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Lubricant additives comprising sulphurised terpenes
专利摘要

The invention comprises the product obtained by heating a sulphurized terpene or a mixture of sulphurized terpenes, formed by reacting a terpene or a mixture of terpenes and sulphur, with elemental phosphorus, e.g. red phosphorus. The terpene may be a monocyclic terpene-preferably commercial dipentene-or a dicyclic terpene, e.g. alphapinene. The sulphurized terpene may be prepared by heating the terpene with an amount ranging from 1.5 to 2 atoms of elemental sulphur per mol. of terpene, e.g. at a temperature of 135 DEG to 200 DEG C. The sulphurization step is preferably carried out in the presence of a rubber vulcanization inhibitor, e.g. tetramethyl thiuram disulphide, a mercapto-benzthiazole or diphenyl guanidine. The sulphurized terpene product is preferably stripped of its more volatile portions by steam distillation either prior to or after heating with elemental phosphorus. The amount of phorphorus used may vary between 1 and 10 per cent by weight based on the weight of sulphurized terpene. A suitable temperature for reaction with the phosphorus is 110 DEG to 200 DEG C., preferably 125 DEG to 175 DEG C., and the heating may be for a period from 1 to 8 hours particularly 2 to 5 hours. The final product can be purified by dissolving it in a suitable volatile solvent, removing unreacted phosphorus by filtration and then recovering the product from the solvent, e.g. by vacuum distillation. In the examples sulphurized dipentene is reacted with phosphorus. Specification 688,293 is referred to.ALSO:A composition containing a lubricating oil and a minor proportion of the product obtained by heating a sulphurized terpene or a mixture of sulphurized terpenes formed by reacting a terpene or a mixture of terpenes and sulphur, with elemental phosphorus. The amount of product used is preferably less than 5 per cent and particularly less than 1 per cent based on the weight of lubricating oil. The terpene may be a monocyclic terpene-preferably commercial dipentene or a dicyclic terpene, e.g. alphapinene. Suitable lubricating oils are mineral oils or synthetic ester type oils, e.g. adipates or sebacates of alcohols in the C7 to C10 range or esters prepared from glycols or polyglycols, aliphatic dibasic acids and monohydric alcohols or monobasic acids as chain terminators. In the examples compositions are prepared by adding the product obtained by heating sulphurized dipentene with phosphorus to a synthetic type of aviation lubricant and to mineral oil which may also contain the barium salt of p-iso-octyl phenol sulphide and calcium mahogany sulphonates. Specification 688,293 is referred to. ......

基本信息
  • 专利类型:

    发明专利

  • 申请/专利号:

    GB1952011530

  • 申请日期:

    1952-05-07

  • 专利申请人:

    埃克森研究工程公司

  • 分类号:

    ["C10M159/00","C10M159/12","C07G99/00"]

  • 发明/设计人:

