GB2320719A - Gasoline detergents - Google Patents

Abstract

This invention provides compounds of formula (I): Z.NH(CH 2 CH 2 NZ) y .Z (I) wherein ```Z is H, C 8-16 straight or branched chain alkanoyl or with the proviso that at least one Z is ```R is C 2-16 straight or branched chain alkyl or dodecylphenyl, ```R' is H, CH 3 or CH 2 CH 3 , ```x is an integer from 12 to 28, and ```y is an integer from 1 to 4.

Description

GASOLINE DETERGENTS This invention relates to novel gasoline detergents, in particular containing a novel linkage based on a terephthalate moiety between conventional hydrocarbyl polyether monool and polyamine groups.

Since automobiles were invented and operated on gasoline, they have accumulated deposits in all fuel systems. These deposits can affect the operation of the vehicle, causing difficult starting, rough idle, stalling, poor acceleration, and increased fuel consumption and pollution emissions. Port fuel injectors (PFI) are the most sensitive engine components, followed by intake valves. Fuel-injected gasoline engines are especially sensitive to deposit formation in all parts of the fuel intake system. The recent rapid increase in the use of this type of engine has precipitated a corresponding growth in the gasoline detergent market over the last several years.

All gasoline in the U.S. market is treated with a PFI detergent at this time. Many older carburetor detergents function as PFI detergents, however, these detergents often contribute to increasing intake valve deposits making them unsuitable for use in modern vehicles. The U.S. government, through the Clean Air Act, also has mandated that all gasoline sold in the U.S. contain an effective amount of an intake valve detergent. This has caused a significant change in the gasoline detergent market over the last seven years, with many market-leading detergents now no longer suitable for use. Only detergents that show intake valve detergency are acceptable in the marketplace now.

Detergents are not sold to gasoline marketers for direct addition to fuel, but rather are formulated with other components into a package. In addition to the detergent, the package usually contains a high-flash hydrocarbon solvent for improved handling (the detergents are usually viscous liquids), a fluidizer or carrier oil to help control intake valve deposits, and a dehaze additive. The fluidizer is usually a petroleumbased or thermally stable synthetic oil.

Gasoline detergents share physical properties in common with aqueous-based detergents. They have one or more long-chain hydrocarbon-soluble tails usually linked through some connecting group to a polar head. Since they must be soluble in gasoline, the hydrophobic tail must be long enough to overcome the insolubility of the polar head. The right mix of hydrophilic and hydrophobic behaviour must be also found to allow the detergent to remove polar, high molecular weight deposits from metal surfaces and to keep them dispersed once in the liquid phase. Intake valve detergents with this ability have significantly higher molecular weights than older carburetor detergents.

Common hydrocarbon-soluble tail fragments include polyolefins of several sorts, especially polypropylene and polybutylene. Polyethers are increasingly commonly being used as the tail fragment. They have an -OCH2CHRrepeat unit, where R = H, CH3, CH2CH3 or mixtures thereof. Homo- and co-polymers of 1,2-butylene oxide (R = CH2CH3) are the most common. As expected, the longer R group gives greater gasoline solubility. These polyethers also have low thermal stability, degrading to volatile by-products upon thermolysis on the hot intake valve surface.

Polyamines are by far the most common head groups.

These are usually ethylenediamine (EDA) or higher oligomers up to tetraethylenepentamine (TEPA) or occasionally alkanolamines. Phosphorus- and sulfurbased head groups cannot be used due to incompatibility with catalytic converters. Imidazoline thione and carboxylate head groups have also been used.

There have been many different types of connector groups described in the literature. Among these are maleic anhydride, phenols via Mannich phenol/ formaldehyde chemistry, carbamates, acrylonitrile, carbonates, diesters, and methacrylates. Occasionally the amine head is directly attached to a hydrocarbonsoluble tail through an amination reaction. Each connector has unique advantages and disadvantages in its use. The most common connectors are maleic anhydride and phenols.

Gasoline detergents may be divided into two groups by molecular weight. Low molecular weight means less than about 500; high means above about 1200 amu. Low molecular weight detergents are effective in keeping carburetor and PFI surfaces clean with only limited effectiveness at cleaning fouled injectors. They also can be adsorbed onto metal surfaces, imparting some corrosion resistance, and de-icing properties. However, they often contribute to intake valve deposits at higher concentrations. Higher molecular weight detergents are effective not only in keeping carburetor and PFI surfaces clean, but also in PFI clean-up. They also can control intake valve deposits and are often used in combination with polymeric carrier fluids.

Another potential problem is in the use of chlorine-containing reagents in the manufacture of the detergent, leading to traces of chlorine being present in the detergent.

US 4,985,047 discloses a gasoline hydrocarbon fuel containing from 0.0005-1.0 wt% of a polyether diamine compound of the formula:

wherein b has a value from 10-80 and [a+c] has a value from 12 to 40.

US 5,039,310 discloses a liquid fuel containing a minor amount of a detergent/dispersant of structure

wherein x is 1 to about 6, y and z are 0 to about 50 and [y+z] equals 10 to 100, R1 is hydrogen or C1 to about C16 hydrocarbyl or aryl group, R2 and R3 are independently hydrogen or C1 to about C5 hydrocarbyl, R4, R5 and R6 are independently hydrogen, C1 to C30 hydrocarbyl or aryl or a nitrogen containing hydrocarbyl group.

