WO2008112636A1

WO2008112636A1 - Chain extenders

Info

Publication number: WO2008112636A1
Application number: PCT/US2008/056415
Authority: WO
Inventors: John Y. Lee; Paul L. Wiggins
Original assignee: Albemarle Corporation
Priority date: 2007-03-13
Filing date: 2008-03-10
Publication date: 2008-09-18
Also published as: TW200902578A

Abstract

This invention provides chain extender compositions. These compositions comprise either (i) N,N'-dicyclohexyl- 1,6-hexanediamine or (ii) an aliphatic secondary α,ω- diamine having a secondary amino straight chain. When said composition comprises (i), said composition is also comprised of a component selected from the group consisting of (a) an aliphatic secondary diamine, (b) an aliphatic secondary diamine and an aliphatic primary diamine, (c) an aliphatic diimine, (d) an aromatic primary diamine, and (e) a combination of any two or more of (a) through (d). When said composition comprises (ii), said composition is also comprised of a component selected from the group consisting of (a) an aliphatic secondary diamine, (d) an aromatic primary diamine, (f) an aliphatic secondary α,ω-diamine having at least one internal secondary amino group, and (g) a combination of any two or more of (a), (d), and (f). Processes for producing polyurethanes, polyureas, and polyurea-urethanes are also provided.

Description

CHAIN EXTENDERS

TECHNICAL FIELD

[0001] This invention relates to the use of cycloaliphatic secondary diamines to form polyurethanes, polyureas, and polyurea-urethanes.

BACKGROUND

[0002] 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 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. 4,528,363, which teaches the use of secondary aliphatic diamines as part of a resin binder, and U.S. 6,218,480 Bl, 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. 4,900,868.

[0003] There is a growing need for chain extenders with slower cure rates, so it would be a further advantage if aliphatic diamines exhibited slower curing rates than those of presently available chain extenders.

SUMMARY OF THE INVENTION

[0004] This invention in part provides chain extenders which are mixtures of an aliphatic secondary α,ω-diamine having at least one internal secondary amino group and one or more other components. This invention also provides in part chain extenders which are mixtures of N,N'-dicyclohexyl-l,6-hexanediamine and one or more other components. These mixtures, when included in formulations for polyurethanes, polyureas, and polyurea-urethanes, produce such polymers at desired cure rates and having desirable physical properties. [0005] One embodiment of this invention provides a chain extender composition. The composition comprises either (i) N,N'-dicyclohexyl-l,6-hexanediamine or (ii) an aliphatic secondary α,ω-diamine having a secondary amino straight chain. When said composition comprises (i), said composition is also comprised of a component selected from the group consisting of (a) an aliphatic secondary diamine, (b) an aliphatic secondary diamine and an aliphatic primary diamine, (c) an aliphatic diimine, (d) an aromatic primary diamine, and (e) a combination of any two or more of (a) through (d). When said composition comprises (ii), said composition is also comprised of a component selected from the group consisting of (a) an aliphatic secondary diamine, (d) an aromatic primary diamine, (f) an aliphatic secondary α,ω-diamine having at least one internal secondary amino group, and (g) a combination of any two or more of (a), (d), and (f).

[0006] Another embodiment of this invention is a process for producing a polymer which is a polyurethane, polyurea, or polyurea-urethane. The process comprises mixing together (A) at least one aliphatic polyisocyanate, (B) at least one polyol and/or at least one polyetheramine, and (C) a chain extender comprised of either (i) N,N'-dicyclohexyl-l,6- hexanediamine or (ii) an aliphatic secondary α,ω-diamine having at least one internal secondary amino group. When the chain extender comprises (i), said composition is also comprised of a component selected from the group consisting of (a) an aliphatic secondary diamine, (b) an aliphatic secondary diamine and an aliphatic primary diamine, (c) an aliphatic diimine, (d) an aromatic primary diamine, and (e) a combination of any two or more of (a) through (d). When the chain extender comprises (ii), said composition is also comprised of a component selected from the group consisting of (a) an aliphatic secondary diamine, (d) an aromatic primary diamine, (f) an aliphatic secondary α,ω-diamine having at least one internal secondary amino group, and (g) a combination of any two or more of (a), (d), and (f).

[0007] Still another embodiment of this invention is a polymer which is a polyurethane, polyurea, or polyurea-urethane, which polymer is formed from ingredients comprising (A) at least one aliphatic polyisocyanate, (B) at least one polyol and/or at least one polyetheramine, and (C) a chain extender comprised of either (i) N,N'-dicyclohexyl-l,6- hexanediamine or (ii) an aliphatic secondary α,ω-diamine having at least one internal secondary amino group. When the chain extender comprises (i), said composition is also comprised of a component selected from the group consisting of (a) an aliphatic secondary diamine, (b) an aliphatic secondary diamine and an aliphatic primary diamine, (c) an aliphatic diimine, (d) an aromatic primary diamine, and (e) a combination of any two or more of (a) through (d). When the chain extender comprises (ii), said composition is also comprised of a component selected from the group consisting of (a) an aliphatic secondary diamine, (d) an aromatic primary diamine, (f) an aliphatic secondary α,ω-diamine having at least one internal secondary amino group, and (g) a combination of any two or more of

(a), (d), and (f).

[0008] 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 Chain Extender Compositions of the Invention

[0009] Chain extender compositions of this invention comprise either N,N'-dicyclohexyl- 1,6-hexanediamine or an aliphatic secondary α,ω-diamine having at least one internal secondary amino group. When the chain extender composition comprises N₅N'- dicyclohexyl-l,6-hexanediamine, one or more other components selected from (a) an aliphatic secondary diamine; (b) an aliphatic secondary diamine and an aliphatic primary diamine; (c) an aliphatic diimine; and (d) an aromatic primary diamine are present in the chain extender composition. Preferred components for use with N,N'-dicyclohexyl-l,6- hexanediamine are aliphatic secondary diamines. The components can be present in the chain extender composition in a variety of proportions; the preferred ratios vary with the type of component(s) (a)-(d).

[0010] When the chain extender composition comprises an aliphatic secondary α,ω- diamine having at least one internal secondary amino group, one or more other components selected from (a) an aliphatic secondary diamine; (d) an aromatic primary diamine; and (f) an aliphatic secondary α,ω-diamine having at least one internal secondary amino group. Preferred components for use with an aliphatic secondary α,ω-diamine having at least one internal secondary amino group include aliphatic secondary diamines. The components can be present in the chain extender composition in a variety of proportions; the preferred ratios vary with the type of component(s) (a), (d), and (f).

I. Components (i) and (ii)

[0011] Component (i) is N,N'-dicyclohexyl-l,6-hexanediamine, which is sometimes also called N,N'-dicyclohexylhexane-l,6-diamine, N,N'-dicyclohexyl-l,6-diaminohexane, or

N,N'-dicyclohexyl-hexamethylenediamine.

