CA2037764A1 - Multifunctional fuel additives - Google Patents

Abstract

MULTIFUNCTIONAL FUEL ADDITIVES

ABSTRACT OF THE DISCLOSURE

A product of reaction obtained from the reaction of (1) a hydrocarbyl diol, an aminodiol or diaminodiol, either alone or in combination with other diols, aminodiols or diaminodiols and (2) a reactive acid and/or anhydride derived from the reaction of benzophenone tetracarboxylic dianhydride or its acid equivalent or pyromellitic dianhydride or its acid equivalent and (a) an aminoalcohol, the product of an amine and an epoxide, or (b) an amino alcohol and an amine or (c) mixtures of (a) and/or (b), wherein said product of reaction has long-chain hydrocarbyl groups attached thereto, which improves the low-temperature properties of distillate fuels when added thereto.

Description

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MULTIFUNCTIONAL FUEL ADDITIVES

FIELD OF THE INVENTION
This invention is directed to multifunctional additives which improve the low-temperature properties of distillate fuels and to fuel compositions containing minor amounts thereof BACKGROUND OF THE INVENTION
Traditionally, the low-temperature properties of distillate fuels have been improved by the addition of kerosene, sometimes in very large amounts (5-70 wt %). The kerosene dilutes the wax in the fuel, i.e., lowers the overall weight fraction of wax, and thereby lowers the cloud point, filterability temperature, and pour point simultaneously. The additives of this invention effectively lower both the cloud point and CFPP (Cold Filter Plugging Point) of distillate fuel without any appreciable dilution of the wax component of the fuel.
Other additives known in the art have been used in lieu of kerosene to improve the low-temperature properties of distillate fuels. Many such additives are polymeric materials with pendent fatty hydrocarbon groups, and are usually derived 2 ~3 3 rl r~

from the free radical polymerization of unsaturated hydrocarbons (olefins, acry]ates, fumarates, etc.).
These additives are limited in their range of activity, however; most improve fuel properties by lowering the pour point and/or filterability temperature. These same additives have little or no effect on the cloud point of the fuelO
U.S. Patents 3,910,987 and 3,910,981 disclose the use of certain aminodiols in the preparation of petroleum additives. U.S. Patent 4,524,007 discloses the use of polycarboxylic acids/anhydrides such as pyromellitic dianhydride reacted with ether capped alcohols to provide demulsifying additives for lubricants.

S~RY OF THE INVBNTION
The additives of this invention are substantially difPerent from the prior art both in terms of structure and function (activity). They are oligomeric and/or polymeric materials obtained via condensation reactions, e.g. the reaction of diols, aminodiols or diaminodiols with acids and/or anhydrides. In terms of activity, these additives effectively lower distillate fuel cloud point, thus providing improved low-temperature fuel properties, and offering a unique and useful advantage over known distillate fuel additives.
The novel additives of this invention have been found to be surprisingly active wax crystal modifier additives for distillate fuels.
Distillate fuel compositions containing minor amounts, such as less than 0~1 wt%, of such additives demonstrate significantly improved low-temperature flow properties, with lower cloud point and lower CFPP filterability temperature.

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The additlves of this invention, which improve the low-temperature properties of distillate fuels, are the reaction products of (1) diols~ aminodiols or diaminodiols, and (2) the product of benzophenone tetracarboxylic dianhydride (BTDA) or pyromellitic dianhydride (PMDA) and aminoalcohols and/or amines, the reaction product having long-chain hydrocarbyl groups attached.
Long-chain hydrocarbyl groups may be introduced into the final reaction product via (1) the various substituted diol comonomers ~diols, aminodiols or diaminodiols) or (2) the substituted amino alcohol and/or amine precursors to the derivatized BDTA or PMDA comonomers or (3) some combination of (1) and (2).
These new additives are especially effective in lowering the cloud point of distillate fuels, and thus improve the low-temperature flow properties of such fuels without the use of any light hydrocarbon diluent, such as kerosene. In addition, the filterability properties are improved as demonstrated by lower CFPP temperatures. Thus, the additives of this invention demonstrate multifunctional activity in distillate fuels.
This invention is also directed to fuel compositions comprising minor amounts of these multifunctional additives.
The additive compositions, described in this application, have cloud point activity, and CFPP activity and are unique in structure and activity. Additive concentrates and fuel compositions containing such additives are also unique. Similarly, the processes for making these additives, additive concentrates, and fuel compositions are uni~le. Accordingly, it is not ~ ~ 3 ~

believed that these novel additive products and fuel compositions thereof were heretofore known or used in the prior art.
These oligomeric/polymeric additives are reaction products derived f r om two types of monomer components. (1) The first monomer type i5 a diol, aminodiol or dlaminodiol, either alone or in combination with other diols, aminodiols or diaminodiols. (2) The second monomer type is a reactive acid/anhydride product, either alone or in combination with other such monomers, derived from the reaction of BTDA or its acid equivalent or PMDA
or its acid equivalent with either ~a~ an aminoalcohol, the product of an amine and an epoxide, or (b) a combination of an aminoalcohol (above, a) and an amine.
The additives of this invention accordingly, have oligomeric (i.e., dimers, trimers, etc.) and/or polymeric structures.
Various hydrocarbyl groups, especially groups with linear paraffinic substructures attached or containing linear paraffinic substructures, are distributed along the backbone of the oligomer and/or polymer, and may be carried by either or both of the comonomers used.

Diols Any diol, either alone or in combination, may be used in this invention. Such diols may encompass, but are not limited to, examples of the following types: 1,2-diols, 1,3-diols, lf4 diols, alpha-omega-diols, ether diols, polyether diols, glyceryl monoesters, and any other hydrocarbyl diol. However, 1,2-octadecanediol, 1,4-butanediol, 1,12-dodecanediol, poly(ethyleneglycol) and 2 C~ 3~ r~ r~

poly(propyleneglycol) are among the preferred reactants.

Aminodiols Any aminodiol, either alone or in combination, may be used in this invention and may include, but is not limited by, examples given below.
Such aminodiols are those diols derived from the reaction of a primary amine with two or more equivalents of an epoxide:

R-NH2 + R1Rl-C~o~C~R1Rl >

H-[O-C(R1R~)-C~R1Rl)~V~ [C(R1R1)-c(R1R1)-o]~-H
R

The reaction conditions for the preparation of the aminodiols is as follows: 80-250C for 1-24 hrs., under autogenous pressure to 25 atmospheres.
The temperature chosen will depend upon for the most part on the particular reactants and on whether or not a solvent is usedc Solvents used will typically be hydrocarbon solvents such as xylene, but any non-polar, unreactive solvent can be used including benzene and toluene and/or mixtures thereof.
Molar ratios of epoxide/primary amine are generally 2:1, but may also include ratios greater than 2:1.
The amine used above may be any primary amine, with each substituent being independently C1-~37~

C100 hydrocarbyl, or hydrocarbyl containing O, N, S,P.

Diaminodiols One of the comonomers, alone or in combination, used in the synthesis of these additives may be a diaminodiol. The diaminodiols of this invention are the reaction products of (1) a diepoxide ard a secondary amine, or (2) an epoxide and a bis secondary amine. These diepoxides include but are not limited to terminal hydrocarbyl diepoxides and diglycidyl ethers. Such a diaminodiol provides the capability of introducing additional linear hydrocarbyl groups along the oligomer/polymer backbone, thus increasing the overall density of linear hydrocarbyl groups in the final additive structure.
However, any diaminodiol may be used in this invention and may include, but is not limited by, examples given below.
In the first class, the diaminodiols are those diols, for example, derived from the reaction of two equivalents of a secondary amine and a diglycidyl ether, according to the following general scheme:

2 H-N(R2R3) + H2C\ ~CH-CH2-o-R4-O-CH2-HC ~ /CH2 (R2R3) N-cH2-~H-cH2-o-R4-o-cH2-cH-cH2-N (R2R3 In a one-pot synthesis the diaminodiol is prepared by suitably reacting an amine or mixture of amines with a diglycidyl ether.

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A second class of aminodiols are those diols derived from the reaction of a bis-secondary amine with two or more equivalents of an epoxide:

R-NH-R'-NH-R + R1R1-C~ ~ -R1Rl - - >

H-tO-C~R~R~)-C(R~R1)]v-N--Rl--N-[~(R1R1~-c(R1R1)-o]~-H
,!~

Molar ratios of epoxide/secondary amine are generally 1:1 for each reactive amine group but may include ratios greater than 1:1.
The amine used above may be any secondary amine, with each substituent being independently C1-C1~ hydrocarbyl, or hydrocarbyl containing 0, N, S, P.