US 5,069,684 discloses a fuel composition containing an additive compound with dispersant or detergent properties based on

wherein x, y and n are integers, y is at least 1, x+y is from 1 to 10, and n is from 1 to 100. R is an alkyl or alkenyl group containing from 8 to about 10000 carbon atoms, R' is H or C1 to C6 alkyl, R" is an alkyl, aryl, alkylaryl, or arylalkyl containing 1 to 100 carbon atoms, R"' is hydrogen or an alkyl, aryl, alkaryl, or arylalkyl containing 1 to 100 carbon atoms; and wherein Z is the arylidene or alkylarylidene moiety of a dicarboxylic acid.

US 5,112,364 discloses a gasoline fuel containing 10 to 2000 mg per kg of fuel of a polyetheramine and/or of a polyetheramine derivative.

SUMMARY OF THE INVENTION The present invention thus provides compounds of formula (I): Z.NH(CH2CH2NZ)y.Z wherein Z is H, C816 straight or branched chain alkanoyl or

with the proviso that at least one Z is

R is C216 preferably C12l6, straight or branched chain alkyl or dodecylphenyl R' is H, CH3 or CH2CH3 x is an integer from 12 to 28 y is an integer from 1 to 4.

Preferred compounds of formula (I) are 1. R = C12, R' = CH3, x = 17, y = 3, n = 2, E79441-125 2. R = C12, R' = CH3, x = 17, y = 4, n = 2, E79441-129 3. R = DDP, R' = CH2CH3, x = 20, y = 3, n = 1.4, E79441-130 4. R = DDP, R' = CH2CH3, x = 20, y = 3, n = 1.4, E79441-134 5. R = C4, R' = CH2CH3, x = 20, y = 4, n = 1.1 + Z = C10 alkanoyl, n = 2 (a mixed adduct) E79441-154 6. R = C13, R' = CH3, x = 16, y = 2, n = 2, E79494-1 7. R = C13, R' = CH3, x = 16, y = 2, n = 2, E79494-9 8. R = C13, R' = CH3, x = 16, y = 3, n = 2, E79494-19 9. R = C13, R' = CH3, x = 16, y = 4, n = 3, E79494-20 10. R = C13, R' = CH3, x = 16, y = 3, n = 3, E79494-47 11. R = C13, R' = CH3, x = 16, y = 1, n = 1, E79494-48 12. R = C4, R' = CH2CH3, x = 13, y = 3, n = 2, E79494-96 in which DDP is dodecylphenyl and n is the molar ratio of the Z group to the polyamine.

Compounds 6-12 are particularly preferred.

DETAILED DESCRIPTION OF THE INVENTION The fact that molecules with a terephthalate linking group can be synthesised is surprising since attempts to link hydrocarbyl polyether monool and polyamine groups using dimethyl malonate, triethyl citrate, itaconic acid and its dimethyl ester all proved unsuccessful or gave products without the required detergent properties. Indeed, initial attempts to form a terephthalate linking group using terephthalic acid and acid catalysts were also unsuccessful, and the present invention utilises an unusual technique based on reacting a terephthalate diester such as dimethyl terephthalate in the presence of a catalyst such as tetraisopropyl titanate to give access to the molecules.

The present invention also thus provides a process for the preparation of compounds of formula (I) as defined above, comprising reacting a hydrocarbyl polyether monool of formula (II): RO- (CH2CHR'O)xH where in R is C216 preferably C12l6, straight or branched chain alkyl or dodecylphenyl R' is H, CH3 or CH2CH3 x is an integer from 12 to 28 with a terephthalic diester of formula (III)

wherein R" is methyl (DMT) and reacting the resulting compound of formula (IV)

wherein R, R', R" and x are as defined above with a polyamine of formula (V) z .HN(CH2CH2NZ) yH where Z is H or C816 straight or branched chain alkanoyl and y is an integer from 1 to 4.

Preferably the terephthalate diester (DMT) is used in excess, the catalyst is tetraisopropyl titanate and the solvent is decane. Using decane gave several unique advantages. Decane boils at 174"C, so that operating under reflux conditions allows to maintenance of the temperature in a range high enough to allow the transesterification to proceed rapidly ( < 1 hour), but not so high that a significant amount of thermal decomposition of the polyether occurred. Methanol and decane are not miscible, so that the methanol reaction by-product can be conveniently removed overhead using a Dean-Stark trap. Also, DMT is not soluble in decane below about 1500C, so that after the reaction was complete, cooling to room temperature caused virtually all of the unreacted DMT to precipitate out of solution.

Alternatively a solvent such as xylene would be expected to be useful in place of decane.

The conversion of the half-ester intermediates to amide products proceeds smoothly either by simple mixing of the polyamine with the neat half-ester, with or without a solvent, and heating at 150-160"C until complete. Often a trace amount of tarry by-product is produced, perhaps from the reaction of trace amounts of DMT present with polyamine. This is filtered out to produce clear, light yellow oils. They are all readily soluble in hexane, toluene, ethanol, or methanol.

The invention also provides a fuel additive composition comprising a compound of formula (I) as defined above and optionally a fuel miscible solvent.

The invention also provides gasoline compositions comprising a compound of formula (I) as defined above in an amount of 10 to 2000 ppm, preferably 30 to 800 ppm and most preferably 50 to 500 ppm, by weight.

As used herein, gasoline refers to motor fuels meeting ASTM Standard D-439, and includes blends of distillate hydrocarbon fuels with oxygenated fuels, such as ethanol, as well as the distillate fuels themselves.

The fuels may be leaded or unleaded, and may contain, in addition to the additive compositions of this invention, any of the other additives conventionally added to gasolines as, for example, scavengers, anti-icing additives, octane requirement improvers, etc.

