Classifications

• • 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
  • C10L1/1966—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 poly-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

Definitions

• the invention relates to wax crystal modifier compounds and their use in improving the flow characteristics of oleagenous fluids especially oils such as crude oil, lubricating oil, fuel oil and distillate oil.
• oils especially lubricating oils, fuel oils, distillate oils, and crude oils, contain straight chain and branched alkanes that crystallize as their temperature is lowered.
• Alkane (wax) crystallization in oleagenous fluids can affect the fluid's ability to flow. This may result in problems such as pipelininig difficulties in crudes.
• the temperature at which wax begins to crystallize in an oil is called the wax appearance temperature (WAT) of the oil.
• WAT wax appearance temperature
• Polymeric and copolymeric additive compounds can be combined with an oil in order to improve an oil's flow properties.
• Such additives known as wax crystal modifiers, are capable of altering the crystallization properties of waxes present in oil.
• wax crystal modifiers improve an oil's flow properties by suppressing the WAT or by modifying the growth of wax crystals in the oil so that the resulting crystals are small enough so as not to affect the oil's flow properties or both.
• dialkyl fumarate vinyl acetate copolymer with C to C ⁇ » alkyls is particularly popular.
• wax crystal modifiers that are capable of improving the flow properties of oleagenous fluids, especially oils such as lubricating oils, crude oils, fuel oils, and distillate oils.
• the invention is a copolymer of dialkyl phenyl fumarate and at least one compound selected from the group consisting of vinyl acetate, styrene, C 3 to C 30 ⁇ olefin, ethylene, and carbon monoxide.
• the invention is a flow improver for use in an oleagenous fluid comprising one or more copolymers from dialkyl phenyl fumarate wherein the alkyl is straight chain or branched and ranges in size from C 6 to C1 50 and at least one compound selected from the group consisting of vinyl actate, styrene, C 3 to C 30 ⁇ olefin, ethylene, and carbon monoxide.
• the invention is a method for improving the flow properties in an oleagenous fluid comprising: adding to a major amount of the oleagenous fluid a minor amount of at least one copolymer of dialkyl phenyl fumarate having C 6 to C 1 50 straight chain or branched alkyl and at least one compound selected from the group consisting of C 3 to C 3 o alpha olefin, ethylene, styrene, and carbon monoxide.
• the invention is a method for forming a copolymer comprising combining under free radical polymerization conditions a C 6 to Ciso dialkyl phenyl fumarate in a solvent selected from the group consisting of hexane, benzene, cyclohexane, and heptane; at least one compound selected from the group consisting of ethylene and carbon monoxide; and an initiator selected from the group consisting of t-butyl peroxypivalate, benzoyl peroxide, t-butylper benzoate, and t-butyl peroxide, for a time, temperature, and pressure sufficient to form the copolymer.
• the invention is a method for forming a copolymer comprising:
• copolymers can be formed having the formula AB wherein A is formed from dialkyl phenyl fumarate and B is formed from at least one compound selected from the group consisting of vinyl acetate, styrene, C 3 to C 3 o ⁇ -olefin, ethylene, and carbon monoxide.
• the invention is also based on the discovery that such copolymers are capable, when used in an effective amount, of improving flow properties like viscosity in oleagenous fluids, especially lubricating oils, fuel oils, distillate oils, and crude oils. While not wishing to be bound by any theory, it is believed that the copolymers of the invention improve the flow properties in oleagenous materials because they function as wax crystal modifiers.
• copolymers of the present invention are represented by the formula AB wherein A is formed from dialkyl phenyl fumarate (DAPhF). As such, these copolymers have the structure: B -
• Comonomer B is formed from at least one compound selected from the group consisting of vinyl acetate, styrene, C 3 to C 3 ⁇ ⁇ -olef ⁇ n, ethylene, and carbon monoxide.
• copolymer is thus used in accordance with its more general meaning where the polymer comprises two or more different monomers.
• R represents independently selected straight chain or branched alkyl groups of from about C 8 to about C ⁇ 50 carbon atoms. Preferred alkyls range from about Cg to about C 0 .
• Copolymers of the present invention are prepared from dialkyl phenyl fumarate esters.
• esters may be prepared by reacting fumaric chloride with an alkyl phenol in the presence of triethylamine.
• copolymers of this invention can be synthesized using free- radical polymerization.
• polymerizaton can be carried out in a standard glass reactor.
• inhibitors from the monomers such as vinyl acetate or styrene are removed via an inhibitor remover column.
• the purified monomers are then placed in tubes with the DAPhF ester monomers. The tubes are capped with septa and flushed with nitrogen for one to four hours before polymerization.
• the relative amounts of monomer A: monomer B in the copolymer can be varied from 5:95 to 95:5 mole percent.
• the reactions can be carried out in solvent or neat.
• solvent should be nonreactive or noninterfering in free radical polymerization can be used.
• solvents include benezene, cyclohexane, hexane, heptane, etc.
