇ CH ₂ -CH ₂ N (CH ₂ CH ₂ OH) ₂ and C ₇ F ₁₅ CF = CH-CH 21.4 g of a mixture of ₂ N (CH ₂ CH ₂ OH) ₂ (65 and 35 mol%, respectively) and 4 g of triethylamine are added dropwise to the solution. Heptanoyl chloride was added dropwise and the solution was added to 60

Heat for 2 hours at. After cooling, triethylamine hydrochloride is filtered off, washed with ether and then evaporated in vacuo to remove solvent. The residue can be seen that the corresponding esters and analysis by IR spectroscopy, having the general formula of the following (in the ester absorption band at 3400cm ^-1 and 1730cm ^-1 alcohol absorption band),:

And

Yield: 94%

Example 2

The reaction is carried out as in Example 1 by replacing the mixture of amino fluoride with an industrial mixture of the same moles of amino fluoride of the general formula:

And

Where n is 56.2%, 27.2%, 12.3%, 3.7% and 0.6% when n is 6, 8, 10, 12 and 14, respectively. The mixture, with an average mass of 510 per mole, contains approximately 65 mole percent saturated aminodiol and 35 mole percent unsaturated aminodiol.

A mixture consisting mainly of esters of the general formula is obtained in a yield of 96%:

And

Example 3

The reaction is carried out as in Example 1, replacing heptanoyl chloride with 8.6 g of lauroyl chloride and diisopropyl ether with 150 g of methyl t-butylether.

Yield 95% was obtained in the mixture whose main structure was determined by IR spectroscopy in the yield of 95% (alcohol absorption band: 3400 cm ^-1 , ester absorption band: 1735 cm ^-1 ):

And

Example 4

Example 3 is repeated by replacing C ₈ F ₁₇ aminodiol and C ₇ F ₁₅ aminodiol with an industrial equimolar mixture of aminodifluorides defined in Example 2.

A mixture containing the ester of the following general formula as a main component is obtained in a yield of 98%.

And

Example 5

에서 단지 1시간동안만 가열한다.The reaction is carried out as in Example 1 by replacing heptanoylchloride and C ₈ F ₁₇ aminodiol and C ₇ F ₁₅ aminodiol with an equivalent molar number of oleylchloride and a mixture of aminodifluorides as in Example 2, respectively. 60

Heat only for 1 hour at.

A mixture was obtained in the form of a dark liquid, the main component of the ester of the following general formula whose structure was determined by IR spectroscopy, with a yield of 94% (alcohol absorption band: 3420 cm ^-1 , ester absorption band: 1740 cm ^-1 ):

And

Example 6

에서 4시간 동안 가열하는 단계만 다르게 실시예 1과 같이 반응을 수행한다.Replace heptanoylchloride with 5.52 g of benzoyl chloride, 60-70

The reaction is carried out as in Example 1 differently from heating only for 4 hours.

The mixture whose main structure was determined by IR spectroscopy was obtained as a viscous yellow liquid with a main component having a viscosity of 95% (alcohol absorption band: 3440 cm ^-1 , ester absorption band: 1720 cm ^-1 ).

And

Example 7

Example 6 is repeated by replacing the C ₈ F ₁₇ aminodiol and C ₇ F ₁₅ aminodiol with an industrial mixture of aminodifluorides as defined in Example 2. The product obtained is a viscous liquid and slightly turbid at ambient temperature. Yield 87%.

Example 8

12.2 g of heptanoyl chloride was dissolved in 120 g of diisopropyl ether in a solution of 22.5 g of a mixture of C ₈ F ₁₇ fluorinated aminodiol and C ₇ F ₁₅ fluorinated aminodiol and 8.3 g of triethylamine as defined in Example 1. Continue to stir at dropwise addition. The solution is heated to reflux for 4 hours. After cooling, triethylamine hydrochloride is filtered off, washed with ether and then distilled under vacuum.

To the by IR spectroscopy to determine the structure and the diester mixture of the general formula obtained in a good fluidity orange liquid, the yield was 88% of a (absorption band at 3440cm ^-1 is not OH, the ester absorption band at 1730cm ^-1 Only exist).

And

Example 9

The reaction is carried out as in Example 8, replacing C ₈ F ₁₇ aminodiol and C ₇ F ₁₅ aminodiol with 20.9 g of an industrial mixture of aminodifluorides as defined in Example 2. The diester yield of the following general formula is 96%.

