US4954274.docx

1、US4954274United States Patent 19Zaweski et al.!l451Patent Number:Date of Patent:4,954,274Sep. 4, 199021(22SULFURIZED OLEFIN EXTREMEPRESSURE ADDITIVESInventors: Edward F, Zaweski, 12260 Brookshire Ave., Baton Rouge, La, 70815; James G. Jolly, 5233 Halls Ferry Dr., Baton Rouge, La. 70817Appl. No.: 363

2、,443Filed: Jun. 6, 19894,204,969 5/1980 Papay et al. .252/454,225,488 9/1980 Horodysky et al.252/454,240,958 12/1980 Braid .一252/454,563,302 1/1986 Griffin et al. . 252!454,645,610 2/1987 Born et al. 252/454,710,273 12/1987 Okamoto .二.一.568/1846尸J7Primary Examiner-William R. Dixon, Jr.Assistant Exam

3、iner-Jerry D. Johnson Related U.S. Application Data63 Continuation of Ser. No. 138,937, Dec. 29, 1987, aban- doned.玩t. C!.5U.S. C!.C10M 135/02252/45; 252/48.8;Field of Search Re 568/18252/45, 48.8; 568/18ferences Cited们J刀8司尸、尺曰尸、尸、一.L l.L l.L l.L U.2,565,493S. PATENT DOCUMENTS8/19513,410,800 11/1968

4、3,697,499 10/1972Gardner.一一一:.，.252/45Ford et a1. . 252/48.8Myers一. 252/48.8Is aBScrSulfurized olefins are produced by reacting sulfurmonochloride with a monoolefm (e.g. isobutene) in thepresence of minor amounts of an active Lewis acid (e.g.ferric chloride) to form an adduct, reacting the adductwit

5、h sulfur and sodium sulfide in an aqueous alkanolmade at a ratio of 0.02-0.4 gram atom of sulfur per grammole of sodium sulfide and then recovering the reactionproduct. Olefin polysulfides obtained by this methodare soluble in both mineral and synthetic lubricating oils(including those of the polyal

6、phaolefin type) and areusable as extreme pressure additives when incorporatedinto such lubricating oils.Sulfurized烯烃反应产生的硫方法用monoolefm(例如isobutene)较小的数量存在一个活跃的路易斯酸(例句。氯化铁)形成一个adduct,反应adduct的用硫和钠硫化物在水alkanol在比例为0.02 -0.4克每克的硫原子鼹鼠的钠硫化物,然后恢复的反应产品。烯烃polysulfides得到这个方法两个都是溶于油和合成润滑油矿物吗16 Claims, No Drawi

7、ngs4,954,2741SULFURIZED OLEFIN EXTREME PRESSURE ADDITIVES This application is a continuation of application Ser.No. 138,937, filed Dec. 29, 1987 now abandoned. BACKGROUND OF THE INVENTION This invention relates to sulfurized olefins and, in 2 In accordance with the invention, the starting olefins ar

8、e the monoethylenically unsaturated aliphatic hydro- carbons referred to as aliphatic monoolefins containing 3 to about 6 carbon atoms. These include 1-butene,5 2-butene, isobutene, 1-pentene, 2-pentene, 2-methyl-l- butene, 3-methyl-l-butene, 2-methyl-2-butene, 1-hex- ene, 2-hexene, 3-hexene, 2-meth

9、yl-lpentene, 2-methyl- 2-pentene, 2-ethyl-2-butene and the like including mix- tures thereof.particular, to polysulfurized olefins used in lubricating 10 Preferably, the olefins are branched-chain olefinsoil compositions and to a method for preparing same. such as isobutene, 2-methyl小butene, 2-methy

10、l-2- Sulfurized olefins are used in lubricants such as crank- butene, 2-methyl-2pentene, and the like. More prefera-case oil and gear lubricants to provide extreme pressure bly, the ethylenic double bond adjoins a tertiary carbonproperties. atom such as isobutylene, the most preferred olefin Papay e

11、t al, U.S. Pat. No. 4,204,969 describes such a 15 The first stage reaction is preferably conducted byproduct in which sulfur monochloride is reacted with adding the olefin to the sulfur monochloride. The olefinan aliphatic monoolefin to obtain an intermediate which can be added as a gas or liquid. P

12、referably, it is addedis reacted with sulfur and sodium sulfide. beneath the surface of the sulfur monochloride as a One problem in the field of sulfurized olefin additives liquid.used for improving the extreme pressure properties of 20 In practice, the olefin is added until the reaction withlubrica

13、nts continues to be the development of a sulfu- the sulfur monochloride stops as indicated by loss ofrized polyolefin additive which is sufficiently soluble in exotherm. An amount of about 0.45-1.5 gram moles ofboth mineral oils and synthetic oils (particularly those olefin for each 0.3-0.75 gram mo

