JPH04320493A - Multifunctional fuel additive - Google Patents

Abstract

PURPOSE: To provide a polyfunctional fuel additive.

CONSTITUTION: This polyfunctional fuel additive comprises: (1) a hydrocarbyldiol, an aminodiol, or a diaminodiol, either alone or in combination with a plurality of other diols, amino diols, or diamino diols; and (2) a product of a reaction of benzophenonetetracarboxylic acid dianhydride or a corresponding acid thereof, or pyromellitic dihydride or a corresponding acid thereof with (a) an amino alcohol, which is a product of an amine and an epoxide, (b) a mixture of an amino alcohol and amine, or (c) a reactive acid derived from a reaction of the component (a) and/or the mixture (b), and/or a reaction product obtd. from a reaction of the anhydride, wherein the reaction product has a long chain hydrocarbyl group bonded thereto and, when added to a distillate fuel, can improve the low-temp. properties of the distillate fuel.

COPYRIGHT: (C)1992,JPO

Description

[Detailed description of the invention]

0001

TECHNICAL FIELD This invention relates to multifunctional additives that improve the low temperature properties of distillate fuels and to fuel compositions containing small amounts thereof.

0002

BACKGROUND OF THE INVENTION In the past, the low temperature properties of distillate fuels were improved by adding kerosene, sometimes in very large amounts (5-70% by weight). Kerosene dilutes the wax in the fuel, ie, lowers the total weight of the wax, thereby simultaneously lowering the cloud point, filterability temperature, and pour point. The additives of the present invention improve cloud point and CFPP (cold filter plugging point) without significantly diluting the wax content of the fuel.
erPlugging Point)).

Other additives known in the art have been used in place of kerosene to improve the low temperature properties of distillate fuels. Many such additives are polymeric materials with pendant aliphatic hydrocarbon groups, usually derived from free radical polymerization of unsaturated hydrocarbons (olefins, acrylates, fumarates, etc.). These additives are limited in their range of activity, but mostly improve fuel properties by lowering pour point and/or filterability temperature. These same additives have little or no effect on the cloud point of the fuel.

US Pat. Nos. 3,910,987 and 3,910,981 disclose the use of certain aminodiols in the production of petroleum additives. No. 4,524,007 discloses the use of polycarboxylic acids/anhydrides, such as pyromellitic dianhydride, reacted with alcohols with ethers to provide demulsifying additives for lubricants. This is disclosed.

[0005]

SUMMARY OF THE INVENTION The additives of the present invention differ substantially from the prior art both in terms of structure and function (activity). They are oligomeric and/or polymeric substances obtained by condensation reactions, for example reaction of diols, aminodiols or diaminodiols with acids and/or anhydrides. In terms of activity, these additives effectively lower the cloud point of distillate fuels, thus improving low temperature fuel properties, yet providing unique and useful advantages over known distillate fuel additives.

The novel additives of the present invention have been found to surprisingly activate wax crystal modifying additives for distillate fuels. Distillate fuel compositions containing small amounts of such additives, such as less than 0.1% by weight, have lower cloud points and lower C
It showed significantly improved cold flow properties along with FPP filterability temperature.

The additive of the present invention that improves the low temperature properties of distillate fuels comprises (1) a diol, aminodiol or diaminodiol and (2) benzophenonetetracarboxylic dianhydride (BTDA) or pyromellitic dianhydride. thing(
PMDA) and amino alcohol and/or amine products, to which long chain hydrocarbyl groups are attached.

The long chain hydrocarbyl groups may include (1) various substituted diol comonomers (diols, aminodiols or diaminodiols) or (2) substituted amino alcohols and/or derived BDTA or PMDA.
An amine precursor to the comonomer or (3) can be introduced into the final reaction product by a combination of (1) and (2).

These new additives are particularly effective in lowering the cloud point of distillate fuels and therefore improve the cold flow properties of these types of fuels by using light hydrocarbon diluents such as kerosene. Improve without using it at all. Additionally, filterability is improved as indicated by lower CFPP temperatures. Therefore, the additives of the present invention exhibit multifunctional activity in distillate fuels.

The invention further relates to fuel compositions containing small amounts of these multifunctional additives. The additive compositions described in this application have cloud point activity and CFPP activity;
Unique in structure and activity. Additive concentrates and fuel compositions containing such additives are also unique. Similarly, the methods of making these additives, additive concentrates, and fuel compositions are unique. Therefore, it is believed that these new additive products and their fuel compositions were not previously known or used in the prior art.

These oligomeric and/or polymeric additives are reaction products derived from two monomer components. (1) The first monomer species is a diol, aminodiol or diaminodiol alone or in combination with other diols, aminodiols or diaminodiols. (2) The second monomer species is BTDA or its acid equivalent or PMDA or its acid equivalent and (a) an amino alcohol that is a product of an amine and an epoxide, or (b) (a.
) reactive acid/anhydride products derived from the reaction with combinations of amino alcohols and amines, either alone or in combination with other such monomers.

[0012] The additives of the present invention therefore have an oligomeric (ie dimeric, trimeric, etc.) and/or polymeric structure. The various hydrocarbyl groups, particularly those attached to or containing linear paraffinic substructures, are distributed along the backbone of the oligomer and/or polymer and are dependent on one or both of the comonomers used. Can be transported.

Diols Any of the diols, alone or in combination, can be used in the present invention. As such a diol,
Examples of the types listed below may include, but are not limited to. namely, 1,2-diols, 1,3-diols, 1,4-diols, α-ω-diols, ether diols, polyether diols, glyceryl monoesters, and any other hydrocarbyl diols. However, 1,2-octadecanediol, 1,4-butanediol, 1,12-dodecanediol, poly(ethylene glycol) and poly(propylene glycol)
are also preferred reactants.

Any of the aminodiolaminodiols can be used in the present invention, alone or in combination, including, but not limited to, the examples given below. Such aminodiols are those derived from the reaction of a primary amine with two or more equivalents of epoxide.

[0015]

The reaction conditions for the production of aminodiol are as follows: self-pressure to 25 atmospheres, 80 to 250
℃ for 1 to 24 hours.

[0017] The choice of temperature is in large part a function of the particular reactants and whether solvents are used. The solvent used is typically a hydrocarbon solvent such as xylene, but any non-polar, non-reactive solvent can be used, including benzene and toluene and/or mixtures thereof.

The molar ratio of epoxide/primary amine is 2:
1 is common, but ratios greater than 2:1 can also be included.

The amine used above has each substituent independently C1-C100 hydrocarbyl or O, N, S,
It may be any primary amine that is a P-containing hydrocarbyl.

Diaminodiols One of the comonomers used, alone or in combination, in the synthesis of these additives may be a diaminodiol. The diaminodiol of the present invention is the reaction product of (1) a diepoxide and 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 diaminodiols provide the ability to introduce additional linear hydrocarbyl groups along the oligomer/polymer backbone, thereby increasing the overall density of linear hydrocarbyl groups in the final additive structure. However, any diaminodiol can be used in the present invention, including but not limited to the examples given below.

In the first class, diaminodiols are diols, such as those derived from the reaction of two equivalents of a secondary amine and a diglycidyl ether, according to the general scheme below.

[0022]

In a one-pot synthesis, diaminodiols are prepared by suitably reacting an amine or a mixture of amines with a diglycidyl ether.

The second class of aminodiols is bis-
Diols such as those derived from the reaction of a secondary amine with two or more equivalents of an epoxide.