And

Example 10

, 3-퍼플루오로옥틸프로판니트릴 23.65g 및 래니(Raney) 니켈 1g을 현탁시켜 자기 교반기가 장치된 1

하스텔로이 씨.(Hastelloy.C) 오토클레이브에 가입해준다. 오토클레이브를 닫고 난 후, 암모니아 19g, 수소 6MPa를 가입하고 내용물을 90

로가열한다. 그다음 교반을 시작하여 압력의 감소가 중단될 때까지 90

로 유지해준다(대략 1.5시간).(a) Ethanol 0.2 in 20 ml of ethanol

, 23.65 g of 3-perfluorooctylpropanenitrile and 1 g of Raney nickel were suspended to provide a magnetic stirrer.

Hastelloy joins the Autoclave. After closing the autoclave, join 19 g of ammonia, 6 MPa of hydrogen and load the contents to 90

Heat to Then start stirring until the pressure stops.

Keep it at approximately 1.5 hours.

의 용융점을 갖는 백색분말 형태로 수득한다.Cool the autoclave, reduce the pressure and remove the nitrogen gas. After filtration of the catalyst and evaporation of ethanol, 21 g of 3-perfluorooctylpropylamine was added to 70 g.

Obtained in the form of a white powder having a melting point of.

하스텔로이씨 오토클레이브에 가입하고, 교반하에 75

에서 가열해준다. 오토클레이브에서 생성물을 제거하여 그 생성물을 133Pa 압력하에서 120

로 1시간동안 유지하여 회색고체이며 용융점이 58∼59

인 N-(3-퍼플루오로옥틸프로필)디에탄올아민 77g이 수득된다.(b) 71.6 g of the amine and 14.2 g of ethylene oxide were loaded with a PTFE bowl and a magnetic stirrer.

Join Hastelloy's Autoclave, 75 with stirring

Heat at Remove the product from the autoclave and remove the product at 120 pressure under 133 Pa

Gray solid with melting point of 58 ~ 59

77 g of phosphorus N- (3-perfluorooctylpropyl) diethanolamine is obtained.

에서 응고되는 오렌지색 액체 24.7g을 수득한다. IR 분광법에서 하기 일반식의 에스테르와 상응하는 3400cm^-1에서 OH 흡수띠 및 1720cm^-1에서의 에스테르 흡수띠가 관찰된다.(c) The reaction is carried out as in Example 1, replacing C ₈ F ₁₇ aminodiol and C ₇ F ₁₇ aminodiol with 22.2 g of N- (3-perfluorooctylpropyl) diethanolamine. About 20

24.7 g of an orange liquid is solidified in. In the following the IR spectroscopy 3400cm ^-1, which corresponds to the ester of formula is an ester in the absorption band of OH absorption band and 1720cm ^-1 are observed.

Example 11

에서 가열해준다.4.3 g of acetyl chloride was added dropwise to a solution of 30 g of a mixture of C ₈ F ₁₇ aminodiol and C ₇ F ₁₅ aminodiol and 5.5 g of triethylamine in 100 g of diisopropyl ether, under constant stirring. 60 for 2 hours

Heat at

After cooling, triethylamine was filtered off and the solvent was evaporated in vacuo to give a mixture of 95% yield in which the ester of the general formula

And

Example 12

The reaction is carried out as in Example 11 by replacing acetyl chloride with methacryl chloride.

A flowable product having a main component of the ester of the following general formula is obtained in a yield of 96%.

And

IR spectroscopy shows an OH absorption band of 3380 cm ⁻¹ and an ester absorption band of 1710 cm ⁻¹ .

Example 13

반응기에 가입하고, 혼합물을 150

에서 4.5시간동안 교반하에 가열해준다. 60

로 냉각한 후, 데칸테이션 방법으로 1.25

10% 수산화나트륨 용액으로 1회, 그리고 1.25

물로 3회 세척하여 최종 세척한 물이 중성이 되게하고 요오다이드 이온을 유리시켜 준다.(a) 1449 g of 1-ureo-2-perfluorooctylethane and 671 g of aniline

Join the reactor and mix the mixture 150

Heated under stirring for 4.5 h. 60

After cooling to 1.25 using the decantation method

Once with 10% sodium hydroxide solution, and 1.25

Wash three times with water to make the final washed water neutral and free the iodide ions.