• Solvents like xylene or oil can also be used. The solvent may be flushed with argon or nitrogen and then added to the monomers.
• the polymerization reactions can be carried out from 40 to 100°C depending on reactivity of monomers, half-life of the initiator used, or the boiling point of the solvent.
• the reactions are carried out under inert atmosphere.
• the solvents are brought to the reaction temperatures, and the initiator (dissolved in the appropriate solvents) is added to the solution.
• Typical free radical initiators includes dialkyl peroxides such as ditertiary-butyl peroxide, 2,5-dimethl-2,5-di-tertiary-butylperoxyhexane, di-cumyl peroxide; alkyl peroxides such as benzoyl peroxide; peroxy esters such as tertiary-butyl peroxypivalate, tertiary-butyl perbenzoate; and also compounds such as azo-bis- isobutyronitrile.
• a free radical initiator with an appropriate half life at reaction temperature of from about 60°C to about 140°C can be used.
• both monomers and initiator are loaded together, flushed with nitrogen, and then brought to reaction temperature. T e mixture is stirred for a time sufficient to ensure that a substantially homogeneous mixture is obtained. The time and temperature if the reactions can be varied. Reactions can be stopped after 1 hour to 48 hours. The resulting copolymer can be isolated by precipitating the polymer in non-solvent (solvent in which polymer is not soluble). The product is then dried in vacuum oven.
• monomers that are gases at room temperature such as ethylene or carbon monoxide
• the reactions are generally carried out in high pressure reactors such as autoclave reactors.
• the reactor is initially charged with monomers like dialkyl phenyl fumarate dissolved in solvent like hexane, and initiator is added.
• Typical initiators include t-butyl peroxypivalate, benzoyl peroxide, t-butylper benzoate, t-butyl peroxide.
• the reactor is sealed and purged with purified nitrogen.
• the reactor is then pressurized with carbon monoxide and/or ethylene monomer to appropriate pressure.
• the pressure can range from about 100 to about 3000 psig.
• the preferred polymerization pressure ranges from about 500 to about 1200 psig.
• Reaction temperature can range from about 40 to about 200°C, depending on solvent and the initiator half-life.
• the pressure of the reaction can be maintained for few hours to 48 hours depending on monomer reactivity, solvent, and the initiator half-life.
• the reactor is allowed to cool to room temperature and is then depressurized.
• the solvent is removed on rotary evaporator to obtain the product.
• the products are generally characterized by standard techniques like FTIR, NMR, and GPC.
• wax crystal modifiers are added to the oleagenous fluid in a concentration ranging from about 10 to about 50,000 ppm based on the weight of the oleagenous fluid.
• the preferred concentration is about 500 ppm.
• oleagenous fluids containing paraffinic (alkane) species that benefit from the addition of the compounds of the invention include crude oils, i.e., oils as obtained from drilling and before refining or separating, fuel oils such as middle distillate fuel oil, and oils of lubricating viscosity ("lubricating oils").
• the oleagenous compositions and additive compounds of the present invention may be used in combination with other co-additives such as ethylene-vinyl acetate copolymers, fumarate-vinyl acetate copolymers, and mixtures thereof.
• copolymer flow improvers of this invention when present in an effective amount are capable of inhibiting the nucleation and growth of wax crystals in oleagenous fluids such as oils. While not wishing to be bound by any theory, it is believed that the presence of an effective amount of copolymer results in a lowering the oil's wax appearance temperature because the copolymer molecules are sufficiently similar to the paraffinic crude species to incorporate themselves into growing wax crystals. Once incorporated, it is believed that the polymeric nature of the flow improver, i.e., its "branchiness" and high molecular weight, prevent the further addition of the crude's paraffinic species to the crystal.
• the presence of the copolymer in the growing wax crystal is also believed to alter the crystals' morphology by inhibiting growth that naturally tends towards undesirable large flat platelets. Such platelets are believed to result from the interlocking, intergrowth, and agglomeration of nucleated wax crystallites. Such changes in crystal shape resulting from copolymer incorporation greatly diminish the wax crystals' ability to interlock, intergrow, and agglomerate.
• the compounds of the present invention are most effective when the molecular weight distribution of the alkyls present in the fumaric species of the copolymer is approximately the same as the molecular weight distribution of the oil's paraffinic species. While the compounds of the present invention are useful in all olegenous fluids containing paraffinic species, the preferred compound will depend on the type of fluid used.
• copolymers with alkyls in the fumarate species ranging from about C 12 to about C ⁇ and molecular weights ranging from about 2000 to about 100,000 are preferred.
• the preferred compounds contain alkyls ranging from about C1 5 to about C o and molecular weights ranging from about 2,000 to about 50,000.
• preferred copolymers contain alkyls ranging from about C 10 to about C 22 and have molecular weights ranging from about 2,000 to about 20,000.
• alkyl chain lengths are sometimes represented by a range of carbon and hydrogen atoms, such as C24-28H49.57. h such cases, the alkyl groups present in the fumaric species of the inventions monomers, polymers, and copolymers are random mixtures of alkyl groups ranging in size, approximately, over the entire range.