[0012] Component (ii) is an aliphatic secondary α,ω-diamine having at least one internal secondary amino group. These diamines are secondary diamines which are in the form of a straight chain, with a secondary amino group bound to each of the two terminal carbon atoms. The straight chain is a secondary amino straight chain, where "secondary amino straight chain" means a straight chain in which at least one of the -CH₂- moieties in a hydrocarbyl straight chain is instead an — NH- moiety. Preferably, an aliphatic secondary α,ω-diamine with at least one internal secondary amino group has about six to about thirty carbon atoms; more preferably, the aliphatic secondary α,ω-diamine with at least one internal secondary amino group has about eight to about twenty-five carbon atoms. [0013] The terminal secondary amino groups of the aliphatic secondary α,ω-diamine are amino hydrocarbyl groups which can be cyclic, branched, or straight chain. Preferably, the amino hydrocarbyl groups are straight chain or, more preferably, branched chain alkyl groups having from three to about twelve carbon atoms. Examples of suitable amino hydrocarbyl groups for the secondary amino groups include ethyl, propyl, isopropyl, n- butyl, sec-butyl, t-butyl, 3,3-dimethyl-2-butyl, pentyl, cyclopentyl, 4-methyl-2-pentyl, 2,4- dimethyl-3-pentyl, hexyl, methylcyclohexyl, heptyl, octyl, cyclooctyl, nonyl, decyl, dodecyl, and the like.

[0014] Suitable aliphatic secondary α,ω-diamines having at least one internal secondary amino group include, but are not limited to, N,N'-di(l-propyl)-diethylenetriamine, N₅N'- diisopropyl-diethylenetriamine, N,N'-di(sec-butyl)-diethylenetriamine, N,N'-di(3,3- dimethyl-2-butyl)-diethylenetriamine, N,N'-di(2-pentyl)-diethylenetriamine, N,N'-di(4- methyl-2-pentyl)-diethylenetriamine, N,N'-di(6-undecyl)-norspermidine, N,N'-di(2,4- dimethyl-3-pentyl)-spermidine, N,N'-diisopropyl-dihexylenetriamine, N,N'-diisopropyl- triethylenetetramine, N,N'-di(sec-butyl)triethylenetetramine, N,N'-diisopropyl- tetraethylenepentamine, N,N'-di(sec-butyl)tetraethylenepentamine, di[2-(N-cyclohexyl- amino)ethyl] amine, di[3 -(N-cyclopentylamino)-propyl] amine, [3 -(N-cyclooctylamino)- propyl)][4-(N-cyclooctyl-amino)butyl]amine, [3-(N-2-methylcyclopentylamino)propyl)]- [5-(N-2-methylcyclo-pentylamino)pentyl]amine, and [3-(N-cyclobutylamino)propyl)] [7- (N-cyclobutylamino)-heptyl]amine. Preferred aliphatic secondary α,ω-diamines having at least one internal secondary amino group include N,N'-diisopropyl-diethylenetriamine and N,N'-di(sec-butyl)-diethylenetriamine.

II. Components (a)-(d) and (f)

[0015] When the chain extender composition comprises (i), N,N'-dicyclohexyl-l,6- hexanediamine, the composition is also comprised of a component selected from the group consisting of (a) an aliphatic secondary diamine; (b) an aliphatic secondary diamine and an aliphatic primary diamine; (c) an aliphatic diimine; (d) an aromatic primary diamine; and (e) a combination of any two or more of (a) through (d). Thus mixtures of subcomponents (a)-(d) in various combinations are within the scope of this invention. [0016] When the chain extender composition comprises (ii), an aliphatic secondary α,ω- diamine having at least one internal secondary amino group, the composition is also comprised of a component selected from the group consisting of (a), (d), and (f). Thus mixtures of subcomponents (a), (d), and (f) in various combinations are within the scope of this invention.

Component (a)

[0017] Aliphatic secondary diamines are component (a). The aliphatic secondary diamines are hydrocarbyl secondary diamines where the hydrocarbyl portion of the diamine is aliphatic, where "hydrocarbyl portion" refers to the moiety to which the amino groups are bound. The hydrocarbyl portion of the aliphatic diamine can be cyclic, branched, or, preferably, straight chain. The amino hydrocarbyl groups of the aliphatic secondary diamine can be cyclic, branched, or straight chain. Preferably, the amino hydrocarbyl groups are straight chain or, more preferably, branched chain alkyl groups having from three to about twelve carbon atoms. Examples of suitable amino hydrocarbyl groups include ethyl, propyl, isopropyl, n-butyl, sec-butyl, t-butyl, pentyl, cyclopentyl, hexyl, methylcyclohexyl, heptyl, octyl, cyclooctyl, nonyl, decyl, dodecyl, and the like. Preferably, the aliphatic secondary diamine has about eight to about forty carbon atoms; more preferably, the aliphatic secondary diamine has about ten to about thirty carbon atoms. Particularly preferred aliphatic secondary diamines have cyclic or straight chain hydrocarbyl portions and have about twelve to about twenty- five carbon atoms. [0018] Aliphatic secondary diamines that can be used in this invention include, but are not limited to, N,N'-diisopropylethylenediamine, N,N'-di-sec-butyl-l,2-diaminopropane, N₅N'- di(2-butenyl)-l,3-diaminopropane, N,N'-di(l-cyclopropylethyl)-l,5-diaminopentane,

N,N'-di(3,3-dimethyl-2-butyl)-l,5-diamino-2-methylpentane, N,N'-diisopropyl-l,6- diaminohexane N,N'-di-sec-butyl- 1 ,6-diaminohexane, N,N'-di(4-methyl-2-pentyl)- 1 ,6- diaminohexane, N,N'-di(3-pentyl)-2,5-dimethyl-2,5-hexanediamine, N,N'-di(4-hexyl)- 1 ,2- diaminocyclohexane, N,N'-dicyclohexyl- 1 ,3-diaminocyclohexane, N,N'-di(l -cyclobutyl- ethyl)- 1 ,4-diaminocyclohexane, N,N'-di(2,4-dimethyl-3-pentyl)-l,3-cyclohexanebis-

(methylamine), N,N'-di(sec-butyl)-4,4'-di(cyclohexylamino)methane, N,N'-di(l-penten-3- yl)- 1 ,4-cyclohexanebis(methylamine), N,N'-diisopropyl- 1 ,7-diaminoheptane, N,N'-di-sec- butyl- 1 ,8-diaminooctane, N,N'-di(2-pentyl)- 1 , 10-diaminodecane, N,N'-di(3-hexyl)- 1,12- diaminododecane, N,N'-di(3-methyl-2-cyclohexenyl)-l ,2-diaminopropane, N,N'-di(2,5- dimethylcyclopentyl)-l,4-diaminobutane, N,N'-di(isophoryl)-l,5-diaminopentane, N₅N'- di(menthyl)-2,5-dimethyl-2,5-hexanediamine, N,N'-di(undecyl)-l,2-diaminocyclohexane, N,N'-di-2-(4-methylpentyl)-isophoronediamine, and N,N'-di(5-nonyl)-isophoronediamine. Preferred aliphatic secondary diamines for use with component (i) include N,N'-di(sec- butyl)-4,4'-di(cyclohexylamino)methane, N,N'-di-(3,3-dimethyl-2-butyl)-l,6-diamino- hexane, N,N'-di(4-methyl-2-pentyl)-l,6-diaminohexane, and N,N'-diisopropyl-l,6- diaminohexane. Preferred aliphatic secondary diamines for use with component (ii) include at least N,N'-di(sec-butyl)-4,4'-di(cyclohexylamino)methane and N,N'-di-(3,3- dimethyl-2 -butyl)- 1 ,6-diaminohexane.