부터 267Pa 압력, 51

까지 증류되는 분액을 제거해준 다음 200Pa 압력, 124∼134

사이에서 비등하는 분액을 수집한다. 용융점이 30

이고 황색 고체 형태인 1-아닐리노-2-퍼플루오로옥틸에탄 1246g이 이에 의해 수득되다.Distill the smaller organic layer to 1600Pa pressure, 70

From 267 Pa pressure, 51

Remove the liquid distilled to 200Pa pressure, 124 ~ 134

Collect aliquots boiling between. Melting point 30

And 1246 g of 1-anilino-2-perfluorooctylethane in the form of a yellow solid are thereby obtained.

하스텔로이 씨 오토클레이브에 충진한다. 질소로 3회 세척한 후, 에틸렌옥사이드 22g을 가입하고 165

에서 8시간동안 교반하에 가열해준다. 에틸렌옥사이드 12g을 가한 다음 163∼164

에서 6시간 더 가열해준다.(b) 221.8 g of product 0.5 with PTFE bowl and magnetic stirrer

Fill the Hastelloy Sea Autoclave. After washing three times with nitrogen, 22 g of ethylene oxide was added and 165

Heated under stirring for 8 hours. 12 g of ethylene oxide was added, and then 163 to 164.

Heat for another 6 hours.

에서 용융하고 있는 아미노알코올

가 96% 이상 함유된 담밤갈색 밀랍성의 고체 238g이 이 실시예에 의해 수득된다.After emptying the autoclave, 35

Amino Alcohols Melting in

238 g of a pale brown waxy solid containing more than 96% of the ethanol was obtained by this example.

Example 14

반응기에 가입해준다.(a) 540 g of aniline and 2-perfluoroalkyl ethyl iodide C _n F _{2n + 1} CH ₂ CH ₂ I having different C _n F _{2n + 1} linear groups at the following weight percent composition ratio and have an average molar mass This 537 mixture is

Join the reactor.

에서 5시간동안 교반하에 가열해주고 60

로 냉각한 후 이 물질을 60

에서 수층이 중성이고 요오다이드 이온이 유리될때까지 10% 수산화나트륨 1

로 1회, 물 1

로 3회 세척해준다.150-152 this mixture

Heated under stirring for 5 hours at 60

After cooling to 60

10% sodium hydroxide until neutral in aqueous layer and free of iodide ions

Once with water 1

Wash 3 times with

에서 267Pa 51

까지 증류되는 분액을 제거하고 필름 증발기에서 증류시킨다(유속 : 200ml/h, 진공도 : 133Pa, 가열온도 : 190

, 캡(Cap)온도 : 100

).1200 Pa 65 by distillation of organic phase

267 Pa 51

Remove the aliquot which is distilled up to and distill in a film evaporator (flow rate: 200 ml / h, vacuum degree: 133 Pa, heating temperature: 190

Cap temperature: 100

).

에서 완전히 액체(적색)인 자주분홍색 형태로 있는 일반식 C_nF_2n+1CH₂CH₂-NH-C₆H₅의 아민 혼합물 845g이 이에 의해 수득된다.Semi-liquid, semi-solid at ambient temperature 45

This gives 845 g of an amine mixture of the general formula C _n F _{2n + 1} CH ₂ CH ₂ -NH-C ₆ H _{5 in} the form of a purple (pink) liquid which is completely liquid (red) at.

에서 6.5시간동안 가열한다. 에틸렌옥사이드 10g을 가한 다음 이 혼합물을 다시 160

에서 6.5시간동안 가열해준다.(b) 200 g of the product and 19 g of ethylene oxide were charged in the same autoclave as in Example 13-b, and the mixture was 160

Heat 6.5 hours at. 10 g of ethylene oxide was added and the mixture was again 160.

Heat 6.5 hours at.

에서는 완전히 액체인 적색 생성물 215g을 수득한다. GC로 분석하여 상기 생성물의 96% 이상이 아미노알코올

의 혼합물로 구성되어 있음을 알아내었다.After cooling and depressurizing the autoclave, the semi-liquid semisolid at ambient temperature is 45

215 g of a completely liquid red product are obtained. Analyzed by GC, more than 96% of the product was amino alcohol

It was found that the mixture consists of.

