Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
  • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
  • C08F220/10—Esters
  • C08F220/22—Esters containing halogen
• • 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
  • C10L1/146—Macromolecular compounds according to different macromolecular groups, mixtures thereof
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
  • C08F222/10—Esters
  • C08F222/12—Esters of phenols or saturated alcohols
  • C08F222/20—Esters containing oxygen in addition to the carboxy oxygen
  • C08F222/205—Esters containing oxygen in addition to the carboxy oxygen the ester chains containing seven or more carbon atoms
• • 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
  • C10L1/20—Organic compounds containing halogen
  • C10L1/206—Organic compounds containing halogen macromolecular compounds
  • C10L1/208—Organic compounds containing halogen macromolecular compounds containing halogen, oxygen, with or without hydrogen
• • 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

Definitions

• the present invention relates to a new class of additives for use in petroleum distillate fuel products. cifically, it relates to a new class of copolymers containing chlorine and to the use of such copolymers as additives for stabilizing petroleum distillate fuels.
• This application is a continuation of Serial .No. 673,156, filed July 22, 1957.
• the present invention provides a new class of ashless additives containing chlorine which are effective in very small quantities for inhibiting the formation of sludge and sediment in petroleum distillate fuels boiling in the range between about 300 and about 900 F.
• Typical'of such fuels are heating oils meeting the requirements'for Grades 1 and 2 fuel oils as set forth in ASTM Specification D-3 9648T, diesel fuels falling Within Grades 1D, 2D and 4D of ASTM Specification D-97551T, and jet engine fuels such as those covered by US.
• Military Specification lviIL-F-5624C The addition of as little as about 0.002 percent by weight of the additive materials of the invention significantly improves the stability of such fuelsand extends the period for which they may be satisfactorily stored under adverse conditions.
• the stabilizing additives of this invention are chlorinecontaining copolymers containing ester groups derived from the reaction of epichlorohydrin with a carboxylic acid group. These copolymers may be prepared by co polymerizing with other polymerizable monomers or mix- More spe- 3,160,484 Patented Dec. 8, 1 964
• the mixed esters which have been found useful in preparing copolymers for stabilizing petroleum distillate fuels in accordance with the invention are long chain saturated aliphatic alcohol-epichlorohydrin mixed esters of unsaturated conjugated dibasic zacids. These esters, re-' ferred to hereinafter as alkyl-chloropropyleneoxy mixed esters are thought to have the general formula:
• R is an alkyl group containing from about 8 to about 24 carbon atoms
• R and R" are constituents selected from the class consisting of hydrogen atoms and methyl groups, at least one such constituent being a hydrogen atom
• 11 may vary from one to three or more, depending upon the quantity of epichlorohydrin employed in preparing the esters.
• alkyl-chloropropyleneoxy mixed esters employed in preparing the 'copolymers of the invention may be readily obtained by first reacting an unsaturated 0011-. jugated dibasic acid with a long chain saturated aliphatic alcohol to form a half ester and then reacting this product with epichlorohydrin in the presence of an acidic (electron acceptor) catalyst to produce the mixed ester.
• epichlorohydrin to the half .ester may also be catalyzed by basic groups, e.g. CH O, OH.
• Suitable unsaturated conjugated dibasic acids forfpreparing the mixed esters in this manner include maleic acid, fumaric acid, citraconic acid, mesaconic acid, and mixtures of such acids.
• the acids in the form of their anhydrides, in whichcasethe half ester can be produced by merely heating one mole of the an- I hydride with one mole of the long chain saturated alitures of such monomers the reaction product of epichlorohydrin with a polymerizable, unsaturated acid; i.e., dibasic acids such as maleic acid and half esters of dibasic acids suchas lauryl hydrogen maleate.
• the chlorine- 'containing copolymers of the invention may also be prepared by'the' reaction of epichlorohydrin with polymers phatic alcohol at a temperature of about to C. for about thirty to about forty-five minutes.
• Other wellknown methods for the production of half esters of dibasic acids may also be employed.
• the long chain saturated aliphatic alcohols reacted with the dibasic acids or acid anhydrides to produce half esters may contain from about 8 to 24 carbon atoms per molecule, those containing ,from about 8 to about 18 carbon atoms being preferred.