CONCLUSION The latest generation of gasoline detergents must provide cleaning of all parts of the automobile fuel intake system including the fuel injectors and intake valves. These detergents are primarily either polyether-based amines or carbamates or polyisobutenylsuccinimides mixed with carrier oils. Our new compositions have advantages over both of these: a) Advantages over polyisobutenylsuccinimides (PIBSI) - Compatibility with all fuels, solvents, and other additive ingredients. The new compositions are readily soluble in hydrocarbons, aromatics, alcohols, and ethers. Current PIBSIs have poor solubility in alcohols and separate at low temperatures from their polyether carriers. A lot of solvent is needed to maintain compatibility. As fuel compositions range toward higher alcohol content, it will become more important to have detergent compatibility.

- Need no carrier oil for good intake valve detergent (IVD) performance, unlike PIBSIs.

- By analogy with other polyether detergents, will not contribute to octane requirement increase (ORI). Used at higher concentrations, our detergents may actually remove cylinder deposits (reverse ORI).

- May have fewer problems with valve sticking.

Polybutylene-based detergents have very high viscosity at low temperatures and so can cause valve sticking problems. Polyether detergents have not shown this problem.

b) Advantages over polyether-based detergents - Less expensive. The compositions are prepared via a two-step route with low cost polypropylene oxide-based hydrocarbyl polyether monools.

- More effective than many others.

The invention is illustrated by the following examples.

E 75274/80 Preparation of 4-Dodecylphenol/BO Detergent Base (ex73093.doc) 4-DDP + 22 BO INGREDIENT EOUIV. MOLES M.W. RET.TIME WEIGHT VOLUME 4-Dodecylphenol (4-DDP) 1.0 0.14 262.44g 36.74g 39.09 mL (Severe irritant!, d=0.94, bp 310-C) 1,2-Epoxybutane, 99% (BO) 22.0 3.08 72.11 224.34g 268.0 mL (Toxic, Cancer suspect agent, flammable, corrosive, mutagen, d=0.837, bp 63-C) Sodium Hydride 0.1 0.014 24.00 0.35g (NaH, 95% powder) (Flammable solid, Corrosive Reacts with water to release H2) PRODUCTS 4-DDP/22BO Adduct 1.0 0.14 1540 261g PROCEDURE Dry all the glassware well. Assemble a 500 mL rb flask with a thermometer, N2 line in, magnetic stirrer, addition funnel, and reflux condenser. Add the 4-DDP to the flask and begin stirring. Then carefully add the NaH dispersion.

Bubbling or fizzing will occur. Cool with an ice bath if the temperature exceeds 25-C. Stir for 5 minutes, and then add the 1,2-epoxybutane quickly through the dropping funnel. Stir for ten minutes, then pour the contents into a suitable jar with a polyethylene liner. Label the flask and take it to the high pressure lab. They will run the heating under pressure (116-C for 24 hours). Take an empty tared jar for the pressure lab technicians to transfer the product into after the reaction is complete.

When the reaction is done, pour the product into a tared rb flask, and rotovap under high vacuum and 600C for two hours. Weigh the flask when done to see if any unreacted 1,2-epoxybutane was removed. Record all observations and label the product well. Note all the physical changes that occur.

E 79441/103 Preparation of TL 2032/DMT adduct (ex121393.doc) Tyzor TPT catalyst, decane solvent INGREDIENT EOUIV. MOLES M.W. RET.TIME WEIGHT VOLUME Dimethyl 1,4-Terephthalate 3.0 0.129 194.19g 25.lg (DMT) TL 2032 1.0 0.043 1170 sog TYZOR TPT 0.05 0.002 284.26 0.61g 0.63 mL (Irritant, Flammable d=0.971) Decane (Irritant) 50 mL PRODUCTS Methanol 1.0 0.043 32 1.4 1.7 mL (Flammable, toxic, bp 65"C) TL 2032/ 1.0 0.043 1316 56.9g Terephthalate mixture Dimethyl 1,4-Terephthalate 2.0 0.034 194.19 16.6g (excess) PROCEDURE Assemble a 250 mL rb flask with a thermometer, mechanical stirrer, Dean Stark trap with condenser, and N2 line into the condenser. Fill the D-S trap with decane. Add 40 mLs of decane, the TL 2032, the DMT, and the TPT to the flask and begin stirring and heating to reflux (around 175-180 C). Methanol should begin to collect in the D-S trap. Heat at reflux until all of the expected methanol (1.7 mL) is collected, then cool quickly to room temperature.

Don't heat longer than necessary.

When the reaction is done, dilute with 50 mLs pet ether, cool, filter out the unreacted DMT (wash the DMT solids with pet ether to recover more product), then pour into a sep funnel and wash the organic solution 2X with 50 mL portions of water. Filter out the precipitated TiO2 if necessary before separating if the water layer is viscous. Dilute the organic layer with more pet ether if needed. Squirt a little methanol into the water layer if the separation is bad. When the washings are done, separate the organic layer, dry with magnesium sulfate, then distill off the decane and other solvent using full vacuum on the rotovap. I expect the product to be an oil. Obtain IR and NMR spectra of the product. Record all observations and yield.

