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  Diimines and secondary diaminesUSPTO Application #: 20080004406Title: Diimines and secondary diamines Abstract: This invention provides aromatic diimines which have imino hydrocarbylidene groups with at least two carbon atoms, and aromatic secondary diamines which have amino hydrocarbyl groups with at least two carbon atoms. Both the aromatic diimines and the aromatic secondary diamines either are in the form of one phenyl ring, or are in the form of two phenyl rings connected by an alkylene bridge; each position ortho to an imino group or an amino group bears a hydrocarbyl group. When in the form of one phenyl ring, there are two imino groups on the ring or two amino groups on the ring; the imino groups or amino groups are meta or para relative to each other. When in the form of two phenyl rings connected by an alkylene bridge, there is either one imino group or one amino group on each phenyl ring. Also provided are processes for forming diimines and secondary diamines. (end of abstract) Agent: Albemarle Corporation - Baton Rouge, LA, US Inventors: John Y. Lee, Paul L. Wiggins, Judith O. Orgad, Mahmood Sabahi, Vernon O. Brandt USPTO Applicaton #: 20080004406 - Class: 525459000 (USPTO) Related Patent Categories: Synthetic Resins Or Natural Rubbers -- Part Of The Class 520 Series, Natural Rubber Compositions Having Nonreactive Materials (dnrm) Other Than: Carbon, Silicon Dioxide, Glass Titanium Dioxide, Water, Hydrocarbon, Halohydrocarbon, Ethylenically Unsaturated Reactant Admixed With A Preformed Reaction Product Derived From: (a) At Least One Polycarboxylic Acid, Ester, Or Anhydride; (b) At Least One Polyhydroxy Compound; And (c) At Least One Fatty Acid Glycerol Ester, Or A Fatty Acid Or Salt Derived From A Naturally Occurring Glyceride, Tall Oil, Or A Tall Oil Fatty Acid, Solid Polymer Derived From -n=c=x Reactant (x Is Chalcogen), Solid Polymer Derived From -n=c=x Reactant And Polyhydroxy Reactant, Solid Polymer Derived From -n=c=x Reactant And Polyhydroxy Reactant Also Derived From Polyamine Reactant The Patent Description & Claims data below is from USPTO Patent Application 20080004406. Brief Patent Description - Full Patent Description - Patent Application Claims
REFERENCE TO RELATED APPLICATIONS [0001] This application is a division of U.S. application Ser. No. 11/390,777, filed Mar. 27, 2006, now allowed, which in turn claims the benefit and priority of U.S. Provisional Application No. 60/665,915, filed Mar. 28, 2005, the disclosures of which are incorporated herein by reference. TECHNICAL FIELD [0002] This invention relates to the preparation of diimines and secondary diamines from primary diamines, and to new aromatic diimines and new aromatic secondary diamines. BACKGROUND [0003] There are many polyfunctional compounds, including diols and aromatic diamines, which are indicated to be useful as chain extenders in the preparation of polyurethane, polyurea, and polyurethane-urea polymers and/or as curing agents for epoxy resins. None of these compounds has a reactivity such as to make it universally ideal, and many fail to provide satisfactory properties in the products made by their use. Thus, there is still a need to find new compounds capable of serving as chain extenders or curing agents. U.S. Pat. No. 4,806,616 teaches the use of certain N,N'-dialkylphenylenediamines as chain extenders in preparing polyurethanes and polyureas. In this connection, also see for example U.S. Pat. No. 4,528,363, which teaches the use of secondary aliphatic diamines as part of a resin binder, and U.S. Pat. No. 6,218,480 B1, which discloses use of aromatic diamines as hardeners for polyurethanes. Secondary aromatic diamines have also been used as anti-degradants for rubber; see U.S. Pat. No. 4,900,868. [0004] Imines are often formed from combination of a primary amine and an aldehyde or ketone. Such imines can be used as flavors (see U.S. Pat. No. 3,625,710) or fragrances (see EP 1067116). [0005] To date, it has not been found possible to obtain aromatic diimines having groups with two or more carbon atoms from aromatic primary diamines where the two amino groups are either on one phenyl ring, or one amino group is on each of two phenyl rings, where the two phenyl rings are connected via an alkylene bridge, and in which each position ortho (immediately adjacent) to each amino group bears a hydrocarbyl substituent. Attempts to prepare diimines via reaction of such primary diamines with acetaldehyde or acetone in the presence or absence of catalysts have not worked; see U.S. Pat. Nos. 5,041,668 and 5,008,453. It had been indicated that the presence of an aryl group on the nitrogen or carbon of an imine group stabilized the imine; however, it