Reactive Acid and/or Anhvdride The other comonomer, alone or in combination, used in the synthesis of these additives is a reactive acid and/or anhydride derived from the reaction of BTDA or its acid equivalent or PMDA or its acid equivalent and alcohols and/or amines to introduce suitable pendant groups derived from the aminoalcohols and/or amines. The pendant groups are some combination of hydrocarbyl, preferably linear hydrocarbyl groups attached to the esters and/or amides of the derivitized dianhydride (DA)~ As used herein "DA" refers generically to either BTDA
or PMDA or their acid equivalents.

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The pendant groups include (a) esters derived from aminoalcohols, which may be derived fr~m a secondary amine capped with an olefin epoxide, (b) combinations of esters and amides derived from the aminoalcohol from (a) and an amine, and (c) combinations of esters derived from two or more different aminoalcohols. These pendant ester and/or amide groups usually contain from 8 to about 100 carbon atoms or more, preferably from about 28 or 30 to 100 carbon atoms or more. The aminoalcohol used above is the reaction product of an epoxide and a secondary amine, in substantially 1:1 molar ratio. Preferred amines are secondary amines such as di(hydrogenated tallow) amine.
Preferred epoxides are such epoxides as 1,2-epoxyoctadecane.
In a one-pot synthesis process the aminodiol is first prepared by suitably reacting an amine or mixture of amines with an epoxide or mixture thereof and then reacting the resultant product with BTDA or PMDA or its acid equivalent.
The reactions can be carried out under widely varying conditions.

Reaction with Acid/AnhYdride to Produce the Multifunctional Additiv_ The additives of this invention are the reaction products obtained by combining the two monomer types described above in differing ratios using standard esterification techniques according to the following stepwise procedures:

(1) DA + HO-~H-CH2-~-R~ + optionally H-N-R2 R
Reactive Acid/Anhydride 2~7~

(2a~ Reactive Acid/Anhydride and Diol Reactive AcidJAnhydride + HO-R~-OH -Oligomer/Polymex (2b) Reactive Acid Anhydride and Aminodiol Reactive Acid/Anhydride + HO-R~-OH
Oligomer/Polymer 2(c) Reactive Acid/Anhydride and Diaminodiol Reactive Acid/Anhydride + HO-R7-OH
~ ~ Oligomer/Polymer Structure of Acid/Anhydride Reaction Products A general structure for the oligomers/polymers derived from BTDA or PMDA
partial ester and diol is as follows:

-[(~A)-(o-lcH-cH2-~-R2)x]-t A general structure for the oligomers/polymers derived from BTDA or PMDA mixed partial ester and diol is as follows:

-[(DA)-~O-~CH-CH2-l-~2)y(0-~H CH2-l-R2)~]-[O-~-O]~-A general structure for the oligomers/polymers derived from BTDA or PMDA
partial ester~amide and diol is as ollows:

2 ~ 3 7 r~ ~ ~

-[(DA)-(O-CH-CH2-~-R2)y(l~R2)~] [-Rs~],~
~2 R R

A general structure, for example, for oligomers/polymers derived from BTDA or PMDA
partial ester and aminodiol is as follows:

-~(DA)-(O-~CH-CH2-~-R2)X] [o R~ o]~

A g e n e ral s t ru c tu re fo r oligomers/polymers derived from BTDA or PMDA mixed partial ester and aminodiol is as follows:

-[(DA)-(O-~H-CH2-~-R2)y(0~clH-cH2-~-R3~z]-[o-R

A g e n e ral st ru ct u re f or oligomers/polymers derived from BTDA or PMDA
partial ester/amide and aminodiol is as follows:

--[ (DA)-(o-lcH-cH2-l-R2)y( ~-R2)z]-[o-R6 - o]~ -A general structure for the oligomers/polymers derived from BTDA or PMD~
partial ester and diaminodiol is as follows:
[(DA)-(O-CIH-cH2-~-R2)x] [o-c~H-cH2-o-R~-o-cH2-clH-O]~-R2 R H2-N(R2R3) C H 2 ~
N(R2R3) Also, oligomers~polymers analogous to these may be derived from DA mixed partial ester, i.e., DA

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derivatlves where the pendant aminoalcohols are different from one another.
A general structur~ for the oligomers~polymers derived from BTDA or PMDA
partial ester/amide and diaminodiol is as follows:

-[ (DA)-(O-CH-C~I2-~ -R2)y~N-R2);~]-[o-cH - cH2-o-R~-o-cH2 ~2 R ~ CH2-N(R2R3) --C~--O ] ~,--~H2-N ( ~2R3 ) Definitions In the above formulas, v + w > 2;
x = y+z = 0.5 to 3.5, preferably from 1 to about 3;
a is 0.25 to about 2, preferably from 0.5 to about 1.25;
R is C1 to about C10O hydrocarbyl, or C1 to about C100 hydrocarbyl containing phosphorus, nitrogen, sulfur andjor oxygen;
R' is a divalent group corresponding to R, i.e., a divalent C1 to C100 hydrocarbyl or a divalent C1 to C10O hydrocarbyl containing phosphorus, nitrogen, sulfur and/or oxygen;
R1, which each may be the same or different, is hydrogen, Cl to about C100 hydrocarbyl or C1 to about C100 hydrocarbyl containing phosphorus, nitrogen, sulfur and/or oxygen;
R2, which each can be the same or different, is C8 to about C50 hydrocarbyl group, preEerably linear either saturated or unsaturated;
R3 is Cl to about C100 hydrocarbyl or C1 to about C100 hydrocarbyl containing phosphorus, nitrogen, sulfur and/or oxygen;

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R4 - C1 to about Cl00 hydrocarbyl, or Cl to about C
hydrocarbyl containing nitrogen, sulfur, phosphorus, boron, silicon and/or oxygen;
F~ is C2-C100 hydrocarbyl; and R6 is the sub-structure of the aminodiol(s) defined above; and R7 is one of the two diaminodiol sub-structures defined above.
The phrase "long-chain hydrocarbyl group"
as used in this application means linear or near linear alkyl or alkenyl groups. Each individual long-chain hydrocarbyl group is usually a C8 to C30 hydrocarbyl group, preferably a C14 to Cz2 hydrocarbyl group.

Amines Any suitable amine may be used.
When used to prepare an amino diol, the amine is preferably any primary amine such as n-octylamine, hydrogenated ~allow amine and aniline.
When the amine is used to prepare a diaminodiol by reaction with a diepoxide, the amine is any secondary amine such as di(hydrogenated tallow) amine and methyl octadecylamine.
When the amine is used to prepare a diaminodiol by reaction with an epoxide, the amine is any bis secondary amine such as piperazine.
When the amine is used as a structural fragment of the reactive anhydride acid, the amine may be any suitable aliphatic or aromatic, arylalkyl or alkylaryl having from 1 to about l00 carbon atoms secondary amine. A highly preferred amine is di(hydrogenated tallow) amine. Other suitable amines include, but are not limited to, ditallow amine, dioctadecylamine, methyl octadecyl amine, and other secondary amines.

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Die~oxides Included within the scope of diepoxides are any diglycidyl ethers and any diepoxide reaction products derived ~Erom any diol, and two molar amounts of epichlorohydrin (or synthetic equivalents) such as 2,2-dimethyl-1,3-propane diol diglycidyl ether.

Epoxides Included within the scope of the epoxides used in preparing aminoalcohols from amines as set forth above, are ethylene oxide, l,2-epoxides, including, for example, 1,2-epoxydecane, 1,2-epoxydodecane, 1,2-epoxytetradecane, 1,2-epoxypentadecane, 1,2-epoxyhexadecane, 1,2-epoxyheptadecane, 1,2-epoxyoctadecane, 1,2-epoxyeicosane and mixtures thereof. Especially preferred are 1,2-epoxyoctadecane and ethylene oxide.

Reaction conditions In general, the additive reaction product can be synthesized under widely varying conditions which are not believed to be critical. The reaction temperature can vary from S0 to 250C, preferably 100 to 250C, mor~ preferably from 150 to 200C, under ambient or autogenous pressure.
However, slightly higher pressures may be used if desired. The pressure may vary from 0.001 atm to lo atm and preferably 0.001 atm to 1 atm. The temperature chosen will depend for the most part on the particular reactants and on whether or not a solvent is used. Solvents when used will typically be hydrocarbon solvents such as xylene, but any non-polar, unreactive solvent can be used including benzene, toluene or mixtures thereof.