[0019] Relative proportions of N,N'-dicyclohexyl-l,6-hexanediamine or an aliphatic secondary α,ω-diamine having at least one internal secondary amino group to aliphatic secondary diamine in the chain extender composition are preferably about 0.1 :1 to about 1 :0.1 on an equivalent basis; more preferably, the relative proportions on an equivalent basis are about 0.5:1 to about 1 :0.5.

Component (b)

[0020] An aliphatic secondary diamine and an aliphatic primary diamine are component (b). The aliphatic secondary diamine and the aliphatic primary diamine can be in any suitable proportion relative to each other, and their combined total amount can be in any relative proportion to the N,N'-dicyclohexyl-l,6-hexanediamine. Preferred proportions of aliphatic secondary diamine to aliphatic primary diamine are in the range of about 0.1 :1 to about 1 :0.1 on an equivalent basis. The proportions of the combined total amount of aliphatic secondary diamine and aliphatic primary diamine relative to the N₅N'- dicyclohexyl-l,6-hexanediamine is preferably in the range of about 0.5:1 to about 1 :0.5 on an equivalent basis.

[0021] Suitable aliphatic secondary diamines for component (b) and preferences therefor are as described above for component (a). Aliphatic primary diamines for component (b) are hydrocarbyl primary diamines where the hydrocarbyl portion of the diamine is aliphatic. The hydrocarbyl portion of the aliphatic diamine can be cyclic, branched, or straight chain. Preferably, the aliphatic primary diamine has about four to about thirty carbon atoms; more preferably, the aliphatic primary diamine has about six to about twenty carbon atoms. Particularly preferred aliphatic diamines have cyclic or straight chain hydrocarbyl portions and have about four to about ten carbon atoms. [0022] Suitable aliphatic primary diamines include, but are not limited to, ethylenediamine, 1 ,2-diaminopropane, 1,3-diaminopropane, 1 ,4-diaminobutane, 1,5- diaminopentane, l,5-diamino-2-methylpentane, 1 ,6-diaminohexane, 2,5-dimethyl-2,5- hexanediamine, 1 ,2-diaminocyclohexane, 1,3-diaminocyclohexane, 1,4- diaminocyclohexane, 2,4-diethyl-6-methyl-l ,3-cyclohexanediamine, 4,6-diethyl-2-methyl- 1 ,3-cyclohexanediamine, 1 ,3-cyclohexanebis(methylamine), 1 ,4-cyclohexanebis- (methylamine), isophorone diamine, bis(p-aminocyclohexyl)methane, bis(3-methyl-4- aminocyclohexyl)methane, 1,8-diamino-p-menthane, 1,7-diaminoheptane, 1,8- diaminooctane, 1,10-diaminodecane, 1,12-diaminododecane, and 3(4),8(9)-bis- (aminomethyl)-tricyclo[5.2.1.0(2,6)]decane (TCD diamine; also called octahydro-4,7- methanoinden- 1 (2),5(6)-dimethanamine or octahydro-4,7-methano- 1 H-indenedimethyl- amine). Preferred aliphatic primary diamines include isophorone diamine and TCD diamine.

[0023] For an aliphatic secondary diamine and an aliphatic primary diamine, a preferred chain extender composition in this invention is one in which the aliphatic secondary diamine is N,N'-di-(3,3-dimethyl-2-butyl)-l,6-diaminohexane.

Component (c)

[0024] Aliphatic diimines (diimines are also called diketimines) are component (c).

Processes for forming diimines from primary diamines are provided in commonly-owned copending U.S. Pat. Application No. 11/390,777, filed March 27, 2006, now U.S. Pat. No.

7,288,677, and PCT Application No. PCT/US2005/47696, filed December 30, 2005, published as WO 2006/104528. Other disclosures of methods for making diimines include

WO 97/01529, U.S. Pat. No. 4,855,500, and U.S. Pat. No. 4,536,518.

[0025] Proportions of N,N'-dicyclohexyl-l,6-hexanediamine to aliphatic diimine in the chain extender composition are generally about 0.1 :1 to about 1 :0.1 on an equivalent basis; preferably, the relative proportions on an equivalent basis are about 0.75:1 to about 1 :0.75.

On a weight basis, the relative proportions of N,N'-dicyclohexyl-l,6-hexanediamine to aliphatic diimine in the chain extender composition are preferably about 0.25:1 to about 5:1; more preferably, the relative proportions on a weight basis are about 0.5:1 to about 3:1.

[0026] The hydrocarbyl portion of the aliphatic diimine can be cyclic, branched, or straight chain hydrocarbyl group, where "hydrocarbyl portion" refers to the moiety to which the imino groups are bound. Preferably, the aliphatic diimine has about six to about forty carbon atoms; more preferably, the aliphatic diimine has about ten to about thirty carbon atoms. The hydrocarbylidene groups of the imino groups of the aliphatic diimine generally have from one to about twenty carbon atoms; the hydrocarbylidene groups may be straight chain, branched, or cyclic. Preferably, the imino hydrocarbylidene groups are straight chain or branched chain alkylidene groups having from three to about six carbon atoms. Examples of suitable imino hydrocarbylidene groups include ethylidene, propylidene, isopropylidene, 1-cyclopropylethylidene, n-butylidene, sec-butylidene, cyclobutylidene, 2-ethylbutylidene, 3,3-dimethyl-2-butylidene, 3-pentylidene, 3-penten-2- ylidene, cyclopentylidene, 2,5-dimethylcyclopentylidene, 2-cyclopentenylidene, hexylidene, methylcyclohexylidene, menthylidene, ionylidene, phorylidene, isophorylidene, heptylidene, 2,6,-dimethyl-3-heptylidene, cyclooctylidene, 5-nonylidene, decylidene, 10-undecenylidene, and the like.

[0027] Aliphatic diimines that can be used in this invention include, but are not limited to, N,N'-diisopropylidene-ethylenediamine, N,N'-di-sec-butylidene- 1 ,2-diaminopropane,

N,N'-di(2-butenylidene)-l,3-diaminopropane, N,N'-di(l-cyclopropylethylidene)-l,5- diaminopentane, N,N'-di(3,3-dimethyl-2-butylidene)-l,5-diamino-2-methylpentane, N₅N'- di-sec-butylidene- 1 ,6-diaminohexane, N,N'-di(3-pentylidene)-2,5-dimethyl-2,5-hexane- diamine, N,N'-di(4-hexylidene)-l ,2-diaminocyclohexane, N,N'-dicyclohexylidene-l ,3- diaminocyclohexane, N,N'-di( 1 -cy clobutylethylidene)- 1 ,4-diaminocyclohexane, N₅N'- di(2,4-dimethyl-3-pentylidene)-l,3-cyclohexanebis(methylamine), N,N'-di(l-penten-3- ylidene)- 1 ,4-cyclohexanebis(methylamine), N,N'-diisopropylidene- 1 ,7-diaminoheptane, N,N'-di-sec-butylidene- 1 ,8-diaminooctane, N,N'-di(2-pentylidene)- 1 , 10-diaminodecane, N,N'-di(3 -hexylidene)- 1,12-diaminododecane, N,N'-di(3-methyl-2-cyclohexenylidene)- 1 ,2-diaminopropane, N,N'-di(2,5-dimethylcyclopentylidene)-l ,4-diaminobutane, N₅N'- di(isophorylidene)-l,5-diaminopentane, N,N'-di(menthylidene)-2,5-dimethyl-2,5- hexanediamine, N,N'-di(undecylidene)-l ,2-diaminocyclohexane, N,N'-di-2-(4- methylpentylidene)-isophoronediamine, and N,N'-di(5 -nonylidene)-isophoronediamine . Component (d)

