US3254063A - Process for preparation of pour depressants - Google Patents

Process for preparation of pour depressants Download PDF

Info

Publication number
US3254063A
US3254063A US164248A US16424862A US3254063A US 3254063 A US3254063 A US 3254063A US 164248 A US164248 A US 164248A US 16424862 A US16424862 A US 16424862A US 3254063 A US3254063 A US 3254063A
Authority
US
United States
Prior art keywords
range
vinyl acetate
concentration
ethylene
monomer
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
US164248A
Inventor
Ilnyckyj Stephen
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
ExxonMobil Technology and Engineering Co
Original Assignee
Exxon Research and Engineering Co
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority to NL259743D priority Critical patent/NL259743A/xx
Priority to NL130129D priority patent/NL130129C/xx
Priority to BE598930D priority patent/BE598930A/xx
Priority to US593A priority patent/US3131168A/en
Priority to GB39/61A priority patent/GB915890A/en
Priority to FR848812A priority patent/FR1286696A/en
Application filed by Exxon Research and Engineering Co filed Critical Exxon Research and Engineering Co
Priority to US164248A priority patent/US3254063A/en
Priority to GB47962/62A priority patent/GB992817A/en
Application granted granted Critical
Publication of US3254063A publication Critical patent/US3254063A/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M145/00—Lubricating compositions characterised by the additive being a macromolecular compound containing oxygen
    • C10M145/02—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M145/06—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to an acyloxy radical of a saturated carboxylic or carbonic acid
    • C10M145/08—Vinyl esters of a saturated carboxylic or carbonic acid
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/10—Liquid carbonaceous fuels containing additives
    • C10L1/14—Organic compounds
    • C10L1/18—Organic compounds containing oxygen
    • C10L1/192—Macromolecular compounds
    • C10L1/195—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
    • C10L1/1955—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds homo- or copolymers of compounds having one or more unsaturated aliphatic radicals each having one carbon bond to carbon double bond, and at least one being terminated by an alcohol, ether, aldehyde, ketonic, ketal, acetal radical
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/10—Liquid carbonaceous fuels containing additives
    • C10L1/14—Organic compounds
    • C10L1/18—Organic compounds containing oxygen
    • C10L1/192—Macromolecular compounds
    • C10L1/195—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
    • C10L1/196—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds derived from monomers containing a carbon-to-carbon unsaturated bond and a carboxyl group or salts, anhydrides or esters thereof homo- or copolymers of compounds having one or more unsaturated aliphatic radicals each having one carbon bond to carbon double bond, and at least one being terminated by a carboxyl radical or of salts, anhydrides or esters thereof
    • C10L1/1963—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds derived from monomers containing a carbon-to-carbon unsaturated bond and a carboxyl group or salts, anhydrides or esters thereof homo- or copolymers of compounds having one or more unsaturated aliphatic radicals each having one carbon bond to carbon double bond, and at least one being terminated by a carboxyl radical or of salts, anhydrides or esters thereof mono-carboxylic
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/10—Liquid carbonaceous fuels containing additives
    • C10L1/14—Organic compounds
    • C10L1/18—Organic compounds containing oxygen
    • C10L1/192—Macromolecular compounds
    • C10L1/195—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
    • C10L1/197—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds derived from monomers containing a carbon-to-carbon unsaturated bond and an acyloxy group of a saturated carboxylic or carbonic acid
    • C10L1/1973—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds derived from monomers containing a carbon-to-carbon unsaturated bond and an acyloxy group of a saturated carboxylic or carbonic acid mono-carboxylic
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/10—Liquid carbonaceous fuels containing additives
    • C10L1/14—Organic compounds
    • C10L1/22—Organic compounds containing nitrogen
    • C10L1/234—Macromolecular compounds
    • C10L1/236—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds derivatives thereof
    • C10L1/2362—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds derivatives thereof homo- or copolymers derived from unsaturated compounds containing nitrile groups
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2209/00—Organic macromolecular compounds containing oxygen as ingredients in lubricant compositions
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2209/00—Organic macromolecular compounds containing oxygen as ingredients in lubricant compositions
    • C10M2209/02—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2209/00—Organic macromolecular compounds containing oxygen as ingredients in lubricant compositions
    • C10M2209/02—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M2209/04—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to an alcohol or ester thereof; bound to an aldehyde, ketonic, ether, ketal or acetal radical
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2209/00—Organic macromolecular compounds containing oxygen as ingredients in lubricant compositions
    • C10M2209/02—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M2209/06—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to an acyloxy radical of saturated carboxylic or carbonic acid
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2209/00—Organic macromolecular compounds containing oxygen as ingredients in lubricant compositions
    • C10M2209/02—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M2209/06—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to an acyloxy radical of saturated carboxylic or carbonic acid
    • C10M2209/062—Vinyl esters of saturated carboxylic or carbonic acids, e.g. vinyl acetate
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2209/00—Organic macromolecular compounds containing oxygen as ingredients in lubricant compositions
    • C10M2209/02—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M2209/08—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to a carboxyl radical, e.g. acrylate type
    • C10M2209/084—Acrylate; Methacrylate
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2209/00—Organic macromolecular compounds containing oxygen as ingredients in lubricant compositions
    • C10M2209/10—Macromolecular compoundss obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2217/00—Organic macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2217/02—Macromolecular compounds obtained from nitrogen containing monomers by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M2217/026—Macromolecular compounds obtained from nitrogen containing monomers by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to a nitrile group
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F02—COMBUSTION ENGINES; HOT-GAS OR COMBUSTION-PRODUCT ENGINE PLANTS
    • F02B—INTERNAL-COMBUSTION PISTON ENGINES; COMBUSTION ENGINES IN GENERAL
    • F02B47/00—Methods of operating engines involving adding non-fuel substances or anti-knock agents to combustion air, fuel, or fuel-air mixtures of engines

