WO2001048032A1 - Polyacrylate esters, their preparation and use as a low-temperature flow-improver in middle distillate oils - Google Patents
Polyacrylate esters, their preparation and use as a low-temperature flow-improver in middle distillate oils Download PDFInfo
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- WO2001048032A1 WO2001048032A1 PCT/GB2000/004796 GB0004796W WO0148032A1 WO 2001048032 A1 WO2001048032 A1 WO 2001048032A1 GB 0004796 W GB0004796 W GB 0004796W WO 0148032 A1 WO0148032 A1 WO 0148032A1
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- polymer
- alcohol
- oil
- middle distillate
- aliphatic
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Classifications
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- 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
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- 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
- C08F8/00—Chemical modification by after-treatment
- C08F8/14—Esterification
-
- 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
- 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 present invention relates to polymers, especially ester polymers, and to their preparation and use, particularly in diesel fuels
- Diesel fuels are middle distillates, generally boiling within the range of 170 to 390°C Such fuels comprise hydrocarbons of varying types and molecular weights Typically, 5 to 30% of the fuel consists of paraffinic hydrocarbons Paraffinic hydrocarbons tend to have limited solubility Thus, when the fuel is cooled, the less soluble, higher molecular weight paraffins tend to come out of solution as waxy crystals The temperature at which this occurs is known as the cloud point of the fuel
- the waxy crystals formed at the cloud point have a strong affinity for each other and readily interlock to form larger crystal agglomerates Thus, if the fuel is cooled further, more wax will come out of solution until there is sufficient to form an interlocking structure
- Such structures may impede or prevent the flow of fuel through, for example, fuel lines and filters, causing operating difficulties in diesel fuel systems, particularly, during the winter, when ambient temperatures are low
- a polymer which may be added to middle distillate oils to reduce the tendency for wax to deposit from such oils
- the medium chain length group is preferably of 4 to 30 carbon atoms, more preferably, 6 to 25 carbon atoms, even more preferably, 10 to 22 carbon atoms, preferably 6-15, more preferably, 9-14 carbons, for example, 12 carbons.
- the molecular weight of the polymer is less than 25,000, for example, less than 20,000, preferably, less than 15,000 and more preferably, less than 10,000.
- the M w of the polymer may be between 80 and 8,000; preferably, between 700 and 5000.
- the molecular weight is between 1800 and 3500.
- the molecular weight distribution (Mw/Mn) is 2-20, for example, 2-6.
- the polymer may be such that at least 10 %, for example, at least 30%, for example, 35 to 45% of the aliphatic groups have said medium length chain group of 4 to 40 carbon atoms.
- Ester (1) may be derived from an ethylenically unsaturated carboxylic acid, and a medium length chain alcohol.
- the unsaturated group of the ethylenically unsaturated carboxylic acid may be alpha, beta or gamma to the carboxylic group.
- Acrylic acids, and in particular, methacrylic acids are preferred.
- the acid may also be a mono, di or tricarboxylic acid. Suitable diacids include fumaric, maleic and crotonic acids.
- the medium length alcohol is preferably linear, but may be branched.
- the alcohol contains 4 - 40 carbon atoms, preferably, 4 to 30, more preferably, 6 to 25 carbon atoms, even more preferably, 10 to 22 carbon atoms.
- Suitable alcohols may contain 8, 10, 12, 14, 16, 18, 20 or 22 carbon atoms.
- suitable alcohols include octanol, decanol, dodecanol, tetradecanol, hexadecanol, octadecanol, eicosanol, docosanol and nafol.
- Branched alcohols such as, for example, 2-methyl dodecyl alcohol are also suitable.
- the alcohol may be natural or synthesised, for example, by oxo or ALFOL processes.
- the alcohols employed may be substantially pure, but are preferably mixtures of alcohols.
- mixtures include natural lauryl alcohols and mixtures of alkanols of even carbon number, with one carbon number predominating with decreasing proportions of alkanols of lower and higher carbon number, as in e.g. a Gaussian distribution.
- Such mixtures may contain at least 50%, for example, at least 80 or 90% (by mole) of one alkanol.