    TYSON, JOHN, TYSON ， LOWENSTEIN-LOM, WALTER, GERALD

  • 权利要求: What we claim is:-1 The product obtained by heating a sulphurised terpene or mixture of sulphurised terpenes formed by reacting a terpene or a mixture of terpenes and sulphur, with elemental phosphorus.2 The product according to Claim 1 wherein the elemental phosphorus is red phosphorus.3 The product according to Claim 1 or Claim 2 wherein the sulphurised terpene is a monocyclic terpene preferably commercial dipentene.4 The product according to any of Claims I to 3 wherein the sulphurised terpene is prepared by heating the terpene with an amount ranging from 1 5 to 2 atoms of elemental 4.25 17.1 3 2.5 18.2 3 3.75 20.9 3 3 16.2 1.76 0 06 0 13 0 32 sulphur per mole of terpene.The product according to any of Claims 1 to 4 wherein the sulphurised terpene is prepared in the presence of a rubber vulcanisation inhibitor preferably a mercaptobenzthiazole.6 The product according to any of Claims 1 to 5 wherein the sulphurised terpene is sulphurised at a temperature of 135-200 C.7 The product according to any of Claims 1 to 6 wherein the sulphurised terpene or product is stripped of its more volatile portions by steam distillation, either prior to or after heating with elemental phosphorus.8 The product according to any of Claims 1 to 7 wherein the sulphurised terpene is heated with between 1 and 10 % by weight, based on the sulphurised terpene, of elemental phosphorus.9 The product according to any of Claims 1 to 8 wherein the sulphurised terpene is heated with elemental phosphorus at a temperature of 110 to 2000 C, preferably 1250 to 1750 C, preferably for a period from 1 to 8 hours, particularly 2 to 5 hours.The product according to any of Claims 1 to 9 wherein the product is dissolved in a suitable volatile solvent, and the unreacted phosphorus is removed by filtration and the product recovered from the solvent, e g, by vacuum distillation.11 A lubricating composition comprising a lubricating oil and a minor proportion, preferably less than 5,% and particularly less than 1 % based on the weight of lubricating oil, of the product of any of Claims 1 to 10.J T TYSON, 33, Davies Street, London, W 1, Agent for the Applicants.PROVISIONAL SPECIFICATION Lubricant Additives comprising Sulphurised Terpenes We, STANDARD OIL DEVELOPMENT COMPANY, a Corporation duly organised and existing under the laws of the State of Delaware, United States of America, of Elizabeth, New Jersey, United States of America, do hereby declare this invention to be described in the following statement:The present invention relates to lubricating oil additives and is concerned primarily with materials having antioxidant properties and obtained by sulphurising terpenes In particular it relates to an after-treatment of the materials obtained by sulphurising monocyclic terpenes by heating with elemental sulphur.The sulphurisation of terpenes by heating with elemental sulphur and the use of the reaction product as an additive for lubricating oils, especially those designed for crankcase use, is well known While all classes of terpenes have been proposed, in practice interest has Batch No.centred round the monocyclic terpenes represented by -dipentene (cl 1-limonene).Commercial dipentene of indeterminate composition and of vegetable origin is commonly employed, and apart from the fact that there is some p-cymene produced during the sulComponent Low boiling material (unidentified) Alpha-pinene -Beta-pinene p-menthane Alpha-terpincol p-cymene Dipentene Terpinolene Fenchone W 24 ( 8) paramenthadiene High boiling material (unidentified) From this it will be seen that commercially the name dipentene is applied to widely varying mixtures In general these contain from 65 30 %o of dipentene with from 5-60 % of terpinolene the residue consisting predominantly of p-cymene and p-menthane Furthermore Simonsen in " The Terpenes " Volume 1, 1947 at page 151 quotes Escourron in saying the dipentene is always a mixture of isomeric monocyclic terpenes, a specimen examined by him containing 80 % cl 1-limonene, 12 % terpinolene and 8 % alpha-terpinene.rhe sulphurisation reaction is normally carried out by heating the terpene with elemental sulphur at a temperature from 13500 C and in an amount ranging from 1 5 to 2 atoms of sulphur per mole of terpene.Preferably there is also present a small amount of an accelerator of the type used as a rubber vulcanisation accelerator Examples are tetramethyl thiuram disulphide, mercaptobenzthiazole and diphenyl guanidine The reaction takes place readily and is exothermic, the product being an oily material normally of a reddish brown colour.In the course of the reaction there is a copious evolution of hydrogen sulphide, especially when a vulcanisation accelerator is employed, and even after this H S has been removed, e g, by blowing with an inert gas, the product still contains loosely bound or corrosive sulphur, as is shown by immersing a bright copper strip in it, when the strip is rapidly stained black by the formation of copper sulphide This effect may be reduced for example by washing with strong caustic alkali.The removal of the more volatile portions of the reaction product by steam distillation as set out in Specification 688,293, is preferred phurisation, the chemistry of the reaction is obscure As in illustration of the variability of the raw material the analyses of two typical commercial dipentenes of United States 10 origin are given below.Sample A % by weight 2.6 2.4 13.7 5.2 17.4 50.5 5.2 1.0 2.0 Sample B % byweight 7 31 2 in order to increase its antioxidant and bearing-corrosion inhibition properties.The product is somewhat corrosive to silver and its antioxidant properties are