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Molar ratios, less than molar ratios or more than molar ratios of the comonomer reactants can be used. Preferentially, a molar ratio of diol, aminodiol or diaminodiol to reactive acid/anhydride of 1:2 to 3.5:1, more preferentially 1:1.25 to 1.5:1 is used.
The times for the reactions are also not believed to be critical. The process is generally carried out in about 1 to about 24 hours to 36 to 48 hours or more.

Fuel Com~ositions In generall the reaction products of ~he present invention may be employed in any amount effective for imparting the desired degree of activity necessary to improve the low temperature characteristics of distillate fuels. In many applications the products are effectively employed in amounts from about 0.001% to about 10% by wPight and preferably from less than about 0.1% to about 5~ of the weight of the total composition. These additives may be used in conjunction wit~ other known low-temperature fuel additives (dispersants, etc.) being used for their intended purpose.
The fuels contemplated are liquid hydrocarbon combustion fuels, including the dist~llate fuels and fuel oils. Accordingly, the fuel oils that may be improved in accordance with the present invention are hydrocarbon fractions having an initial boiling point of at least about 250F (121C) and an end-boiling point no higher than about 750F (399C) and boiling substantially continuously throughout their distillation range.
Such fuel oils are generally known as distillate fuel oils. It is to be understood, however, that ~ ~ 3 7 ~

this term i5 not restricted to straight run distillate fractions. The distillate fuei oils can be straight run distillate fuel oil~, catalytically or thermally crac~ed (including hydrocracked) distillate fuel oils, or mixtures of straight run distillate fuel oils, naphthas and the like, with cracked distillate stocks. Moreover, such fuel oils can be treated in accordance with well-known commercial methods, such as, acid or caustic treatment, hydrogenation, solvent refining, clay treatment, etc.
The distillate fuel oils are characterized by their relatively low viscosities, pour points, and the like. The principal property which characterizes the contemplated hydrocarbons, however, is the distillation range. As mentioned hereinbefore, this range will ~enerally lie between about 250F (121C) and about 750F (400C).
Obviously, the distillation range of each individual fuel oil will cover a narrower boiling range falling, nevertheless, within the above-specified limits. Likewise, each fuel oil will boil substantially continuously throughout its distillation range.
Contemplated among the fuel oils are Nos.
1, 2 and 3 fuel oils used in heating and as diesel fuel oils, and the jet combustion fuels. The domestic fuel oils generally conform to the specification set forth in A.S.T.M. Speci~ications D396-48T. Specifications for diesel fuels are defined in A.S.T.M. Specification D975-48T.
Typical jet fuels are defined in Military Specification MIL-F-5624B.

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EXAMPLES
The following examples are illustrative only and are not meant to limit the scope of the invention.
Example 1 Preparation of Additive 1 Di(hydrogenated tallow) amine (50.0 grams, 0.10 mol; from Akzo Chemie), and 1,2-epoxyoctadecane (33.6 grams, 0.125 mol; e.g.
Vikolox 18 from Viking Chemical) were combined and heated at 170~ for 16-18 hours. Benzophenone tetracarboxylic dianhydride (17.7 grams, 0.055 mol;
e.g. BTDA from Allco Chemical Corporation), 1,12 dodecanediol (5.06 grams, 0.025 mol; e.g. from Aldrich Chemical Company), and xylene (approximately 50 ml) were added and heated at reflux (190-200C) with azeotropic removal of water for 24 hours. Volatiles were then removed from the reaction medium at 190-200-C, and the reaction mixture was hot filtered through diatomaceous earth to give 92.5 grams of the final product.

Example 2 Preparation of Additive 2 According to the procedure used for Example 1 (above~, di(hydrogenated tallow) amine (50.0 grams, 0.10 mol), and 1,2-epoxyoctadecane (33.6 grams, 0.125 mol) were combined. Then, benzophenone tetracarboxylic dianhydride (17.7 grams 0.055 mol~, 1,12 dodecanediol (9.11 grams, 0.045 mol), and xylene (approximately 50 ml) were added and allowed to react. Excess ~ylene was added to facilitate filtration, and was subsequently removed by evaporative distillation. After isolation, 102.0 grams of the final product was obtained.

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~xample 3 Preparation of Additive 3 According to the proceclure used for Example 1 (above), di(hydrogenated tallow) amine (50.0 grams, 0.10 mol), and 1,2-epoxyoctadecane (33.6 grams, 0.125 mol) were combined. Then, benzophenone tetracarboxylic dianhydride (17.7 gram~ 0.055 mol), poly(propyleneglycol) with avg. M.W. 400 (10.0 grams, 0.025 mol; from Texaco Chemical Company), and xylene (approximately 50 ml) were added and allowed to react. After isolation, 97.8 grams of the final product was obtained.

Example 4 Preparation of Additive 4 According to the procedure used for Example 1 (above), di(hydrogenated tallow) amine (50.0 grams, 0.10 mol), and 1,2-epoxyoctadecane ~33.6 grams, 0.125 mol) were combined. Then, benzophenone tetracarboxylic dianhydride (17.7 grams 0.055 mol), poly(propyleneglycol) with avg. M.W. 400 (21.0 grams, 0.052 mol), and xylene (approximately 50 ml) were added and allowed to react. After isolation, 111. 2 grams of the final product was obtained.

Example 5 Preparation of Additive 5 According to the procedure used for Example 1 (above), di(hydrogenated tallow) amine (40.0 grams, 0.08 mol), and 1,2-epoxyoctadecane ~26.8 grams, O.10 mol) were combined. Then, benzophenone tetracarboxylic dianhydride (14.2 grams 0.044 mol), poly(propyleneglycol) with avg. M.W. 2000 (40.0 grams, O A O20 mol; from Texaco Chemical Company), and xylene (appr~ximately 50 ml~ wexe added and ~37~

allowed to react. After lsolation, 109.7 grams of the ~inal product was obtained.

Example 6 Preparation of Additive 6 According to the procedure used for Example 1 ~ab~ve), di(hydrogenated tallow) amine (35.0 grams, 0.07 mol), and 1,2-epoxyoctadecane (23.5 grams, 0.088 mol) were combined. Then, benzophenone tetracarboxylic dianhydride (12.4 qrams 0.038 mol), poly(propyleneglycol) with avg. M.W. 2000 (73.5 grams, 0.037 mol; and xylene (approximately 50 ml) were added and allowed to react~ After isolation, 131.4 grams of the final product was obtained.

Exam~le 7 Preparation of Additive ~
According to the procedure used for Example 1 (above), di(hydrogenated tallow) amine (51.0 grams, 0.10 mol), and 1,2-epoxyoctadecane (14.2 grams, 0.050 mol) were combined. Then, benzophenone tetracarboxylic dianhydride (16.1 grams 0.050 mol), poly(propyleneglycol) with avg.
M.W. 400 (20.0 grams, 0.050 mol; and xylene (approximately 50 ml) were added and allowed to react. After isolation, 90.7 grams of the final product was obtained.

Example 8 Preparation of Additive 8 Piperazine (1.44 g, 0.017 mol; e.g. from Aldrich Chemical Company), di(hydrogenated tallow) amine (50.0 g, 0.10 mol; e.g. Armeen 2HT from Akzo Chemie), and 1,2-epoxyoctadecane (44.8g, 0.167 mol;
e.g. Vikolox 18 from Viking Chemical) were combined ~ ~ ~ r) 7 and heated at 160 to 190C for 18 to 24 hours.
Benzophenone tetracarboxylic dianhydride (11.8 g, 0.037 mol; e.g. BTDA from Allco Chemical Corporation) and xylen~ (approximately 50 ml) were added and heated at reflux (180 to 200-C) with azeotropic removal of water for 24 hours.
Volatiles were then removed from the reaction medium at 190 to 200 C, and the reaction mixture was hot filtered through diatomaceous earth to give 97.5 g of the final product.

Example 9 _eParation of Additive g According to the procedure used for Example 8, piperazine (3.45 g, 0.040 mol), di(hydrogenated tallow) amine (40.0 g, 0.080 mol), and 1,2-epoxyoctadecane (53.7 g, 0.200 mol) were combined. Then, benzophenone tetracarboxylic dianhydride (7.85 g, 0.036 mol) and xylene ~approximately 50 ml) were added and allowed to react. After isolation, 105.9 g of the final product was obtained.