Example 15

반응기에 충진하고, 교반하에 150

에서 5시간동안 가열한다. 내용물을 95

로 냉각시키고 95

에서 데칸테이션 방법에 의해 10% 수산화나트륨 0.4

로 세척한다. 수층이 중성이 되고 요오다이드 이온이 유리될때까지 65

에서 물 1

로 3회 세척해준다.(a) 287 g of 1-ureo-2-perfluorooctylethane and 199 g of p-phenetidine are replaced with 2

Filled in the reactor, 150 with stirring

Heat at for 5 hours. Contents 95

Cooled to 95

10% sodium hydroxide by decantation method in 0.4

Wash with. 65 until the aqueous layer is neutral and the iodide ions are released

Water from 1

Wash 3 times with

에서 증류되는 분액을 제거한 다음 133Pa하에서 증류한다. 141∼145

에서 비등하는 분액을 수집하고 69∼70

에서 용융하고 오렌지색 고체 형태로 있는 1-(P-펜에티디노)-2-퍼플루오로옥틸에탄 조생성물(순도 : 90%) 210g을 이에 의해 수득한다.Distillation of the organic phase 200Pa 88-92

The aliquot which is distilled at is removed and then distilled under 133 Pa. 141-145

Collect aliquots boiling from 69 to 70

210 g of 1- (P-pentetidino) -2-perfluorooctylethane crude (purity: 90%) is thereby obtained which melts in the form of an orange solid.

에서 7시간동안 가열한다. 냉각시킨 후 오토클레이브에서 생성물을 방출해내어 용융점이 40

인 담밤갈색 형태의 조생성물 1-(N-히드록시에틸-p-펜에티디노)-2-퍼플루오로옥틸에탄 137g(암적색 액체)을 수득한다.(b) 130.7 g of the product was charged in the same autoclave as in Example 13-b, 14 g of ethylene oxide was added, and the contents were 178 to 180.

Heat at 7 hours. After cooling, the product is discharged from the autoclave and the melting point is 40

137 g (dark red liquid) of crude product 1- (N-hydroxyethyl-p-phenetidino) -2-perfluorooctylethane in the form of phosphorus pale brown.

Example 16

반응기에 충진시키고, 그 혼합물을 115∼120

에서 4.5시간 가열한 다음, 5.5시간 150

에서 교반하에 가열한다. 이 물질을 수층이 중성이고 요오다이드 이온이 유리될 때까지 95

에서 10% 수산화나트륨 0.4

로 1회, 65

에서 물 1

로 3회, 데칸테이션 방법으로 세척한다.(a) 287 g of 1-ureo-2-perfluorooctylethane and 184.5 g of o-anisidine

Charged in the reactor, the mixture was 115-120

Heated for 4.5 hours at 5.5 hours 150

Heated under stirring. Keep this material until the water layer is neutral and the iodide ions are released.

10% sodium hydroxide at 0.4

Once, 65

Water from 1

3 times with a decantation method.

에서 용융하는 오렌지색 형태의 생성물 1-(o-아니시디노)-2-퍼플루오로옥틸에탄 240g을 수집한다.Extra o-anisidine is removed by transporting with steam, and the organic layer is removed at 133 Pa, 130 Distill in Purity is more than 97%, 62-63

Collect 240 g of product 1- (o-anisidino) -2-perfluorooctylethane in orange form that melts at.

스테인레스강 오토클레이브에 가입하고 내용물을 178∼180

에서 8시간동안 가열해준다. 에틸렌옥사이드 18g 및 4MPa 질소를 3회 가해주고, 첨가해줄 때마다 교반하에 178∼180

에서 6시간동안 가열해준다.(b) 120.6 g of the product and 17.4 g of ethylene oxide were 0.3 equipped with a PTFE bowl and a magnetic stirrer.

Join stainless steel autoclave and load contents 178-180

Heat for 8 hours at. 18 g of ethylene oxide and 4 MPa nitrogen are added three times, and each time it is added, 178-180 under stirring

Heat for 6 hours at.

로 1시간동안 유지해준 다음, 60

에서 물 100ml로 2회 세척해준다. 약간의 진공하에서 증류하는 분액을 제거해 준 후, 암적색 액체 형태의 조생성물 1-(N-히드록시에틸-o-아니시디노)-2-퍼플루오로옥틸에탄 112g을 수득한다.After cooling and emptying the product in the autoclave, the product was then cooled to 120 at 133 Pa.

For 1 hour, then 60

Wash twice with 100 ml of water. After removing the aliquots under slight vacuum, 112 g of crude 1- (N-hydroxyethyl-o-anisidino) -2-perfluorooctylethane in the form of a dark red liquid are obtained.