has been reported that at least some of the compounds previously believed to be stable aromatic imines had been misidentified and were really polymers formed from unstable imines. In this connection, see Distefano et al., J. Chem. Soc. Perkin Trans. II, 1985, pp. 1623-1627. [0006] It would be desirable to have routes to such diimines, and to have routes to aromatic secondary diamines that can be obtained from such diimines. There is a growing need for chain extenders with slower cure rates, so it would be a further advantage if these aromatic secondary diamines exhibited slower curing rates than those of presently available chain extenders. SUMMARY OF INVENTION [0007] This invention in part provides processes for preparing diimines in which the imino hydrocarbylidene groups have at least two carbon atoms, where the diimine is (a) an aromatic diimine which is either in the form of one phenyl ring having two imino groups on the ring, in which each position ortho to an imino group (--N.dbd.R) bears a hydrocarbyl group, or in the form of two phenyl rings connected by an alkylene bridge and having one imino group on each ring, in which each position ortho to an imino group bears a hydrocarbyl group, (b) an aromatic diimine in which at least one position ortho to each imino group has a hydrogen atom as a substituent, and which aromatic diimine is either in the form of one phenyl ring having two imino groups on the ring or in the form of two phenyl rings connected by an alkylene bridge and having one imino group on each ring, or (c) an aliphatic diimine, where the diimine is made by reacting a primary diamine with at least one ketone and/or aldehyde. The art teaches that diimines of type (a) could not be made. These aromatic diimines, which surprisingly can be made, are compositions of the invention. Aromatic secondary diamines made from aromatic diimines of type (a) are also compositions of the invention. Surprisingly, such aromatic secondary diamines exhibit slower curing rates than those of presently available chain extenders. Slower cure rates are desirable for certain proprietary commercial applications. By hydrogenating (reducing) aromatic diimines of type (a), the corresponding novel aromatic secondary diamines of the invention are formed. Processes for forming secondary diamines, including the aromatic secondary diamines that are compositions of the invention, from primary diamines in one step are also provided by this invention. In all of the processes of this invention, relatively mild pressure and temperature conditions are used; advantageously, ordinary process apparatus can be employed, so there is no need for specialized equipment, such as that required for high-pressure reactions. This is of particular significance in processes where hydrogen gas is employed in the formation of secondary diamines. The process technology of this invention can be used to prepare a wide variety of known diimines and secondary diamines via reaction of primary diamines with ketones or aldehydes. [0008] One embodiment of this invention provides, as new compositions of matter, aromatic diimines wherein each imino group (--N.dbd.R) has at least two carbon atoms, and wherein the diimine either is in the form of one phenyl ring having two imino groups on the ring, which imino groups are meta or para relative to each other, and in which each position ortho to an imino group bears a hydrocarbyl group, or is in the form of two phenyl rings connected by an alkylene bridge and having one imino group on each ring, and in which each position ortho to an imino group bears a hydrocarbyl group. The aromatic diimines of the invention can be represented by the structures: where each R.sup.a may be the same or different, and each R.sup.a is a hydrocarbyl group, R.sup.b is an alkylene bridge, and each R.sup.a is a hydrocarbylidene group having at least two carbon atoms. [0009] Another embodiment of this invention provides, as new compositions of matter, aromatic secondary diamines wherein each amino group (--NHR) has at least two carbon atoms, and wherein the secondary diamine either is in the form of one phenyl ring having two amino groups on the ring, which amino groups are meta or para relative to each other, and in which each position ortho to an amino group bears a hydrocarbyl group, or is in the form of two phenyl rings connected by an alkylene bridge and having one amino group on each ring, and in which each position ortho to an amino group bears a hydrocarbyl group. The aromatic diamines of the invention can be represented by the structures: where each R.sup.a may be the same or different, and each R.sup.a is a hydrocarbyl group, R.sup.b is an alkylene bridge, and each R.sup.d is a hydrocarbyl group