Example 10 Preparation_of Additive 10 ~ ccording to the procedure used for Example 8, n-octylamine (2.75 g, 0.017 mol; e.g. fxom Aldrich Chemical Company, di(hydrogenated tallow) amine (50.0 g, 0.100 mol), and 1,2-epoxyoctadecane ~44.8 g, 0.167 mol) were combined. Then, benzophenone tetracarboxylic dianhydride (11.8 g, 0.037 mol) and xylene (approximately ~0 ml) were added and allowed to react. After isolation, 98.2 g of the final product was obtained.

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Example 11 ~Paration_of Additive 11 According to the procedure used for Example 8, n-octylamine (6.61 g, 0.040 mol, di(hydrogenated tallow) amine (40.0 g, 0.080 mol), and 1,2-epoxyoctadecane (64.7 g, 0.200 mol) were combined. Then, benzophenone tetracarboxylic dianhydride (14.2 g, 0.044 mol) and xylene (approximately ~0 ml) were added and allowed to react. After isolation, 103.0 g of the final product was obtained.

Example 12 Pre~aration of Additive 12 According to the procedure used for Example 8, hydrogenated tallow amine (4.31 g, 0.017 mol; e.g.
Armeen HT from Akzo Chemie), di(hydrogenated tallow) amine (50.0 g, 0.100 mol), and 1,2-epoxyoctadecane (44.8 g, 0.16~ mol) were combined.
Then, benzophenone tetracarboxylic dianhydride (11.8 g, 0.037 mol) and xylene (approximately 50 ml~ were added and allowed to react. After isolation, 103.4 g of the final product was obtained.

Example 13 Preparation of Additive 13 According to the procedure used for Example 8, hydrogenated tallow amine (10.3 g, 0.040 mol, di(hydrogenated tallow) amine (40.0 g, 0.080 mol), and l,2-epoxyoctadecane ~53.7 g, 0.200 mol) were combined. Then, benzophenone tetracarboxylic dianhydride (14.2 g, 0.044 mol) and xylene (approximately 50 ml) were added and allowed to 2 ~ 3 r~ 7 ~ ~

react. After isolation, 108.2 g of thQ final product was obtained.

Example 14 Preparation of Additive 14 According to the procedure used for Example 8, di(hydrogenated tallow) amine (50.0 g, 0.100 mol), and 1,2-epoxyoctadecane (33.6 g, 0.125 mol) were combined. Then, Ethomeen T/12 (8.66 g, 0.025 mol; an aminodiol derived from tallow amine and two equivalents of ethylene oxide, e.g. from Akzo Chemie), benzophenone tetracarboxylic dianhydride (17.7 g, 0.055 mol~ and xylene (approximately 50 ml) were added and allowed to react. After isolation, 100.5 g of the final product was obtained.

Example 15 Preparation of Additive 15 According to the procedure used for Example 8, di(hydrogenated tallow) amine ~50.0 g, 0.100 mol) and 1,2-epoxyoctadecane (33.6 g, 0.125 mol) were combined. Then, Ethomeen T/12 (18.2 q, 0.052 mol) benzophenone tetracarboxylic dianhydride (17.7 g, 0.055 mol) and xylene (approximately 50 ml) were added and allowed to react. After isolation, 109.2 g of the final product was obtained.

ExamPle 16 Preparation of Additive 16 According to the procedure used for Example 8, di(hydrogenated tallow) amine (5000 g, 0.100 mol), and 1,2-epoxyoctadecane (33.6 g, 0.125 mol) were combined. Then, Ethomeen T/12 (12.0 g, C~ ~ 3 ~) r~

0.025 mol); an aminodiol derived from tallow amine and five equivalents of ethylene oxide, e.g. from Akzo Chemie), benzophenone tetracar~oxylic dianhydride (17.7 g, 0.055 mol) and xylene (approximately 50 ml) were added and allowed to react. Af er isolation, 89.2 g of the final product was obtained.

Example 17 Preparation of Additive 17 According to the procedure used for Exa~ple 8, di(hydrogenated tallow) amine (50.0 g, 0.100 mol) and 1,2-epoxyoctadecane (33.6 g, 0.125 mol~ were combined. Then, Ethomeen T/15 (25.1 g, 0.052 mol), benzophenone tetracarboxylic dianhydride (17.7 g, 0.055 mol) and xylene (approximately 50 ml) were added and allowed to react. After isolation, 86.7 g of the final product was obtained.

Exam~le 18 Preparation of Additive 18 a-Octylamine (5.17 g, 0.040 mol), and 1,2-epoxyoctadecane (34.2 g~ 0.12 mol) were combined and were reacted together at 140 to 170C
for 23 hours. Di(hydrogenated tallow) amine (40.8 g, 0.80 mol) was added to the reaction mixture and was heated at 170C for six to seven hours. Then, benzophenone tetracarboxylic dianhydride (12.9 g, 0.040 mol) and xylene (approximately 50 ml) were added and heated at reflux (190C) with azeotropic removal of water for 24 hours. Volatiles were then removed from the reaction medium at 199 to 200 C, and the reaction mixture was hot filtered through diatomaceous earth to give 84.8 g of the final product.

~xam~le 19 Pre~arat~on o~j~dditive 19 Di(hydrogenated tallow) amine (60.0 g, O.12 mol; e.g. Armeen 2HT from ~kzo Chemie), 2,2-dimethyl-1,3-propaned~ol diglycidyl ether ~10.9 g, o.osO mol; e.g. Azepoxy N form AZS Corporation), and 1,2-epoxyoctadecane (14.2 g, 0.053 mol; e.g.
Vikolox 18 for Viking Chemical) were combined and heated at 140 to 150C for three hours, and at 165 to 170~C for 16 to 20 hours. Benzophenone tetracarboxylic dianhydride (17.0 g, 0.053 mol;
e.g. BTDA from Allco Chemical Corporation) and xylene (approximately S0 ml) were added and heated at reflux (180 to 190C) with azeotropic removal of water for 24 hours. Volatiles were then removed from the reaction medium at l90-C, and the reaction mixture was hot filtered through diatomaceous earth to give 90.2 g of the final producS.

Exam~le 20 Preparation of Additive 20 According to the procedure used for Example 19, di(hydrogenated tallow) amine (60.0 g, 0.12 mol), 2,2-dimethyl-1,3-propanediol diglycidyl ether (6.29 g, 0.029 mol), and 1,2-cpoxyoctadecane (24.4 g, 0.091 mol) were combined. Then, benzophenone tetracarboxylic dianhydride (12.9 g, 0.040 mol)- and xylene (approximately 50 ml) were added and allowed to react. After isolation, 95.0 g of the final product was obtained.

Example 21 Preparation of Additive 21 According to the procedure used for Example 19, di(hydrogenated tallow) amine (60.0 g, 2~37 l~i~

0.12 mol), 1,4-butanediol diglycidyl ether (~.38 g, 0.029 mol; e.g. Araldite RD-2 from Ciba-Geigy Company), and 1,2-epoxyoctadecane (24.4 g, 0.091 mol) were combined. Then, benzophenone tetracarboxylic dianhydride (12.9 g, 0.040 mol) and xylene (approximately 50 ml) were added and allowed to react. After isolation, 96.8 g of the final product was obtained.

Example_22 Preparation of Additive 22 According to the procedure used for Example 19, di(hydrogenated tallow) amine (60.0 g, 0.12 mol), a polyetherglycol diglycidyl ether with an average molar weight of 380 (11.0 g, 0.029 mol;
e.g. DER 736 from Dow Chemical Company), and 1,2-epoxyoctadecane (24.4 g, 0.091 mol) were combined.
Then, benzophenone tetracarboxylic dianhydride (12.9 g, 0.040 mol) and xylene (approximately 50 ml) were added and allowed to react. After isolation, 98.0 g of the final product was obtained.

Example 23 Preparation of Additive 23 According to the procedure used for Example 19, di(hydrogenated tallow) amine (60.0 g, 0.12 mol), a polyetherglycol diglycidyl ether with an average molar weight of 630 (15.3 g, 0.024 mol;
e.g. DER 732 from Dow Chemical Company), and 1,2-epoxyoctadecane (20.3 g, 0.076 mol) were combined.
Then, benzophenone tetracarboxylic dianhydride (10.7 g, 0.033 mol) and xylene (approximately 50 ml) were added and allowed to react. After isolation, 88.9 g of the ~inal product was obtained.