[0028] Aromatic primary diamines are component (d) of the chain extenders of this invention. The relative proportions of N,N'-dicyclohexyl-l,6-hexanediamine or aliphatic secondary α,ω-diamine having at least one internal secondary amino group to aromatic primary diamine in the chain extender composition are generally about 0.1 :1 to about 1 :0.1 on an equivalent basis; preferably, the relative proportions on an equivalent basis are about 0.75:1 to about 1 :0.75. On a weight basis, the relative proportions of N,N'-dicyclohexyl- 1,6-hexanediamine or aliphatic secondary α,ω-diamine having at least one internal secondary amino group to aromatic primary diamine in the chain extender composition are preferably about 0.25:1 to about 5:1; more preferably, the relative proportions on a weight basis are about 0.5:1 to about 3:1.

[0029] One type of aromatic primary diamine that can be used in this invention is 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 phenyl rings may have, but need not have, one or more hydrocarbyl groups on the phenyl ring(s). Hydrocarbyl groups, when present on the phenyl rings, may be the same or different. When both amino groups are on one phenyl ring, the amino groups may be in any position relative to each other on the ring; preferably, the amino groups are meta or para relative to each other. When the amino groups are on two phenyl rings connected by an alkylene bridge, they may be in any position on the rings; preferably, each amino group is meta or para relative to the alkylene bridge. The alkylene bridge of the two-ring diamine has from one to about six carbon atoms; preferably, the alkylene bridge has from one to about three carbon atoms. More preferably, the alkylene bridge has one or two carbon atoms; highly preferred is an alkylene bridge having one carbon atom. The hydrocarbyl groups, when present on the phenyl ring(s), are as described above for the aromatic diimines. When one or more hydrocarbyl groups are present on the phenyl ring(s), the hydrocarbyl groups can have from one to about twenty carbon atoms; preferably, the hydrocarbyl groups have from one to about six carbon atoms.

[0030] Suitable aromatic primary diamines of this type having both amino groups on one phenyl ring include, but are not limited to, 1 ,2-benzenediamine, 1,3-benzenediamine, 1,4- benzenediamine, 4-ethyl-l,2-benzenediamine, 2-isopropyl-l,3-benzenediamine, 4-tert- butyl- 1 ,3-benzenediamine, 2-pentyl- 1 ,4-benzenediamine, 4,5-dihexyl-l ,2- benzenediamine, 4-methyl-5-heptyl- 1 ,3-benzenediamine, 4,6-di-n-propyl- 1 ,3- benzenediamine, 2,5-dioctyl-l,4-benzenediamine, 2,3-diethyl-l,4-benzenediamine, and 4,5,6-trihexyl-l,3-benzenediamine.

[0031] Examples of suitable aromatic primary diamines of this type in which one amino group is on each of two phenyl rings include 2,2'-methylenebis(benzeneamine), 2,3'- methylenebis-(benzeneamine), 2,4'-methylenebis(benzeneamine), 3,3'-methylenebis- (benzeneamine), 3 ,4'-methylenebis(benzeneamine), 4,4'-methylenebis-(benzeneamine), 4,4'-(l ,2-ethanediyl)bis-(benzeneamine), 3,4'-(l ,3-propanediyl)bis-(benzeneamine), 2,2'- methylenebis(5-tert-butyl-benzeneamine), 3,3'-methylenebis(2-methylbenzeneamine), 3,3'-methylenebis(5-pentylbenzeneamine), 3,3'-methylenebis(6-isopropylbenzeneamine), 4,4'-methylenebis(2-methylbenzeneamine), 4,4'-methylenebis(3-sec-butylbenzeneamine), 4,4'-(l,2-ethanediyl)bis(2-methylbenzeneamine), 3,3'-methylenebis(2,4-dipentylbenzene- amine), 3,3'-methylenebis(5,6-diisopropylbenzene-amine), 4,4'-methylenebis(2,3-di-sec- butylbenzeneamine), 4,4'-methylenebis(3,5-di-tert-butylbenzeneamine), and the like. [0032] Another type of aromatic primary diamine that can be used in this invention, which is a preferred type of aromatic primary diamine, is an aromatic primary diamine in which each position ortho (immediately adjacent) to an amino group bears a hydrocarbyl group, and which aromatic primary 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, or is in the form of two phenyl rings connected by an alkylene bridge and having one amino group on each ring. The hydrocarbyl groups on the phenyl rings (adjacent to the amino groups) generally have up to about twenty carbon atoms, and the hydrocarbyl groups may be the same or different. The alkylene bridge of the two-ring primary diamine has from one to about six carbon atoms; preferably, the bridge has from one to about three carbon atoms. More preferably, the alkylene bridge has one or two carbon atoms; especially preferred as the alkylene bridge is a methylene group. Particularly preferred hydrocarbyl groups on the phenyl ring(s) are methyl, ethyl, isopropyl, butyl, and mixtures of two or more of these groups. Here, butyl groups include n-butyl, sec-butyl, and t-butyl groups.

[0033] More preferred aromatic primary diamines with two amino groups on one phenyl ring have the amino groups meta relative to each other. Highly preferred hydrocarbyl groups are methyl, ethyl, isopropyl, butyl, and mixtures thereof, where the preference for butyl groups includes n-butyl, sec-butyl, and t-butyl groups. Particularly preferred are aromatic primary diamines in which the hydrocarbyl group between the two meta amino groups is a methyl group, while the two remaining hydrocarbyl groups are ethyl groups, and those in which the hydrocarbyl group between the two meta amino groups is an ethyl group, while one of the two remaining hydrocarbyl groups is a methyl group and the other is an ethyl group, and mixtures thereof. More preferred aromatic primary diamines are also those in which one amino group is on each of two phenyl rings, where the two phenyl rings are connected via an alkylene bridge, and have both amino groups para relative to the alkylene bridge. An especially preferred aromatic primary diamine of this type is a compound where each hydrocarbyl group ortho to an amino group is an ethyl group and the alkylene bridge is a methylene group.

[0034] A preferred aromatic primary diamine is one in which each position ortho to an amino group bears a hydrocarbyl group, and which aromatic primary diamine 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 the aromatic primary diamine has amino groups are meta relative to each other, and/or the ortho hydrocarbyl groups are methyl, ethyl, isopropyl, butyl, or mixtures thereof.