- Examples of such mixtures are commercially produced lauryl alcohol with a majority of a 12 carbon alkanol and smaller amounts of 8, 10 and 14 carbon alkanols
- Commercial mixtures of at least two of, for example, 8, 10, 12, 14, 16, 18, 20 or 22 carbon alcohols may be used.
- the medium length chain aliphatic alcohol may also be employed as a mixture of alcohols with a bimodal distribution of the carbon number content, e g with at least 25% moles of each of 2 alcohols, especially alcohols different in at least 1, or at least 3 carbons, such as 1-6 e g 2 or especially 3-6 e g 4 or 6 carbons Examples of such mixtures are 8 and 12, or 10 and 14 or 8 and 14 carbon alkanols.
- ester (1) is an acrylate of an alcohol selected from the group consisting of.
- no more than two alcohols are selected from said group Where two alcohols are selected, they preferably have carbon numbers which differ by two Ester (1) may also be derived from an ethylenically unsaturated alcohol and a medium length chain carboxylic acid
- the unsaturated group of the ethylenically unsaturated alcohol may be alpha, beta or gamma to the alcohol group
- the ethylenically unsaturated alcohol preferably contains 2 to 6 carbon atoms It may be an allyl alcohol, a methallyl alcohol, or a vinyl alcohol
- the medium length carboxylic acid is preferably linear, but may be branched
- the acid is preferably saturated and may contain 4 to 40 carbons, for example, preferably, 4 to 30, more preferably, 6 to 25 carbon atoms, even more preferably, 10 to 22 carbon atoms
- Suitable acids may comprise 8, 10, 12, 14, 16, 18, 20, or 22 carbon atoms
- Suitable acid are n-octanoic, n-decanoic, n-undecanoic, n-dodecanoic, n- tridecanoic, n-tetradecanoic acids
- the acids may be substantially pure, but are preferably mixtures of acids, for example, as in lauric acid or mixtures of acids of even carbon number with one carbon number predominating with decreasing proportions of acids of lower and higher carbon numbers, as in e g a Gaussian distribution
- Such mixtures may contain at least 50%, for example, at least 80 or 90% (by mole) of one alkanoic acid and smaller amount(s) of other alkanoic acid(s).
- Examples of such mixtures are commercial lauric acid consisting predominantly of acids having 12 carbon atoms. Small * amounts of acids comprising 10 and 14 carbon atoms are also present.
- the acid may also be used as a mixture of acids with a bimodal distribution of the carbon number content.
- ester (2) is different to ester (1), but falls within the same definition as ester (1).
- ester (2) is an ester of an aliphatic carboxylic acid with an aliphatic alcohol, wherein either the acid or the alcohol is ethylenically unsaturated and the other of the acid or alcohol has a medium length chain group of 4-40 carbon atoms.
- ester (2) is also derived from an ethylenically unsaturated carboxylic acid, and a medium length chain alcohol.
- ester (1) is derived from an ethylenically unsaturated alcohol, and a medium length chain carboxylic acid
- ester (2) is also derived from an ethyleneically unsaturated alcohol, and a medium length chain carboxylic acid.
- the polymer of the present invention may also comprise structural units derived from an ester (3).
- Ester (3) is an ester of an aliphatic carboxylic acid and an aliphatic alcohol, wherein either the acid or the alcohol is ethylenically unsaturated and the other of the acid or alcohol has a short chain aliphatic group of 1 - 4 carbon atoms.
- units derived from ester (3) may form 10 to 60 ml %, preferably, 20 to 40 mol % of the resulting polymer.
- ester (3) is derived from an ethyleneically unsaturated carboxylic acid and an aliphatic alcohol of 1 to 4 carbon atoms. Suitable alcohols include methanol, ethanol, propanol and butanol. Methanol and t-butanol are preferred.
- ester (3) is derived from an ethylenically unsaturated alcohol and a carboxylic acid of 1 to 4 carbon atoms.