Example 17

원추형 플라스크에 가입하고 기름중탕으로 가열해준다.A mixture of amino fluoride C ₈ F ₁₇ CH ₂ CH ₂ -NH-CH ₂ CH ₂ OH and C ₇ F ₁₅ CF = CH-CH ₂ -NH-CH ₂ -CH ₂ OH (67 and 33 mol%, respectively) 57.5 10g and 1,2-epoxyhexane 0.1g with a magnetic stirrer equipped with a condenser

Join the conical flask and heat it in an oil bath.

에서 6시간동안 교반하에 가열해주고, 불화아미노 알코올의 동일한 혼합물 4g을 다시 첨가해주고 내용물을 110

에서 3시간 더 가열해준다.Contents 105-110

Heat under stirring for 6 h at 4 h and add 4 g of the same mixture of amino alcohol fluoride again

Heat 3 hours at

에서 점성력이 있는 하기 일반식의 오렌지색 액체 형태의 화합물의 혼합물 69.5g이 수득된다.40

69.5 g of a mixture of the compounds in the form of an orange liquid of the following general formula which are viscous at

And

Example 18

에서 3.75시간 가열해준다.24.8 g of the same mixture of amino alcohol fluoride and 9.2 g of 1,2-epoxydodecane were added to the same apparatus as in Example 17, and the contents were stirred while stirring.

Heat 3.75 hours at.

에서 점성력이 있으며, 하기 일반식의 아미노디올의 혼합물로 이루어진 오렌지색 액체 33g이 수득된다.40

At viscous power, 33 g of an orange liquid consisting of a mixture of aminodiols of the general formula

And

Example 19

에서 7.75시간동안 가열해준다. 불화아미노알코올 혼합물 3.6g을 다시 첨가한 다음에 내용물을 교반하에 120

에서 2시간동안 더 가열해주고, 4시간 동안 140

에서 가열해준다.26.1 g of the same mixture of amino alcohol fluoride and 14.15 g of 1,2-epoxyoctadecane were added to the same apparatus as in Example 17 and the contents were stirred under 120

Heat 7.75 hours at. 3.6 g of amino alcohol fluoride mixture was added again, and then the contents were stirred.

Heat for 2 hours at 140

Heat at

에서 용융하며 하기 일반식의 아미노디올로 이루어진 밤갈색 고체 생성물이 42g 수득된다.40

42 g of a brownish brown solid product which melted at and consisting of the aminodiol of the general formula

And

Example 20

Amino alcohol fluoride mixed with 21.6 g of 1,2-epoxybutane and the composition weight% of the following straight chain C _n F _{2n + 1} C _n F _{2n + 1} -C ₂ H ₄ -NH-C ₂ H ₄ OH (67 Mole%) and 146.8 g of a mixture of C _n-1 F _2n-1 -CF = CH-CH ₂ -NH-C ₂ H ₄ OH (33 mole%) join the same autoclave as in Example 13-b.

로 먼저 가열하고, 1,2-에폭시부탄 3.2g을 첨가한 다음 그 내용물을 107

에서 4.5시간동안 더 가열해준다.87-88 for 6 hours

First with 3.2 g of 1,2-epoxybutane and then the contents of 107

Heat for 4.5 hours at.

에서 증류되는 분류액을 제거한 다음, 주위온도에서 소량의 침전물을 가지나 30

에서 그 침전이 완전히 용해되는 황색액체 154g이 수득된다. 상기 생성물은 하기 일반식의 아미노디올 혼합물이다.After cooling the product is removed from the autoclave and 133Pa 80

After removing the distillate from distillation at 30 ° C, there is a small amount of precipitate at ambient temperature.

154 g of a yellow liquid are obtained, in which the precipitate is completely dissolved. The product is an aminodiol mixture of the general formula

And

Example 21

원추형 플라스크에 가입하고 기름중탕으로 가열한 다음, 내용물을 120∼125

에서 3시간 동안 가열한다.476 g of a mixture of amino alcohol fluoride as in Example 20 and 184 g of 1,2-epoxydodecane were attached with a condenser and equipped with a magnetic stirrer.

Join the conical flask, heat it in an oil bath, and load the contents from 120 to 125

Heat for 3 hours.

에서는 침전이 용해되며 점성적인 황색 액체 형태의 하기 일반식의 아미노디올 혼합물 651g을 수득한다.At ambient temperature, small amounts of precipitate are formed.