[0025]

The epoxide/secondary amine molar ratio is typically 1:1 for each reactive amine group, but can include ratios greater than 1:1.

The amine used above has each substituent independently C1-C100 hydrocarbyl or O, N, S,
Any secondary amine that is a hydrocarbyl containing P. Reactive Acids and/or Anhydrides Other comonomers used, alone or in combination, in the synthesis of these additives include BTDA or its acid equivalents or PMDA or its acid equivalents with alcohols and/or amines. , reactive acids and/or anhydrides derived from reactions that introduce suitable side groups derived from amino alcohols and/or amines. The side groups are a combination of hydrocarbyl groups, preferably linear hydrocarbyl groups attached to a derivatized dianhydride (DA) ester and/or amide. "DA" as used herein generally refers to BTDA or PMDA, or their acid equivalents.

As side groups, (a) esters derived from amino alcohols, which can be derived from secondary amines bonded to oleic epoxides;
b) combinations of esters and amides derived from amino alcohols from (a) and amines, and (c)
Examples include combinations of esters derived from two or more of various amino alcohols. These ester and/or amide side groups typically have from 8 to about 100 or more carbon atoms, preferably from about 28 or 30 to 100 or more carbon atoms. The amino alcohol used above is the reaction product of an epoxide and a secondary amine in a molar ratio of approximately 1:1, the preferred amine being a secondary amine such as di(hydrogenated tallow) amine. A preferred epoxide is an epoxide such as 1,2-epoxyoctadecane.

[0029] In a one-pot synthesis method, aminodiols can be prepared by suitably reacting an amine or a mixture of amines with an epoxide or a mixture thereof, and then reacting the resulting product with BTDA or PMDA or its acid equivalent. First manufactured by. The reaction can be carried out under a wide variety of conditions.

Reaction with Acids/Anhydrides to Produce Multifunctional Additives The additives of the present invention can be prepared using a standard esterification process in which the two monomer species described above are mixed in various ways using a standard esterification process in the stepwise manner described below. obtained by combining in the ratio of

(1) Reactive acid/anhydride

[0032]

(2a) Reactive acids/anhydrides and diols

[0034]

(2b) Reactive acids/anhydrides and aminodiols

[0036]

(2c) Reactive acids/anhydrides and diaminodiols

[0038]

Structure of Acid/Anhydride Reaction Product The general structure of an oligomer/polymer derived from a partial ester of BTDA or PMDA and a diol is as follows.

[0040]

The general structure of oligomers/polymers derived from mixed partial esters of BTDA or PMDA and diols is as follows.

[0042]

The general structure of oligomers/polymers derived from BTDA or PMDA partial esters/amides and diols is as follows.

[0044]

For example, the general structure of an oligomer/polymer derived from a BTDA or PMDA partial ester and an aminodiol is as follows.

[0046]

The general structure of oligomers/polymers derived from BTDA or PMDA mixed partial esters and amino diols is as follows.

[0048]

The general structure of an oligomer/polymer derived from a BTDA or PMDA partial ester/amide and an aminodiol is as follows.

[0050]

The general structure of an oligomer/polymer derived from a BTDA or PMDA partial ester and a diaminodiol is as follows.

[0052]

Furthermore, oligomers/polymers similar to these may be derived from DA mixed partial esters, ie DA derivatives having different amino alcohols in the side groups.

Oligomer derived from BTDA or PMDA partial ester/amide and diaminodiol/
The general structure of the polymer is as follows.

[0055]

Definition In the above formula, v+w is 2 or more; x=y+z
is from 0.5 to 3.5, preferably from 1 to about 3; a is 0
．． 25 to about 2, preferably 0.5 to about 1.25;
R is C1 to about C100 hydrocarbyl, or C1 to about C100 with phosphorus, nitrogen, sulfur and/or oxygen
is hydrocarbyl; R′ is a divalent group corresponding to R;
i.e., a divalent C1-C100 hydrocarbyl, or a divalent C1-C100 hydrocarbyl having phosphorus, nitrogen, sulfur and/or oxygen; each R1 may be the same or different; hydrogen, C1 to about C
100 hydrocarbyl, or C1 to about C100 hydrocarbyl having phosphorus, nitrogen, sulfur and/or oxygen; each R2 may be the same or different and is a C8 to about C50 hydrocarbyl group, preferably linear saturated or unsaturated; R3 is C1 to about C100 hydrocarbyl, or C1 to about C100 hydrocarbyl with phosphorus, nitrogen, sulfur and/or oxygen; R4 is C1 to about C100 hydrocarbyl, or nitrogen, sulfur, phosphorous , a C1 to about C100 hydrocarbyl having boron, silicon and/or oxygen;
R5 is a C2-C100 hydrocarbyl; R6 is one or more aminodiol substructures as defined above; and R7 is one of the two diaminodiol substructures defined above.

The expression "long chain hydrocarbyl group" as used in this application means a linear or linear alkyl or alkenyl group. Each individual long chain hydrocarbyl group is typically a C8-C30 hydrocarbyl group, preferably a C14-C22 hydrocarbyl group.

Amine Any suitable amine can be used.

When used to make aminodiols, the amine is preferably any primary amine such as n-octylamine, hydrogenated tallow amine and aniline.

When an amine is used to make a diaminodiol by reaction with a diepoxide, the amine is any secondary amine such as di(hydrogenated tallow) amine and methyloctadecylamine.

When an amine is used to make a diaminodiol by reaction with an epoxide, the amine is any bis-secondary amine such as piperazine.

When the amine is used as the structural fragment of the reactive acid anhydride, the amine can be any suitable aliphatic or aromatic arylalkyl or alkylaryl secondary amine having from 1 to about 100 carbon atoms. It is. A highly preferred amine is di(hydrogenated tallow) amine. Other suitable amines include, but are not limited to, tallow amine, dioctadecyl amine, methyloctadecyl amine, and other secondary amines.

Diepoxides Included within the scope of diepoxides are any diglycidyl ethers and any diepoxide reaction products derived from any diol and two molar amounts of epichlorohydrin (or synthetic equivalent). , for example 2,2-dimethyl-1,3-propanediol-diglycidyl ether.

Epoxides Included within the range of epoxides used in the preparation of amino alcohols from the amines listed above are ethylene oxide, 1,2-epoxides such as 1,2-epoxydecane, 1,2-epoxide dodecane. , 1,2-epoxytetradecane, 1,2-epoxypentadecane, 1
, 2-epoxyhexadecane, 1,2-epoxyheptadecane, 1,2-epoxyoctadecane, 1,2-epoxyeicosane, and mixtures thereof. Particularly preferred are 1,2-epoxyoctadecane and ethylene oxide.

Reaction Conditions In general, additive reaction products can be synthesized under a wide variety of conditions which are not believed to be critical. The reaction temperature is between 50°C and 250°C under ambient pressure or self-pressurization.
, preferably 100°C to 250°C, more preferably 1
The temperature can be between 50°C and 200°C. however,
Slightly higher pressures may be used if desired. pressure is 0
．． 001 atm to 10 atm, preferably 0.001 atm to
It may be 1 atm. The choice of temperature is, in large part, related to the particular reactants and solvents used. The solvent, if used, is typically a hydrocarbon solvent such as xylene, but any non-polar unreacted solvent can be used, including benzene, toluene or mixtures thereof.

[0066]Molar ratios, less than molar ratios, or greater than molar ratios of comonomer reactants can be used. Optionally, a molar ratio of diol, aminodiol or diaminodiol to reactive acid/anhydride is used from 1:2 to 3.5:1, more preferably from 1:1.25 to 1.5:1.