E 79441/120 Preparation of DDP/18BO/DMT adduct (ex121793 .doc) Tyzor TPT catalyst, decane solvent INGREDIENT EOUIV. MOLES M.W. RET.TIMg WEIGHT VOLUME Dimethyl 1,4-Terephthalate 3.0 0.192 194.19g 37.3g (DMT) (mp=140-142) E75274-80 (4-DDp/so 1.0 0.064 1560 100g adduct) TYZOR TPT 0.05 0.0032 284.26 0.91g 0.94 mL (Irritant, Flammable d=0.971) Decane (Irritant) 200 mL PRODUCTS Methanol 1.0 0.064 32 2.05g 2.6 mL (Flammable, toxic, bp 65"C) TL 2032/ 1.0 0.064 1722 110.2g Terephthalate mixture Dimethyl 1,4-Terephthalate 2.0 0.128 194.19 24.8g (excess) PROCEDURE Assemble a 500 mL rb flask with a thermometer, mechanical stirrer, Dean Stark trap with condenser, and N2 line into the condenser. Fill the D-S trap with decane. Add the decane, the E75274-80, the DMT, and the TPT to the flask and begin stirring and heating to reflux (around 180-185"C). Methanol should begin to collect in the D-S trap. Heat at reflux until all of the expected methanol (2.6 mL) is collected, then cool quickly to room temperature. Don't heat longer than necessary.

When the reaction is done, cool with ice, then add 100 mL of water and stir vigorously (30 min) in the same flask. This should hydrolyze the TPT to TiO2.

Filter out the unreacted DMT and the precipitated TiO2. Dilute with more pet ether if needed. Wash the solids with pet ether to recover more product, then pour into a sep funnel and wash the organic solution again with 100 mL of water. When the washings are done, separate the organic layer, dry with magnesium sulfate, then distill off the decane and other solvent using full vacuum on the rotovap. I expect the product to be an oil. Obtain IR and NMR spectra of the product. Record all observations and yield.

E 79441/136 Preparation of polyBO/DMT adduct (ex011294.doc) Tyzor TPT catalyst, decane solvent INGREDIENT EOUIV. MOLES M.W. RKT.TIfl WEIGHT VOLUME Dimethyl 1,4-Terephthalate 2.0 0.133 194.19g 25.9g (DMT) (mp=140-142) DOW XU-13428.03(polyBO) 1.0 0.067 1500 100g TYZOR TPT 0.05 0.003 284.26 0.95g 0.98 mL (Irritant, Flammable d=0.971) Decane (Irritant) 175 mL PRODUCTS Methanol 1.0 0.067 32 2.14 2.7 mL (Flammable, toxic, bp 65"C) polyBO/ 1.0 0.067 1662 111.4g Terephthalate mixture Dimethyl 1,4-Terephthalate 1.0 0.067 194.19 13.0g (excess) PROCEDURE Assemble a 500 mI, rb flask with a thermometer, mechanical stirrer, Dean Stark trap with condenser, and N2 line into the condenser. Fill the D-S trap with decane. Add the remaining decane, the DOW XU-13428.03, the DMT, and the TPT to the flask and begin stirring and heating to reflux (around 180 C).

Methanol should begin to collect in the D-S trap. Heat at reflux until all of the expected methanol (2.6 mL) is collected, then cool quickly to room temperature. Don't heat longer than necessary.

When the reaction is done, cool with ice to near 0-5"C, then add 100 mL of water and stir vigorously (30 min) in the same flask. This should hydrolyze the TPT to TiO2. Filter out the unreacted DMT and the precipitated TiO2.

Dilute with more cold pet ether if needed. Wash the solids with pet ether to recover more product, then pour into a sep funnel and wash the organic solution again with 100 mL of water. When the washings are done, separate the organic layer, dry with magnesium sulfate, then cool again (overnight) to precipitate more unreacted DMT. Distill off the decane and pet ether using full vacuum on the rotovap. I expect the product to be an oil. Obtain IR and NMR spectra of the product. Record all observations and yield.

E 79441/140 Preparation of decanoic acid/DEPA adduct (ex011394.doc) No catalyst INGREDIENT EOUIV. MOLES M.W. RET. TIMB WEIGHT VOLUME Decanoic Acid 2.0 0.29 194.19g 50g (Irritant, Hygroscopic) Tetraethylenepentamine 1.0 0.145 189.31 27.47g 27.5 mL (TEPA) (d=0.998, Corrosive, Toxic!) Xylene 75 mL PRODUCTS Water 2.0 0.29 18 5.22g 5.22 mL (bp 65"C) Decanoic acid/TEPA adduct 1.0 0.145 497.8 72.18g PROCEDURE Assemble a 250 mL rb flask with a thermometer, mechanical stirrer, Dean Stark trap with condenser, and N2 line into the condenser. Fill the D-S trap with xylene. Add the TEPA, the decanoic acid, and the remaining xylene to the flask and begin stirring and heating to reflux (around 150 C). Water should begin to collect in the D-S trap. Heat at reflux until all of the expected water (5.22 mL) is collected, then cool until to room temperature. Monitor the pot temperature throughout.

When the reaction is done, cool, filter out any suspended solid (if needed), then rotovap off the solvent using full vacuum. I expect the product to be a low-melting waxy solid. Obtain NMR and IR spectra of the product.

Record all observations and weight of recovered product.

E 79441/148 Preparation of Emkarox/DMT adduct (ex012494.doc) Tyzor TPT catalyst, decane solvent INGREDIENT EOUIV. MOLES M.W. RET.TIME WEIGHT VOLUME Dimethyl 1,4-Terephthalate 2.0 0.177 194.19g 34.4g (DMT) (mp=140-142) Emkarox DFA-2 1.0 0.089 1130 100g TYZOR TPT 0.05 0.005 284.26 1.42g 1.46 mL (Irritant, Flammable d=0.971) Decane (Irritant) 200 mL PRODUCTS Methanol 1.0 0.089 32 2.85 3.6 mL (Flammable, toxic, bp 65"C) Emkarox/ 1.0 0.089 1292 114g Terephthalate mixture Dimethyl 1,4-Terephthalate 1.0 0.089 194.19 17.3g (excess) PROCEDURE Assemble a 1 L rb flask with a thermometer, mechanical stirrer, Dean-Stark trap with condenser, and N2 line into the condenser. Fill the D-S trap with decane. Add the remaining decane, the Emkarox, the DMT, and the TPT to the flask and begin stirring and heating to reflux (around 180"C). Methanol should begin to collect in the D-S trap. Heat at reflux until all of the expected methanol (3.6 mL) is collected, then cool quickly to room temperature. Don't heat longer or hotter than necessary.