Description

May 31, 1966 s. ILNYCKYJ PROCESS FOR PREPARATION OF FOUR DEPRESSANTS Filed Jan. 4, 1962 Inventor Stephan llnyckyj By ()1 7 W Patent Attorney United States Patent 3,254,063 PROCESS FOR PREPARATION OF POUR DEPRESSANTS Stephen Ilnyckyj, Sarnia, Ontario, Canada, assignor to Esso Research and Engineering Company, a corporation of Delaware Filed .lan. 4, 1962, Ser. No. 164,248 11 Claims. (Cl. 260-873) The present invention is concerned with the manufacture of improved pour depressants, particularly for use with middle distillates. The pour depressant of the present invention comprises copolymers of ethylene with up to about 50% by weight of an olefinically unsaturated aliphatic monomer containing from about 3 to 5 carbon atoms per molecule. The copolymers of a particular average molecular weight are obtained by controlling the conditions of reaction. The preferred copolymer of the present invention is a particular copolymer of ethylene and vinyl acetate.
The present application is a continuation-in-part of Ser. No. 1,838 filed Ian. 5, 1960, US. Patent No. 3,093,623 entitled Process for the Manufacture of Improved Pour Depressants for Middle Distillates, Inventor Stephan Ilnyckyj, which in turn is a continuation-impart of Ser. No. 835,587 filed Aug. 24, 1959, now abandoned entitled Process for the Manufacture of Improved Pour Depres-' sants for Middle Distillates, Inventor, Stephan Ilnyckyj.
In accordance with the present invention, pour depressants of improved potency are secured by utilizing relatively small quantities of mercaptans or carbon tetrachloride during the copolymerization step.
With the increase in the use of hydrocarbon fuels of all kinds, a serious problem has arisen in areas frequently subjected to low temperatures in the cold test characteristics of fuels. Particularly, serious problems have been encountered with heating oils and diesel and jet fuels that have too high a pour point, resulting either in distributional or operating difiiculties or both. For example, the distribution of heating oils by pumping or syphoning is rendered difiicult or impossible at temperatures around or below the pour point of the oil. Furthermore, the flow of the oil at such temperatures through the filters cannot be maintained, leading to the failure of the equipment to operate.
Also the low temperature properties of petroleum distillate fuels boiling in the range between about 250 and about 750 F. have attracted increasing attention in recent years because of the growth of market for such fuels in subarctic areas and because of the development of turbo-jet aircraft capable of operating at altitudes where temperatures of 50 F. or lower may be encountered.
It is, therefore, an object of the present invention to set forth an improved process for the manufacture of very effective pour depressants for middle distillates and lighter oils. In general, these oils boil in the range from about 250 to 750F.
It is a still further object of the present invention to provide heating oils, diesel fuel oils, kerosenes and jet fuels having low pour points. Aviation turbo-jet fuels in which the polymers may be used normally boil between about 250 and about 550 F. and are used in both military and civilian aircraft. Such fuels are more fully defined by U.S. military specifications MIL-F5 624C, MIL- F-25554A, MILF-25558A, and amendments thereto. Kerosenes and heating oils will normally have boiling ranges between about 300 and about 750 F. and are more fully described in ASTM specification D-39648T and supplements thereto, where they are referred to as No. 1 and No. 2 fuel oils. Diesel fuels in which the polymers may be employed are described in detail in ASTM specification D975-53T and later versions of the same specification.