Reaction time also does not appear to be critical. Generally, the treatment is carried out for about 1 to about 24 hours to 36 to 48 hours or more.

Fuel Compositions Generally, the reaction products of this invention can be used in any effective amount that provides the desired activity needed to improve the low temperature properties of distillate fuels. In many applications, the products are effectively used in amounts of about 0.001% to about 10%, preferably less than about 0.1% to about 5% by weight of the total composition. These additives can be used in conjunction with other known low temperature fuel additives (such as dispersants) used for their intended purpose.

The fuels considered are distillate fuels and liquid hydrocarbon combustion fuels such as fuel oil. Accordingly, fuel oils that can be improved by the present invention are hydrocarbon fractions having an initial boiling point of at least about 250°F (121°C) and a final boiling point of about 750°F (399°C) or less; It boils almost continuously throughout the distillation temperature range. This type of fuel oil is commonly known as distillate fuel oil. However, it is to be understood that this term is not limited to straight-run fractions. Distillate fuel oil refers to straight-run distillate fuel oil, catalytically cracked or thermally cracked (including hydrocracking) distillate fuel oil, or straight-run distillate fuel oil, distillate feedstock that has been cracked with naphtha, etc. It can be a mixture of Additionally, fuel oils of this type can be processed by well-known commercial methods such as acid or caustic processing, hydrogenation, solvent refining, clay processing, and the like.

Distillate fuel oils are characterized by their relatively low viscosity, pour point, etc. However, the main property characterizing the considered hydrocarbons is the distillation temperature range. As stated above in the text, this range is approximately 250°F (121°C)
~750°F (400°C) is typical. Obviously, the distillation temperature range for each individual fuel oil falls within a narrower boiling point range that is also within the ranges specified above. Similarly, each fuel oil boils nearly continuously throughout its distillation temperature range.

Among the fuel oils considered are fuel oils Nos. 1, 2 and 3 used for heating and as diesel fuel oils and jet combustion fuels. Generally speaking, household fuel oil is A. S. T. M. Standard D396-4
Applies to the standards shown in 8T. The standard for diesel fuel is A. S. T. M. Defined in standard D975-48T. Typical jet fuel is US military standard MIL-F-
5624B.

[0072]

EXAMPLES The following examples are merely illustrative and are not meant to limit the scope of the invention.

[0073]

[Example 1] Production method of additive 1 (hydrogenated beef tallow) amine [50.0 g, 0.10 mol;
From Akzo Chemie]
and 1,2-epoxyoctadecane [33.6 g, 0
．． 125 mol; for example, Viking Chemical (Vik
Vicolox (Vi from ing Chemical)
kolox) 18] and heated at 170°C for 16-18 hours. Benzophenone tetracarboxylic dianhydride [17.7 g, 0.055 mol; e.g.
BTDA from Corporation), 1,
12-Dodecanediol [5.06 g, 0.025 mol; e.g. Aldrich Chemical Company (Al
(drich Chemical Company)
] and xylene (approximately 50 ml) were added under reflux to remove water azeotropically (from
°C) for 24 hours. Next, reduce the volatiles to 190-200
The reaction medium was removed at 0.degree. C. and the reaction mixture was filtered hot through diatomaceous earth to yield 92.5 g of final product.

[0074]

Example 2 Preparation of Additive 2 By the method used in Example 1 (described above), di(hydrogenated tallow)amine (50.0 g, 0.10 mol) and 1,
2-Epoxyoctadecane (33.6g, 0.125mol) was mixed. Next, benzophenone tetracarboxylic dianhydride (17.7 g, 0.055 mol), 1,12
-Dodecanediol (9.11 g, 0.045 mol) and xylene (about 50 ml) were added and reacted. Excess xylene was added to facilitate filtration, followed by removal by evaporative distillation. After isolation, 102.0 g of final product was obtained.

[0075]

Example 3: Preparation of Additive 3 By the method used in Example 1 (described above), di(hydrogenated beef tallow)amine (50.0 g, 0.10 mol) and 1,
2-Epoxyoctadecane (33.6g, 0.125mol) was mixed. Next, benzophenone tetracarboxylic dianhydride (17.7 g, 0.055 mol), poly(propylene glycol) with an average molecular weight of 400 [10.0
g, 0.025 mol; Texaco Chemical Company
y)] and xylene (approximately 50 ml) were added and allowed to react. After isolation, 97.8 g of final product were obtained.

[0076]

Example 4 Preparation of Additive 4 By the method used in Example 1 (described above), di(hydrogenated tallow)amine (50.0 g, 0.10 mol) and 1,
2-Epoxyoctadecane (33.6g, 0.125mol) was mixed. Next, benzophenone tetracarboxylic dianhydride (17.7 g, 0.055 mol), poly(propylene glycol) with an average molecular weight of 400 (21.0
g, 0.052 mol) and xylene (approximately 50 ml) were added and reacted. After isolation, 111.2 g of final product were obtained.

[0077]

Example 5 Method of Preparing Additive 5 By the method used in Example 1 (described above), di(hydrogenated beef tallow)amine (40.0 g, 0.08 mol) and 1,2
-Epoxyoctadecane (26.8g, 0.10mol)
were mixed. Next, benzophenone tetracarboxylic dianhydride (14.2 g, 0.044 mol), average molecular weight 2
000 poly(propylene glycol) (40.0g,
0.020 mol; from Texaco Chemical Company) and xylene (approximately 50 ml) were added and allowed to react. After isolation, 109.7 g of final product were obtained.

[0078]

Example 6: Preparation of Additive 6 By the method used in Example 1 (described above), di(hydrogenated beef tallow)amine (35.0 g, 0.07 mol) and 1,
2-Epoxyoctadecane (23.5g, 0.088mol) was mixed. Next, benzophenone tetracarboxylic dianhydride (12.4 g, 0.038 mol), poly(propylene glycol) with an average molecular weight of 2000 (73.5
g, 0.037 mol) and xylene (approximately 50 ml) were added to react. After isolation, 131.4 g of final product were obtained.

[0079]

Example 7 Preparation of Additive 7 By the method used in Example 1 (described above), di(hydrogenated beef tallow)amine (51.0 g, 0.10 mol) and 1,
2-Epoxyoctadecane (14.2 g, 0.050 mole) was mixed. Next, benzophenone tetracarboxylic dianhydride (16.1 g, 0.050 mol), poly(propylene glycol) with an average molecular weight of 400 (20.0
g, 0.050 mol) and xylene (approximately 50 ml) were added to react. After isolation, 90.7 g of final product was obtained.

[0080]

Example 8 Preparation of Additive 8 Piperazine (1.44 g, 0.017 mole; e.g., from Aldrich Chemical Company), di(hydrogenated tallow) amine [50.0 g, 0.10 mole; e.g. Armeen 2H from Akzo Chemie
T] and 1,2-epoxyoctadecane (44.8g
, 0.167 mol;
Heated for ~24 hours. Benzophenone tetracarboxylic dianhydride (11.8 g, 0.037 mol; e.g. BTDA from Alco Chemical Corporation) and xylene (approximately 50 ml) were added and the water was removed azeotropically at reflux (180 ~200°C) for 24 hours. The volatiles were then removed from the reaction medium at 190-200<0>C and the reaction mixture was filtered hot through diatomaceous earth to yield 97.5 g of final product.

[0081]

[Example 9] Method for producing additive 9 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 mixed. Next, benzophenone tetracarboxylic dianhydride (7.8
5 g, 0.036 mol) and xylene (approximately 50 ml)
was added and reacted. After isolation, 105.9 g of final product
was gotten.