not outstanding at high temperatures, e g, of the order of 2500 C.It has now been found according to the present invention that these properties may be markedly improved by heating the sulphurised product with elemental phosphorus For obvious reasons of safety, red phosphorus is the preferred form.While no theory is advanced as to the mechanism of the reaction which occurs when the sulphurised terpene is heated with phosphorus, it appears that the finished product contains phosphorus in combined form and not in solution The solubility of the products vary with different treating procedures Some products have only slight solubility in mineral oils but have excellent solubility in synthetic ester type lubricants Synthetic esters which may be illustrated by the adipates and sebacates of alcohols in the C 7 to C 1, range, and by complex esters prepared from glycols or polyglycols, aliphatic dibasic acids and monohydric alcohols or monobasic acids as chain terminators are an extremely important class of lubricant especially for use in aviation engines operating at extremely high temperatures.In general amounts of phosphorus between 1 and 10 % by weight based on the sulphurised terpene are found satisfactory, the lower proportions being used when the additive is intended for use in a mineral oil and the higher proportions when intended for use in a synthetic lubricant of ester or polyglycol ether type Suitable temperatures range from about to 200 ' C, with 1250 to 175 C being 735,231 trate the invention further.EXAMPLE 1.A batch of steam-stripped sulphurised dipentene, prepared as described in Specification 688,293 was heated for 2 hours at 150 C with 8 % by weight of red phosphorus The product was dissolved in benzol, filtered and vacuum distilled to remove the solvent The resultant bottoms material contained 27 % of sulphur and 4 8 % of phosphorus by weight.It was sparingly soluble in mineral oil but readily soluble in a commercially available synthetic ester type of aviation lubricant The phosphorised additive and the original sulphurised dipentene were tested for antioxidant potency in 0 4 % concentration in this lubricant by heating the lubricant in a beaker at 2500 C for six hours in the presence of a bronze cage-steel ball ball race, and the measuring the viscosity increase of the lubricant at 21 G 01 C and 1000 C at the end of the test In the case of the phosphorised additive the increases were 100 % and 175 % respectively while for the plain sulphurised additive the increase at 2100 C was 1400 %, while at 1000 C the lubricant was a solid gel.EXAMPLE 2.A further series of preparations was carried out using as the starting material a batch of sulphurised dipentene which had not been steam-stripped Four batches were prepared as indicated below The sulphur content of the starting material was 21 5 %.1 2 3 4.preferred The reaction time may vary from 1 to 8 hours with a preferred range of about 2 to 5, the longer times corresponding to lower temperatures and vice versa While it is not necessary to use a solvent during the reaction, it has been found advantageous to dissolve the phosphorised product in a suitable volatile solvent, e g, benzol or white spirit and then to filter off the unreacted phosphorus, the solvent then being stripped off, e g, by vacuum distillation.As pointed out earlier, the properties of the crude sulphurised terpene are improved by removal of the more volatile fractions by steam distillation as set forth in Specification 688,293 The conditions for this are not unduly critical and the operation may be carried out at say 115-120 ' C until substantially all of the steam volatile material has been re2 Q moved overhead In practice this will normally amount to between 15 and 30 % of the crude product.It has been found that the stage at which the after-phosporisation of the present invention is carried out out has a marked influence on the solubility characteristics of the product If it is carried out before steam-stripping the finished material is still adequately soluble in mineral oils, whereas treatment of the steam-stripped sulphurised product tends to give a product of low mineral oil solubility, but good solubility in synthetic oils of the type referred to.The following Examples will serve to illusBatch No.% red phosphorus used Average temperature O C.Reaction time, hours % sulphur in product % phosphorus in product In all cases the resultant products were freely soluble in mineral oils and when tested in 0 66 % concentration in a mineral lubricating oil albo containing 4 84 % of a detergent additive consisting of a 2 1 blend of the barium salt of isooctyl phenol sulphide and calcium mahogany sulphonates showed silver corrosions ranging from one quarter to one half of those given by the non-phosphorised additive in a similar blend.While the process of the invention has been described with reference to the aftertreatment of sulphurised monocyclic terpenes 4.25 17.1 1.76 3 2.5 18.2 0.06 3 3.75 20.9 0.13 3 3 16.2 0.32 especially dipentene, having a sulphur content of 20-30 % by weight, it is also applicable to other sulphurised terpenes such as the dicyclic terpenes which may be exemplified by alphapinene Also it is within the scope of the invention to phosphorise the terpene before treatment with sulphur, although the aftertreatment is much preferred.J T TYSON, Brettenham House, (Sixth Floor South), Lancaster Place, London, W C 2, Agent for the Applicants.Leamington Spa: Printed for Her Majesty's Stationery Office, by the Courier Press -1955.Published at The Patent Office, 25, Southampton Buildings, London, W C 2, from which copies may be obtained./N.s O 735,231
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