When the reaction is done, cool with ice to near 0-5"C, then add 100 mL of cold water and stir vigorously (30 min) in the same flask. This should hydrolyze the TPT to TiO2. Filter out the unreacted DMT and the precipitated Tiro2. Dilute with more cold pet ether if needed. Wash the solids with pet ether to recover more product, then pour into a sep funnel and wash the organic solution again with 100 mL of water. When the washings are done, separate the organic layer, dry with magnesium sulfate, then cool again (overnight) to precipitate more unreacted DMT. Distill off the decane and pet ether using full vacuum on the rotovap. I expect the product to be an oil. Obtain IR and NMR spectra of the product. Record all observations and yield.

E 79441/125 Preparation of TL 2032/DMT adduct + TETA (ex010594.doc) INGREDIENT EOUIV. MOLES M.W. WEIGHT VOLUME TL2032/Terephthalate 2.0 0.0046 1316 6.0g mixture (E79441-103) Triethylenetetramine (TETA) 1.0 0.0023 146.24 0.34g 0.34 mL (d=0.982, Corrosive, Toxic!, Lachrymator, Sensitizer, Hygroscopic, Possible mutagen/teratogen, readily absorbed through skin!, bp 340"C) PRODUCTS Methanol 1.0 0.0046 32 0.15g 0.19 mL (Flammable, toxic, bp 65 C) TL 2032/DMT TETA amide 1.0 0.0023 2744 6.3g PROCEDURE Assemble a 25 mL rb flask with a thermometer, magnetic stirrer, simple distillation head, and vacuum line into the condenser. Add the TETA and the E79441-103 adduct to the flask and begin stirring and heating to llO"C. Pull a vacuum on the reaction using house vacuum. I expect methanol to begin to distill (fine bubbles in the reaction mass) when the reaction starts. Continue heating until the bubbling stops. Ice down the receiver beforehand to trap the methanol. Don't heat longer than necessary.

When the reaction is done, cool and filter out any solids.

Pull a sample and take an IR. A new amide band (-1650 cm-l) should appear and the 1724 cam~1 band for the starting material shrink in size but not disappear. I expect the product to be an oil. If the IR looks good, obtain an NMR spectra of the product.

Record all observations and yield.

E 79441/129 Preparation of TL 2032/DMT adduct + TEPA (ex010794.doc) INGREDIENT EOUIV. MOLES M.W. WEIGHT VOLUME TL2032/Terephthalate 2.0 0.0052 1330 6.9g mixture (E79441-103) Triethylenepentamine (TEPA) 1.0 0.0026 189.31 0.49g 0.49 mL (d=0.998, Corrosive, Toxic!) PRODUCTS Methanol 1.0 0.0052 32 0.17g 0.21 mL (Flammable, toxic, bp 65to) TL 2032/DMT TEPA amide 1.0 0.0026 2785 7.2 PROCEDURE Assemble a 25 mL rb flask with a thermometer, magnetic stirrer, simple distillation head, and vacuum line into the condenser. Add the TEPA and the E79441-103 adduct to the flask and begin stirring and heating to 1200C. Pull a vacuum on the reaction using house vacuum. I expect methanol to begin to distill (fine bubbles in the reaction mass) when the reaction starts. Continue heating until the bubbling stops. Ice down the receiver beforehand to trap the methanol. Don't heat longer than necessary or higher than 125"C.

When the reaction is done, cool and filter out any solids.

Pull a sample and take an IR. A new amide band (-1650 cam~1) should appear and the 1724 cam~1 band for the starting material shrink in size but not disappear. I expect the product to be an oil. If the IR looks good, obtain an NMR spectra of the product.

Record all observations and yield.

E 79441/130 Preparation of 4-DDP.20BO/DMT adduct + TETA (ex010694.doc) INGREDIENT EOUIV. MOLES M.W. WEIGHT VOLUME 4-DDP20BO/Terephthalate 1.4 0.0087 1722 l5.Og mixture (E79441-120) Triethylenetetramine (TETA) 1.0 0.0062 146.24 0.91g 0.93 mL (d=0.982, Corrosive, Toxic, Lachrymator, Sensitizer, Hygroscopic, Possible mutagen/teratogen, readily absorbed through skin!, bp 340"C) PRODUCTS Methanol 1.4 0.0087 32 0.28g 0.35 mL (Flammable, toxic, bp 65 C) 4-DDP/BO/DMT TETA amide 1.0 0.0062 2512 15.57g PROCEDURE Assemble a 25 or 50 mL rb flask with a thermometer, magnetic stirrer, simple distillation head, and vacuum line into the condenser. Add the TETA and the E79441-120 adduct to the flask and begin stirring and heating to 120"C. Pull a vacuum on the reaction using house vacuum. I expect methanol to begin to distill (fine bubbles in the reaction mass) when the reaction starts. Continue heating until the bubbling stops. Ice down the receiver beforehand to trap the methanol. Don't heat longer than necessary or higher than 125"C.

When the reaction is done, cool and filter out any solids.