[0035] Examples of more preferred aromatic primary diamines include 3,6-di-n-butyl-l,2- benzenediamine, 2,4,6-triethyl-l,3-benzenediamine, 2,4-diethyl-6-methyl-l,3-benzene- diamine, 4,6-diethyl-2-methyl- 1 ,3-benzenediamine, 2,4-diisopropyl-6-methyl- 1 ,3- benzenediamine, 2-methyl-4,6-di-sec-butyl- 1 ,3-benzenediamine, 2-ethyl-4-isopropyl-6- methyl-l,3-benzenediamine, 2,3,5-tri-n-propyl-l,4-benzenediamine, 2,3-diethyl-5-sec- butyl- 1 ,4-benzenediamine, 3 ,4-dimethyl-5 ,6-diheptyl- 1 ,2-benzenediamine, 2,4,5 ,6-tetra- n-propyl- 1 ,3-benzenediamine, 2,3 ,5 ,6-tetraethyl- 1 ,4-benzenediamine, 2,2'-methylenebis(6- n-propylbenzeneamine), 2,2'-methylenebis(3,6-di-n-propylbenzeneamine), 3,3'- methylenebis(2,6-di-n-butylbenzeneamine), 4,4'-methylenebis(2,6-diethylbenzeneamine), 4,4'-methylenebis(2,6-diisopropylbenzeneamine), 4,4'-methylenebis(2-isopropyl-6- methylbenzeneamine), 4,4'-(l ,2-ethanediyl)bis(2,6-diethylbenzeneamine), 4,4'-(l ,2- ethanediyl)bis(2,6-diisopropylbenzeneamine), 2,2'-methylenebis(3,4,6-tripentylbenzene- amine), 3 ,3'-methylenebis(2,5 ,6-trihexylbenzeneamine), 4,4'-methylenebis(2,3 ,6- trimethylbenzeneamine), 4,4'-methylenebis(2,3,4,6-tetramethyl-benzeneamine), and the like. Of these more preferred types of aromatic primary diamines, particularly preferred are 4,4'-methylenebis(2,6-diethylbenzeneamine), 4,4'-methylenebis-(2,6-diisopropyl- benzeneamine), and a mixture of 2,4-diethyl-6-methyl-l,3-benzene-diamine and 4,6- diethyl-2-methyl-l,3-benzenediamine (DETDA, Ethacure^® 100).

[0036] Those of skill in the art will recognize that there are several ways to name the aromatic primary diamines used in this invention. For example, the structure

which represents a particularly preferred aromatic primary diamine in this invention, can be called 2,4-diethyl-6-methyl-l,3-benzenediamine, 2,4-diethyl-6-methyl-l,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 this 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.

Component (f)

[0037] Aliphatic secondary α,ω-diamines having at least one internal secondary amino group are component (f). Suitable aliphatic secondary diamines for component (f) are as described above for component (ii). Preferred aliphatic secondary α,ω-diamines having at least one internal secondary amino group for component (f) include N,N'-di(3,3-dimethyl-

2-butyl)-diethylenetriamine and di[2-(N-cyclohexyl-amino)ethyl]amine.

Component (g) [0038] As mentioned above, when the chain extender composition comprises (ii), mixtures of subcomponents (a), (d), and (f) in various combinations are within the scope of this invention. Component (g) is a combination of any two or more of (a), (d), and (f). Preferred combinations for (g) include combinations of at least one component (a) and at least one component (d); more preferably, such combinations include only one component (a) and one component (d). Preferred diamines for component (g) are the same as those described above for components (a), (d), and (f). A preferred combination for (g) is N₅N'- di-(3,3-dimethyl-2-butyl)-l,6-diaminohexane and a mixture of 2,4-diethyl-6-methyl-l,3- benzene-diamine and 4,6-diethyl-2-methyl-l,3-benzenediamine (DETDA, Ethacure^® 100). [0039] Relative proportions of an aliphatic secondary α,ω-diamine having at least one internal secondary amino group to component (g) in the chain extender composition are preferably about 0.1 :1 to about 1 :0.1 on an equivalent basis; more preferably, the relative proportions on an equivalent basis are about 0.1 :1 to about 1 :0.5.

Processes of the Invention

[0040] In the processes of the invention, a polymer which is a polyurethane, polyurea, or polyurea-urethane is made by mixing together at least one polyisocyanate, at least one polyol and/or at least one polyetheramine, and a chain extender composition of the invention. As is well known in the art, other components may also be included when making the polyurethane, polyurea, or polyurethane -urea, such as one or more flame retardants, thermal stabilizers, and/or surfactants. In some processes of the invention, the polyol or polyetheramine, chain extender composition, and when used, optional ingredients, are blended together to form a first mixture, followed by blending this first mixture with the isocyanate to form a second mixture; this second mixture is allowed to cure. In other processes of this invention, the isocyanate and the polyol or polyetheramine are blended together to form a prepolymer, which prepolymer is then mixed together with the chain extender composition to form the desired polymer. In still other processes of the invention, the isocyanate is mixed with polyol or polyetheramine to form a quasiprepolymer; polyol or polyetheramine is mixed with the chain extender composition to form a mixture; and then the mixture is mixed with the quasiprepolymer to form the desired polymer. Thus, the chain extender composition is reacted with an aliphatic polyisocyanate and at least one polyol and/or at least one polyetheramine or with a prepolymer or a quasiprepolymer of the isocyanate and the polyol or polyetheramine. In the practice of this invention, use of quasiprepolymers is preferred way of producing polyureas.

[0041] The aliphatic polyisocyanates are organic polyisocyanates having at least two isocyanate groups. Generally, the isocyanates have a free -NCO content of at least about 0.1% by weight. Aliphatic polyisocyanates that can be used in the practice of this invention include isophorone diisocyanate (IPDI), cyclohexylene diisocyanate, 4,4'- methylenedicyclohexyl diisocyanate (H 12MD I); mixed aralkyl diisocyanates including tetramethylxylyl diisocyanates; and polymethylene isocyanates including 1,4- tetramethylene diisocyanate, 1,5-pentamethylene diisocyanate, 1,6-hexamethylene diisocyanate (HMDI), 1 ,7-heptamethylene diisocyanate, 2,2,4-and 2,4,4- trimethylhexamethylene diisocyanate, 1,10-decamethylene diisocyanate, and 2-methyl- 1,5-pentamethylene diisocyanate. A preferred aliphatic polyisocyanate is isophorone diisocyanate (IPDI). Examples of isocyanates that can be used are also taught in, for example, U.S. 4,595,742.

