Organic compounds -- part of the class 532-570 series – Organic compounds – Fatty compounds having an acid moiety which contains the...
Reexamination Certificate
1998-07-21
2001-08-14
Carr, Deborah D. (Department: 1621)
Organic compounds -- part of the class 532-570 series
Organic compounds
Fatty compounds having an acid moiety which contains the...
C554S025000, C554S149000, C554S169000, C554S227000, C528S295500, C528S296000, C530S211000
Reexamination Certificate
active
06274750
ABSTRACT:
FIELD OF THE INVENTION
This invention relates to processes for the preparation of dimer and trimer fatty acid esters.
BACKGROUND OF THE INVENTION
Processes for the preparation of dimeric fatty acids are known to the art.
Dimeric fatty acids are used as Intermediates for the preparation of polyamides useful, inter alia, as a component of ink compositions, adhesives, surface coating materials, and sealants.
SUMMARY OF THE INVENTION
The present invention relates to mixtures of dimeric and trimeric fatty acid C
1-4
alkyl esters and to processes for their preparation. These mixtures of esters can be used to prepare polyamides that are useful as a component of ink compositions, adhesives, surface coating materials, and sealants.
DETAILED DESCRIPTION OF THE INVENTION
Other than in the operating examples, or where otherwise indicated, all numbers expressing quantities of ingredients or reaction conditions used herein are to be understood as modified in all instances by the term“about”.
A first embodiment of the process of the invention comprises the steps of
A) epoxidizing an unsaturated or partially hydrogenated fatty acid glyceride;
B) transesterifying the epoxidized glyceride with a C
1-4
alkanol to obtain epoxidized fatty acid C
1-4
alkyl esters; and
C) ring opening and dimerizing the epoxidized fatty acid C
1-4
alkyl esters.
In step A) the glyceride is an unsaturated or partially hydrogenated fatty acid glyceride, which can be a mono-, di- or tri- glyceride, or a mixture of such glycerides, and is preferably predominantly a triglyceride. Natural or synthetic oils having a monounsaturated fatty acid chain or chains, e.g. having a high oleic acid content are preferred. Soybean oil and castor oil are preferred triglyceride oils for use herein. Other useful oils include tall oil, sunflower oil, safflower oil, rapeseed oil, fish oils, vegetable oils, linseed oil, and oiticica oil. The fatty acid chains preferably contain from 8 to 24 carbon atoms, more preferably from 12 to 18 carbon atoms.
Step A) is carried out using a peracid or combination of peracids, such as hydrogen peroxide or an organic peroxide, e.g. performic acid, or an inorganic peroxide such as sodium or potassium peroxide. Hydrogen peroxide and/or performic acid is preferred.
The step A) reaction temperature can range from 20° C. to 100° C., preferably from 60 to 75° C. The glycerides are reacted until all unsaturated chains have at least one epoxy group. Preferably the oxirane content should be in the range of from 4.0 to 6.0% with an iodine value of from 4 to 70, and preferably less than 30.0.
When hydrogen peroxide is used in step A), an aqueous solution of from 50 to 70% H
2
O
2
is preferred. Also preferred is to carry out this step in the presence of formic acid, acetophosphonic acid, and phosphoric acid, in addition to the hydrogen peroxide.
Moreover, useful epoxidized oils including epoxidized soybean oil are commercially available, and they can be used if desired in the process of the invention, thus eliminating the need for step A) of the process.
Step B) is carried out by reacting the epoxidized glyceride with a C
1-4
alkanol, preferably methanol, although ethanol, propanol, isopropyl alcohol, n-butanol, or isobutyl alcohol can also be used. The reaction is preferably carried out at a temperature in the range of from 25° to 85° C., more preferably in the range of from 35 to 55° C. in the presence of an effective quantity of a catalyst. Any catalyst useful in carrying out transesterification reactions can be employed, such as sodium methoxide or zinc oxide, provided the catalyst does not cause opening of the epoxy groups.
The ratio by weight of C
1-4
alkanol to epoxidized glyceride is from 1:1 to 0.25:1, preferably from 0.75:1 to 0.4:1, and more preferably from 0.5:1 to 0.6:1. The catalyst can be present in from 0.05% to 5%, preferably from 0.1 to 4% by weight, based on the weight of the epoxidized glyceride.