Pull a sample and take an IR. A new amide band (-1650 cam~1) should appear and the 1724 cm~1 band for the starting material shrink in size but not disappear. I expect the product to be an oil. If the IR looks good, obtain an NMR spectra of the product.

Record all observations and yield.

E 79441/134 Preparation of 4-DDP.20BO/DMT adduct + TETA (ex011094.doc) INGREDIENT EOUIV. MOLBS M.W. WEIGHT VOLUME 4-DDP20BO/Terephthalate 1.4 0.0087 1722 l5.Og mixture (E79441-120) Triethylenetetramine (TETA) 1.0 0.0062 146.24 0.91g 0.93 mL (d=0.982, Corrosive, Toxic!, Lachrymator, Sensitizer, Hygroscopic, Possible mutagen, readily absorbed through skin!, bp 340 C) Toluene 20 mL PRODUCTS Methanol 1.4 0.0087 32 0.28g 0.35 mL (Flammable, toxic, bp 65or) 4-DDP/BO/DMT TETA amide 1.0 0.0062 2512 15.57g PROCEDURE Assemble a 50 or 100 mL rb

E 79441/154 Preparation of decanoic acid/TEPA adduct + polyBO/DMT adduct (ex0l2594.doc) INGREDIENT EOUIV. MOLES M.W. WEIGHT VOLUME Decanoic acid/TEPA adduct 1.0 0.0055 498 2.74g (E79441-140) polyBO/DMT adduct 1.1 0.006 1662 10.0g (E79441-136) Xylene 15 mL PRODUCTS Methanol 1.1 0.006 32 0.19g 0.24 mL (Flammable, toxic, bp 65"C) Decan. acid/TEPA/ 1.0 12.55g polyBO/DMT adduct PROCEDURE Assemble a 50 or 100 mL rb flask with a thermometer, magnetic stirrer, reflux condenser and N2 line into the condenser. Add the decanoic acid/TEPA adduct (E79441-140), the polyBO/DMT adduct E79441-136) and the remaining xylene to the flask and begin stirring and heating to reflux (about 140-150"C). Heat at reflux until for two hours, then pull a small sample1 rotovap, and take an IR of the oil. Check for the presence of amide product (1653 and 1575-1558 cm-l bands). Continue reflux for another 2 hours and sample again as above. Check for growth of the amide bands.

Continue heating at reflux until the reaction is complete.

When the reaction is done, cool, filter out any suspended solid (if needed), then rotovap off the solvent using full vacuum.

I expect the product to be an oil. Obtain IR spectra of the product. Test its solubility in heptane. Record all observations and weight of recovered product.

E 79494-1 Preparation of Emkarox/DMT adduct + DETA (ex012794.doc) INGREDIENT EOUIV. MOLES M.W. WEIGHT VOLUME Emkarox/DMT adduct mixture 2.0 0.0116 1292 15.0g (E79441-148) Diethylenetriamine (DETA) 1.0 0.006 103.2 0.60g 0.63 mL (d=0.955, Corrosive, Highly Toxic!) Xylene 25 ml' PRODUCTS Methanol 2.0 0.006 32 0.37g 0.47 mL (Flammable, toxic, bp 65"C) Emkarox/DMT DETA amide 1.0 0.006 2666 15.5 PROCEDURE Assemble a 100 mL rb flask with a thermometer, magnetic stirrer, reflux condenser and N2 line into the condenser. Add the DETA and the E79441-148 adduct to the flask and begin stirring and heating to reflux (140-150"C). Hold at reflux for 2 hours, then sample. Rotovap the sample and take an IR. Check for the presence of amide product (1653 and 1575-1558 cm-l bands).

Continue reflux for another 2 hours and sample again as above.

Check for growth of the amide bands. Continue heating at reflux until the reaction is complete.

When the reaction is done, cool, filter out any solids. Pack out into two vials, one for TGA and one for Pet. Lab. Test the solubility in heptane. Record all observations and yield.

E 79494-9 Preparation of Emkarox/DMT adduct + DETA (ex020194.doc) INGREDIENT EOUIV. MOLES M.W. WEIGHT VOLUME Emkarox/DMT adduct mixture 2.0 0.0116 1292 l5.Og (E79441-148) Diethylenetriamine (DETA) 1.0 0.006 103.2 0.60g 0.63 mL (d=0.955, Corrosive, Highly Toxic!) PRODUCTS Methanol 2.0 0.0116 32 0.37g 0.47 mL (Flammable, toxic, bp 65"C) Emkarox/DMT DETA amide 1.0 0.006 2666 15.5 PROCEDURE Assemble a 50 mL rb flask with a thermometer, magnetic stirrer, simple distillation head, and house vacuum line into the distillation head. Ice down the collection flask. Add the DETA and the E79441-148 adduct to the flask and begin stirring and heating under vacuum to 150"C. Hold at 150"C until no more bubbling is visible or 0.47 mL of methanol is collected, then sample. Take an IR. Check for the presence of amide product (1653 and 1575-1558 cam~1 bands). Continue heating at 150"C until reaction is complete.

When the reaction is done, cool, filter out any solids. Pack out into two vials, one for TGA and one for Pet. Lab. Test the solubility in heptane. Record all observations and yield.