- Suitable acids include formic acid, acetic acid, propaionic acid and buytyric acid. Acetic acid and propionic acid are preferred
- the polymers of the invention may also contain structural units from other unsaturated monomers e g ones monomers containing at least one N and/or S atom or O atom in an ether linkage
- the polymers of the present invention may be obtained by direct polymerisation of ester (1), optionally, with ester (2) and/or (3).
- ester (1) optionally, with ester (2) and/or (3)
- the constituent ester monomers may be co-polymerised together directly
- the polymerisation may be performed in a conventional manner with or without a diluent
- a hydrocarbon diluent such as hexane, heptane, or a higher boiling hydrocarbon oil may be employed
- the polymerisation may be carried out at a temperature of 25-120°C, such as 60-100°C
- a free radical catalyst such as a peroxide or an azo catalyst
- Suitable free radical catalysts include benzoyl peroxide
- a suitable azo catalyst is azobis isobutyronitrile
- the polymerisation is usually performed under inert conditions, for example, under nitrogen or argon
- the polymerisation time may be 0 5-40 hr, preferably 5-25 hr, at a reaction temperature of 60-100°C
- the reaction product may be purified by evaporation under vacuum to remove unreacted monomer, and/or precipitation of the product with methanol from a liquid aromatic or aliphatic hydrocarbon solution of the product
- the polymers may also be produced by transesterification
- a process for production the production of a polymer comprising the transesterification of at least one polymer of the ester (3) with an aliphatic alcohol or carboxylic acid having an aliphatic group of 4-40 carbon atoms
- the alcohol or carboxylic acid has 4 to 30 carbon atoms, more preferably, 6 to 25 carbon atoms, even more preferably, 10 to 22 carbon atoms, preferably 6-16, and most preferably, 9-14 carbons, for example, 12 carbon atoms
- an aliphatic alcohol is employed
- a polyacrylate is transesterified with an alcohol having 4 to 40 carbon atoms
- the polyacrylate has a molecular weight of 1000 to 3000, more preferably, 1500 to 2500, for example, about 2000 - 2100
- a suitable polyacrylate is polymethylacrylate.
- the polymethacrylate employed has a molecular weight of 1000 to 3000, more preferably, 1500 to 2500, for example, about 2000 - 2100.
- the transesterified product may comprise 15 to 85% by weight, preferably, 55 to
- the transesterified product may comprise 15 to 85% by weight, more preferably, 30 to 40% by weight, most preferably, 35 to 40% by weight of units derived from the alcohol or carboxylic acid
- the transesterified product comprises 60 to 63% by weight of units derived from the polymethacrylate and 37 to 40% of units derived from the alcohol or carboxylic acid
- the alcohol is a C 12 or C16 alcohol
- the transesterification product of the invention may be purified, or used as such In the case of the latter, the transesterification product may contain unreacted polymer and/or unreacted alcohol or acid
- the unreacted alcohol or acid may be present in amount of 1-50%, for example, 10 - 50 % by weight, based on the weight of polymer (3)
- the unreacted alcohol or acid may optionally be removed.
- the transesterification reaction may be performed at 50-150°C, for example, 60- 120°C
- the reaction time may bel -30 hours, preferably, 5-20 hours
- a catalyst may be used to catalyse the transesterification reaction
- Suitable catalysts include organic soluble strong acids and basic catalysts
- Suitable acids include aromatic sulphuric acids, such as p-toluene sulphonic acid
- Suitable basic catalysts include metal alkoxides
- Suitable metal alkoxides include polyvalent metal alkoxides such as tetra methyl or tetra ethyl titanate, and alkali metal alkoxides such as sodium methoxide or ethoxide
- Such alkoxides may be added as such or may be prepared in situ
- Amounts of the basic catalyst may be 0 05-5% e g 0 1-1% by weight of the feed polymer
- the present invention also provides a method of reducing wax formation and/or deposition in a wax-containing middle distillate oil, said method comprising mixing a polymer of the present invention with said oil
- said oil is mixed with a polymer of the present invention which is prepared using the transesterification process described above
- the middle distillate oil employed is typically a * petroleum based oil obtainable from crude oil.