Exam~le 24 Pre~aration of Additive 24 According to the procedure used for Example 19, di(hydrogenated tallow) amine (60.0 g, 0.12 mol), 2,2-dimethyl-1,3-propanediol diglycidyl ether (10.2 g, 0.047 mol), and 1,2-epoxyoctadecane (14.4 g, 0.054 mol) were combined. Then, benzophenone tetracarboxylic dianhydride (7.60 g, 0.024 mol), phthalic anhydride (3.49 g, 0.024 mol;
e.g. from Aldrich Chemical Company), and xylene (approximately 50 ml) were added and allowed to react. After isolation, 87.5 g of the final product was obtained.

Example 25 Preparation~ Additive 25 According to thle procedure used for Example 19, di~hydrogenatedl tallow) amine (60.0 g, 0.12 mol), 1,4-butanediol diglycidyl ether (13.6 g, 0.047 mol), and 1,2-epoxyoctadecane (14.4 g, 0.054 mol) were combined. Then, benzophenone tetracarboxylic dianhydride (7.60 g, 0.024 mol), phthalic anhydride (3.49 g. 0.024 mol), and xylene (approximately 50 ml) were added and allowed to react. After isolation, 88.6 g of the final product was obtained.

Example 26 Preparation of Additive 26 According to the procedure used for Example 19, di(hydrogenated tallow) amine (60.0 g, 0.12 mol), DER 736 (17.9 g, 0.047 mol), and 1,2-epoxyoctadecane ~14.4 g, 0.054 mol) were combined.
Then, benzophenone tetracarboxylic dianhydride (7.60 g, 0.024 mol), phthalic anhydride (3.49 g, 0.024 mol), and xylene ~approximately 50 ml) were added and allowed to react. After isolation, 93.0 g of the final product was obtained.

Example 27 Preparation of Additive 27 According to the procedure used for Example 19, di(hydrogenated tallow) amine (50.0 g, 0.10 mol), DER 732 (24.8 g, 0.039 mol), and 1,2-epoxyoctadecane (12.0 g, 0.045 mol) were combined.
Then, benzophenone tetracarboxylic dianhydride (6.33 g, Q.020 mol), phthalic anhydride (2.91 g, 0.020 mol), and xylene (approximately 50 ml) were r~ 7 added and allowed to react. After isolation, 87.2 g of the final product was obtained.

Example 28 PreParatio~ of Additive 28 According to the procedure used for Example 19, di(hydrogenated tallow) amine (61.2 g, 0.12 mol), 2,2-dimethyl-1,3-propanediol diglycidyl ether (6.49 g, 0.030 mol), and 1,2-epoxyoctadecane (8.55 g, 0.030 mol) were combined. Then, benzophenone tetracarboxylic dianhydride (9.67 g, 0.030 mol) and xylene ~approximately 50 ml) were added and allowed to react. After isolation, 76.4 g of the final product was obtained.

xample 29 Preparation of Additive 29 Di(hydrogenated tallow) amine (49.9 g, o.$o mol; e.g. Armeen 2HT from Akzo Chemie), and 1,2-epoxyoctadecane (33.6 g, 0.125 mol; e.g. Vikolox 18 from Viking Chemical) were combined and heated at 165~C for 18 hours. Pyromellitic dianhydride (6.23 g, 0.028 mol; e.g. PMDA from Allco Chemical Corp.), 1,2-octadecanediol (2.05 g, 0.007 mol; e.g. Vikinol 18 from Viking Chemical), and xvlene (approximately 50 ml) were added and heated at reflux (180 to 240~C) with azeotropic removal of water for 24 to 36 hours. Volatiles were then removed from the reaction medium at 190 to 200C, and the reaction mixture was hot filtered through diatomaceous earth to give 82.7 g of the final product.

~ 7~i~

xample 30 ~reParation o~ Additive 30 According to the procedure used for Example 29, di(hydrogenated tallow) amine (49.9 g, 0.10 mol), and 1,2-epoxyoctadecane (33.6 g, 0.125 mol) were combined. Then, pyromellitic dianhydride (7.27 g, 0.033 mol), 1,2-octadecanediol (4.78 g.
0.017 mol), and xylene (approximately 50 ml) were added and allowed to react. After isolation, 85.0 g of the final product was obtained.

Example 31 Preparation of Additive 31 According to the procedure used for Example 29, di(hydrogenated tallow) amine (49.9 g, 0.10 mol), and l,2-epoxyoctadecane (33.6 g, 0.125 mol) were combined. Then, pyromellitic dianhydride (8.72 g, 0.040 mol), 1,2-octadecanediol (8.60 g, 0.030 mol), and xylene (approximately 50 ml) were added and allowed to react. After isolation, 90.5 g of the final product was obtained.

ExamPle 32 Preparation of Additive 32 According to the procedure used for Example 29, di(hydrogenated tallow) amine (49.9 g, 0~10 mol), and 1,2-epoxyoctadecane (33.6 g, 0.125 mol) were combined. Then, pyromellitic dianhydride (7.27 g, 0.033 mol), 1,4-butanediol (1.50 g, 0.017 mol; e.g. from Aldrich Chemical Company), and xylene (approximately 50 ml) were added and allowed to react. After isolation, 81.6 g of the final product was obtained.

ExamP~~ 33 Preparation of Add~tiv~ 33 According to the procedure used for Example 29, di(hydrogenated tallow) amine (49.9 g, 0.10 mol), and 1,2-epoxyoctadecane (33.6 g, 0.125 mol) were combined. Then, pyxomellitic dianhydride (8.72 g, 0.040 mol), 1,4-butanediol (2.70 g, 0O030 mol), and xylene (approximately 50 ml) were added and allowed to react. After isolation, 84.3 g of the final product was obtained.

Example 34 Preparation of Additive 34 Di(hydrogenated tallow) amine (49.9 g, 0.10 mol), and 1~2-epoxyoctadecane (33.6 g, 0.125 mol) were combined and heated at 170-C ~or 18 hours.
Pyromellitic dianhydride (8.00 g, 0.037 mol~, 1,12-dodecanediol (3.37 g, 0.017 mol: e.g. from Aldrich Chemical Company), and xylene (approximately 50 ml) were added and heated at reflux (190 to 200-C) with a2eotropic removal of water for 24 hours.
Volatiles were then removed from the reaction medium at 190 to 200C, and the reaction mixture was hot filtered through diatomaceous earth to give 87.1 g of the final product.

Example 35 Pre~aration of Additive 35 According to the procedure used for Example 34, di(hydrogenated tallow) amine (49.9 g, 0.10 mol), and 1,2-epoxyoctadecane (33.6 g, 0.125 mol) were combined. Then, pyromellitic dianhydride (12.0 g, 0.055 mol, 1,12-dodecanediol (9.11 g, 0.045 mol), and xylene (approximately 50 ml) were ~ ~ 3 ~

added and allowed to react. After isolation, 91.4 g of the final product wa~ obtalned.

Example 36 Pre~aration o~ Additive 36 According to the procedure used for Example 34, di(hydrogenated tallow) amine (49.9 g, 0.10 mol), and l,2-epoxyoctadecane ~33.6 g, 0.125 mol) were comhined. Then, pyromellitic dianhydride (8.00 g, 0.037 mol, poly~ethyleneglycol with average M.W. 400 (6.67 g, 0.017 mol; e.g. from Aldrich Chemical Company), and xylene (approximately 50 ml) were added and allowed to react. After isolation, 84.7 g of the final product was obtained.

Exam~le 37 _eparation of Additive 37 According to the procedure used for Example 34, di(hydrogenated tallow) amine (49.9 g, 0.10 mol), and 1,2-epoxyoctadecane (33.6 g, 0.125 mol) were combined. Then, pyromellitic dianhydride (12.0 g, 0.055 mol, poly(ethyleneglycol with average M.W. 400 (22.0 g, 0.055 mol, and xylene (approximately 50 ml) were added and allowed to react. After isolation, 78.0 g of the final product was obtained.

Example 38 Preparation of Additive 38 According to the procedure used for Example 34, di(hydrogenated tallow) amine (49.9 g, 0.10 mol), and l,2-epoxyoctadecane (33.6 g, 0.12S mol) were combined. Then, pyromellitic dianhydride (8.00 g, 0.037 mol, poly(propyleneglycol with 7 ~ i~

averaye M.W. 400 (6.67 g, 0.017 mol; e.g. JEFFOX
PPG 400 from Texaco Chemical Company), and xylene (approximately 50 ml) were added and allowed to react. After isolation, 88.2 g of the final product was obtained.