E 79494-19,-77 Preparation of Emkarox/DMT adduct + TETA (ex012694.doc) INGREDIENT EOUIV. MOLES M.W. WEIGHT VOLUME Emkarox/DMT adduct mixture 2.0 0.008 1292 10.0g (E79441-148) Triethylenetriamine (TETA) 1.0 0.004 146 0.57g 0.58 mL (d=0.982, Corrosive, Toxic!, Lachrymator, Sensitizer, Hygroscopic, Possible mutagent/teratogen, Readily absorbed through skin!, bp 340 C) PRODUCTS Methanol 2.0 0.008 32 0.25g 0.31 mL (Flammable, toxic, bp 65"C) Emkarox/DMT TETA amide 1.0 0.004 2666 10.3 PROCEDURE Assemble a 25 or 50 mL rb flask with a thermometer, magnetic stirrer, simple distillation head, and house vacuum line into the distillation head. Ice down the collection flask. Add the TETA and the E79441-148 adduct to the flask and begin stirring and heating under vacuum to 160"C. Hold at 160"C until no more bubbling is visible or 0.31 mL of methanol is collected, then sample. Take an IR. Check for the presence of amide product (1653 and 1575-1558 cm-l bands). Continue heating at 1500C until reaction is complete.

When the reaction is done, cool, filter out any solids. Pack out into two vials, one for TGA and one for Pet. Lab. Test the solubility in heptane. Record all observations and yield.

E 79494-20 Preparation of Emkarox/DMT adduct + TEPA (ex012894.doc) INGREDIENT EOUIV. MOLES M.W. WEIGHT VOLUME Emkarox/DMT adduct mixture 3.0 0.008 1292 10.0g (E79441-148) Tetraethylenetriamine (TEPA) 1.0 0.003 189.31 0.49g 0.49 mL (d=0.998, Corrosive, Toxic!) PRODUCTS Methanol 3.0 0.008 32 0.25g 0.31 mL (Flammable, toxic, bp 65 C) Emkarox/DMT TEPA amide 1.0 0.003 3969 10.2 PROCEDURE Assemble a 25 or 50 mL rb flask with a thermometer, magnetic stirrer, simple distillation head, and house vacuum line into the distillation head. Ice down the collection flask. Add the TEPA and the E79441-148 adduct to the flask and begin stirring and heating under vacuum to 160"C. Hold at 1600C until no more bubbling is visible or 0.31 mL of methanol is collected, then sample. Take an IR. Check for the presence of amide product (1653 and 1575-1558 cm-l bands). Continue heating at 1500C until reaction is complete.

When the reaction is done, cool, filter out any solids. Pack out into two vials, one for TGA and one for Pet. Lab. Test the solubility in heptane. Record all observations and yield.

E 79494-47 Preparation of Emkarox/DMT adduct + TETA (ex022894.doc) INGREDIENT EOUIV. MOLES M.W. WEIGHT VOLUME Emkarox/DMT adduct mixture 2.0 0.008 1292 10.0g (E79441-148) Triethylenetriamine (TETA) 1.0 0.003 146 0.38g 0.38 mL (d=0.982, Corrosive, Toxic!, Lachrymator, Sensitizer, Hygroscopic, Possible mutagent/teratogen, Readily absorbed through skin!, bp 340eC) PRODUCTS Methanol 3.0 0.008 32 0.25g 0.31 mL (Flammable, toxic, bp 65"C) Emkarox/DMT TETA amide 1.0 0.003 2666 10.13 PROCEDURE Assemble a 25 or 50 mL rb flask with a thermometer, magnetic stirrer, simple distillation head, and house vacuum line into the distillation head. Ice down the collection flask. Add the TETA and the E79441-148 adduct to the flask and begin stirring and heating under vacuum to 160"C. Hold at 160"C until no more bubbling is visible or 0.31 mL of methanol is collected, then sample. Take an IR. Check for the presence of amide product (1653 and 1575-1558 cam~1 bands). Continue heating at 150"C until reaction is complete.

When the reaction is done, cool and filter through a basick alumina column and then super cell. Dilute in pet ether or hexane if needed. Pack out into two vials, one for TGA and one for Pet.

Lab. Record all observations and yield.

E 79494-48 Preparation of Emkarox/DMT adduct + EDA (ex030194.doc) INGREDIENT EOUIV. MOLES M.W. WEIGHT VOLUME Emkarox/DMT adduct mixture 1.0 0.008 1292 10.0g (E79441-148) Ethylenediamine (EDA) 3.0 0.023 60.10 1.40g 1.56 mL (Corrosive, Flammable, d=0.899, b.p.=117.3, m.p.=8.5) PRODUCTS Methanol 1.0 0.008 32 0.25g 0.31 mL (Flammable, toxic, bp 65us) Emkarox/DMT EDA amide 1.0 0.008 1320 l0.22g Excess EDA 2.0 0.015 60.1 0.93g 1.04 mL PROCEDURE Assemble a 25 or 50 mL rb flask with a thermometer, magnetic stirrer, reflux condenser and N2 Line. Add the EDA and the E79441-148 adduct to the flask and begin stirring and heating to reflux. Hold at reflux for 6 hours, then switch the condenser to a simple distillation head. Distill off the methanol byproduct and excess EDA under vacuum (1.4 mL). When the distillation is complete, cool, and filter through a basic alumina column and then super cell. Dilute in pet ether or hexane if needed. Shoot the distillate on the GC to confirm that both EDA and methanol were recovered. Pack out into two vials, one for TGA and one for Pet.

Lab. Record all observations and yield.