- the middle distillate oil is obtainable as a fraction distilling in the lighter fuel oil (e g kerosene or jet fuel range) to the heavy fuel oil range (eg heating oil)
- Middle distillates may comprise atmospheric or vacuum distillates, cracked gas oil or blends of straight run and thermally and/or catalytically cracked distillates
- suitable middle distillates include kerosene, jet fuel, diesel fuel, heating oil, visbroken gas oil, light cycle oil, vacuum gas oil, light fuel oil and fuel oil
- the boiling range or the middle distillate measured is usually 100-500°C eg 140-400°C Diesel oil eg for vehicles which may be for summer or especially winter use, is preferred
- the middle distillate oil may comprise hydrocarbons which may be primarily aliphatic or aromatic in nature Preferably, however, the oil comprises mixtures of aliphatic and aromatic hydrocarbons
- the hydrocarbon may contain 0 01 to 30%, for example, 0 1 to 5% by weight of wax
- the middle distillate oil may have a cloud point value of at least -20°C, for example, -20 to 5°C, more specifically, -15 to 0 °C In certain embodiments, the middle distillate oil may have a cloud point of-15 to - 5°C, for example, between -6 and -7°C
- the polymers of the present invention may reduce the cloud point of the middle distillate oil by more than 0 2°C, preferably, more than 0 5°C, more preferably, more than 1°C, for example, between 0 2 and 3°C
- the pour point of the middle distillate oil may be 1-20°C, for example, 1-10°C lower than the WAT (Wax Appearance Temperature) value
- the pour point may be - 30°C to 0°C e g -20°C to -5°C
- the polymers of the invention may reduce the pour point value of the liquid hydrocarbon by at least 3°C e g 3-21°C such as 6-15°C
- the cold filter plugging point (CFPP) of the middle distillate oil may be at least -20°C, for example, 0 to -20°C, more specifically, -15 to -5°C, for example, -10 to -5°C
- the polymers of the present invention may reduce the CFPP of the middle distillate oil by more than 0 5°C, preferably, more than 1°C, more preferably, more than 2°C, and most preferably, more than 3°C, for example, by 3 to 10°C
- the middle distillate o_l may also contain at least one additive.
- Suitable additives include conventional flow improvers, such as a polyoxyalkylene compounds, ethylene vinyl acetate (EVA) copolymers, and nitrogenous compounds, preferably having at least one long chain such as of 4-40 carbons, hydrocarbyl bonded directly to nitrogen such as an amine salt or amide.
- Suitable polyoxyalkylene compounds include polyoxyethylene diester, diether or ester/ether or mixtures thereof.
- suitable additives include detergents, anti foams, ignition improvers, lubricity additives and/or corrosion inhibitors.
- Mixtures of additives may be present in the middle distillate oil.
- the polymer of the present invention may be added to the middle distillate oil, such that the final concentration of the polymer in the oil is 2 - 10,000, preferably, 5 - 10,000 ppm, more preferably, 10 - 8,000 ppm, even more preferably, 20-5000 ppm, yet more preferably, 50-1000ppm.
- the final concentration of the polymer in the oil may be 100 to 600 ppm, or more specifically, 250 to 500 ppm based on the weight of oil.
- the polymer of the invention may be added to the middle distillate oil/middle distillate oil-containing mixture either batchwise, continually or continuously.
- the polymer may be contacted with a moving liquid body of the oil, preferably, by adding the polymer to a line containing flowing liquid oil, upstream of a cooler location where wax deposition may occur in the absence of said compound.
- the polymers of the invention may be added to a tank of the oil e.g. to inhibit deposition of wax.
- the polymer may first be dissolved in a liquid solvent, and the resulting solution added to the middle distillate oil.
- Suitable solvents include hydrocarbon solvents such as toluene and/or xylene.
- the resulting solution may also comprise at least one of the aforementioned additives.
- the resulting solution or concentrate is such that each of the polymer and additive(s) is present in an amount of at least 1% e.g. at least 5% (by weight). It has been found that when the polymers of the present invention are used in combination with certain additives, in particular, conventional flow improvers such as EVA, the activity of the additives is enhanced.