[0082]

[Example 10] Process for producing additive 10 According to the method used in Example 8, n-octylamine (2
．． 75 g, 0.017 mol; e.g. from Aldrich Chemical Company), di(hydrogenated tallow) amine (
50.0 g, 0.100 mole) and 1,2-epoxyoctadecane (44.8 g, 0.167 mole) were mixed. Next, benzophenone tetracarboxylic dianhydride (11.8 g, 0.037 mol) and xylene (ca.
0 ml) was added to react. After isolation, the final product 98
．． 2g was obtained.

[0083]

[Example 11] Production method of additive 11 N-octylamine (6
．． 61 g, 0.040 mole), di(hydrogenated tallow) amine (40.0 g, 0.080 mole) and 1,2-epoxyoctadecane (64.7 g, 0.200 mole). Next, benzophenone tetracarboxylic dianhydride (14.2 g, 0.044 mol) and xylene (ca.
0 ml) was added to react. After isolation, the final product 10
3.0 g was obtained.

[0084]

[Example 12] Process for producing additive 12 Hydrogenated beef tallow amine (4.
31 g, 0.017 mol; e.g. Almene HT from Akzo Chemie), di(hydrogenated tallow) amine (50
．． 0 g, 0.100 mol) and 1,2-epoxyoctadecane (44.8 g, 0.167 mol) were mixed. Next, benzophenone tetracarboxylic dianhydride (1
1.8 g, 0.037 mol) and xylene (approximately 50 m
1) was added and reacted. After isolation, the final product 103.
4g was obtained.

[0085]

[Example 13] Process for producing additive 13 Hydrogenated beef tallow amine (10
．． 3g, 0.040 mol), di(hydrogenated beef tallow)amine (
40.0 g, 0.080 mole) and 1,2-epoxyoctadecane (53.7 g, 0.200 mole) were mixed. Next, benzophenone tetracarboxylic dianhydride (
14.2 g, 0.044 mol) and xylene (approximately 50
ml) was added and reacted. After isolation, the final product 108
．． 2g was obtained.

[0086]

Example 14: Preparation of Additive 14 Using the method used in Example 8, di(hydrogenated beef tallow)amine (50.0 g, 0.100 mol) and 1,2-epoxyoctadecane (33.6 g, 0.1 mol) were prepared. 125 mol) were mixed. Next, Ethomeen T/12
(8.66 g, 0.025 mol; aminodiol derived from tallow amine and 2 equivalents of ethylene oxide, e.g. from Akzo Chemie), benzophenonetetracarboxylic dianhydride (17.7 g, 0.055 mol)
and xylene (approximately 50 ml) were added to react. After isolation, 100.5 g of final product were obtained.

[0087]

[Example 15] Method for producing additive 15 Di(hydrogenated beef tallow) amine (50.0 g, 0.100 mol) and 1,2-epoxyoctadecane (33.6 g, 0 .125 mol) were mixed. Next, Etmain T/12 (18.2g, 0.
052 mol), benzophenonetetracarboxylic dianhydride (17.7 g, 0.055 mol) and xylene (about 50 ml) were added and reacted. After isolation, the final product 1
09.2g was obtained.

[0088]

[Example 16] Method for producing additive 16 Di(hydrogenated beef tallow) amine (50.0 g, 0.100 mol) and 1,2-epoxyoctadecane (33.6 g, 0 .125 mol) were mixed. Next, Etmain T/12 (12.0 g, 0.
025 mol; aminodiol derived from tallow amine and 5 equivalents of ethylene oxide, e.g. from Akzo Chemie), benzophenone tetracarboxylic dianhydride (17.7 g, 0.055 mol) and xylene (
50 ml) and allowed to react. After isolation, 89.2 g of final product were obtained.

[0089]

[Example 17] Method for producing additive 17 By the method used in Example 8, di(hydrogenated beef tallow) amine (50.0 g, 0.100 mol) and 1,2-epoxyoctadecane (33.6 g, 0 .125 mol) were mixed. Next, Etmain T/15 (25.1 g, 0.
052 mol), benzophenonetetracarboxylic dianhydride (17.7 g, 0.055 mol) and xylene (about 50 ml) were added and reacted. After isolation, the final product 8
6.7g was obtained.

[0090]

Example 18 Preparation of Additive 18 n-octylamine (5.17 g, 0.040 mol) and 1,2-epoxyoctadecane (34.2 g, 0.04 mol).
12 mol) and simultaneously reacted at 140 to 170°C for 23 hours. Di(hydrogenated beef tallow)amine (40.8g,
0.80 mol) to the reaction mixture and at 170°C
heated for an hour. Benzophenone tetracarboxylic dianhydride (12.9 g, 0.040 mol) and xylene (approximately 50 ml) were then added and heated at reflux (190° C.) for 24 hours to azeotropically remove water. The volatiles were then removed from the reaction medium at 190-200<0>C and the reaction mixture was filtered hot through diatomaceous earth to yield 84.8 g of final product.

[0091]

[Example 19] Preparation method of additive 19 Di(hydrogenated beef tallow) amine (60.0 g, 0.12 mol;
For example, Armene 2HT from Akzo Chemie),
2,2-dimethyl-1,3-propanediol-diglycidyl ether [10.9 g, 0.050 mol; e.g.
azepoxy (Azepo
xy)N], and 1,2-epoxyoctadecane (1
4.2 g, 0.053 mol; e.g.
Heated at 165-170°C for 3 hours and 16-20 hours at 165-170°C. Benzophenone tetracarboxylic dianhydride (17.
0 g, 0.053 mol; e.g. BTDA from Alco Chemical Corporation) and xylene (approximately 50
ml) and refluxing to azeotropically remove water (
180-190°C) for 24 hours. The volatiles were then removed from the reaction medium at 190° C. and the reaction mixture was filtered hot through diatomaceous earth to yield 90.2 g of final product.

[0092]

[Example 20] Process for producing additive 20 By the method used in Example 19, di(hydrogenated beef tallow)amine (60.0 g, 0.12 mol), 2,2-dimethyl-
1,3-propanediol-diglycidyl ether (6
．． 29 g, 0.029 mole) and 1,2-epoxyoctadecane (24.4 g, 0.091 mole) were mixed. Next, benzophenone tetracarboxylic dianhydride (1
2.9 g, 0.040 mol) and xylene (approximately 50 m
1) was added and reacted. After isolation, final product 95.0
g was obtained.

[0093]

[Example 21] Method for producing additive 21 Di(hydrogenated beef tallow) amine (60.0 g, 0.12 mol), 1,4-butanediol diglycidyl ether [8.38 g] , 0.029 mol; for example, Ciba Geigy Company (Chiba Geigy Company)
- Araldite (A from Geigy Company)
raldite) RD-2], and 1,2-epoxyoctadecane (24.4 g, 0.091 mol) were mixed. Next, benzophenone tetracarboxylic dianhydride (
12.9 g, 0.040 mol) and xylene (approx.
ml) was added and reacted. After isolation, the final product 96.
8g was obtained.

[0094]

[Example 22] Method for producing additive 22 By the method used in Example 19, di(hydrogenated beef tallow) amine (60.0 g, 0.12 mol) was prepared with an average molecular weight of 380.
polyether glycol-diglycidyl ether [1
1.0 g, 0.029 mol; e.g. Dow Chemical
Company (Dow Chemical Comp
DER736] and 1,2-epoxyoctadecane (24.4 g, 0.091 mol) were mixed. Next, benzophenonetetracarboxylic dianhydride (12
．． 9 g, 0.040 mol) and xylene (approximately 50 ml
) was added and reacted. After isolation, 98.0 g of final product
was gotten.