[0042] When the chain extender composition comprises (ii), an aliphatic secondary α,ω- diamine having a secondary amino straight chain, aromatic polyisocyanates can be used in the processes of this invention. Aromatic polyisocyanates that can be used with an aliphatic secondary α,ω-diamine having a secondary amino straight chain are organic polyisocyanates having at least two isocyanate groups. Generally, the isocyanates have a free -NCO content of at least about 0.1% by weight. Aromatic polyisocyanates that can be used in the practice of this invention include phenylene diisocyanate, toluene diisocyanate (TDI), xylene diisocyanate, 1,5 -naphthalene diisocyanate, chlorophenylene 2,4-diisocyanate, bitoluene diisocyanate, dianisidine diisocyanate, tolidine diisocyanate, alkylated benzene diisocyanates, methylene -interrupted aromatic diisocyanates such as methylenediphenyl diisocyanates, especially 4,4'-methylenediphenyl diisocyanate (MDI), alkylated analogs of methylene-interrupted aromatic diisocyanates (such as 3,3'-dimethyl- 4,4'-diphenylmethane diisocyanate), and polymeric methylenediphenyl diisocyanates. A preferred aromatic polyisocyanate is 4,4'-methylenediphenyl diisocyanate (MDI). Examples of isocyanates that can be used are also taught in, for example, U.S. 4,595,742. [0043] Isocyanate-reactive polyols and polyetheramines (sometimes referred to as amine- terminated polyols) that are typically used in making polyurethanes, polyureas, and polyurea-urethanes range in molecular weight from about 60 to over 6,000. The polyols can be dihydric, trihydridic, or polyhydric polyols, but are usually dihydric. Examples of suitable polyols include poly(ethyleneoxy) glycols, dipropylene glycol, poly(propyleneoxy) glycols, dibutylene glycol, poly(butyleneoxy) glycols, and the polymeric glycol from caprolactone, commonly known as polycaprolactone. The polyetheramines used to make polyurethanes, polyureas, and polyurea-urethanes are amine-capped polyols which are the reaction product of a polyol and then an amine with alkylene oxides as well as amine-capped hydroxyl-containing polyesters. Polyetheramines typically have a molecular weight of about 200 to about 6000. Several commercially available polyetheramines known as Jeffamines^® available from Huntsman Chemical Company and include Jeffamine^® T-5000, a polypropylene oxide triamine of about 5000 molecular weight, XTJ-509, a polypropylene oxide triamine of about 3000 molecular weight, XTJ-510, a polypropylene oxide diamine of about 4000 molecular weight, and Jeffamine^® D-2000, a polypropylene oxide diamine of about 2000 molecular weight. Jeffamine^® T-5000 and Jeffamine^® D-2000 are preferred polyetheramines in the practice of this invention.

[0044] Proportions of polyol and/or polyetheramine to the chain extender composition are typically about 75:25 to about 50:50, and preferably are about 70:30 to about 55:45. More preferably, the proportions of polyol and/or polyetheramine to the chain extender composition are about 65:35 to about 60:40. Normally and preferably, the polyisocyanate and the polyol and/or polyetheramine are brought together in approximately equal volumes.

[0045] In preferred processes of the invention, the chain extenders are N,N'-dicyclohexyl- 1,6-hexanediamine and N,N'-di-(3,3-dimethyl-2-butyl)-l,6-diaminohexane or N₅N'- dicyclohexyl-l,6-hexanediamine and a mixture of 2,4-diethyl-6-methyl-l,3-benzene- diamine and 4,6-diethyl-2-methyl-l,3-benzenediamine (Ethacure^® 100, Albemarle Corporation). In other preferred processes of the invention, the chain extenders are N₅N'- diisopropyl-diethylenetriamine and N,N'-di-(3,3-dimethyl-2-butyl)-l,6-diaminohexane or N,N'-diisopropyl-diethylenetriamine and N,N'-di(3,3-dimethyl-2-butyl)- diethy lenetriamine .

Polymers formed by the Invention

[0046] The polymers formed by the invention are polyurethanes, polyureas, and polyurea- urethanes (sometimes called polyurea-polyurethanes). Because of their differing gel times

(cure rates), these polymers can be used in different applications. Polyurethanes, polyureas, and polyurea-urethanes made with the chain extender compositions of the invention have more desirable gel times, and, at a minimum, the physical properties of the polymers are not adversely affected by the use of the chain extender compositions of the invention. In fact, a stiffer polymer is obtained when made from chain extender compositions in which N,N'-dicyclohexyl-l,6-hexanediamine is used, in comparison to polymers made with the individual chain extenders.

[0047] Preferred polymers formed by this invention are formed when N,N'-dicyclohexyl- 1,6-hexanediamine and N,N'-di-(3,3-dimethyl-2-butyl)-l,6-diaminohexane or N₅N'- dicyclohexyl-l,6-hexanediamine and a mixture of 2,4-diethyl-6-methyl-l,3- benzenediamine and 4, 6-diethyl-2 -methyl- 1,3-benzenediamine (Ethacure^® 100) are used as chain extenders in the formation of the polymers. Other preferred polymers formed by this invention are formed when N,N'-diisopropyl-diethylenetriamine and N,N'-di-(3,3- dimethyl-2 -butyl)- 1,6-diaminohexane or N,N'-diisopropyl-diethylenetriamine and N₅N'- di(3,3-dimethyl-2-butyl)-diethylenetriamine are used as chain extenders in the formation of the polymers.

[0048] The following examples are presented for purposes of illustration, and are not intended to impose limitations on the scope of this invention.

EXAMPLE 1

[0049] In this Example, a pneumatic dispensing gun (DP-400-85-1, Mixpac Systems AG, Switzerland) was used in conjunction with a static mixer. The static mixer was either a plastic spiral bell mixer with 30 elements and an inner diameter of 0.37 inches (-0.94 cm; EA 370-30, Ellsworth Adhesives) or a plastic bell mixer with 48 elements and an inner diameter of 0.25 inches (-0.64 cm; Statomix^® MS 06-48).

[0050] Polyurea formulations containing isophorone diisocyanate (IPDI), Jeffamine^® D- 2000 (a polyetheramine, Huntsman Chemical), N,N'-dicyclohexyl- 1,6-diaminohexane, and another aliphatic secondary diamine are prepared. The isocyanate is mixed together with a portion of the Jeffamine^® D-2000 to form a quasiprepolymer. The remainder of the Jeffamine^® D-2000 is blended with the N,N'-dicyclohexyl- 1,6-diaminohexane and the other aliphatic secondary diamine to form a mixture. This mixture is then added to one compartment of the pneumatic mixing gun; the quasiprepolymer is added to the other compartment. The mixture and quasiprepolymer are mixed (reacted) by pushing them through a static mixer onto a steel plate and curing at room temperature. Four formulations were prepared, each containing a different aliphatic secondary diamine with the N,N'-dicyclohexyl-l,6-diaminohexane. The other aliphatic secondary diamines were N,N'-di(sec-butyl)-4,4'-di(cyclohexylamino)methane, N,N'-di-(3,3-dimethyl-2-butyl)-l,6- diaminohexane, N,N'-(4-methyl-2-pentyl)-l,6-diaminohexane, and N,N'-diisopropyl-l,6- diaminohexane. Another formulation is prepared; in this formulation, aliphatic primary diamines, a mixture of 2,4-diethyl-6-methyl-l,3-benzenediamine and 4,6-diethyl-2- methyl-l,3-benzenediamine (Ethacure^® 100, Albemarle Corporation), is mixed with the N,N'-dicyclohexyl-l,6-diaminohexane.