- a mixture comprising a middle distillate oil, a conventional flow improver and a polymer of the present invention.
- This mixture may be prepared by adding the polymer of the present invention to a mixture comprising a middle distillate oil and a conventional flow improver, or adding a conventional flow improver to a mixture comprising a middle distillate oil and the polymer of the present invention.
- the polymer of the present invention and the conventional flow improver may be added simultaneously to a middle distillate oil.
- Suitable middle distillate oils, polymers of the present invention and conventional flow improvers include those described earlier in this specification.
- the preferred conventional flow improver employed is EVA.
- the preferred polymer of the present invention is one prepared by transesterification. Most preferably, this transesterified polymer is prepared by the transesterification of polymethacrylate and an alcohol. In one embodiment of the invention, the transesterified product comprises 60 to 63% by weight of units derived from the polymethacrylate and 37 to 40% of units derived from a C 12 or C16 alcohol.
- the starting polymethacrylate may have a molecular weight of 1500 to 3000, preferably, 2000 to 2500, for example, about 2100.
- the amount of polymer present in the mixture of the present invention may be 2 - 10,000, preferably, 5 - 10,000 ppm, more preferably, 10 - 8,000 ppm, even more preferably, 20-5000 ppm, and yet more preferably, 50-l OOOppm.
- the final concentration of the polymer in the oil may be 100 to 600 ppm, or more specifically, 250 to 500 ppm based on the weight of oil.
- the amount of conventional flow improver present may be 10-10,000 ppm, preferably, 20-5000 ppm, more preferably, 50-1000 ppm, even more preferably, 100 to 600 ppm, for example, 250 to 500 ppm based on the weight of oil.
- the mixture of the present invention may also contain 5-2000 ppm e.g. 30-1000 ppm (on the same basis) of medium chain alcohol, e.g of 8-14 or 10-12 carbons, such as described for use in the preparation of the ester polymer.
- Yet another aspect of the present invention is the use of a polymer as described above in a method for reducing at least one of the cloud point, CFPP and pour point of a middle distillate oil.
- the present invention also provides the use of a polymer as described above for enhancing the flow characteristics (such as pour point, cloud point and/or cold filter plugging point (CFPP)) of a mixture comprising a middle distillate oil and a conventional flow improver, such as EVA
- Example 2 The procedure of Example 1 was followed with poly(methyl acrylate), MW
- Example 4 The procedure of Example 1 was followed with poly(methyl acrylate), MW 2,100, (5 13 g) and Nafol 1618H (4 40 g) The sodium methoxide catalyst (94 5 mg) was added after 1 5 hours The reaction was run for 10 5 hours Proton NMR indicated a degree of transesterification of 38%
- Example 4 The procedure of Example 1 was followed with poly(methyl acrylate), MW 2,100, (5 13 g) and Nafol 1618H (4 40 g) The sodium methoxide catalyst (94 5 mg) was added after 1 5 hours The reaction was run for 10 5 hours Proton NMR indicated a degree of transesterification of 38%
- Example 4 The procedure of Example 1 was followed with poly(methyl acrylate), MW 2,100, (5 13 g) and Nafol 1618H (4 40 g) The sodium methoxide catalyst (94 5 mg) was added after 1 5 hours The reaction was run for 10 5 hours Proton NMR indicated a degree of transesterification of 38%