The process of the present invention produces copolymers of ethylene and up to about by weight of an olefinically unsaturated aliphatic monomer containing from about 3 to 5 carbon atoms per molecule. In general, these compounds may comprise vinyl acetate, vinyl propionate, methyl methacrylate, allyl ethyl ether, divinyl ether, acrylonitrile, vinylacetonitrile and the like.
The preferred copolymers comprise ethylene-vinyl acetate copolyrner. It is preferredthat the parts by weight of ethylene in the copolymer be in the range from about to 99% as compared to parts by weight of vinyl acetate in the range from about 40 to about 1%. A very desirable polyethylene vinyl acetate copolymer contains about 15% to 28% by weight of vinyl acetate as, for example, about 20 parts by weight of vinyl acetate.
The molecular weights of the ethylene-vinyl acetate copolymer are critical and should be in the range from about 1,000 to 3,000, preferably in the range from about 1,500 to 2,200. The molecular weights are determined by K. Rasts method (Ber. 55, 1051, 3727 (1922)).
The ethylene-vinyl acetate copolymer as described above is used in a concentration in the range from about .001 to 0.2% by weight, preferably in a concentration in the range from about .005 to 0.1% by weight.
In accordance with the present invention, the polymerization process is conducted in a solvent as, for example, toluene or hexane. It is preferred, however, to use a benzene solvent. The initiator comprises any peroxy compound, preferably di-tertiary-butyl-peroxide. The temperature of the polymerization reaction is in the range from about 280 to 340 F. A very desirable temperature is about 300 F. The pressure is in the range from about 700 to 2,000 pounds, preferably 800 or 900 pounds. The autoclave or similar equipment containing the solvent, initiator and vinyl acetate is purged with nitrogen, then with ethylene before charging with a sufiicient amount of ethylene to yield the desired pressure when heated to the reaction temperature. During the polymerization, additional ethylene is added to maintain the pressure at the desired level. Polymerization is considered complete when the pressure drops less than 50 p.s.i.g. per hour. The product is stripped free of solvent and unreacted vinyl acetate under vacuum.
The present invention maybe more fully understood by reference to the drawing illustrating one embodiment of the same. Referring specifically to the drawing, reactor 1 is first purged with nitrogen, introduced by means of line 2 and pump 3. Reactor 1 is then purged with ethyl: ene which is introduced by means of line 2 and pump 3. Gases are removed from reactor 1 by means of line 4. The reactor is maintained at a positive pressure in the range from about 50 to pounds absolute.
Approximately 220 parts by weight of benzene is in- .troduced into reactor -1 from benzene storage 5 by means of line 6 and pump 7. Reactor 1 is then raised to a temperature of 300 F. by means of heating element 8 Wherein a heating fluid or equivalent is introduced by means of line 9 and withdrawn by meansof line 10. Reactor 1 is held at 300 F. during the course of the reaction by the removal of heat or by the addition of heat thereto. Ethylene is introduced by means of line 2 so as to raise the pressure of the reactor to about 900 pounds.
The addition of vinyl acetate and of di-tertiary-butylperoxide is started concurrently. The vinyl acetate is withdrawn from storage zone 11 and introduced into the reactor by means of line 12 and pump 13. Approximate-1y 55 parts by weight of vinyl acetate is added over a two hour period. The peroxide is introduced by passing benzene into storage zone 14 by means of line 15 and then introducing the solution into the reactor 1 by means of line 16 and pump 17. Approximately 5.5 parts by weight of peroxide are combined with 16.5 parts by weight of benzene. The resulting 22 parts by weight of 25% peroxide solution in benzene is added to reactor 1 over a three hour period.