[0095]

[Example 23] Method for producing additive 23 By the method used in Example 19, di(hydrogenated beef tallow) amine (60.0 g, 0.12 mol) was prepared with an average molecular weight of 630.
polyether glycol-diglycidyl ether [1
5.3 g, 0.024 mol; e.g. Dow Chemical
DER732] and 1,2-epoxyoctadecane (20.3 g, 0.076 mol) were mixed. Next, benzophenone tetracarboxylic dianhydride (10.7 g, 0.033 mole) and xylene (ca.
0 ml) was added to react. After isolation, the final product 88
．． 9g was obtained.

[0096]

[Example 24] Process for producing additive 24 By the method used in Example 19, di(hydrogenated beef tallow)amine (60.0 g, 0.12 mol), 2,2-dimethyl-
1,3-propanediol-diglycidyl ether (1
0.2 g, 0.047 mol) and 1,2-epoxyoctadecane (14.4 g, 0.054 mol) were mixed. Next, 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)
was added and reacted. After isolation, 87.5 g of final product was obtained.

[0097]

[Example 25] Method for producing additive 25 Di(hydrogenated beef tallow) amine (60.0 g, 0.12 mol), 1,4-butanediol diglycidyl ether (13.6 g) were prepared by the method used in Example 19. , 0.047 mol) and 1,2-epoxyoctadecane (14.4 g
, 0.054 mol) were mixed. Subsequently, benzophenonetetracarboxylic dianhydride (7.60 g, 0.024
mol), phthalic anhydride (3.49 g, 0.024 mol) and xylene (about 50 ml) were added and reacted. After isolation, 88.6 g of final product were obtained.

[0098]

[Example 26] Method for producing additive 26 Di(hydrogenated beef tallow) amine (60.0 g, 0.12 mol), DER736 (17
．． 9 g, 0.047 mol) and 1,2-epoxyoctadecane (14.4 g, 0.054 mol) were mixed. Next, benzophenone tetracarboxylic dianhydride (7.
60 g, 0.024 mol), phthalic anhydride (3.49
g, 0.024 mol) and xylene (approximately 50 ml) were added to react. After isolation, 93.0 g of final product was obtained.

0099

[Example 27] Method for producing additive 27 According to the method used in Example 19, di(hydrogenated beef tallow)amine (50.0 g, 0.10 mol), DER732 (24
．． 8 g, 0.039 mole) and 1,2-epoxyoctadecane (12.0 g, 0.045 mole) were mixed. Next, benzophenone tetracarboxylic dianhydride (6.
33g, 0.020 mol), phthalic anhydride (2.91
g, 0.020 mol) and xylene (approximately 50 ml) were added and reacted. After isolation, 87.2 g of final product were obtained.

[0100]

[Example 28] Process for producing additive 28 By the method used in Example 19, di(hydrogenated beef tallow)amine (61.2 g, 0.12 mol), 2,2-dimethyl-
1,3-propanediol diglycidyl ether (6.
49 g, 0.030 mole) and 1,2-epoxyoctadecane (8.55 g, 0.030 mole) were mixed. Subsequently, benzophenonetetracarboxylic dianhydride (9
．． 67 g, 0.030 mol) and xylene (approximately 50 m
1) was added and reacted. After isolation, the final product 76.4
g was obtained.

[0101]

Example 29: Preparation of Additive 29 Di(hydrogenated beef tallow) amine (49.9 g, 0.10 mol;
For example, Almene 2HT from Akzo Chemie) and 1,2-epoxyoctadecane (33.6 g, 0.5 g,
125 mol; e.g. Vicolox 18) from Viking Chemical were mixed and heated at 165° C. for 18 hours. Pyromellitic dianhydride (6.23 g, 0.028 mol; e.g. PMDA from Arco Chemical Corporation), 1,2-octadecanediol [2.05
g, 0.007 mol; e.g., Vikinol 18 from Viking Chemical] and xylene (approximately 50 ml) and refluxed (180-240° C.) for 24-36 hours to azeotropically remove water. Heated. Subsequently, the volatiles were removed from the reaction medium at 190-200<0>C and the reaction mixture was filtered hot through diatomaceous earth to yield 82.7 g of final product.

[0102]

[Example 30] Method for producing additive 30 Di(hydrogenated beef tallow) amine (49.9 g, 0.10 mol) and 1,2-epoxyoctadecane (33.6 g, 0 .125 mol) were mixed. Next, pyromellitic dianhydride (7.27g
, 0.033 mol), 1,2-octadecanediol (
4.78 g, 0.017 mol) and xylene (approximately 50
ml) was added and reacted. After isolation, the final product 85.
0 g was obtained.

[0103]

[Example 31] Method for producing additive 31 By the method used in Example 29, di(hydrogenated beef tallow)amine (49.9 g, 0.10 mol) and 1,2-epoxyoctadecane (33.6 g, 0 .125 mol) were mixed. Next, pyromellitic dianhydride (8.72g
, 0.040 mol), 1,2-octadecanediol (
8.60 g, 0.030 mol) and xylene (approximately 50
ml) was added and reacted. After isolation, the final product 90.
5g was obtained.

[0104]

[Example 32] Method for producing additive 32 Di(hydrogenated beef tallow)amine (49.9 g, 0.10 mol) and 1,2-epoxyoctadecane (33.6 g, 0 .125 mol) were mixed. Next, pyromellitic dianhydride (7.27g
, 0.033 mol), 1,4-butanediol (1.5
0 g, 0.017 mol; eg, from Aldrich Chemical Company) and xylene (approximately 50 ml) were added and allowed to react. After isolation, 81.6 g of final product were obtained.

[0105]

[Example 33] Method for producing additive 33 Di(hydrogenated beef tallow)amine (49.9 g, 0.10 mol) and 1,2-epoxyoctadecane (33.6 g, 0 mol) were prepared by the method used in Example 29. .125 mol) were mixed. Next, pyromellitic dianhydride (8.72g
, 0.040 mol), 1,4-butanediol (2.7
0 g, 0.030 mol) and xylene (approximately 50 ml)
was added and reacted. After isolation, 84.3 g of final product
was gotten.

[0106]

[Example 34] Production method of additive 34 Di(hydrogenated beef tallow) amine (49.9 g, 0.10 mol)
and 1,2-epoxyoctadecane (33.6 g, 0
．． 125 mol) were mixed and heated at 170°C for 18 hours. Pyromellitic dianhydride (8.00 g, 0.037 mol), 1,12-dodecanediol (3.37 g, 0.03 mol),
017 mol; e.g. from Aldrich Chemical Company) and xylene (approx. 50 ml) under reflux (190-200°C) to azeotropically remove water
Heated for 24 hours. The volatiles were then removed from the reaction medium at 190-200<0>C and the reaction mixture was filtered hot through diatomaceous earth to yield 87.1 g of final product.

[0107]

[Example 35] Method for producing additive 35 Di(hydrogenated beef tallow)amine (49.9 g, 0.10 mol) and 1,2-epoxyoctadecane (33.6 g, 0 .125 mol) were mixed. Next, pyromellitic dianhydride (12.0g
, 0.055 mol), 1,12-dodecanediol (9
．． 11 g, 0.045 mol) and xylene (approximately 50 m
1) was added and reacted. After isolation, the final product 91.4
g was obtained.