In precipitates are dissolved and yield 651 g of an aminodiol mixture of the general formula in the form of a viscous yellow liquid.

And

Example 22

에서 가열한다. 온도는 자발적으로 134

로 상승한다. 내용물을 113∼115

로 냉각하고 1시간동안 이 온도에서 유지해준다.570 g of the same aminofluoride mixture as in Example 20 and 144.3 g of styrene oxide were charged in the same apparatus as in Example 21, and the contents were stirred under 113 with stirring.

Heat at Temperature spontaneously 134

To rise. Contents 113-115

Cool down and hold at this temperature for 1 hour.

에서는 유동성이 있는 오렌지색 액체 702g이 수득된다. NMR 분석은 상기 생성물이 하기 일반식의 아미노디올을 78몰%의 비율로 함유하고 있음을 보여준다.Very viscous at ambient temperature 40

702 g of a flowable orange liquid are obtained. NMR analysis shows that the product contains aminodiol of the formula of 78 mol%.

And

And the remaining 22 mol% of the product is the aminodiol of the general formula.

And

Example 23

스테인레스강 오토클레이브에 가입하고 오토클레이브 내부를 진공으로 해준다음, 액체 질소로 냉각시키고 퍼를루오로에틸 요오다이드 246g 및 비닐리덴 플루오라이드를 그안에 가입해준다. 내용물을 145

에서 21시간동안 교반하에 가열해준 다음, 비닐리덴 플루오라이드 64g을 다시 가입하고 내용물을 145

에서 21시간 더 가열해준다.(a) 6 g of a mixture consisting of 4.5 g ethanolamine and 1.5 g cuprous chloride.

Join a stainless steel autoclave and vacuum the inside of the autoclave, cool with liquid nitrogen, add 246 g of perluoroethyl iodide and vinylidene fluoride therein. Contents 145

Heated under stirring for 21 hours at, then re-add 64 g of vinylidene fluoride and add the contents to 145.

Heat another 21 hours at.

After cooling and washing the autoclave, a product having the following main components is collected and the GC analysis of the main components is as follows.

에서 비등하는 분액을 수집한다. 화합물 C₂F₅-(CH₂CF₂)₂I 28.6g이 수득된다.The product was distilled under vacuum and 4666 Pa 59

Collect aliquots boiling from 28.6 g of compound C ₂ F _5- (CH ₂ CF ₂ ) ₂ I are obtained.

에서 압력을 2.6MPa로 유지하기 위해 에틸렌을 7시간 동안 주입해준다.(b) 4 g of a mixture consisting of 3 g of ethanolamine and 1 g of cupric chloride, and 374 g of C ₂ F ₅ (CH ₂ CF ₂ ) ₂ I are joined to the same autoclave. 145

Ethylene is injected for 7 hours to keep the pressure at 2.6 MPa.

에서 비등하는 분액을 수집한다. 이 생성물의 무게는 276g이며 54

에서 용융하며, 백색고체인 화합물 C₂F_5-(CH₂CF₂)₂-CH₂CH₂I로 이루어져 있다.Reduce autoclave pressure and wash, then distill product to 70-75

Collect aliquots boiling from This product weighs 276 g and is 54

It melts at and consists of the compound C ₂ F _5- (CH ₂ CF ₂ ) ₂ -CH ₂ CH ₂ I as a white solid.

반응기에 충진해준다. 내용물을 가열환류하고 환류온도에서 7시간동안 유지해준다.(c) 0.25 g of the compound and 100 g of t-amyl alcohol.

Fill the reactor. The contents are heated to reflux and maintained at reflux for 7 hours.

로 1회, 물 3

로 3회 세척해 준 다음 6000Pa 31

에서 증류되는 분액을 제거해준다. 잔류물 무게는 60.8g이며 아미노알코올 C₂F₅(CH₂CF₂)₂C₂H₄NHC₂H₄OH로 되어있다.After cooling, the contents were left to stand and the upper layer collected and decanted at ambient temperature by 10% NaOH solution 0.1

Once with water 3

3 washes with 6000 Pa 31

Remove the aliquots from the distillation. The residue weighs 60.8 g and consists of aminoalcohol C ₂ F ₅ (CH ₂ CF ₂ ) ₂ C ₂ H ₄ NHC ₂ H ₄ OH.