In accordance with the present invention, during the addition of the vinyl acetate a mercaptan as, for example, dodecyl mercaptan is continuously added by means of line 18. The amount of mercaptan added to the reaction mixture is such as -to yield .02 to .4 wt. percent, preferably .1 to .2 wt. percent of mercaptan sulfur per total amount of vinyl acetate used in the copolymerization.
After the addition of the peroxide has been completed, the reactor is held for an additional one-half hour at a temperature of about 300 F. The ethylene is added continuously so as to maintain the pressure at about 900 pounds. In operation, approximately 934 parts by weight by vinyl acetate are used in conjunction with from about 2,800 to 3,800 parts by weight of ethylene.
At the end of the reaction, the reactor is allowed to cool to about 160 F. and the reaction product is withdrawn by means of line 19 and passed into separation zone 20. Excess ethylene is removed overhead from separation zone 20 by means of line 21. The polymer product comprising the copolymer in a benzene solution may be withdrawn by means of line 22 and further handled as desired. Under certain instances, it may be desirable to separate at least a portion of the benzene from the copolymer. Under these conditions, the benzene copolymer product is passed to separation zone 23- -by means of line 24. Benzene is removed overhead by means of line 25, while a copolymer product is withdrawn by means of line 26. i
The quantity mentioned above may be somewhat varied. For example, based upon 55 parts by weight of vinyl acetate, the amount of benzene utilized may vary from about 180 to 300 parts by weight, and the amount of di-tertiary-butyl-peroxide may vary from about 3 to 8 parts by weight. Also as mentioned, the amount of ethylene utilized varies from about 2,800 to 3,800 parts by weight, or approximately 938 parts by weight of vinyl acetate. The time of reaction also may be varied from about 2 to 4 hours, depending upon other operating variables.
In order to further illustrate the invention, a number of operations were conducted in accordance with the above described technique. The results of these operations are illustrated in the following table:
per total amount of vinyl acetate used in the copolymerizationl Thus, when utilizing dodecyl mercaptan, the amount used is a concentration equal to 0.1 to 2.0 wt. percent, preferably 0.5 to -1.0 wt. percent of the total amount of vinyl acetate used in the copolymerization.
In accordance with the present invention, the reactants are preferably added continuously to the reactor, as described above.
What is claimed is:
1. Process for the manufacture of a pour depressant comprising a copolymer of ethylene and an aliphatic vinyl monomer which comprises reacting ethylene and said monomer in a benzene solvent at a temperature in the range of from about 280 to 340 F. and at a pressure in the range from about 700 to 2,000 pounds under conditions wherein the concentration of the vinyl monomer in the solvent solution varies from about 4 to 14%, whereby a polymer having a molecular weight in the range from about 1,000 to 3,000 is secured and wherein the concentra tion of the vinyl acetate in the product will vary from about 1 to 40% and adding to said benzene solvent an aliphatic mercaptan containing from about 1 to 18 carbon atoms in the molecule in a concentration to yield .02 to .4 wt. percent of mercaptan sulfur per total amount of vinyl acetate used in the copolymerization.
2. Process as defined by claim 1 wherein the concentration of the vinyl monomer in the solvent solution varies from about 4 to 7 /2%, whereby the concentration of the vinyl monomer in the product will vary from about 15 to about 25%.