[0108]

[Example 36] Method for producing additive 36 Di(hydrogenated beef tallow)amine (49.9 g, 0.10 mol) and 1,2-epoxyoctadecane (33.6 g, 0 .125 mol) were mixed. Next, pyromellitic dianhydride (8.00g
. After isolation, 84.7 g of final product were obtained.

[0109]

[Example 37] Method for producing additive 37 Di(hydrogenated beef tallow) amine (49.9 g, 0.10 mol) and 1,2-epoxyoctadecane (33.6 g, 0 mol) were prepared by the method used in Example 34. .125 mol) were mixed. Next, pyromellitic dianhydride (12.0g
, 0.055 mol), poly(ethylene glycol) having an average molecular weight of 400 (22.0 g, 0.055 mol), and xylene (about 50 ml) were added and reacted. After isolation, 78.0 g of final product was obtained.

[0110]

[Example 38] Process for producing additive 38 Di(hydrogenated beef tallow)amine (49.9 g, 0.10 mol) and 1,2-epoxyoctadecane (33.6 g, 0 .125 mol) were mixed. Next, pyromellitic dianhydride (8.00g
, 0.037 mol), poly(propylene glycol) with an average molecular weight of 400 [6.67 g, 0.017 mol;
JEFFOX PPG-400 from Chemical Company] and xylene (approximately 50 ml) were added and allowed to react. After isolation, 88.2 g of final product was obtained.

[0111]

[Example 39] Method for producing additive 39 Di(hydrogenated beef tallow)amine (49.9 g, 0.10 mol) and 1,2-epoxyoctadecane (33.6 g, 0 mol) were prepared by the method used in Example 34. .125 mol) were mixed. Next, pyromellitic dianhydride (12.0g
, 0.055 mol), poly(propylene glycol) having an average molecular weight of 400 (22.0 g, 0.055 mol), and xylene (about 50 ml) were added and reacted. After isolation, 112.6 g of final product were obtained.

[0112]

Example 40: Preparation of Additive 40 The method used in Example 34 was used to prepare di(hydrogenated tallow)amine (40.0 g, 0.08 mol) and 1,2-epoxyoctadecane (26.8 g, 0.08 mol). 10 mol) were mixed. Next, pyromellitic dianhydride (9.60 g, 0.
044 mol), poly(propylene glycol) with an average molecular weight of 2000 (40.0 g, 0.020 mol; Jefox PPG-2 from Texaco Chemical Company)
000) and xylene (approximately 50 ml) were added and allowed to react. After isolation, 105.0 g of final product was obtained.

[0113]

[Example 41] Method for producing additive 41 Di(hydrogenated beef tallow) amine (35.0 g, 0.07 mol) and 1,2-epoxyoctadecane (23.5 g, 0 .088 mol) were mixed. Next, pyromellitic dianhydride (8.40g
, 0.038 mol), poly(propylene glycol) having an average molecular weight of 2000 (73.5 g, 0.037 mol), and xylene (about 50 ml) were added and reacted. After isolation, 131.7 g of final product were obtained.

[0114]

[Example 42] Method for producing additive 42 Di(hydrogenated beef tallow) amine (51.0 g, 0.10 mol) and 1,2-epoxyoctadecane (14.2 g, 0 .050 mol) were mixed. Next, pyromellitic dianhydride (10.9g
, 0.050 mol), 1,12-dodecanediol (9
．． 11 g, 0.045 mol) and xylene (approximately 50 m
1) was added and reacted. After isolation, the final product 71.6
g was obtained.

[0115]

Example 43: Preparation of Additive 43 Di(hydrogenated beef tallow)amine (40.8 g, 0.080 mol) and 1,2-epoxyoctadecane (11.4 g, 0.08 mol) were prepared by the method used in Example 34. 040 mol) were mixed. Next, pyromellitic dianhydride (8.72g
, 0.040 mol), poly(propylene glycol) having an average molecular weight of 2000 (40.0 g, 0.020 mol), and xylene (about 50 ml) were added and reacted. After isolation, 89.5 g of final product were obtained.

[0116]

Example 44 Preparation of Additive 44 Aniline (1.55 g, 0.017 mole; e.g., from Aldrich Chemical Company) and 1,2-
Epoxyoctadecane (33.6g, 0.125mol;
For example, Vicolox from Viking Chemical18)
were mixed and heated at 160-190°C for 18-24 hours. Di(hydrogenated tallow)amine (50.0 g, 0.10 mol; e.g. Almene 2HT from Akzo Chemie)
) to the reaction mixture at 120°C, 165-185
Heated at <0>C for 18-24 hours. Pyromellitic dianhydride (7.27 g, 0.033 mol; e.g. PMDA from Alco Chemical Corporation) and xylene (approximately 50 ml) were added at reflux to azeotropically remove water (140- 230°C) for 24 hours. The volatiles are then removed from the reaction medium at 190-200°C and the reaction mixture is filtered hot through diatomaceous earth to yield the final product 93.
Yielded 4g.

[0117]

[Example 45] Process for producing additive 45 Aniline (2.51g
, 0.027 mol), and 1,2-epoxyoctadecane (48.3 g, 0.180 mol). Next, di(hydrogenated tallow)amine (45.0 g, 0.090 mol) was added and reacted. Pyromellitic dianhydride (7
．． 85 g, 0.036 mol) and xylene (approximately 50 m
1) was added to the mixture and allowed to react. After isolation, 92.3 g of final product were obtained.

[0118]

[Example 46] Method for producing additive 46 Piperazine (1.44
g, 0.017 mol; e.g., from Aldrich Chemical Company) and 1,2-epoxyoctadecane (44.8 g, 0.167 mol). Di(hydrogenated tallow)amine (50.0 g, 0.100 mole) was added and reacted. Subsequently, pyromellitic dianhydride (7
．． 27 g, 0.033 mol) and xylene (approximately 50 m
1) was added and reacted. After isolation, the final product 96.9
g was obtained.

[0119]

[Example 47] Method for producing additive 47 Piperazine (3.88
g, 0.045 mol) and 1,2-epoxyoctadecane (60.4 g, 0.225 mol) were mixed. two(
Hydrogenated beef tallow amine (45.0 g, 0.090 mol) was added and reacted at 200°C. Next, pyromellitic dianhydride (10.8 g, 0.050 mol) and xylene (about 50 ml) were added and reacted. After isolation, 99.2 g of final product was obtained.

[0120]

[Example 48] Process for producing additive 48 Using the method used in Example 44, n-octylamine (
2.15 g, 0.017 mol; e.g. Aldrich
Chemical Company) and 1,2-epoxyoctadecane (44.8 g, 0.167 mole) were mixed. Di(hydrogenated tallow)amine (50.0 g, 0.100 mole) was added and reacted. Subsequently, pyromellitic dianhydride (7.27 g, 0.033 mol) and xylene (about 50 ml) were added and reacted. After isolation, the final product 9
3.9g was obtained.

[0121]

[Example 49] Process for producing additive 49 Using the method used in Example 44, n-octylamine (
5.82 g, 0.045 mole) and 1,2-epoxyoctadecane (60.4 g, 0.225 mole) were mixed. Di(hydrogenated beef tallow)amine (45.0g, 0.090
mol) was added and allowed to react. Next, pyromellitic dianhydride (10.8 g, 0.050 mol) and xylene (
About 50 ml) was added and reacted at 200°C. After isolation,
107.0 g of final product was obtained.