EXAMPLE 2 [0051] In this example, the isocyanate was 4,4'-methylenediphenyl diisocyanate (MDI,

15.2% NCO, Rubinate^R 9480, Huntsman Chemical). Jeffamine^R D-2000 and Jeffamine ^R T-5000 (polyetheramines, Huntsman Chemical) were used to make the polyureas, with the

(R) (R)

Jeffamine D-2000 and Jeffamine T-5000 in varying ratios. A pneumatic dispensing gun (DP-400-85-1, Mixpac Systems AG, Switzerland) was used in conjunction with a static mixer. The static mixer was either a plastic spiral bell mixer with 30 elements and an inner diameter of 0.37 inches (EA 370-30, Ellsworth Adhesives) or a plastic bell mixer

® with 48 elements and an inner diameter of 0.25 inches (Statomix MS 06-48).

(R) (R)

[0052] Polyurea formulations containing isocyanate, Jeffamine D-2000 and Jeffamine

T-5000, and the chain extenders were prepared, with the N,N'-di(3,3-dimethyl-2-butyl)- diethylenetriamine and N,N'-di-(3,3-dimethyl-2-butyl)-l,6-diaminohexane being used in varying ratios. In another run, the chain extenders were N,N'-di(3,3-dimethyl-2-butyl)-

® diethylenetriamine, N,N'-di-(3,3-dimethyl-2-butyl)-l,6-diaminohexane, and Ethacure

® 100-LC (Albemarle Corporation), which is Ethacure 100 of lower color with a stabilizer

® present at ppm levels. Ethacure 100 (Albemarle Corporation) is a mixture of 2,4- diethyl-6-methyl-l,3-benzenediamine and 4,6-diethyl-2-methyl-l,3-benzenediamine. A comparative run without any N,N'-di(3,3-dimethyl-2-butyl)-diethylenetriamine was also performed.

® [0053] The isocyanate was mixed together with a portion of the Jeffamine ® polyetheramines to form a quasiprepolymer. The remainder of the Jeffamine polyetheramines was blended with the chain extender(s) to form a mixture. This mixture was then added to one compartment of the pneumatic mixing gun; the quasiprepolymer was added to the other compartment. The mixture and quasiprepolymer were mixed (reacted) by pushing them through a static mixer onto a steel plate and cured at room

® temperature. Amounts of the chain extenders and Jeffamine polyethyeramines by weight are listed in Table 1. The amount of N,N'-di(3,3-dimethyl-2-butyl)- diethylenetriamine listed in Table 1 is also the amount per hundred parts of isocyanate. The cured polymers were subjected to testing. Properties of the polyureas are summarized in Table 1.

TABLE 1

CD

l>0

O

[0054] Components referred to by chemical name or formula anywhere in the specification or claims hereof, whether referred to in the singular or plural, are identified as they exist prior to coming into contact with another substance referred to by chemical name or chemical type (e.g. , another component, a solvent, or etc.). It matters not what chemical changes, transformations and/or reactions, if any, take place in the resulting mixture or solution as such changes, transformations, and/or reactions are the natural result of bringing the specified components together under the conditions called for pursuant to this disclosure. Thus the components are identified as ingredients to be brought together in connection with performing a desired operation or in forming a desired composition. Also, even though the claims hereinafter may refer to substances, components and/or ingredients in the present tense ("comprises", "is", etc.), the reference is to the substance, component or ingredient as it existed at the time just before it was first contacted, blended or mixed with one or more other substances, components and/or ingredients in accordance with the present disclosure. The fact that a substance, component or ingredient may have lost its original identity through a chemical reaction or transformation during the course of contacting, blending or mixing operations, if conducted in accordance with this disclosure and with ordinary skill of a chemist, is thus of no practical concern. [0055] The invention may comprise, consist, or consist essentially of the materials and/or procedures recited herein.

[0056] As used herein, the term "about" modifying the quantity of an ingredient in the compositions of the invention or employed in the methods of the invention refers to variation in the numerical quantity that can occur, for example, through typical measuring and liquid handling procedures used for making concentrates or use solutions in the real world; through inadvertent error in these procedures; through differences in the manufacture, source, or purity of the ingredients employed to make the compositions or carry out the methods; and the like. The term about also encompasses amounts that differ due to different equilibrium conditions for a composition resulting from a particular initial mixture. Whether or not modified by the term "about", the claims include equivalents to the quantities.

[0057] Except as may be expressly otherwise indicated, the article "a" or "an" if and as used herein is not intended to limit, and should not be construed as limiting, the description or a to a single element to which the article refers. Rather, the article "a" or "an" if and as used herein is intended to cover one or more such elements, unless the text expressly indicates otherwise. [0058] Each and every patent or publication referred to in any portion of this specification is incorporated in toto into this disclosure by reference, as if fully set forth herein. [0059] This invention is susceptible to considerable variation in its practice. Therefore the foregoing description is not intended to limit, and should not be construed as limiting, the invention to the particular exemplifications presented hereinabove.

Claims

THAT WHICH IS CLAIMED IS:

1. A chain extender composition which comprises either (i) N,N'-dicyclohexyl-l,6- hexanediamine or (ii) an aliphatic secondary α,ω-diamine having at least one internal secondary amino group; and when said composition comprises (i), said composition is also comprised of a component selected from the group consisting of:

(a) an aliphatic secondary diamine,

(b) an aliphatic secondary diamine and an aliphatic primary diamine,

(c) an aliphatic diimine,

(d) an aromatic primary diamine, and

(e) a combination of any two or more of (a) through (d); or when said composition comprises (ii), said composition is also comprised of a component selected from the group consisting of:

(a) an aliphatic secondary diamine,

(d) an aromatic primary diamine,

(f) an aliphatic secondary α,ω-diamine having at least one internal secondary amino group, and

(g) a combination of any two or more of (a), (d), and (f).

2. A composition as in Claim 1 wherein (a) has at least one of the following features: the hydrocarbyl portion of the diamine is a straight chain; the amino hydrocarbyl groups are straight chain or branched chain alkyl groups; the aliphatic secondary diamine has about ten to about thirty carbon atoms; and/or (d) 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, or 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.

3. A composition as in Claim 2 comprising (i) and (a), wherein (a) is N,N'-di(sec- butyl)-4,4'-di(cyclohexylamino)methane, N,N'-di-(3,3-dimethyl-2-butyl)- 1 ,6-diaminohexane, N,N'-(4-methyl-2-pentyl)-l,6-diaminohexane, or N,N'-diisopropyl-l,6-diaminohexane, or comprising (ii) and (a), wherein (a) is N,N'-di(sec-butyl)-4,4'-di(cyclohexylamino)methane or N,N'-di-(3,3-dimethyl-2-butyl)-l,6-diaminohexane.

4. A composition as in Claim 1 comprising (i) and (b), wherein the aliphatic secondary diamine has at least one of the following features: about ten to about thirty carbon atoms; the hydrocarbyl portion of the diamine is a straight chain; the amino hydrocarbyl groups are straight chain or branched chain alkyl groups.

5. A composition as in Claim 1 comprising (i) and (c), wherein (c) has imino hydrocarbylidene groups having at least one of the following features: branched chain alkylidene groups; from three to about six carbon atoms.

6. A composition as in Claim 2 wherein (d) is a mixture of 2,4-diethyl-6-methyl-l,3- benzenediamine and 4,6-diethyl-2-methyl-l,3-benzenediamine.