• Straight chain primary alcohols such as dodecyl, cetyl, eicosyl and docosyl molecule and has the following approximate composiv tion:
• Lorol is thus a commercialmixture of saturated all-L phatic alcohols containing from 10 to. 1.8 atoms per molecule and having :an average chain length of J additives of the invention are normally obtained by the oxonation and hydrogenation of a C copolymer of propylene and butene.
• the copolymer itself is in reality a mixture of isomers and the resultant oxo-alcohol may have the following general analysis:
• the half esters prepared by reacting the dibasic acid and alcohol are in turn reacted with epichlorohydrin in 4 catalyst used was acidic or dilute acid if the catalyst was basic and then water washed.
• the mixed esters prepared as described above are c0- polymerized with a polymerizable organic monomer containing a vinyl group in order to produce stabilizing additives for incorporation in petroleum distillate fuels.
• Suitable monomers containing vinyl groups include hydrocarbons such styrene; isobutylene, and butadiene; esters such as allyl acetate, vinyl propionate and methyl methacrylate; ethers such as allyl ethyl ether and divinyl ether; nitriles such as acrylonitrile and vinylacetonitrile.
• organic monomers in the polymerization mixture may be varied from about 2:1 toabout 1:20.
• the polymerizae tion may be carried out in a suitable solvent in order to control reaction velocity and molecular weight.
• Oxygen generally will beexcluded during the polymerization by the use of a blanket of an inert gas such as nitrogen or carbon dioxide.
• the polymerization time may vary from about 1 to '36 hours.
• weightsof from about 6,000 to about 20,000 are par ticularly preferred.
• an acidic (electron acceptor) catalyst such as boron trifluoride, boron trifluoride etherate,- aluminum' trichlo ride, aluminum tribromideflor the like or a basic catalyst such as NaOCH or NaOH.
• the reaction is carried 'out' by slowly adding the epichl'orohydrin to, the halfester mixed with catalyst over approximately a one to two hour period.
• the temperature at which the addition is carried out may range between about 100 C. and 180 e.
• the esterzepichlorohydrin ratio may range Jetween aboutlzl to about 1:4. Under these conditions ;he addition of the epichlorohydrin molecule to the half aster takesplace through the epoxy group and the chlofine atom of the epichlorohydrin is unaffected;
• the copolymer may be freedo-f solvent and employed for the stabilizing of distillatefuels.
• the copolymer may be incorporated into petroleum distillate fuels in concentrations of from about 0.002 to about 2 percent by weight in order to stabilize such fuels.
• Example 4 Employing the reactants of Example 3, a polymer containing 0.25 mole of isooctyl chloropropyleneoxy maleate and 0.75 mole of tallow fumarate per mole of vinyl acetate was prepared; The reaction conditions and catalyst were the same as those of Example 3 except that the mixture was heated for 1.5 hours.
• EXAMPLE 6 The reactants employed in Example 5 were copolym erized to give a copolymer containing 0.25 mole of a mixed ester and 0.75. mole of tallow fumarateper mole of EXAMPLE 7 Lorol hydrogen maleate, an acid ester of maleic acid and a mixture of saturated C to C aliphatic alcohols derived from the hydrogenation of coconut oil, was reacted with epichlorohydrin in equimolar quantities by heating the reactants after slow addition of the epichlorohydrin to the half ester in xylene solution in the presence of 1 percent by weight of boron trifluoride etherate catalyst; The reaction was carried out at a temperature of 155 C. and was continued for 17 hours.
• the resulting mixed ester was washed with 5 percent sodium hydroxide in water and then dried.
• the Total Acid Number of the mixed ester expressed as milligrams of KOH per gram of the ester, was 4.5, against a calculated value of zero.
• the mixed ester contained 5.5% chlorine against a calculated value of 6.7% by weight.
• the product from this reaction was mixed with vinyl acetate'in a molar ratio of 1.4
• EXAMPLE 8 The copolymers prepared in Examples 3,4, 5, 6 and 7 were incorporated at a concentration of 0.01% by weight of the 50% benzene solution into samples of a heating oil comprising a blend of about 50 percent virgin distillate and about 50 percent cracked stock. Typical properties of such a heating oil are as follows;
• the additives of the invention substantially reduced sediment formationin the oil.