[0122]

[Example 50] Process for producing additive 50 Hydrogenated beef tallow amine (4
．． 31 g, 0.017 mol; Almene HT from Akzo Chemie), and 1,2-epoxyoctadecane (44.8 g, 0.167 mol) were mixed. Di(hydrogenated tallow)amine (50.0 g, 0.100 mole) was added and reacted. Next, pyromellitic dianhydride (7.2
7 g, 0.033 mol) and xylene (approximately 50 ml)
was added and reacted at 200°C. After isolation, the final product 9
5.9g was obtained.

[0123]

[Example 51] Process for producing additive 51 Hydrogenated beef tallow amine (1
1.6 g, 0.045 mol) and 1,2-epoxyoctadecane (60.4 g, 0.225 mol) were mixed. Di(hydrogenated tallow)amine (45.0 g, 0.090 mol) was added and reacted. Next, pyromellitic dianhydride (10.8 g, 0.050 mol) and xylene (about 50 ml) were added and reacted at 200°C. After isolation, 116.1 g of final product were obtained.

[0124]

Example 52: Preparation of Additive 52 The method used in Example 44 was used to prepare di(hydrogenated tallow)amine (50.0 g, 0.100 mol) and 1,2-epoxyoctadecane (33.6 g, 0.1 mol). 125 mol) were mixed. Next, Etmain T/12 (5.77g, 0.
017 mol; aminodiol derived from tallow amine and 2 equivalents of ethylene oxide, e.g. from Akzo Chemie), pyromellitic dianhydride (8.00 g
, 0.037 mol) and xylene (about 50 ml) were added and reacted at 200°C. After isolation, the final product 90.
7g was obtained.

[0125]

Example 53: Preparation of Additive 53 Di(hydrogenated beef tallow)amine (50.0 g, 0.100 mol) and 1,2-epoxyoctadecane (33.6 g, 0.1 mol) were prepared by the method used in Example 44. 125 mol) were mixed. Next, Etmain T/12 (19.0g, 0.
055 mol), pyromellitic dianhydride (12.0 g,
0.055 mol) and xylene (approximately 50 ml) were added and reacted at 200°C. After isolation, the final product 102.
0 g was obtained.

[0126]

Example 54: Preparation of Additive 54 Di(hydrogenated beef tallow)amine (50.0 g, 0.100 mol) and 1,2-epoxyoctadecane (33.6 g, 0.1 mol) were prepared by the method used in Example 44. 125 mol) were mixed. Next, Etmain T/15 (7.98g, 0.
017 mol; aminodiol derived from tallow amine and 5 equivalents of ethylene oxide, e.g. from Akzo Chemie), pyromellitic dianhydride (8.00 g
, 0.037 mol) and xylene (about 50 ml) were added and reacted at 200°C. After isolation, the final product 90.
1 g was obtained.

[0127]

Example 55: Preparation of Additive 55 Di(hydrogenated beef tallow)amine (50.0 g, 0.100 mol) and 1,2-epoxyoctadecane (33.6 g, 0.1 mol) were prepared by the method used in Example 44. 125 mol) were mixed. Next, Etmain T/15 (26.3g, 0.
055 mol), pyromellitic dianhydride (12.0 g,
0.055 mol) and xylene (approximately 50 ml) were added and reacted at 200°C. After isolation, the final product 108.
7g was obtained.

[0128]

[Example 56] Method for producing additive 56 Piperazine (3.88
g, 0.045 mol) and 1,2-epoxyoctadecane (38.5 g, 0.135 mol) were mixed. two(
Hydrogenated beef tallow amine (45.9 g, 0.090 mol) was added and reacted. Next, pyromellitic dianhydride (9
．． 82 g, 0.045 mol) and xylene (approx. 50 m
1) was added and reacted at 200°C. After isolation, 87.9 g of final product was obtained.

[0129]

[Example 57] Process for producing additive 57 Di(hydrogenated beef tallow) amine (60.0 g, 0.12 mol;
For example, Armene 2HT from Akzo Chemie),
2,2-dimethyl-1,3-propanediol-diglycidyl ether (6.29 g, 0.029 mol; e.g. Azepoxy N from AZ Corporation) and 1,2-epoxyoctadecane (24.
4 g, 0.091 mol; e.g. Vicolox 18) from Viking Chemical were mixed and heated at 140<0>C for 3 hours and at 165-170<0>C for 16-20 hours. Pyromellitic dianhydride (8.72 g, 0.040 mol; e.g. PMDA from Arco Chemical Corporation) and xylene (approximately 50 ml) were added and the water was removed azeotropically at reflux (180 - 190℃)
Heated for 24 hours. The volatiles were then removed from the reaction medium at 190° C. and the reaction mixture was filtered hot through diatomaceous earth to yield 89.1 g of final product.

[0130]

[Example 58] Process for producing additive 58 By the method used in Example 57, di(hydrogenated beef tallow)amine (60.0 g, 0.12 mol), 2,2-dimethyl-
1,3-propanediol-diglycidyl ether (1
0.9 g, 0.050 mole) and 1,2-epoxyoctadecane (14.2 g, 0.053 mole) were mixed. Subsequently, 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 final product were obtained.

[0131]

Example 59: Process for producing Additive 59 Di(hydrogenated beef tallow) amine (60.0 g, 0.12 mol), 1,4-butanediol-diglycidyl ether (8. 38g, 0.029
eg, Araldite RD-2 from Ciba Geigy Company) and 1,2-epoxyoctadecane (24.4 g, 0.091 mole) were mixed. next,
Pyromellitic dianhydride (8.72 g, 0.040 mol) and xylene (about 50 ml) were added and reacted. After isolation, 93.7 g of final product were obtained.

[0132]

Example 60: Preparation of Additive 60 Using the method used in Example 57, di(hydrogenated beef tallow) amine (60.0 g, 0.12 mol), 1,4-butanediol-diglycidyl ether (14. 5g, 0.050
mol) and 1,2-epoxyoctadecane (14.2
g, 0.053 mol) were mixed. Next, pyromellitic dianhydride (11.5 g, 0.053 mol) and xylene (about 50 ml) were added and reacted. Excess xylene solvent was added to facilitate filtration of the final reaction product, which was then removed under reduced pressure. After isolation, 107.4 g of final product were obtained.

[0133]

[Example 61] Method for producing additive 61 By the method used in Example 57, di(hydrogenated beef tallow) amine (60.0 g, 0.12 mol) was prepared with an average molecular weight of 380.
polyether glycol-diglycidyl ether (1
1.0 g, 0.029 mol; e.g. Dow Chemical
DER736) and 1,2-epoxyoctadecane (24.4 g, 0.091 mol) were mixed. Next, pyromellitic dianhydride (11.5 g, 0
．． 040 mol) and xylene (approximately 50 ml),
Made it react. After isolation, 90.2 g of final product was obtained.

[0134]

[Example 62] Process for producing additive 62 By the method used in Example 57, di(hydrogenated beef tallow)amine (60.0 g, 0.12 mol), DER736 (19
．． 2 g, 0.050 mole) and 1,2-epoxyoctadecane (14.2 g, 0.053 mole) were mixed. Next, pyromellitic dianhydride (11.5 g, 0.05
3 mol) and xylene (approximately 50 ml) were added to react. After isolation, 88.4 g of final product were obtained.