Example 39 Pre~aration of Additive 39 According to the procedure used for Example 34, di(hydrogenated tallow) amine (49.9 g, 0.10 mol), and 1,2-epoxyoctadeCane (33.6 g, 0.12S mol) were com~ined. Then, pyromellitic dianhydride (12.0 g, 0.055 mol, poly(propyleneglycol with average M.W. 400 (22.0 g, 0.055 mol), and xylene (approximately 50 ml) were added and allowed to react. After isolation, 112.6 g of the final product was obtained.

Example 4Q
Preparation of Additive 40 According to the procedure used for Example 34, di(hydrogenated tallow) amine (40.0 g, 0.08 mol), and 1,2-epoxyoctadecane (26.8 g, 0.10 mol) were combined. Then, pyromellitic dianhydride (9.60 g, 0.044 mol, poly(propyleneglycol with average M.W. 2000 (40.0 g, 0.020 mol; JEFFOX PPG-2000 from Texaco Chemical Company), and xylene (approximately 50 ml) were added and allowed to react. After isolation, 105.0 g of the final product was obtained.

Example ~1 Preparation of Additive 41 According to the procedure used for Example 34, di~hydrogenated tallow) amine (35.0 g, 0O07 7 1~ ~

mol), and 1,2-epoxyoctadecane (23.5 g, 0.088 mol) were combined. Then, pyromellitic dianhydride (8.40 g, 0.038 mol, poly(propyleneglycol with average M.W. 2000 (73.5 g, 0.037 mol), and xylene (approximately 50 ml) were added and allowed to react. After isolation, 131.7 g of the final product was obtained.

Example 42 Preparation of Additive 42 According to the procedure used for Example 34, di(hydrogenated tallow) amine (51.0 g, 0.10 mol), and 1,2-epoxyoctadecane (14.2 g, 0.050 mol) were combined. Then, pyromellitic dianhydride (10.9 g, 0.050 mol, 1,12-dodecanediol (9.11 g, 0.045 mol),Jand xylene (approximately 50 ml) were added and allowed to react. After isolation, 71.6 g of the final product was obtained.

Exam~le 43 Pre~aration of Additive 43 According to the procedure used for Example 34, di(hydrogenated tallow) amine (40.8 q, 0.080 mol), and 1,2-epoxyoctadecane (11.4 g, 0.040 mol) were combined. Then, pyromellitic dianhydride (8.72 g, 0.040 mol, poly(propyleneglycol with average M.W. 2000 (40.0 g, 0.020 mol), and xylene (approximately 50 ml) were added and allowed to react. After isolation, 89.5 g of the final product was obtained.

Example 44 Preparation of Additive 44 Aniline (1.55 g, 0.017 mol; e.g. from Aldrich Chemical Company), and 1,2-epoxyoctadecane ~33.6 g, 2 0 3 7 r;~

0.125 mol: e.g. Vikolox 18 from Viking Chemical) were combined and heated at 160 to 190~C for 18 to 24 hour~. Di(hydrogenated tallow) amine (50.0 g, 0.10 mol; e.g. Armeen 2 HT form Akzo Chemie) was added to the reaction mixture at 120'C, and then heated at 165 to 185-C for 18 to 24 hours.
Pryromellitic dianhydride (7.27 g, 0.033 mol: e.g.
PMDA from Allco Chemical Corporation) and xylene (approximately 50 ml) were added and heated at reflux (140 to 230-C), with azeotropic removal of water for 24 hours. Volatiles were then removed from the reaction medium at 190 to 200C, and the reaction mixture was hot filtered through diatomaceous earth to give 93.4 g of the final product.

Example 45 Preparation of Additive 45 According to the procedure used for Example 44, aniline (2.51 g, 0.027 mol), and 1,2-epoxyoctadecane (48.3 g, 0.180 mol) were combined.
Di(hydrogenated tallow) amine (45.0 q, 0.090 mol) was then added and reacted. Pyromellitic dianhydride (7.85 g, 0.036 mol) and xylene (approximately 50 ml) were added to the mixture and allowed to react. After isolation, 92.3 q of the final product was obtained.

Example 46 Preparation of Additive 46 According to the procedure used for Example 44, piperazine (1.44 g, 0.017 mol, e.g. from Aldrich Chemical Company) and 1,2-epoxyoctadecane (44.8 g, 0.167 mol) were combined. Di(hydrogenated tallow) amine ~50.0 g, 0.100 mol) was added and 7 ~ '~

reacted. Then, pyromellitiG dianhydride (7.27 g, 0.033 mol) and xylene (approximately 50 ml) were added and allowed to react. After isolation, 96.9 g of the final product wa~ obtained.

Example_47 Preparation of Additive 47 According to the procedure used for Example 44, piperazine (3.88 g, 0.045 mol), and 1,2-epoxyoctadecane (60.4 g, 0.225 mol) were combined.
Di(hydrogenated tallow) amine (45.0 g, 0.090 mol) was added and reacted at 200~C. Then, pyromellitic dianhydride (10.8 g, 0.050 mol) and xylene (approximately 50 ml) were added and allowed to react. After isolation, 99.2 g of the final product was obtained.

Example 48 Preparation of Additive 48 According to the procedure used for Example 44, n-octylamine (2.15 g, 0.017 mol; e.g. ALdrich Chemical Company), and 1,2-epoxyoctadecane (44.8 g, 0.167 mol) were combined. Di(hydrogenated tallow) amine (50.0 g, 0.100 mol) was added and reacted.
Then, pyromellitic dianhydride (7.27 g, 0.033 mol) and xylene (approximately 50 ml) were added and allowed to react. After isolation, 93.9 g of the final product was obtained.

Example 49 Preparation of Additive 49 According to the procedure used for Example 44, n-octylamine (5.82 g, 0.045 mol), and 1,2-epoxyoctadecane (60.4 g, 0.225 mol~ were combined.
Di(hydrogenated tallow) amine ~45.0 g, OOO90 mol) 7 ~ ~

wa~ added and reacted. Then, pyromellitic dianhydride (10.8 g, 0.050 mol) and xylene (approximately 50 ml) were added and allowed to react at 200 C. After isolation, 107.0 g of the final product was obtained.

ExamPle 5 0 Preparation of Additive 50 According to the procedure used for Example 44, hydrogenated tallow amine (4.31 g, 0.017 mol:
Armeen HT from Akzo Chemie), and 1,2-epoxyoctadecane (44.8 g, 0.167 mol) were combined.
Di(hydrogenated tallow) amine (50.0 g, 0.100 mol) was added and reacted. Then, pyromellitic dianhydride (7.27 g, 0.033 mol) and xylene (approximately 50 ml) were added and allowed to react at 200C. After isolation, 95.9 g of the final product was obtained.

Exam~le 51 Preparation of Additive 51 According to the procedure used for Example 44, hydrogenated tallow amine (11.6 g, 0.045 mol~, and 1,2-epoxyoctadecane (60.4 g, 0.225 mol) were cambined. Di(hydrogenated tallow~ amine (45.~ g, 0.090 mol) was added and reacted. Then, pyromellitic dianhydride (10.8 g, 0.050 mol) and xylene (approximately 50 ml) were added and allowed to react at 200C. After isolation, 116.1 g of the final product was obtained.

Exam~le 52 Preparation of Additive 52 According to the procedure used for Example 44, di(hydrogenated tallow) amine (50.0 y, 0.100 ~77~'~

mol), and 1~2-epoxyoctadecane (33.6 g, 0.125 mol) were combined. Then, Ethomeen T/12 (5.77 g, 0.017 mol; an aminodiol derlved from tallow amine and two equivalents of ethylene oxide, e.g. from Akzo Chemie), pyromellitic dianhydride (8.00 g, 0.037 mol) and xylene (approximately 50 ml) were added and allowed to react at 200-C. After isolation, 90.7 g of the final product was obtained.

Example 53 Preparation of Additive 53 According to the procedure used for Example 44, di(hydrogenated tallow) amine (50.0 g, 0.100 mol), and 1,2-epoxyoctadecane (33.6 g, 0.125 mol) were combined. Then, Ethomeen T/12 (19.0 g, 0.055 mol), pyromellitic dianhydride (12.0 g, 0.055 mol) and xylene (approximately 50 ml) were added and allowed to react at 200 C. After isolation, 102.0 g of the final product was obtained.