7. A composition as in Claim 1 comprising (ii) and (f), wherein (f) is N,N'-di(3,3- dimethyl-2-butyl)-diethylenetriamine or di[2-(N-cyclohexyl-amino)ethyl]amine, or comprising (ii) and (g), wherein (g) is comprised of (a) and (d).

8. A composition as in Claim 8 wherein (a) is N,N'-di(sec-butyl)-4,4'- di(cyclohexylamino)methane or N,N'-di-(3,3-dimethyl-2-butyl)-l,6-diaminohexane, and/or wherein (d) is a mixture of 2,4-diethyl-6-methyl-l,3-benzenediamine and 4,6-diethyl-2-methyl- 1 ,3-benzenediamine.

9. A composition as in any of Claims 3, 6, 7, or 8 wherein (ii) is N,N'-diisopropyl- diethylenetriamine or N,N'-di(sec-butyl)-diethylenetriamine.

10. A process for producing a polymer, which process comprises mixing together (A) at least one polyisocyanate, (B) at least one polyol and/or at least one polyetheramine, and (C) a chain extender comprised of either (i) N,N'-dicyclohexyl- 1 ,6-hexanediamine or (ii) an aliphatic secondary α,ω-diamine having at least one internal secondary amino group; when said chain extender comprises (i), said polyisocyanate is an aliphatic polyisocyanate, and said composition is also comprised of a component selected from the group consisting of:

(a) an aliphatic secondary diamine,

(b) an aliphatic secondary diamine and an aliphatic primary diamine,

(c) an aliphatic diimine,

(d) an aromatic primary diamine, and

(e) a combination of any two or more of (a) through (d); or when said chain extender comprises (ii), said composition is also comprised of a component selected from the group consisting of:

(a) an aliphatic secondary diamine,

(d) an aromatic primary diamine,

(g) a combination of any two or more of (a), (d), and (f).

11. A process as in Claim 10 wherein (a) has at least one of the following features: the hydrocarbyl portion of the diamine is a straight chain; the amino hydrocarbyl groups are straight chain or branched chain alkyl groups; the aliphatic secondary diamine has about ten to about thirty carbon atoms; and/or (d) is a mixture of 2,4-diethyl-6-methyl-l,3-benzenediamine and 4,6-diethyl-2-methyl-l,3- benzenediamine.

12. A process as in Claim 11 comprising (i) and (a), wherein (a) is N,N'-di(sec-butyl)- 4,4'-di(cyclohexylamino)methane, N,N'-di-(3,3-dimethyl-2-butyl)-l ,6-diaminohexane, N,N'-(4- methyl-2-pentyl)- 1 ,6-diaminohexane, or N,N'-diisopropyl- 1 ,6-diaminohexane, or comprising (ii) and (a), wherein (a) is N,N'-di(sec-butyl)-4,4'-di(cyclohexylamino)methane or N,N'-di-(3,3- dimethyl-2-butyl)- 1 ,6-diaminohexane.

13. A process as in Claim 10 comprising (ii) and (f), wherein (f) is N,N'-di(3,3- dimethyl-2-butyl)-diethylenetriamine or di[2-(N-cyclohexyl-amino)ethyl]amine, or comprising (ii) and (g), wherein (g) is comprised of (a) and (d).

14. A process as in Claim 13 wherein (a) is N,N'-di(sec-butyl)-4,4'- di(cyclohexylamino)methane or N,N'-di-(3,3-dimethyl-2-butyl)-l,6-diaminohexane, and/or wherein (d) is a mixture of 2,4-diethyl-6-methyl-l,3-benzenediamine and 4,6-diethyl-2-methyl- 1 ,3-benzenediamine.

15. A process as in any of Claims 12, 13, or 14 wherein (ii) is N,N'-diisopropyl- diethylenetriamine or N,N'-di(sec-butyl)-diethylenetriamine.

16. A process as in any of Claims 10-15 wherein (A) is isophorone diisocyanate, and/or wherein (B) is at least one polyetheramine.

17. A process as in any of Claims 10-15 comprising (ii), wherein (A) is 4,4'- methylenediphenyl diisocyanate, and/or wherein (B) is at least one polyetheramine.

18. A process as in any of Claims 10-15 wherein a quasiprepolymer is formed during the process, or wherein a prepolymer is formed during the process.

19. A polymer formed from ingredients comprising (A) at least one polyisocyanate, (B) at least one polyol and/or at least one polyetheramine, and (C) a chain extender comprised of either (i) N,N'-dicyclohexyl- 1 ,6-hexanediamine or (ii) an aliphatic secondary α,ω-diamine having at least one internal secondary amino group; when said chain extender comprises (i), said polyisocyanate is an aliphatic polyisocyanate, and said composition is also comprised of a component selected from the group consisting of:

(a) an aliphatic secondary diamine,

(b) an aliphatic secondary diamine and an aliphatic primary diamine,

(c) an aliphatic diimine,

(d) an aromatic primary diamine, and

(a) an aliphatic secondary diamine,

(d) an aromatic primary diamine,

(g) a combination of any two or more of (a), (d), and (f).

20. A polymer as in Claim 19 wherein (a) has at least one of the following features: the hydrocarbyl portion of the diamine is a straight chain; the amino hydrocarbyl groups are straight chain or branched chain alkyl groups; the aliphatic secondary diamine has about 10 to about thirty carbon atoms; and/or (d) is a mixture of 2,4-diethyl-6-methyl-l,3-benzenediamine and 4,6-diethyl-2-methyl-l,3- benzenediamine.

21. A polymer as in Claim 20 comprising (i) and (a), wherein (a) is N,N'-di(sec- butyl)-4,4'-di(cyclohexylamino)methane, N,N'-di-(3,3-dimethyl-2-butyl)- 1 ,6-diaminohexane, N,N'-(4-methyl-2-pentyl)-l,6-diaminohexane, or N,N'-diisopropyl-l,6-diaminohexane, or comprising (ii) and (a), wherein (a) is N,N'-di(sec-butyl)-4,4'-di(cyclohexylamino)methane or N,N'-di-(3,3-dimethyl-2-butyl)-l,6-diaminohexane.

22. A polymer as in Claim 19 comprising (ii) and (f), wherein (f) is N,N'-di(3,3- dimethyl-2-butyl)-diethylenetriamine or di[2-(N-cyclohexyl-amino)ethyl]amine, or comprising (ii) and (g), wherein (g) is comprised of (a) and (d).

23. A polymer as in Claim 22 wherein (a) is N,N'-di(sec-butyl)-4,4'- di(cyclohexylamino)methane or N,N'-di-(3,3-dimethyl-2-butyl)-l,6-diaminohexane, and/or wherein (d) is a mixture of 2,4-diethyl-6-methyl-l,3-benzenediamine and 4,6-diethyl-2-methyl- 1 ,3-benzenediamine.

24. A polymer as in any of Claims 21-23 wherein (ii) is N,N'-diisopropyl- diethylenetriamine or N,N'-di(sec-butyl)-diethylenetriamine.

25. A polymer as in any of Claims 19-24 wherein (A) is isophorone diisocyanate, and/or wherein (B) is at least one polyetheramine.

26. A polymer as in any of Claims 19-24 comprising (ii), wherein (A) is 4,4'- methylenediphenyl diisocyanate, and/or wherein (B) is at least one polyetheramine.