having at least two carbon atoms. [0010] Another embodiment of this invention is a process for forming a secondary diamine. The process comprises mixing together at least one ketone or aldehyde, at least one acid ion exchange resin, at least one hydrogenation agent, and at least one primary diamine, such that a secondary diamine is formed. The primary diamine is I) an aromatic primary diamine in which at least one position ortho to each amino group has a hydrogen atom as a substituent, and which aromatic primary diamine is either in the form of one phenyl ring having two amino groups on the ring or in the form of two phenyl rings connected by an alkylene bridge and having one amino group on each ring, or II) an aromatic primary diamine in which each position ortho to an amino group bears a hydrocarbyl group, and which aromatic primary diamine is either in the form of one phenyl ring having two amino groups on the ring, which amino groups are meta or para relative to each other or is in the form of two phenyl rings connected by an alkylene bridge and having one amino group on each ring, or III) an aliphatic primary diamine. When the primary diamine is I), the hydrogenation agent is a hydride transfer agent, a dissolving metal reagent, a borane reductant, or hydrogen with a hydrogenation catalyst, where the hydrogenation catalyst is sulfided platinum on carbon, sulfided palladium on carbon, or a mixture thereof. When the primary diamine is II), the hydrogenation agent is a dissolving metal reagent or hydrogen with a hydrogenation catalyst, where the hydrogenation catalyst is sulfided platinum on carbon, sulfided palladium on carbon, or a mixture thereof, or is selected from the group consisting of palladium on carbon, platinum on carbon, and a mixture of both of these, when used with hydrogen sulfide or at least one strong acid. When the primary diamine is III), the hydrogenation agent is a hydride transfer agent, a dissolving metal reagent, a borane reductant, or hydrogen with a hydrogenation catalyst, where the hydrogenation catalyst is sulfided platinum on carbon, sulfided palladium on carbon, or a mixture thereof. [0011] Still another embodiment of this invention is a process for forming a diimine. The process comprises mixing together at least one ketone or aldehyde, at least one acid ion exchange resin, and at least one primary diamine, such that a diimine is formed. The primary diamine is I) an aromatic primary diamine in which at least one position ortho to each amino group has a hydrogen atom as a substituent, and which aromatic primary diamine is either in the form of one phenyl ring having two amino groups on the ring or in the form of two phenyl rings connected by an alkylene bridge and having one amino group on each ring, or II) an aromatic primary diamine in which each position ortho to an amino group bears a hydrocarbyl group, and which aromatic primary diamine is either in the form of one phenyl ring having two amino groups on the ring, which amino groups are meta or para relative to each other or is in the form of two phenyl rings connected by an alkylene bridge and having one amino group on each ring, or III) an aliphatic primary diamine. Often this process further comprises mixing together at least a portion of the diimine and a hydrogenation agent. When the primary diamine used in forming the diimine is I) or III), the hydrogenation agent is a hydride transfer agent, a dissolving metal reagent, a borane reductant, or hydrogen with a hydrogenation catalyst, wherein the hydrogenation catalyst is sulfided platinum on carbon, sulfided palladium on carbon, or a mixture thereof. When the primary diamine used in forming the diimine is II), the hydrogenation agent is a dissolving metal reagent or hydrogen with a hydrogenation catalyst, where the hydrogenation catalyst is sulfided platinum on carbon, sulfided palladium on carbon, or a mixture thereof, or is selected from the group consisting of palladium on carbon, platinum on carbon, and a mixture of both of these, when used with hydrogen sulfide or at least one strong acid, such that a secondary diamine is formed. [0012] Another embodiment of this invention is a process for forming an aromatic secondary diamine. The process comprises mixing together at least one ketone or aldehyde, hydrogen, a hydrogenation catalyst selected from sulfided platinum on carbon, sulfided palladium on carbon, and a mixture thereof, and at least one primary diamine, such that a secondary diamine is formed. When the primary diamine is I) an aromatic primary diamine in which at least one position ortho to each amino group has a hydrogen atom as a substituent, and which aromatic primary diamine is either in the form of one phenyl ring having