Example 54 Pre~aration of Additive 54 According to the procedure used for Example 44, di(hydrogenated tallow) amine (50.0 g, 0.100 mol), and 1,2-epoxyoctadecane (33.6 g, 0.125 mol) were combined. Then, Ethomeen T/15 (7.98 g, 0.017 mol; an aminodiol derived from tallow amine and five equivalents of ethylene oxide, e.g. from Akzo Chemie), pyromellitic dianhydride (8.00 g, 0.037 mol) and xylene (approximately 50 ml) were added and allowed to react at 200C. After isolation, 90.1 g of the final product was obtained.

~ ~J ~

Example S5 Preparation of Additive 5~
According to the procledure used for Example 44, di(hydrogenated tallow~ amine (50.0 g, 0.100 mol), and 1~2-epoxyoctadecane (33.6 ~, 0.125 mol3 were combined. Then, Ethom~een T/15 (26.3 g, 0.055 mol), pyromellitic dianhydride (12.0 g, 0.055 mol~
and xylene (approximately 50 ml) were added and allowed to react at 200-C. After isolation, 108.7 g of the final product was obtained.

Example 56 Preparation of Additive 56 According to the procedure used for Example 44, piperazine (3.88 q, 0.045 mol), and 1,2-epoxyoctadecane (38~5 g, 0.135 mol) were combined.
Di(hydrogenated tallow) amine (45.9 g, 0.090 mol), was added and reacted. Then pyromellitic dianhydride (9.82 g, 0.045 mol) and xylene (approximately 50 ml) were added and allowed to react at 200 C. After isolation, 87.9 g of the final product was obtained.

Example 57 Preparation of Additive 57 Di(hydrogenated tallow) amine ~60.0 g, 0.12 mol; e.g. Armeen 2HT from Akzo Chemie), 2,2-dimethyl-1,3--propanediol diglycidyl ether (6.29 g, 0.029 mol; e.g. Azepoxy N from AZS Corporation), and 1,2-epoxyoctadecane (24.4 g, 0.091 mol; e~g.
Vilolox 18 for Viking Chemical) were combined and heated at 140C for three hours, and at 165 to 170-C for 16 to 20 hour~. Pyromellitic dianhydride (8.72 g, 0.040 mol; e.g. PMDA from Allco Chemical Corporation and xylene (approximately 50 ml) were r~

3~
added and heated at reflux ~180 to l90 C) with azeotropic removal of water for 24 hours.
Volatiles were then removed from the reaction medium at 190C, and the reaction mixture was hot filtered through diatomaceous earth to give 89.1 g of the final product.

Example 5~
Preparation of Additive 58 According to the procedure used for Example 57, di(hydrogenated tallow) amine (60.0 g, 0.12 mol), 2,2'dimethyl-1,3-propanediol diglycidyl ether (10.9 g, O.OS0 mol), and 1,2-epoxyoctadecane (14.2 g, 0.053 mol) were combined. Then, pyromellitic dianhydride (11.5 g, 0.053 mol) and xylene (approximately 50 ml) were added and allowed to react. After isolation, 84.7 g of the final product was obtained.

Example 59 preparation of Additive 59 According to the procedure used for Example 57, di~hydrogenated tallow) amine (60.0 g, 0.12 mol), 1,4-butanediol diglycidyl ether (8.38 g, O.029 mol; e.g. Araldite RD-2 from Ciba-Geigy Company), and 1,2-epoxyoctadecane (24.4 g, 0.091 mol) were combined. Then, pyromellitic dianhydr~de (8.72 g, 0.040 mol) and xylene (approximately 50 ml) were added and allowed to react. After isolation, 93.7 g of the final product was obtained.

2~37rl6a~

Example 60 Preparation 0~ Additive 60 According to the procedure used for Example 57, di(hydrogenated tallow) amine (60.0 g, 0.12 mol3, 1,4-butanediol diglycidyl ether (14.5 g, 0.050 mol), and ~,2-epoxyoctadecane (14.2 g, 0.053 mol) were combined. Then, pyromellitic dianhydride (11.5 g, 0.053 mol) and xylene (approximately 50 ml) were added and allowed to react. Excess xylene solvent was added to facilitate filtration of the final reaction product, and then was removed under reduced pressure. After isolation, 107.4 g of the final product was obtained.

Example 61 P e~aration of Additive 61 According to the procedure used for Example 57, di~hydrogenated tallow~ amine (60.0 g, 0.12 mol), a polyetherglycol diglycidyl ether with an average molar weight of 380 (11.0 g, 0.029 mol;
e.g. DER 736 from Dow Chemical Company), and 1,2-epoxyoctadecane (24.4 g, 0.091 mol) were combined.
Then, pyromellitic dianhydride (11.5 g, 0.040 mol) and xylene (approximately 50 ml) were added and allowed tD react. After isolation, 90.2 g of the final product was obtained.

Example 62 Preparation of Additive 62 According to the procedure used for Example 57, di~hydrogenated tallow) amine (60.0 g, 0.12 mol), DER 736 (19.2 g, 0.050 mol), and 1,2-epoxyoctadecane (14.2 g, 0.053 mol) were combined.
Then, pyromellitic dianhydride (11.5 g, 0.053 mol) and xylene (approximately 50 ml) were added and c,~ r~

4n allowed to reactO After :isolation~ 88.4 g of the final product was obtained.

Examp~
Preparation of Addi~ive 63 According to the procedure used for Example 57, di(hydrogenated tallow) amine (50.0 g, 0.10 mol), a polyetherylycol diglycidyl ether with an average molar weight of 630 (15.3 g, 0.024 mol;
e.g. DER 736 from Dow Chemical Company), and 1,2-epoxyoctadecane ~20.3 g, 0.076 mol) were combined~
Then, pyromellitic dianhydride (7~27 g, 0.033 mol) and xylene (approximately 50 ml) were added and allowed to react. After isolation, 84.0 g of the final product was obtained.

Example 64 Preparation of Additive 64 According to the procedure used for Example 57, di(h~drogenated tallow) amine (60.0 g, 0.12 mol), 2,2~dimethyl-1,3-propanediol diglycidyl ether (10.2 g, 0.047 mol), and 1,2-epoxyoctadecane (14.4 g, 0.054 mol) were combined. Then, pyromellitic dianhydride (5.14 g, 0.024 mol), phthalic anhydride (3.49 g, 0.024 mol; e.g. from Aldrich Chemical Company), and xylene (approximately 50 ml) were added and allowed to react. After isolati~n, 82.2 g of the final product was obtained.

Example 65 Preparation of Additive 65 ~ ccording to the procedure used for Example 57, di(hydrogenated tallow~ amine (60.0 g, 0.12 mol), 1,4-butanediol diglycidyl ether (13.6 g, 0.047 mol), and 1,2-epoxyoctadecane (5.14 g, 0.0~4 ~7~
~1 mol~ were combined. Then, pyromellitic dianhydride (11.5 g, 0.053 mol~, phthalic anhydride (3.49 g, 0.024 mol~, and xylene (approximately 50 ml) were added and allowed to react. After isolation, 88.8 g of the final product was obtained.

Example 66 Prepara ion of Additive 66 According to the procedure used for Example 57, di(hydrogenated tallow) amine (60.0 g, 0.12 mol), DER 736 (17.9 g, 0.047 mol), and 1,2-epoxyoctadecane (14.4 g, 0.054 mol) were combined.
Then, pyromellitic dianhydride (5.14 g, 0.024 mol), phthalic anhydride (3.49 g, 0.024 mol), and xylene (approximately 50 ml) were added and allowed to react. After isolation, 89.4 g of the final product was obtained.

Example 67 Preparation of Additive 67 According to the procedure used for Example 57, di(hydrogenated tallow) amine (50.0 g, 0.10 mol), DE~ 736 (24.8 g, 0.039 mol), and 1,2-epoxyoctadecane (12.0 g, 0.045 mol) were combined.
Then, pyromellitic dianhydride (4.28 g, 0~020 mol), phthalic anhydride (2.91 q, 0.020 mol), and xylene (approximately 50 ml) were added and allowed to react. After isolation, 84.5 g of the final product was obtained.