[0135]

[Example 63] Process for producing additive 63 By the method used in Example 57, di(hydrogenated beef tallow) amine (50.0 g, 0.10 mol) was prepared with an average molecular weight of 630.
polyether glycol-diglycidyl ether (1
5.3 g, 0.024 mol; e.g. Dow Chemical
DER736) and 1,2-epoxyoctadecane (20.3 g, 0.076 mol) were mixed. Next, pyromellitic dianhydride (7.27 g, 0
．． 033 mol) and xylene (approximately 50 ml),
Made it react. After isolation, 84.0 g of final product was obtained.

[0136]

[Example 64] Process for producing additive 64 By the method used in Example 57, di(hydrogenated beef tallow)amine (60.0 g, 0.12 mol), 2,2-dimethyl-
1,3-propanediol-diglycidyl ether (1
0.2 g, 0.047 mol) and 1,2-epoxyoctadecane (14.4 g, 0.054 mol) were mixed. Next, pyromellitic dianhydride (5.14 g, 0.0
24 mol), phthalic anhydride (3.49 g, 0.024
mol; eg, from Aldrich Chemical Company) and xylene (approximately 50 ml) were added and allowed to react. After isolation, 82.2 g of final product were obtained.

[0137]

[Example 65] Method for producing additive 65 Di(hydrogenated beef 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
, 0.024 mol) were mixed. Subsequently, pyromellitic dianhydride (11.5 g, 0.053 mol), phthalic anhydride (3.49 g, 0.024 mol) and xylene (about 50 ml) were added and reacted. After isolation, 88.8 g of final product was obtained.

[0138]

[Example 66] Method for producing additive 66 Di(hydrogenated beef tallow) amine (60.0 g, 0.12 mol), DER736 (17
．． 9 g, 0.047 mol) and 1,2-epoxyoctadecane (14.4 g, 0.054 mol) were mixed. Subsequently, pyromellitic dianhydride (5.14 g, 0.0
24 mol), phthalic anhydride (3.49 g, 0.024
mol) and xylene (approximately 50 ml) were added and reacted. After isolation, 89.4 g of final product was obtained.

[0139]

[Example 67] Process for producing additive 67 By the method used in Example 57, di(hydrogenated beef tallow) amine (50.0 g, 0.10 mol), DER736 (24
．． 8 g, 0.039 mole) and 1,2-epoxyoctadecane (12.0 g, 0.045 mole) were mixed. Subsequently, pyromellitic dianhydride (4.28 g, 0.0
20 mol), phthalic anhydride (2.91 g, 0.020
mol) and xylene (approximately 50 ml) were added and reacted. After isolation, 84.5 g of final product were obtained.

[0140]

[Example 68] Process for producing additive 68 By the method used in Example 57, di(hydrogenated beef tallow)amine (61.2 g, 0.12 mol), 2,2-dimethyl-
1,3-propanediol-diglycidyl ether (6
．． 49 g, 0.030 mole) and 1,2-epoxyoctadecane (8.55 g, 0.030 mole) were mixed. Next, pyromellitic dianhydride (6.54 g, 0.0
30 mol) and xylene (approximately 50 ml) were added and reacted. After isolation, 74.2 g of final product were obtained.

Preparation of Additive Concentrate A concentrate having a total volume of 100 ml was prepared by dissolving 10 g of the additive in a xylene mixed solvent. Any insoluble particles in the additive concentrate were removed by filtration before use.

Test Methods The cloud point of spiked distillate fuels was determined using two methods.

(a) Automatic cloud point test based on the apparatus/method detailed in US Pat. No. 4,601,303; test designation (below) is "AUTO CP".

(b) Commercially available Herzog (
Automatic cloud point test based on Herzog) cloud point tester; test designation (below) is "HERZOG".

Cold filterability was measured using the Cold Filter Plugging Point (CFPP) test. This test method is described in “Journal of the
Institute of Petroleum
m”, Volume 52, No. 510, June 1966, 173-
It is described on page 185.

[0146]

[0148]

[0149]

The test data clearly shows that small amounts of the additives of the present invention improve the low temperature properties of distillate fuels.

Although the invention has been described with preferred embodiments, it is to be understood that modifications and changes may be made without departing from the spirit and scope of the invention, as will be readily apparent to those skilled in the art. be. Such modifications and changes are considered to be within the terms and scope of the appended claims.

Claims (24)

[Claims] Claim 1: (1) hydrocarbyl diol, amino diol or diaminodiol alone or in combination with other diols, aminodiol or diaminodiol; and (2) benzophenonetetracarboxylic dianhydride or its acid equivalent; Pyromellitic dianhydride or its acid equivalent and (a) an amino alcohol that is the product of an amine and an epoxide, or (b) an amino alcohol and an amine, or (c) (a
) and/or (b), wherein said reaction product has long chain hydrocarbyl groups attached to it. reaction product with 2. The reaction is carried out at ambient temperature or at about 50°C.
2. The reaction product of claim 1, wherein the reaction product is carried out at ambient or slightly elevated pressures in submolar, supermolar or substantially molar amounts of the reactants at temperatures between 250 DEG C. and reflux. 3. A product according to claim 1, wherein said dianhydride is benzophenonetetracarboxylic dianhydride. 4. A product according to 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 of claim 1, wherein reactant (1) is a diaminodiol. 8. The product of claim 1, claim 2, claim 5, claim 6, or claim 7, wherein the amine is a di(hydrogenated tallow) amine. 9. A large amount of liquid hydrocarbyl fuel, (
1) Hydrocarbyl diol, amino diol or diaminodiol alone or in combination with other diols, aminodiol or diaminodiol and (2) benzophenonetetracarboxylic dianhydride or its acid equivalent or pyromellitic dianhydride or its acid equivalent with (a) an amino alcohol that is the product of an amine and an epoxide, or (b) an amino alcohol and an amine, or (c) a mixture of (a) and/or (b). A composition containing a small amount of a reaction product of a reactive acid and/or anhydride that has improved cold flow properties. 10. The composition of claim 9, wherein the amine is a 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 fuel oil is fuel oil No. 1 or No. 2.
10. The composition according to claim 9, selected from Nos. 1 and 3. 14. The composition of claim 9, wherein said fuel oil is a heated 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 diesel fuel oil. 17. The additive product comprises about 0.0 of the total composition.
10. The composition of claim 9, comprising from 0.01% to about 10% by weight. 18. The composition of claim 9, comprising from about 0.1% to about 5% by weight of the additive product. 19. A process for producing a reaction product suitable for use as a cold flow improving additive for liquid hydrocarbyl fuels, comprising: (1) a hydrocarbyl diol, amino diol or diaminodiol alone or other Combination with multiple diols, aminodiols or diaminodiols and (2) benzophenonetetracarboxylic dianhydride or its acid equivalent or pyromellitic dianhydride or its acid equivalent, and (a) production of amines and epoxides. an amino alcohol or (b) an amino alcohol and an amine or (c
) reacting a reactive acid and/or anhydride derived from the reaction with a mixture of (a) and/or (b), wherein said reaction product has long chain hydrocarbyl groups attached to it. Law. 20. A method of improving the flowability of a liquid hydrocarbon fuel comprising adding a small amount of the low temperature additive product of claim 1 to the liquid hydrocarbon fuel. 21. The method of claim 20, comprising adding a low temperature additive product to the fuel at about 0.001% to about 10% by weight of the composition. 22. A concentrated solution suitable for use in producing a liquid hydrocarbyl fuel comprising an inert solvent and the additive product of claim 1 dissolved therein. 23. The concentrate according to claim 22, wherein the solvent is xylene or a mixture of xylenes. 24. The concentrate of claim 22, wherein the concentrate comprises about 10 g of additive product per 100 ml of concentrate sample.