3. Process for the manufacture of a pour depressant comprising a copolymer of ethylene and an aliphatic vinyl monomer which comprises reacting ethylene and said monomer in a benzene solvent at a temperature in the .range of from about 280 to 340 F. and at a pressure in the range from about 700 to 2,000 pounds under conditions wherein the concentration of the vinyl monomer in the solvent solution varies from about 4 to 14%, whereby a polymer having a molecular weight in the range from about 1,000 to 3,000 is secured and wherein the concentration of the vinyl acetate in the product will vary from about 1 to 40% and adding to said benzene solvent a modifier selected from the group consisting of carbon tetrachloride and an aliphatic mercaptan containing from about 1 to 18 carbon atoms in the molecule, said modifier being present in a concentration of from about 0.33 to 1.0% by volume based upon the vinyl acetate.
Efiecl of dodecyl mercaptan and carbon tetrachloride on quality of the pour depressant [Conditions of copolymerization: 1800 ml. of benzene, 300ml. of vinyl acetate over 3 hours, 30 ml. of Di-t-butyl peroxide over 3% hours, 900 p.s.i.g., 300 F., total reaction time 3% hours] Modifier None Dodeeyl Mercaptan Carbon Tetrachloride Modifier in Vinyl Acetate, vol. percent- Nil 0. 33 1. 0 2. 0 4. 0 0. 33 1. 0 2. 0 Yield, g 797 750 738 679 541 715 699 662 Vmyl'Acetate, wt. percent--. 29. 0 27. 0 30. 6 30. 7 34. 0 24. 6 27.1 Molecular Weight 2, 700 2, 950 2, 685 1, 750 2, 440 2, 475 1, 800 Viscosity at 100 F., es 150 130 11 161 180 161 Four Depression, F.:
With 0.015 Wt. percent 65 15 45 45 25 With 0.025 wt. percent 50 85 85 85 '25 7O 45 1 50/50 solution of copolymer in 400500 F. naphtha. 2 In a 50/50 blend of virgin and cracked gas oils, ASTM pour 20 F.
4. Process as defined by claim 1 wherein said mercaptan contains from about 10 to 14 carbon atoms in the molecule.
5. Process as defined by claim 1 wherein the time period is in the range from about 2 to 6 hours, wherein the temperature is in the range of from about 290 to 310 F., wherein the pressure is in the range from about 650 to 1,000 pounds, and wherein the concentration of the vinyl acetate in a benzene solution varies from about .53 to about 10%.
'6. Process as defined by claim 1 wherein the reaction is preferably 0.1 to 0.2 Wt. percent of mercaptan sulfur initiated byape'roxy compound, di-tertiary-butyl-peroxide.
7. Process as defined by claim 1 wherein the reaction is carried out in an autoclave which is purged with nitrogen, then with ethylene and then charged with a sufficient amount of ethylene to yield the desired pressure when heated to the reaction temperature.
8. Process as defined by claim 1 wherein addition ethylene is added to the reaction mixture whenever the pressure drops by about 100 p.s.i.g.
9. Process as defined by claim 1 wherein unreacted vinyl acetate is stripped under vacuum when the reaction is completed.
10. Process as defined by claim 1 wherein saidaliphatic mercaptan is dodecyl mercaptan.
11. Process as defined by claim 3 wherein the modifier consists essentially of carbon tetrachloride present in a concentration of about .331.0% by volume based upon the volume of vinyl acetate present.
6 References Cited by the Examiner UNITED STATES PATENTS 2,395,381 2/1946 Squires 26087.3 2,3 96,785 3/1946 Hanford 260-873 2,947,735 8/1960 Bartl 260-873 3,093,623 6/1963 Ilnyckyj 26087.3
OTHER REFERENCES Wiles et al.: Industrial and Engineering Chemistry, vol.
10 41, N0. 8, pp. 1679-1682.
Schildknecht: Vinyl and Related Polymers, pp. 106 and 504, Wiley (1957).
JOSEPH L. SCHOFER, Prirnary Examiner.
15 LOUISE P. QUAST, JOSEPH R. LIBERMAN, WIL- LIAM H. SHORT, Examiners.
JOHN F. MCNALLY, Assistant Examiner.