에서 가열해준다. 상기 온도에서 교반을 계속해준 다음, 에틸렌옥사이드 (4.4

/h) 및 질소(0.5

/h)의 혼합물을 대기압하에서 4.5시간동안 버블링에 의해 주입해준다. 적색 페이스트 형태의 아미노디올 C₂F₅(CH₂CF₂)₂-C₂H₄-N(C₂H₄OH)₂조생성물 72g이 이에 의해 수득된다.(d) 64 g of the amino alcohol were added to the same apparatus as in Example 17 and 65 was stirred.

Heat at Stirring was continued at this temperature, followed by ethylene oxide (4.4

/ h) and nitrogen (0.5)

/ h) is injected by bubbling for 4.5 hours under atmospheric pressure. 72 g of aminodiol C ₂ F ₅ (CH ₂ CF ₂ ) ₂ -C ₂ H ₄ -N (C ₂ H ₄ OH) ₂ crude product in the form of a red paste are thereby obtained.

Example 24

Under constant stirring at ambient temperature, 4.7 g of heptanoyl chloride was added dropwise to 100 ml of acetone in a solution of 12 g of aminodiol and 3.2 g of triethylamine of the previous example. After the dropwise addition of heptanoyl chloride is complete, the contents are heated at reflux for 2 hours, then cooled and the triethylamine hydrochloride is filtered and the solvent is distilled off under reduced pressure to evaporate. The residue is redissolved in ethyl ether, and then the solution is filtered to remove the remaining triethylamine hydrochloride precipitate until the end. To the evaporation of the ether, and then by the IR spectroscopy that the structure is determined is obtained is an ester of the general formula (OH absorption band, in the ester absorption band at 1735cm ^-1 3360cm ^-1). Yield: 98%

Example 25

The reaction is carried out as in Example 24, replacing heptanoyl chloride with 4.45 g of benzoyl chloride. To the by the IR spectroscopy that the structure is determined by the esters of formula are obtained (OH absorption band, in the ester absorption band at 1710cm ^-1 3330cm ^-1).

Example 26

에서 3시간동안 가열해준다. 1,2-에폭시도데칸 18g을 다시 첨가해준 다음 내용물을 100

에서 6시간동안 가열해주고, 3-퍼플루오로옥틸프로필아민 3.8g을 다시 첨가해준 다음 110

에서 5시간동안 계속 가열해준다.48.2 g of 3-perfluorooctylpropylamine and 18.5 g of 1,2-epoxydodecane were added to the same apparatus as in Example 17 and 80 to 90 under stirring

Heat for 3 hours at. Add 18g of 1,2-epoxydodecane and add 100

Heat for 6 hours, and add 3.8 g of 3-perfluorooctylpropylamine again

Keep heating at for 5 hours.

에서 용융하는 하기 아미노디올 87g이 수득된다.40 in light beige solid form

87 g of the following aminodiol are obtained that melt at.

[Abrasion Resistance Test]

Wear resistance of lubricating compositions containing mineral oil Neutral Solvent 200 as a base oil and a fluorinated compound according to the invention as an additive is measured on a SHELL EP 4-ball machine, which method Is described in "Annual Book of ASTM Standrds", Part 24, p680-688 (1979).

This test is carried out on 12 mm diameter spheres rotating at 1500 rpm on three different spheres fixed and lubricated during the test. A load of 40 or 70 daN is hung by a lever device that pushes three stationary spheres towards the upper sphere located on the shaft.

The wear resistance of the lubricant is determined by the average value of the worn diameters on the three fixed spheres after one hour of operation.

The results obtained by the different fluorinating additives according to the present invention are listed together in Table I, the additives are classified in the form of Fx, and x is the number of the example for explaining the method of preparing the fluorinating additive. The weight ratio of the fluorinated additives contained in the base oil is recorded in the second column.

TABLE I

Abrasion resistance efficiency diagram of the lubricating composition obtained by adding a commercially available main additive which forms a part of the lubricating oil composition of the SAE15W40 standard for petrol engines except mineral oil 200N, ie, zinc dithiophosphate substituted with a fluorinated compound according to the present invention. It is determined by the same method. Common main additives for SAE15W40 oils include detergents (large bases with sulfate added), dispersions (succinimides) and antioxidants (aromatic amines). The results of this test are summarized in Table II below.

TABLE II

The same method is used to study the wear resistance of the lubricating composition to which zinc dithiophosphate and the fluorinated derivative according to the present invention are bound, and the concentrations of zinc, phosphorus and sulfur are lower than those of commercial lubricating oils.