two amino groups on the ring or in the form of two phenyl rings connected by an alkylene bridge and having one amino group on each ring, the process is conducted at a temperature in the range of about 20.degree. C. to about 120.degree. C. and at a hydrogen pressure in the range of about 14 to about 125 pounds per square inch. When the primary diamine is II) an aromatic primary diamine in which each position ortho to an amino group bears a hydrocarbyl group, and which aromatic primary diamine is either in the form of one phenyl ring having two amino groups on the ring, which amino groups are meta or para relative to each other or is in the form of two phenyl rings connected by an alkylene bridge and having one amino group on each ring, the process is conducted at a temperature in the range of about 75.degree. C. to about 140.degree. C. and at a hydrogen pressure in the range of about 14 to about 150 pounds per square inch. When the primary diamine is III) an aliphatic primary diamine, the process is conducted at a temperature in the range of about 20.degree. C. to about 140.degree. C. and at a hydrogen pressure in the range of about 14 to about 150 pounds per square inch. [0013] A further embodiment of the invention is a formulation which is formed from ingredients comprising at least one polyol and/or at least one polyetheramine, at least one isocyanate, and at least one aromatic secondary diamine. The aromatic secondary diamine is at least one of the aromatic secondary diamines described above as new compositions of matter. [0014] A still further embodiment of the invention is a method for producing a polyurethane, polyurea, or polyurea-urethane. The method comprises blending at least one polyol and/or at least one polyetheramine, at least one isocyanate, and at least one aromatic secondary diamine. The aromatic secondary diamine is at least one of the aromatic secondary diamines described above as new compositions of matter. [0015] These and other embodiments and features of this invention will be still further apparent from the ensuing description and appended claims. FURTHER DETAILED DESCRIPTION OF THE INVENTION [0016] Certain terms that are commonly used in the art can be used to refer to various aspects of the present invention. Imines that are products of a reaction of a primary amine and a carbonyl compound are sometimes called Schiff bases, and such imines are formed by at least some of the processes of the invention. When the carbonyl compound used to form the imine is a ketone, such an imine is occasionally referred to as a ketimine; similarly, when the carbonyl compound used to form the imine is an aldehyde, such an imine is occasionally referred to as an aldimine. The formation of a secondary amine from a primary amine and an aldehyde or ketone is often referred to as reductive alkylation or reductive amination, and the terms "reductive alkylation" and "reductive amination" can be used to describe some of the processes of the invention. [0017] Those of skill in the art will recognize that there are several ways to name the aromatic primary diamines used in the processes of the invention, as well as the aromatic diimines and the aromatic secondary diamines that are compositions of the invention. For example, the structure which represents a particularly preferred aromatic primary diamine in the processes of the invention, can be called 2,4-diethyl-6-methyl-1,3-benzenediamine, 2,4-diethyl-6-methyl-1,3-phenylenediamine, 3,5-diethyl-2,4-diaminotoluene, or 3,5-diethyl-toluene-2,4-diamine. Similarly, the structure which represents another particularly preferred aromatic primary diamine in the processes of the invention, can be called 4,4'-methylenbis(2,6-diethylbenzeneamine), 4,4'-methylenbis(2,6-diethylaniline), or 3,3',5,5'-tetraethyl-4,4'-diaminodiphenylmethane. [0018] While the term "secondary diamine" is used throughout this document to refer to diamines produced by the processes of this invention in which both amino groups are secondary, it is to be understood that the processes of this invention produce diamines in which only one of the amino groups is secondary (and the other amino group is primary), albeit usually in small amounts, because the processes of the invention do not necessarily produce diamine(s) where both amino groups are secondary in 100% yield. When the term "aromatic secondary diamine" is used to refer to compositions of the invention, it does not generally include aromatic diamines in which one amino group is secondary and the other amino group is primary, except as impurities present (usually in small amounts) in the aromatic secondary diamines. Compositions of the Invention Continue reading... 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