Claims (2)

1. PROCESS FOR THE MANUFACTURE OF A POUR DEPRESSANT COMPRISING A COPOLYMER OF ETHYLENE AND AN ALIPHATIC VINYL MONOMER WHICH COMPRISES REACTING ETHYLENE AND SAID MONOMER IN A BENZENE SOLVENT AT A TEMPERATURE IN THE RANGE OF FROM ABOUT 280* TO 340*F. AND AT A PRESSURE IN THE RANGE FROM ABOUT 700 TO 2,000 POUNDS UNDER CONDITIONS WHEREIN THE CONCENTRATION OF THE VINYL MONOMER IN THE SOLVENT SOLUTION VARIES FROM ABOUT 4 TO 14%, WHEREBY A POLYMER HAVING A MOLECULAR WEIGHT IN THE RANGE FROM ABOUT 1,000 TO 3,000 IS SECURED AND WHEREIN THE CONCENTRATION OF THE VINYL ACETATE IN THE PRODUCT WILL VARY FROM ABOUT 1 TO 40% AND ADDING TO SAID BENZENE SOLVENT AN ALIPHATIC MERCAPTAN CONTAINING FROM ABOUT 1 TO 18 CARBON ATOMS IN THE MOLECULE IN A CONCENTRATION TO YIELD .02 TO .4 WT. PERCENT OF MERCAPTAN SULFUR PER TOTAL AMOUNT OF VINYL ACETATE USED IN THE COPOLYMERIZATION.
3. PROCESS FOR THE MANUFACTURE OF A POUR DEPRESSANT COMPRISING A COPOLYMER OF ETHYLENE AND AN ALIPHATIC VINYL MONOMER WHICH COMPRISES REACTING ETHYLENE AND SAID MONOMER IN A BENZENE SOLVENT AT A TEMPERATURE IN THE RANGE OF FROM ABOUT 280* TO 340*F. AND AT A PRESSURE IN THE RANGE FROM ABOUT 700 TO 2,000 POUNDS UNDER CONDITIONS WHEREIN THE CONCENTRATION OF THE VINYL MONOMER IN THE SOLVENT SOLUTION VARIES FROM ABOUT 4 TO 14%, WHEREBY A POLYMER HAVING A MOLECULAR WEIGHT IN THE RANGE FROM ABOUT 1,000 TO 3,000 IS SECURED AND WHEREIN THE CONCENTRATION OF THE VINYL ACETATE IN THE PRODUCT WILL VARY FROM ABOUT 1 TO 40% AND ADDING TO SAID BENZENE SOLVENT A MODIFIER SELECTED FROM THE GROUP CONSISTING OF CARBON TETRACHORIDE AND AN ALIPHATIC MERCAPTAN CONTAINING FROM ABOUT 1 TO 18 CARBON ATOMS IN THE MOLECULE, SAID MODIFIER BEING PRESENT IN A CONCENTRATION OF FROM ABOUT 0.33 TO 1.0% BY VOLUME BASED UPON THE VINYL ACETATE.
US164248A 1960-01-05 1962-01-04 Process for preparation of pour depressants Expired - Lifetime US3254063A (en)

Priority Applications (8)

Application Number Priority Date Filing Date Title
NL130129D NL130129C (en) 1960-01-05
BE598930D BE598930A (en) 1960-01-05
NL259743D NL259743A (en) 1960-01-05
US593A US3131168A (en) 1960-01-05 1960-01-05 Process for the manufacture of pour depressants for middle distillate fuels
GB39/61A GB915890A (en) 1960-01-05 1961-01-02 Process for the manufacture of improved pour point depressants for middle distillates
FR848812A FR1286696A (en) 1960-01-05 1961-01-04 Process for the production of improved products lowering the freezing point of middle distillates
US164248A US3254063A (en) 1962-01-04 1962-01-04 Process for preparation of pour depressants
GB47962/62A GB992817A (en) 1960-01-05 1962-12-19 Improved process for preparation of pour depressants

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
US164248A US3254063A (en) 1962-01-04 1962-01-04 Process for preparation of pour depressants

Publications (1)

Publication Number Publication Date
US3254063A true US3254063A (en) 1966-05-31

Family

ID=22593632

Family Applications (1)

Application Number Title Priority Date Filing Date
US164248A Expired - Lifetime US3254063A (en) 1960-01-05 1962-01-04 Process for preparation of pour depressants

Country Status (1)

Country Link
US (1) US3254063A (en)

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3454378A (en) * 1966-02-04 1969-07-08 Union Carbide Canada Ltd Pour point depressant for middle distillates
US3627838A (en) * 1964-12-11 1971-12-14 Exxon Research Engineering Co Process for manufacturing potent pour depressants
US3661541A (en) * 1969-04-22 1972-05-09 Exxon Research Engineering Co Fuel oil compositions containing a mixture of polymers to improve the pour point and flow properties
US4076679A (en) * 1976-01-21 1978-02-28 The Dow Chemical Company Rapid setting polyurethane elastomers and process of preparation
US5141663A (en) * 1990-08-31 1992-08-25 Olin Corporation Fire resistant hydraulic fluid composition
US5681359A (en) * 1996-10-22 1997-10-28 Quantum Chemical Corporation Ethylene vinyl acetate and isobutylene terpolymer as a cold flow improver for distillate fuel compositions