Step C) is carried out by reacting the epoxidized fatty acid C
1-4
alkyl esters from step B) in the presence of a ring opening agent at a temperature in the range of from 25 to 115° C., preferably from 40 to 115° C. It is preferred to use approximately molar quantities of ring opening agents based on oxirane groups.
The ring opening agents that can be used in step C) alone or in combination include phosphoric acid, phosphorous acid, hypophosphorous acid, phosphorus trichloride, monoalkyl phosphates, e.g. methylphosphoric acid and butyl hydrogen phosphate, boron halides, boric acid, boronic acids, e.g. R (B) OH
2
where R is a C
1-6
alkyl group, disulfonic acids, phosphonic acids, e.g. derivatives of the hypothetical phosphonic acid (HP(O)(OH)
2
) such as acetophosphonic acid or RPO(OH)
2
where R can be an alkyl or aromatic hydrocarbon group, phosphonamides, i.e. amides of the above phosphonic acid derivatives, polybasic carboxylic acids, e.g. malonic, succinic, glutaric, adysic, sebacic, fumaric, phthalic and isophthalic acids, and hydroxycarboxylic acids, e.g. glycolic, hydroxymalonic, citric, and tartaric acids.
Optionally, a polyhydroxy-substituted alkane can also be present in the step C) reaction mixture. Polyhydroxy-substituted alkanes that can be used herein include alkylene glycols, e.g. ethylene glycol, propylene glycol, and 1,4-butane diol, trimethylol propane, pentaerythritol, and the like. The polyhydroxy alkane can be used in a quantity ranging from 0.1 to 5 moles, preferably from 0.2 to 0.5 moles of hydroxyl group per mole of oxirane group in the epoxidized fatty acid C
1-4
alkyl ester.
The step C) reaction will produce a reaction mixture containing predominantly dimers, with smaller quantities of trimers. In addition, quantities of higher oligomers and monomers may also be present.
The reaction mixture from step C) containing the dimeric and trimeric fatty acid C
1-4
alkyl esters can then be reacted with at least one polyamine at a temperature in the range of from 125 to 250° C., preferably from 150 to 225° C. to produce polyamides. The reaction proceeds well in the absence of any catalyst. The polyamines can be alkylene diamines, alkylene triamines, alkylene tetraamines, alkylene pentamines, and alkylene hexamines, e.g. ethylenediamine, diethylenetriamine, triethylenetetraamine, and pentaethylenehexamine. Generally, where the polyamides are to be used as curing agents for epoxy resins, an excess of polyamine is used. Where the polyamides are to be used as ink resins, approximately stoichiometric quantities of the ester and amine functionality are employed.
A second embodiment of the process of the invention comprises the steps of
A) transesterifying an unsaturated or partially hydrogenated glyceride with a C
1-4
alkanol to obtain olefinically unsaturated fatty acid C
1-4
alkyl esters;
B) epoxidizing the unsaturated fatty acid C
1-4
alkyl esters; and
C) ring opening and dimerizing the epoxidized fatty acid C
1-4
alkyl esters.
In step A) the glyceride is identical to the glycerides used in step A) of the first embodiment of the invention.
Step A) of this second embodiment can be carried out at a temperature in the range of from 25 to 250° C., preferably from 175 to 210° C., and more preferably from 180 to 200° C. with stirring in pressure equipment such as an autoclave for a period of from 1 to 5 hours, preferably from 1.5 to 2.5 hours, depending on the reaction temperature. Reaction pressures can range from 200 to 500 psig, preferably from 300 to 350 psig.
Step B) can be carried out in the same manner as given above for step A) of the first embodiment, i.e. by the use of a peracid.
Step C) of this second embodiment is carried out in the same manner as step C) of the first embodiment.
The reaction mixture from step C) can then be reacted with polyamines to produce polyamides.
The processes of the invention have a number of advantages over known methods for producing dimers and trimers useful for reaction with polyamines.
Such advantages include
1. Depending on the ring opening agent used for reacting with the epoxidized compound, hydroxyl groups or other polar groups can be f
Bueno Ramiro Carielo
Bueno De Almeida Wanderson
Sato Setsuo
Carr Deborah D.
Cognis Corporation
Drach John E.
Millson, Jr. Henry E.
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