- Example 5 The procedure of Example 1 was followed with poly(methyl acrylate), MW 2, 100, (5 23 g) and 1-eicosanol (5 27 g) Xylene was used as the solvent instead of toluene The reaction was run for 14 5 hours After 1 5 hours sodium methoxide catalyst was added (0 118 g) Proton NMR indicated a degree of transesterification of 40% Example 5
- Example 6 The procedure of Example 1 was followed with poly(methyl acrylate), MW 2, 100, (5 17 g) and 1-docosanol (5 71 g) Xylene was used as the solvent instead of toluene The reaction was run for 14 5 hours After 1 5 hours sodium methoxide catalyst was added (0 118 g) Proton NMR indicated a degree of transesterification of 42% Example 6
- Example 7 The procedure of Example 1 was followed witn " poly(methyl acrylate), MW 2,100, (3.08g) and 1-docosanol (6.66 g). Xylene was used as the solvent instead of toluene. The reaction was run for 10 hours. After 1.25 hours sodium methoxide catalyst (47 mg) was added. Additional sodium methoxide (71 mg) was added another 1 45 hours later. 1H NMR indicated a degree of transesterification of 83% There was 6% of the initial 1-docosanol left unreacted. Example 7
- Example 9 The procedure of Example 7 was followed with poly(methyl acrylate), MW 2,100, (5 08 g) and 1-hexdecanol (4 30 g) and sodium methoxide (142 mg) The reaction was run for 9 hours Proton NMR spectroscopy indicated a degree of transesterification of 40% Example 9
- Example 10 The procedure of Example 7 was followed with poly(methyl acrylate), MW 2, 100, (5.08 g) and 1-octadecanol (4 80 g). The reaction was run for 9 hours and 142 mg of sodium methoxide catalyst was used in total Proton NMR indicated a degree of transesterification of 40%
- Example 10 The procedure of Example 7 was followed with poly(methyl acrylate), MW 2, 100, (5.08 g) and 1-octadecanol (4 80 g). The reaction was run for 9 hours and 142 mg of sodium methoxide catalyst was used in total Proton NMR indicated a degree of transesterification of 40% Example 10
- Example 7 The procedure of Example 7 was followed with poly(methyl acrylate), MW 2,100, (5 08g) and 1 -tetradecanol (3 81 g). The reaction was run for 8 hours 1 hour into the reaction sodium methoxide catalyst was added (47 mg) After another hour a second portion of sodium methoxide catalyst (47 mg) was added 1H NMR indicated a degree of transesterification of 37%. The product was present at 17% w/w in toluene Example 11
- the cloud point and CFPP of a middle distillate oil having the characteristics in Table 1 below were measured using IP 219/ASTM D2500 and IP 309, respectively The cloud point was found to be -6 5°C, and the CFPP, -9°C
- Example 7 The polymer produced in Example 7 was then added to the middle distillate oil of Table 1, such that the amount of polymer in the resulting mixture was 500 ppm
- the cloud point and CFPP of the resulting mixture were -7 5 and -17°C, respectively
- Example 7 the polymer produced in Example 7 and EVA were added to the middle distillate of Table 1 , such that the resulting mixture contained 500 ppm of the polymer of Example 7 and 250 ppm of EVA
- the CFPP of the resulting mixture was found to be -27°C
- EVA was added to a heating oil in the proportions described in Table 2 below, and the CFPPs of the resulting mixtures were measured
- the heating oil employed had a density of 0 845 glcm", a cloud point of 0 4, an initial boiling point of 170°C, and a final boiling point of 387°C
- Example 7 the polymer produced in Example 7 was added to the mixtures of Comparative Example A, in an amount of 5% of the amount of EVA already present in each of the respective mixtures.
- the CFPPs of the resulting mixtures were measured (see Table 3)
- Example 15 a blend of heating oil, EVA (lOOppm) and polymer of Example 7 (lOppm) was prepared.