The results obtained in Table III are listed below, where additive A is a dialkyldithiophosphate as a wear resistant additive and additive B is zincalkylaryldithiophosphate as an antioxidant.

TABLE III

The results show that the fluorinating additive according to the present invention can be combined with zinc dithiophosphate to give a composition containing low concentrations of zinc with remarkable wear resistance.

As for the wear resistance of the fluorinated compounds according to the invention, the FALEX device and zinc dithiophosphate described in "ASTM Standard Yearbook," part 24, p. 594-601 (1978), are also substituted with the fluorinated compounds according to the invention. Test with type SAE15W40 lubricant. The load of 250 kg was applied for 3 hours, and the rupture or weight loss (wear) of the apparatus was recorded. The results obtained are listed in Table IV below.

TABLE IV

[Engine Bench Test]

Two mixed SAE15W40 type petrol engine oils of the fluorinated compounds according to the present invention were tested on an engine bench compared to commercially available lubricating oils containing zincdialkyldithiophosphate (abrasion resistant additive commonly used in engine oils). .

Control oil (O ₁ ) is a commercial lubricating oil that contains, in addition to zincdialkyldithiophosphate, other conventional additives (cleaning agents, dispersants, antioxidants, viscosity enhancers and coagulants) that form part of the lubricating composition.

Oils by the invention (O ₂₎ and the oil (O ₃₎ is a zinc dialkyl dithio phosphate oil (O ₂₎ In the 0.3% compound F13 and oils (O ₃₎ in only one point substituted by 0.3% of compound F1 Different from the control oil (O ₁ ).

This test is carried out under the following conditions.

Engine: RENAULT 20TS with cylinder volume 2000 cm3, engine power 81 kW and normal engine speed 5600 rpm, type 829/7

Operating time: 10 hours

Test cycle (after operation): 100 hours without oil change

Output: full load

After periodic inspection of the lubricant and inspection of the coolant temperature (inlet and outlet), the engine section was analyzed and graded according to European standard MO2A78. The results are listed in the table below.

TABLE V

[Thermal Stability Test]

/h의 기류에서 생성물 시료의 온도를 증가시키고(2

/분), 200

, 250

및 300

에서의 무게 손실을 기록함으로써 수행된다.In order to evaluate the lubricating oil characteristics under similar conditions as the engine, the fluorinated compounds according to the present invention are thermogravimetrically analyzed in the atmosphere. This test is 10

increase the temperature of the product sample at an airflow of / h (2

/ Min), 200

, 250

And 300

This is done by recording the weight loss at.

The results obtained are shown in the table below. The properties of the following fluorinated compounds recommended in the prior art (French Patent No. 2,520,377) are listed at the beginning of Table VI for comparison.

(n: same as defined in Example 2 above)

Table VI

Claims (4)

Polyfluorine compounds of the general formula:

Wherein Rf is a perfluororadical, a is an integer from 0 to 10, b is 0 or 1, but at the same time can be 1 only when a is 0 and c is 1, and c is an integer between 1 and 4, , a is 2 if the number other than 0, Y is a 2-hydroxy-1-phenylethyl group, R ₁ and R ₁ ′ may be the same or different, each of a hydrogen atom, alkyl containing 1 to 20 carbon atoms Radicals, cycloalkyl radicals containing 5 or 6 carbon atoms, or optionally substituted aryl radicals, R ₂ and R ₂ ′ may be the same or different and each is an acyl of a hydrogen atom or an aliphatic, cycloaliphatic or aromatic carboxylic acid If the residue is and a + m + n is zero, then one of the symbols R ₁ and R ₂ is a radical other than hydrogen or methyl radical, and m and n are each 0 or 1. The polyfluoro compound according to claim 1, wherein Rf is a perfluoroalkyl radical containing 2 to 20 carbon atoms of straight or branched chain. The polyfluoro compound according to claim 1 or 2, wherein the polyfluorine compound is represented by the following general formula.

Wherein Rf is a perfluoro radical, the sum of (b + c) is 2 and R ₁ "is a hydrogen atom or methyl radical, and R ₃ is an aliphatic, alicyclic, or aromatic radical. The polyfluoro compound according to claim 1 or 2, wherein the polyfluoro compound is of the general formula:

Wherein Rf is perfluororadical, (b + c) is 2 and R ₁ ″ is an alkyl radical containing 2 to 16 even carbon atoms.