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2395381A (en) * 1943-02-25 1946-02-19 Du Pont Process of preparing ethylene polymers
US2396785A (en) * 1941-03-15 1946-03-19 Du Pont Process for polymerizing olefins with other polymerizable organic compounds
US2947735A (en) * 1957-01-02 1960-08-02 Bayer Ag Process for the production of copolymers of ethylene
US3093623A (en) * 1960-01-05 1963-06-11 Exxon Research Engineering Co Process for the manufacture of improved pour depressants for middle distillates

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2396785A (en) * 1941-03-15 1946-03-19 Du Pont Process for polymerizing olefins with other polymerizable organic compounds
US2395381A (en) * 1943-02-25 1946-02-19 Du Pont Process of preparing ethylene polymers
US2947735A (en) * 1957-01-02 1960-08-02 Bayer Ag Process for the production of copolymers of ethylene
US3093623A (en) * 1960-01-05 1963-06-11 Exxon Research Engineering Co Process for the manufacture of improved pour depressants for middle distillates

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3627838A (en) * 1964-12-11 1971-12-14 Exxon Research Engineering Co Process for manufacturing potent pour depressants
US3454378A (en) * 1966-02-04 1969-07-08 Union Carbide Canada Ltd Pour point depressant for middle distillates
US3661541A (en) * 1969-04-22 1972-05-09 Exxon Research Engineering Co Fuel oil compositions containing a mixture of polymers to improve the pour point and flow properties
US4076679A (en) * 1976-01-21 1978-02-28 The Dow Chemical Company Rapid setting polyurethane elastomers and process of preparation
US5141663A (en) * 1990-08-31 1992-08-25 Olin Corporation Fire resistant hydraulic fluid composition
US5681359A (en) * 1996-10-22 1997-10-28 Quantum Chemical Corporation Ethylene vinyl acetate and isobutylene terpolymer as a cold flow improver for distillate fuel compositions

Similar Documents

Publication Publication Date Title
US3627838A (en) Process for manufacturing potent pour depressants
US3093623A (en) Process for the manufacture of improved pour depressants for middle distillates
US3159608A (en) Copolymerization of ethylene and vinyl acetate
US5200484A (en) Terpolymers of ethylene, their preparation and their use as additives for mineral oil distillates
EP0206756B1 (en) Living catalysts, complexes and polymers therefrom
US3126364A (en) Process for the manufacture of pour depressant
US3341309A (en) Terpolymer pour point depressant and method of manufacture
US3642459A (en) Copolymers of ethylene with unsaturated esters and oil compositions containing said copolymers
NO178769B (en) Terpolymerisates of ethylene, their preparation and use as additives for mineral oil distillates, and mineral oil distillates
US3131168A (en) Process for the manufacture of pour depressants for middle distillate fuels
NO310826B1 (en) Terpolymerisates of ethylene, their process for preparation, mixtures as well as mineral oil or mineral oil distillates of the same
US3792983A (en) Ethylene and acrylate esters, their preparation and their use as wax crystal modifiers
US3254063A (en) Process for preparation of pour depressants
CA1222348A (en) Ethylene-alkyne copolymers, their preparation and their use as additives to petroleum distillates
US3236612A (en) Middle distillate composition of improved pour characteristics
CA2242428C (en) Copolymers based on ethylene and unsaturated carboxylic esters and their use as mineral oil additives
US4419106A (en) Hydrocarbon oils with improved pour points
US5684108A (en) Ethylene-based copolymers and their use as flow improvers in mineral oil middle distillates
US3260728A (en) Process for polymerizing ethylene with lauryl methacrylate and n-vinyl-2-pyrrolidone
US3812034A (en) Pour point depression
US4547202A (en) Hydrocarbon oils with improved pour points
US3915668A (en) Crude oils and residual fuel oils containing a terpolymer of ethylene, vinyl ester, and dialkylvinyl carbinol
US3471273A (en) Graft copolymer pour point depressors
US3565947A (en) Terpolymer pour point depressant
CA1271895A (en) The use of ethylene terpolymers as additives in mineral oil and miniral oil distillates