- the CFPP of the blend was found to be -16°C Example 15
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Abstract
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Priority Applications (2)
Application Number | Priority Date | Filing Date | Title |
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AU25298/01A AU2529801A (en) | 1999-12-23 | 2000-12-14 | Polyacrylate esters, their preparation and use as a low-temperature flow-improver in middle distillate oils |
EP00988967A EP1244712A1 (en) | 1999-12-23 | 2000-12-14 | Polyacrylate esters, their preparation and use as a low-temperature flow-improver in middle distillate oils |
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GBGB9930596.3A GB9930596D0 (en) | 1999-12-23 | 1999-12-23 | Compounds |
GB9930596.3 | 1999-12-23 |
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WO2001048032A1 true WO2001048032A1 (en) | 2001-07-05 |
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PCT/GB2000/004796 WO2001048032A1 (en) | 1999-12-23 | 2000-12-14 | Polyacrylate esters, their preparation and use as a low-temperature flow-improver in middle distillate oils |
Country Status (5)
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US (1) | US20030041508A1 (en) |
EP (1) | EP1244712A1 (en) |
AU (1) | AU2529801A (en) |
GB (1) | GB9930596D0 (en) |
WO (1) | WO2001048032A1 (en) |
Cited By (7)
Publication number | Priority date | Publication date | Assignee | Title |
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WO2004048502A1 (en) * | 2002-11-22 | 2004-06-10 | Basf Aktiengesellschaft | Use of homopolymers of ethylenically unsaturated esters for improving the action of cold flow improvers |
WO2011084552A2 (en) | 2009-12-17 | 2011-07-14 | Air Products And Chemicals, Inc. | Polymeric compositions for personal care products |
US8361432B2 (en) | 2010-12-08 | 2013-01-29 | Fluor Enterprises, Inc. | Reactor, a retained catalyst structure, and a method for improving decomposition of polysulfides and removal of hydrogen sulfide in liquid sulfur |
US8663596B2 (en) | 2010-01-25 | 2014-03-04 | Fluor Enterprises, Inc. | Reactor, a structure packing, and a method for improving oxidation of hydrogen sulfide or polysulfides in liquid sulfur |
US10131776B2 (en) | 2009-09-25 | 2018-11-20 | Evonik Oil Additives Gmbh | Composition to improve cold flow properties of fuel oils |
US11999920B2 (en) | 2020-09-14 | 2024-06-04 | Ecolab Usa Inc. | Cold flow additives for plastic-derived synthetic feedstock |
US12031097B2 (en) | 2022-10-12 | 2024-07-09 | Ecolab Usa Inc. | Antifouling agents for plastic-derived synthetic feedstocks |
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WO2014033733A1 (en) * | 2012-07-24 | 2014-03-06 | Reliance Industries Limited | A method for removing chlorides from hydrocarbon stream by steam stripping |
CA3064009A1 (en) | 2017-05-23 | 2018-11-29 | Ecolab Usa Inc. | Dilution skid and injection system for solid/high viscosity liquid chemicals |
WO2018217889A1 (en) | 2017-05-23 | 2018-11-29 | Ecolab Usa Inc. | Injection system for controlled delivery of solid oil field chemicals |
Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4153423A (en) * | 1975-03-28 | 1979-05-08 | Exxon Research & Engineering Co. | Polymer combinations useful in distillate hydrocarbon oils to improve cold flow properties |
US4588640A (en) * | 1984-07-10 | 1986-05-13 | Petrolite Corporation | Particulate compositions |
JPS63270795A (en) * | 1987-04-30 | 1988-11-08 | Dai Ichi Kogyo Seiyaku Co Ltd | Crude oil composition having improved low-temperature fluidity |
US5441545A (en) * | 1985-08-28 | 1995-08-15 | Exxon Chemical Patents Inc. | Middle distillate compositions with improved low temperature properties |
US5744523A (en) * | 1992-10-28 | 1998-04-28 | Th. Goldschmidt Ag | Use of polyacrylate esters as dispersants |
WO1998021446A1 (en) * | 1996-11-14 | 1998-05-22 | Bp Exploration Operating Company Limited | Inhibitors and their uses in oils |
Family Cites Families (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2403267A (en) * | 1943-08-24 | 1946-07-02 | Standard Oil Dev Co | Diesel fuels |