• EXAMPLEQ' The additives of the invention are effective in jet fuels as well as in middle distillate heating "oils; To demonstrate this, the products of Examples 3 and 4 were incorporated into samples of a'jet fuel covered by US. Mili tary Specification MIL-F-5624C which boiled between 300'and 550 F. Thesesamples were subjected to a CPR Fuel Coker Test. The tests were carried out by passing the samples through hot preheater tubes which brought the fuel temperature to400 F. The heated fuel was then passed througha sintered metal micronic filter heated; to a temperature of 500 F. The pressure drop acrossthe filter and the deposit formed onthe preheater tubes were measured 'for each sample and compared with the values obtained with the uninhibited fuel. Data from this test are shown in Table II.
• the additives of the invention produce a marked improvement in the stability of distillate fuels and in some respects are superior tocommercial additives It will be understood that the additives of the invention may be incorporated into petroleum distillate fuels inconiunction with other additives designed to correct other fuel deficiencies. The additives may also be used in the form of amine or other derivatives rather than as straight :opolymers. a
• a copolymer of along chain saturated aliphatic alco 'sol-chloropropyleneoxy mixed ester of an unsaturated :onjugated dibasic acid said acid having from 4 to 5 carbon atoms per molecule and a polymerizable organic rnonomer selected from the group consisting of (a) a vinyl ester of a short chainfatty acid and (b) a mixture of a vinyl ester of a short chain'fa'tty acid and along :hain saturated aliphatic alcohol ester of a conjugated unsaturated dibasic acid, said acidcontaining from 4 to 5 :arbon atoms per molecule, and wherein the mole ratio of said mixed ester-to said monomer is between 2: l and 1:20, and said copolymer has a molecular weight of from 3,000 :0 about 100,000.
• the saidv vinyl ester of a short chainfatty acid is vinyl acetate.
• An oil soluble copolymer of an alkyl C to C chloropropyleneoxy maleate anda vinyl acetate said copolymer having a mole ratio of maleate to acetate of between 2:1 and 1:20 and having a molecular weight of 6,000 to about 20,000.
• An'oil soluble copolymer of an 'alkyl C to C chloropropyleneoxy maleate and a monomeric mixture of vinyl acetate and alkyl fumarate said copolymer having a mole ratio of maleate to monomer mixture of between 221 and 1:20 and a molecular weight between 6,000 and about 20,000.
• a copolymer of a long chain saturated aliphatic alcohol-chloropropyleneoxy mixed ester of an unsaturated conjugated dibasic acid said acid having from 4 to 5 carbon atoms per molecule and styrene and wherein the mole ratio of said mixed ester to styrene is between 2:1
• conjugated dibasic acid said acid having from 4 to 5 carbon atoms per molecule and methyl methacrylate and wherein the mole ratio of said mixed ester to methyl methacrylate is between 2:1 and 1:20 and said copolymer has a molecular weight of between 3,000 and 100,000.
• Arfuel composition as defined by claim 12 wherevin the concentration of said copolymer is from about in said mixed ester is Lorol-chloropropyleneoxy maleate.
• a fuel composition as defined by claim 12 wherein said vinyl ester comprises vinyl acetate.
• a fuel composition as defined by claim 12 wherein said 'mixed ester is isooctyl chloropropyleneoxy maleate. 17. A fuel composition as defined by claim 12 wherein said mixed ester is tallow-chloropropyleneoxy maleate. 18. .A fuel composition as defined in claim 12 where! in said unsaturatedconjugated dibasic. acid is a butene dioic acid.
• a petroleum distillate fuel boiling in the range between about 300 F. and about 900 F. having incorporated therein from about 0.002 to about 2.0% by weight of an oil soluble copolymer of an alkyl C to C chloropropyleneoxy mixed ester of a butenedioic acid having a mixed ester to chloropropyleneoxy ratio of between 1:1 and 1:4 and a monomer selected from the group consisting of (a) vinyl acetate and (b) a mixture of vinyl acetate and a C to C saturated aliphatic ester ofa butenedioic acid, said copolymer having a mole ratio of mixed ester to monomer of between 2:1 and 1:20 and a molecular weight between 6,000 and about 20,000.

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• Chemical & Material Sciences (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Organic Chemistry (AREA)
• Oil, Petroleum & Natural Gas (AREA)
• Health & Medical Sciences (AREA)
• Medicinal Chemistry (AREA)
• Polymers & Plastics (AREA)
• Engineering & Computer Science (AREA)
• General Chemical & Material Sciences (AREA)
• Liquid Carbonaceous Fuels (AREA)
• Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

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Citations (9)

• 1958
  • 1958-06-26 FR FR1207570D patent/FR1207570A/fr not_active Expired
  • 1958-07-18 NL NL229710A patent/NL97760C/xx active
  • 1958-07-18 BE BE569574A patent/BE569574A/xx unknown
• 1961
  • 1961-07-25 US US126531A patent/US3160484A/en not_active Expired - Lifetime

Patent Citations (9)

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