E 79494-96 Preparation of DOW XU/DMT adduct + TETA (ex060194.doc) Polybutylene oxide terephthalate ester amide amine INGREDIENT EOUIV. MOLES M.W. WEIGHT VOLUME DOW XU 1000mw/DMT adduct 2.0 0.018 1662 30.0g mixture (E79497-45) Triethylenetetramine (TETA) 1.0 0.009 146 1.32g 2.34 mL (d=0.982, Corrosive, Toxic!, Lachrymator, Sensitizer, Hygroscopic, Possible mutagent/teratogen, Readily absorbed through skin!, bp 340 C) PRODUCTS Methanol 2.0 0.028 32 0.58g 0.73 mL (Flammable, toxic, bp 65"C) Emkarox/DMT TETA amide 1.0 0.009 3438 30.74g PROCEDURE Assemble a 100 mL rb flask with a thermometer, magnetic stirrer, simple distillation head, and house vacuum line into the distillation head. Ice down the collection flask. Add the TETA and the E79497-45 adduct to the flask and begin stirring and heating under slight vacuum to 150"C. Hold at 150"C until no more bubbling is visible or 0.73 mL of methanol is collected.

When the reaction is done, cool, and filter out any solids on a super-cell mat on a fine frit. Pack out to take to Pet. Lab.

Record all observations and yield. Take an IR.

GLOSSARY IV = intake valve IVD = intake valve detergent PFI = port fuel injector PIB = poly(isobutene) PIBSA = polyisobutenylsuccinic anhydride TEPA = tetraethylenepentamine TETA = triethylene tetramine DETA = diethylene triamine EDA = ethylene diamine bbl = barrel of fuel (42 gallons) DMT = dimethyl terephthalate TYZOR TPT = tetraisopropyl titanate TGA = Thermal Gravimetric Analysis Emkarox, TL 2032 = tradenames for C13 or C12 hydrocarbyl poly(propylene oxide) monools DOW XY xxxxx = tradenames for butyl poly(butylene oxide) monools Claims 1. Compounds of formula (I): Z NH (CH2CH2NZ)y.Z (I) wherein Z is H, C8-16 straight or branched chain alkanoyl or

with the proviso that at least one Z is

R is C2-16 straight or branched chain alkyl or dodecylphenyl, R' is H, CH3 or CH2CH3, x is an integer from 12 to 28, and y is an integer from 1 to 4.

2. Compounds as claimed in claim 1 wherein R is C1216 straight or branched chain alkyl.

3. Compounds as claimed in claim 1, wherein: R = C12 alkyl, R'=CH,, x=17, y=3, n=2, or R = C12 alkyl, P'=CH3, x=17, y=4, n=2, or R = dodecylphenyl, R'=CH2CH3, x=20, y=3, n=1.4, or R = C4 alkyl, R'=CH2CH3, x=20, y=4, n=l.l + Z=C10 alkanoyl, n=2 (a mixed adduct), wherein n is the molar ratio of the Z group to the polyamine.

4. Compounds as claimed in claim 1, wherein: R = C13 alkyl, R'=CH3, x=16, y=2, n=2, or R = C13 alkyl, R'=CH,, x=16, y=3, n=2, or R = C13 3 alkyl, R'=CH,, x=16, y=4, n=3, or R = C13 alkyl, P'=CH3, x=16, y=3, n=3, or R = C13 alkyl, P'=CH3, x=16, y=l, n=l, or R = C alkyl, P'=CH2CH3, x=13, y=3, n=2, wherein n is the molar ratio of the group Z to the polyamine.

5. A process for the preparation of a compound as claimed in any one of the preceding claims, comprising reacting a hydrocarbyl polyether monool of formula (II): RO-(CH2CHR'O)XH (11) wherein R is C216 straight or branched chain alkyl, R' is H, CH3 or CH2CH3, and x is an integer from 12 to 28, with a terephthalic diester of formula (III):

where in R is methyl, and reacting the resulting compound of formula (IV):

wherein R, R', R" and x are as above with a polyamine of formula (V): Z.HN(CH2CH2NZ)yH (V) wherein Z is H or C8l6 straight or branched chain alkanoyl, and y is an integer from 1 to 4.

6. A process as claimed in claim 5 wherein R is C12l6 straight or branched chain alkyl.

7. A fuel additive composition comprising a compound of formula (I) as claimed in any one of claims 1 to 4.

8. A fuel additive composition as claimed in claim 7 further comprising a fuel miscible solvent.

9. A gasoline composition comprising a compound of formula (I) as claimed in any one of claims 1 to 4 in an amount of 10 to 2000 ppm by weight.

10. A gasoline composition as claimed in claim 9 wherein the compound of formula (I) is present in an amount of 30 to 800 ppm by weight.

11. A gasoline composition as claimed in claim 9 wherein the compound of formula (I) is present in an amount of 50 to 500 ppm by weight.

12. A gasoline composition as claimed in any one of claims 9 to 11 further comprising one or more of the following additives: scavengers, anti-icing additives, octane requirement improvers.

13. Compounds as claimed in claim 1 substantially as described herein.

14. Compositions as claimed in claim 7 and claim 9 substantially as described herein.

The Office Application No: GB 9626866.9 Examiner: Alan Kerry Claims searched: 1-14 Date of search: 11 March 1998 Patents Act 1977 Search Report under Section 17 Databases searched: UK Patent Office collections, including GB, EP, WO & US patent specifications, in: UK Cl (Ed.P): C3R RJ Int Cl (Ed.6): CO8G 65/32; CIOL 1/22; ClOM 149/14 Other: Online database: WPI Documents considered to be relevant:

Category Identity of document and relevant passage Relevant to claims A US 5069684 (BLAIN) - see Claim 1, Example 2 and column 7, X & s line 22 X Document indicating lack of novelly or inventive step Y Document indicating lack of inventive step if combined with one or more other documents of same category.

& Member of the same patent family A Documtt indicatiag technological background andlor state of the art.

P Document published on or after the declared priority date but before the filing date of this invention.

E Patent document published on or after, but with priority date earlier than. the filing date of this application.

An Executive Agencv of the Department of Trade and Industry