US3275427A (en) * | 1963-12-17 | 1966-09-27 | Exxon Research Engineering Co | Middle distillate fuel composition |
US3445205A (en) * | 1964-09-25 | 1969-05-20 | Sinclair Research Inc | Fuel oil composition having improved low temperature properties |
GB1285087A (en) * | 1969-12-18 | 1972-08-09 | Shell Int Research | Oil compositions |
US3904385A (en) * | 1972-05-08 | 1975-09-09 | Texaco Inc | Polyacrylates and waxy residual fuel compositions thereof |
CA1071865A (en) * | 1975-03-28 | 1980-02-19 | Max J. Wisotsky | Polymer combinations useful in distillate hydrocarbon oils to improve cold flow properties |
US4153422A (en) * | 1975-04-07 | 1979-05-08 | Exxon Research & Engineering Co. | Polymer combinations useful in distillate hydrocarbon oils to improve cold flow properties |
US5281329A (en) * | 1989-07-14 | 1994-01-25 | Rohm Gmbh | Method for improving the pour point of petroleum oils |
US6265360B1 (en) * | 1999-11-12 | 2001-07-24 | The Lubrizol Corporation | Compositions containing wax modifiers |
-
1999
- 1999-12-23 GB GBGB9930596.3A patent/GB9930596D0/en not_active Ceased
-
2000
- 2000-12-14 WO PCT/GB2000/004796 patent/WO2001048032A1/en not_active Application Discontinuation
- 2000-12-14 EP EP00988967A patent/EP1244712A1/en not_active Withdrawn
- 2000-12-14 AU AU25298/01A patent/AU2529801A/en not_active Abandoned
- 2000-12-14 US US10/168,404 patent/US20030041508A1/en not_active Abandoned
Patent Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4153423A (en) * | 1975-03-28 | 1979-05-08 | Exxon Research & Engineering Co. | Polymer combinations useful in distillate hydrocarbon oils to improve cold flow properties |
US4588640A (en) * | 1984-07-10 | 1986-05-13 | Petrolite Corporation | Particulate compositions |
US5441545A (en) * | 1985-08-28 | 1995-08-15 | Exxon Chemical Patents Inc. | Middle distillate compositions with improved low temperature properties |
JPS63270795A (en) * | 1987-04-30 | 1988-11-08 | Dai Ichi Kogyo Seiyaku Co Ltd | Crude oil composition having improved low-temperature fluidity |
US5744523A (en) * | 1992-10-28 | 1998-04-28 | Th. Goldschmidt Ag | Use of polyacrylate esters as dispersants |
WO1998021446A1 (en) * | 1996-11-14 | 1998-05-22 | Bp Exploration Operating Company Limited | Inhibitors and their uses in oils |
Non-Patent Citations (1)
Title |
---|
DATABASE CHEMABS [online] CHEMICAL ABSTRACTS SERVICE, COLUMBUS, OHIO, US; UKAI, MASAHIRO ET AL: "Low-temperature flow improvers for wax-rich crude oils", XP002162008, retrieved from STN Database accession no. 110:234535 * |
Cited By (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2004048502A1 (en) * | 2002-11-22 | 2004-06-10 | Basf Aktiengesellschaft | Use of homopolymers of ethylenically unsaturated esters for improving the action of cold flow improvers |
US10131776B2 (en) | 2009-09-25 | 2018-11-20 | Evonik Oil Additives Gmbh | Composition to improve cold flow properties of fuel oils |
WO2011084552A2 (en) | 2009-12-17 | 2011-07-14 | Air Products And Chemicals, Inc. | Polymeric compositions for personal care products |
US8663596B2 (en) | 2010-01-25 | 2014-03-04 | Fluor Enterprises, Inc. | Reactor, a structure packing, and a method for improving oxidation of hydrogen sulfide or polysulfides in liquid sulfur |
US8361432B2 (en) | 2010-12-08 | 2013-01-29 | Fluor Enterprises, Inc. | Reactor, a retained catalyst structure, and a method for improving decomposition of polysulfides and removal of hydrogen sulfide in liquid sulfur |
US11999920B2 (en) | 2020-09-14 | 2024-06-04 | Ecolab Usa Inc. | Cold flow additives for plastic-derived synthetic feedstock |
US12031097B2 (en) | 2022-10-12 | 2024-07-09 | Ecolab Usa Inc. | Antifouling agents for plastic-derived synthetic feedstocks |
Also Published As
Publication number | Publication date |
---|---|
EP1244712A1 (en) | 2002-10-02 |
AU2529801A (en) | 2001-07-09 |
GB9930596D0 (en) | 2000-02-16 |
US20030041508A1 (en) | 2003-03-06 |
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