Exam~le 68 Preparation of Additive 68 According to the procedure used for Example 57, di(hydrogenated tallow) amine (61.2 g, 0.12 mol), 2,2-dimethyl-1,3-propanediol diglycidyl ether 2~3r~)7~4 (6.49 g, 0.030 mol), and 1,2-epoxyoctadecane (8.55 g, 0.030 mol) were combined. Then, pyromellitic dianhydride (6.54 g, 0.030 mol), and xylene (approximately 50 ml) were added and allowed to react. After isolation, 74.2 g of the ~inal product was obtained.

Preparation of Additive Concentrate A concentrate solution of 100 ml total volume was prepared by dissolving 10 grams of additive in mixed xylenes solvent. Any insoluble particulates in the additive concentrate were removed by filtration before use.

Test Procedures The cloud point of the additized distillate fuel was determined using two procedures:
(a) an automatic cloud point test based on the equipment/procedure detailed in U.S. 4,601,303; the test designation (below) is "AUT0 CP", (b) an automatic cloud point test based on the commercially available Herzog cloud point tester; the test designation (below) is "HERZOG".
The low-temperature filterability was determined using the Cold Filter Plugging Point (CFPP~ test. This test procedure is described in "Journal of the Institute of Petroleum," Volume 52, Number 510, June 1966, pp. 173-185.

~77~

Test Fuel Characteristiçs FUEL A F~ 1 API ~ravity 35. 5 34 .1 Cloud Point, ' F
Auto CP 15 22 Herzog 16 . 4 23 . 4 CFPP, F 9 16 Pour Point, F 10 0 TABLE
Additive Effects on the Cloud Point and Filterability (CFPP) of Distillate Fuel (Additive Concentration = O. 1 W~ %) IMPROVEMENT IN PERFORMANCE TEMPERATURE ( F) Diesel Fuel A Diesel Fuel B
Cloud Point Cloud Point Addltive Auto CP Herzoq CFPP Auto CP Herzoq CFPP
1 2.4 4 7.7 4 2 1.8 6 6.7 4 3 3.3 6 6.7 2 4 2.7 6 6.1 4 3.6 4 7 6 6 3.4 6 5.8 4 7 2.1 4.3 7 8 1.5 4 6.3 9 9 1.6 6 6.7 7 1.8 6 6.3 9 11 2.0 6 7.4 11 12 1.6 6 6.1 6 13 1.6 6 6.1 7 14 2.7 4 7.9 6 2.2 4 7.6 7 3776~
4~
16 1.6 6 7.011 17 1.8 6 7.011 18 2.1 7.4 6 19 5 3.4 4 11 5.8 4 1.8 6 6.7 9 21 1.5 -6 6.7 9 22 1.8 4 7.6 6 23 2 6 7.6 6 24 3 2.4 4 8 6.3 7 1 2.2 4 7.2 4 26 2 2.5 4 5.4 o 27 3 2.5 4 6.5 4 28 1.2 7.4 7 29 4 2 4 6 5.9 4 4 2.2 4 7 5.9 2 31 3 2.4 6 8 5.4 4 32 4 2.2 4 6 4.9 2 33 3 2.4 4 7 5.9 2 1.8 6 6.7 7 36 1.6 6 6.1 9 37 1.5 4 4.7 6 38 2 6 6.511 39 2 4 7.4 6 3.8 4 7.2 6 41 3.3 6 6.3 6 42 1.6 7.0 9 43 2.7 4.3 6 44 3 2.2 4 7 6.7 9 3 2.5 6 7 7 6 46 1.8 6 6.8 9 47 2 6 7.211 48 3 2.2 6 7 6.8 9 49 1.8 6 6.811 2 2 6 7 6.5 7 ~Y~7~

51 1.8 ~ 5.97 52 2 1.6 ~ 7 6.39 53 2 2 4 7 6.611 54 3 1.8 ~ 7 6.111 2 2 ~6 6 6.111 56 1.8 8.113 57 2.2 ~ ~-0 9 58 4 3.4 4 11 6.64 59 1.6 6 6.79 3.1 4 6.74 61 2.2 6 7.74 62 3.6 4 6.84 63 1.8 6 7.411 64 3 2.~ 4 1~ 5~09 3 ~.0 4 8 5.~7 66 3 2.0 4 8 5.~2 67 4 2.0 4 9 5.02 68 1.2 7.96 The test data clearly show that minor amounts of the additives of the present invention improve low-temperature characteristics of distillate fuels.
Although the present invention has been described with preferred embodiments, it is to be understood that modifications and variations may be utilized without departing from the spirit and scope of this invention, as those skilled in the art will readily understand. Such modifications and variations are considered to be within the purview and scope of the appended claims.

Claims (24)

1. A product of reaction obtained from the reaction of (1) a hydrocarbyl diol, an aminodiol or diaminodiol, either alone or in combination with other diols, aminodiols or diaminodiols and (2) a reactive acid and/or anhydride derived from the reaction of benzophenone tetracarboxylic dianhydride or its acid equivalent or pyromellitic dianhydride or its acid equivalent and (a) an aminoalcohol, the product of an amine and an epoxide, or (b) an amino alcohol and an amine or (c) mixtures of (a) and/or (b), wherein said product of reaction has long-chain hydrocarbyl groups attached thereto.

2. The product of reaction of claim 1 wherein said reaction is carried out at temperatures varying from ambient or about 50° to about 250°C or reflux, in less than molar, more than molar or substantially molar amounts of reactants under ambient or slightly higher pressures.

3. The product of claim 1, wherein said dianhydride is benzophenone tetracarboxylic dianhydride.

4. The product of claim 1, wherein said dianhydride is pyromellitic dianhydride or its acid equivalent.

5. The product of claim 1, wherein reactant (1) is a diol.

6. The product of claim 1, wherein reactant (1) is an aminodiol.

7. The product o claim 1, wherein reactant (1) is a diaminodiol.

8. The product of claim 1, 2, 5, 6 or 7, wherein the amine is di(hydrogenated tallow) amine.

9. A composition comprising a major amount of a liquid hydrocarbyl fuel and a minor low-temperature flow properties improving amount of an additive product of the reaction of (1) a hydrocarbyl diol, an aminodiol or diaminodiol, either alone or in combination with other diols, aminodiols or diaminodiols and (2) a reactive acid and/or anhydride derived from the reaction of benzophenone tetracarboxylic dianhydride or its acid equivalent or pyromellitic dianhydride or its acid quivalent and (a) an aminoalcohol, the product of an amine and an epoxide, or (b) an amino alcohol and an amine or (c) mixtures of (a) and/or (b).

10. The composition of claim 9, wherein the amine is di(hydrogenated tallow) amine.

11. The composition of claim 9, wherein said liquid hydrocarbyl is selected from distillate fuels and fuel oils.

12. The composition of claim 9, wherein said fuel is a distillate fuel oil.

13. The composition of claim 9, wherein said fuel oil is selected from fuel oils Nos. 1, 2 or 3.

14. The composition of claim 9, wherein said fuel oil is a heating fuel oil.

15. The composition of claim 9, wherein said fuel oil is a jet combustion fuel.

16. The composition of claim 9, wherein said fuel oil is a diesel fuel oil.

17. The composition of claim 9, comprising from about 0. 001% to about 10% by weight of the total composition of the additive product.

18. The composition of claim 9, comprising from about 0.1% to about 5% by weight of the additive product.

19. A process of preparing a product of reaction suitable for use as a low-temperature flow properties improver additive for liquid hydrocarbyl fuel which comprises reacting (1) a hydrocarbyl diol, an aminodiol or diaminodiol, either alone or in combination with other diols, aminodiols or diaminodiols and (2) a reactive acid and/or anhydride derived from the reaction of benzophenone tetracarboxylic dianhydride or its acid equivalent or pyromellitic dianhydride or its acid equivalent and (a) an aminoalcohol, the product of an amine and an epoxide, or (b) an amino alcohol and an amine or (c) mixtures of (a) and/or (b), wherein said product of reaction has long-chain hydrocarbyl groups attached thereto.

20. A method of improving the flow characteristics of liquid hydrocarbon fuels comprising adding thereto a minor amount of a low-temperature additive product as described in claim 1.

21. The method of claim 20, comprising adding to said fuel about 0.001% to about 10% by weight of the composition of the low-temperature additive product.

22. A concentrate solution suitable for use in preparing liquid hydrocarbyl fuels comprising an inert solvent and the additive product of claim 1 dissolved therein.

23. The concentrate of claim 22, wherein said solvent is xylene or a mixture of xylenes.

24. The concentrate of claim 22, wherein the concentrate contains about 10 g of additive product per 100 ml of concentrate sample.