14、le of sulfur monochlo-of the polyalphaolefin type) to be usable as extreme ride usually suffices. A preferred amount is aboutpressure additives. 25 1.7-2.0 gram moles of olefin per gram mole of sulfur This problem is addressed in Born et al, U.S. Pat. No. monochloride.4,645,610 which teaches that th

15、e solubility of such ole- As stated hereinabove, the reaction of the olefin andfin polysulfide additives in both mineral and synthetic the sulfur monochloride is carried out in the presence ofoils is inversely proportional to the sulfur content of the minor amounts of an active Lewis acid. The Lewis

16、 acidadditive. That is, as the sulfur content of the additive 30 can be added to the sulfur monochloride initially, addedincreases the solubility of the additive in both mineral to the reaction mixture continuously or periodicallyand synthetic oils (particularly those of the polyal- during the cours

17、e of the olefin addition, or it can bephaolefin type) decreases. Reportedly, olefin polysul- mixed with the olefin and added together with the ole-fide additives of high sulfur content having enhanced fm. The preferred mode of addition is to add the entiresolubility in both mineral and synthetic oil

18、s can be ob- 35 amount initially to the sulfur monochloride and thentamed according to Born et al by contacting an addition add the olefin.product produced by the reaction of at least one ali- The term active Lewis acid refers to any Lewis acidphatic monoolefin containing 2 to 5 carbon atoms and or

19、electron acceptor which when utilized in accordancesulfur monochloride or dichloride with a hydrocarbyl with the teachings set forth herein produces an adducthalide and at least one sulfur compound selected from 40 which, after sulfurization, affords a lubricant additivesulfides, hydrosulfides and p

20、olysulfides of alkali metals, possessing sufficient solubility in either mineral or syn-ammonium or alkaline-earth metals and usually elemen- thetic oils (especially those of the polyalphaolefin type)tal sulfur in an aqueous or aqueous alcoholic medium at to function as an extreme pressure additive

21、in such oils.certain reaction conditions. Examples of Lewis acids which can be used in the prac- Griffin et al, U.S. Pat. No. 4,563,302 also reports that 45 tice of the invention include aluminum bromide, alumi-sulfurized olefins having improved solubility in lubri- num fluoride, boron trifluoride,

22、boron trichloride, stan-Gating oils (especially in alpha-olefin oligomer synthetic nic chloride, titanium tetrachloride, ferric chloride,oils) can be obtained by reacting an alkyl mercaptan, ferric bromide, aluminum chloride, and the like. Ferricsulfur, sodium sulfide and, optionally, sodium hydrosu

23、l- chloride is the preferred Lewis acid for use in the prac-fide in an aqueous alcohol medium with an adduct pre- 50 tice of the present invention and is readily availablepared by reacting a monoolefin with sulfur monochlo- commercially.ride or sulfur dichloride. The amount of Lewis acid used in the

24、 practice of the _invention is an amount which will produce olefin polv- 一一一-一-一一一-一sutnaes of sutnctent somoutty m mmerat ana syntneuc Unexpectedly, it has now been discovered that sulfu- 55 oils that they can be used in such oils as effective ex-rized olefinic compounds which are soluble in both t

25、reme pressure additives. The amount may vary withmineral and synthetic oils of lubricating viscosity at the specific Lewis acid used. The amount required isconcentrations sufficient to improve the extreme pres- readily determined experimentally by adding the partic-sure properties of such oils (incl

26、uding those of the pp- ular Lewis acid selected for use in the preparation of thelyalphaolefin type) can be obtained by reacting sulfur 60 adduct to the reaction mixture of sulfur monochloridemonochloride with aliphatic monoolefin in the presence and monoolefin until an adduct is produced, which, as

27、of minor amounts of an active Lewis acid and thereafter indicated previously, after sulfurization affords an addi-reacting the adduct so produced with sulfur and sodium tive possessing the desired solubility and extreme pres-sulfide in aqueous alkanol. The adduct, produced in this sure properties bo

28、th in mineral and synthetic oils.fashion, after sulfurization affords a lubricant additive 65 In general, minor amounts which can vary fromsufficiently soluble in both mineral and synthetic oils to about 0.025 percent to about 5.0 percent by weight ofbe usable as an extreme pressure additive in eith

29、er type Lewis acid based on the weight of sulfur monochlorideof lubricant. are used in the invention. A preferred amount is from34,954,2744about 0.05 percent to about 3.0 percent by weight. Themost preferred is about 0.1 percent by weight. The first stage reaction can be conducted at any tem-peratur

30、e high enough to cause the reaction to proceed,but not so high as to cause decomposition of the reac- tams or products. A useful range is about 300-1000 C. Amore preferred range is about 400-750 C. and a mostpreferred range is about 500-600 C. The first stage reaction should be conducted for atime s

31、ufficient to complete the reaction between the sulfur monochloride and olefin. This is usually limitedby heat removal. Olefin feed rate is preferably con-trolled to hold the temperature within the desiredrange. When the sulfur monochloride has been con-sumed, the temperature will drop. External heat may be added to continue the reaction for a further time, butthis does not appear to be necessary. The overall ti