• Example 1 Reaction of fumaric chloride and dodecyl phenol.
• Example 2 The synthesis of dialkyl phenyl fumarate monomer (C ⁇ nPhF
• C 3 o+ olefm alkylated phenol was synthesized by reaction of phenol with C 3 o+ alpha olefm using a strongly acidic resin (obtained from Aldrich, Inc., Milwaukee, WI under the tradename AMBERLYST 15TM) comprising divinyl benzene-crosslinked polystyrene, to which sulfonic groups are attached, as a catalyst.
• C 30 + phenol fumarate ester was synthesized using a procedure similar to that used to synthesize dodecyl phenol fumarate.
• An IRspectrum of the product showed absorption peaks due to ester carbonyl at 1757 and 1710 cm "1 and the double bond peak at 1641 cm "1 .
• the product also showed a peak at 1606 cm due to an aromatic ring.
• the aliphatic region of the spectrum suggests that alkyl chains are substantially linear.
• C 24 - 2 8 + olefm alkylated phenol was synthesized by reaction of phenol with C 2 4- 2 8 + alpha olefm using a strongly acidic resin (obtained from Aldrich, Inc., Milwaukee, WI under the tradename AMBERLYST 15TM) comprising divinyl benzene-crosslinked polystyrene, to which sulfonic groups are attached, as a catalyst.
• C 2 4- 3 0+ phenol fumarate ester synthesized using a procedure similar to that used to synthesize dodecyl phenol fumarate.
• An IR spectrum of the product showed absorption peaks due to ester carbonyl at 1746 and 1710 cm "1 and the double bond peak at 1645 cm "1 .
• the product also showed a peak at 1605 cm '1 due to an aromatic ring.
• the aliphatic region of the spectrum suggests that alkyl chains are substantially linear.
• Example 4 The synthesis of dialkyl phenyl fumarate/carbon monoxide copolymer
• Copolymers of dialkyl phenyl fumarate with vinyl acetate were synthesized with R groups of C12H25, C24-28, H49. 5 , C 30 H i. Such copolymers have the structure
• Copolymers were formed using free-radical polymerization techniques as follows:
• Hydroquinone inhibitor was removed from the vinyl acetate by passing it through an inhibitor remover column.
• the purified vinyl acetate was placed in tubes with the dialkyl phenyl fumarate ester monomers.
• the tubes were capped with septa and flushed with nitrogen for one hour.
• the solvent was flushed with nitrogen and added to the tubes containing the monomers.
• the solutions were brought to their reaction temperatures, and the initiator (dissolved in the appropriate solvents) was added to each monomer solution.
• both monomers and initiator were loaded together, flushed with nitrogen, and then brought to reaction temperature. The mixtures were stirred overnight. The next day, the polymer solutions were precipitated in methanol and vacuum dried.
• Table 1 sets forth copolymerization reaction details.
• 3% azobisisobutyronitrile is available from Aldrich, Inc., Milwaukee, WI under the tradename ALBNTM, and 3% [l,l'-azobis(cyanocyclohexane)] is an available from DuPont Chemicals, Wilmington, DE under the tradename V-88TM.
• C ⁇ PhF Didodecylphenol fumarate
• PI1F Di[p-alkyl (C 30 ) phenyl] fumarate
• PhF Di[p-alkyl (C 24 - 2 s)phenyl] fumarate
• Dialkyl phenyl fumarate - styrene copolymer having the structure:
• R C 3 oH 6 i or C24- 28 H4 9 .57
• Copolymers were synthesized according to the polymerization conditions set forth in Examples 5 through 9.
• Tables 3 and 4 show the polymerization conditions and characterization results, respectively.
• DSC differential scanning colormetry
• WAT is a measure of the thermodynamic barrier for the formation of a stable nucleus for further crystal growth. It is the temperature at which stable wax crystals first begin to appear. For wax crystallization to take place, solutions have to be supercooled to cross this thermodynamic free energy barrier to nucleation. A lowering of the WAT is desirable, because it indicates a larger thermodynamic barrier for further wax crystal growth. Additives that interfere with the nucleation stage of wax formation increase the free energy barrier and, thereby, decrease the WAT. Larger decrease in WAT indicate better performance of the wax crystal modifier additive.
• Table 5 shows that the additives of the present invention are effective wax crystal modifiers.

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• Chemical & Material Sciences (AREA)
• Oil, Petroleum & Natural Gas (AREA)
• Health & Medical Sciences (AREA)
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• Chemical Kinetics & Catalysis (AREA)
• General Chemical & Material Sciences (AREA)
• Organic Chemistry (AREA)
• Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
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• 1999
  • 1999-05-13 CA CA002333571A patent/CA2333571A1/en not_active Abandoned
  • 1999-05-13 WO PCT/EP1999/003313 patent/WO1999062973A1/en not_active Application Discontinuation
  • 1999-05-13 EP EP99955277A patent/EP1091987A1/de not_active Withdrawn
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