WO2008039715A1

WO2008039715A1 - Chain extenders

Info

Publication number: WO2008039715A1
Application number: PCT/US2007/079291
Authority: WO
Inventors: Paul L. Wiggins; John Y. Lee; Judit Orgad; Michael J. Wilhelm
Original assignee: Albemarle Corporation
Priority date: 2006-09-25
Filing date: 2007-09-24
Publication date: 2008-04-03

Abstract

This invention provides chain extender compositions. These compositions comprise (i) an aromatic primary diamine in which at least one position ortho to each 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, and (ii) an aromatic primary diamine in which at least one position ortho to each amino group bears a tertiary hydrocarbyl group, and which aromatic primary diamine is in the form of two phenyl rings connected by an alkylene bridge and having one amino group on each ring. Processes for producing polyurethanes, polyureas, and polyurea-urethanes are also provided.

Description

CHAIN EXTENDERS

TECHNICAL FIELD

[0001] This invention relates to the use of aromatic primary 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 aromatic 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 two particular types of aromatic primary diamines. 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

(i) an aromatic primary diamine in which at least one position ortho to each 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, and (ii) an aromatic primary diamine in which at least one position ortho to each amino group bears a tertiary hydrocarbyl group, and which aromatic primary diamine is in the form of two phenyl rings connected by an alkylene bridge and having one amino group on each ring.

[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 aromatic polyisocyanate, (B) at least one polyol and/or at least one polyetheramine, and (C) a chain extender comprised of

(i) an aromatic primary diamine in which at least one position ortho to each 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, and

(ii) an aromatic primary diamine in which at least one position ortho to each amino group bears a tertiary hydrocarbyl group, and which aromatic primary diamine is in the form of two phenyl rings connected by an alkylene bridge and having one amino group on each ring. [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 aromatic isocyanate, (B) at least one polyol and/or at least one polyetheramine, and (C) a chain extender comprised of

[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

[0009] A feature of this invention is that it does not involve the use of sulfur-containing compounds (e.g., those with alkylthio groups) as part of the chain extender compositions of the invention. Although compounds with alkylthio groups can be relatively odor- free when pure, precautions, such as the exclusion of oxygen, must be taken to prevent their decomposition, which often results in substances having unpleasant odors. Thus, such precautions are not necessary when handling the chain extender compositions of the invention.

Chain Extender Compositions of the Invention

[0010] Chain extender compositions of this invention are made up of a substituted aromatic primary diamine having both amino groups on one phenyl ring with a hydrocarbyl group ortho to each amino group, and an aromatic primary diamine having two phenyl rings with one amino group on each ring and a tertiary substituent ortho to each amino group.

I. Component (i)

[0011] Aromatic primary diamines of component (i) are those in which at least one position ortho (immediately adjacent) to each 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. 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. 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. Preferably, the hydrocarbyl groups are straight chain or branched chain alkyl groups.

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, phenyl, benzyl, and the like. Hydrocarbyl groups other than those ortho to the amino groups may be present on the phenyl ring. [0012] 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. [0013] Suitable aromatic primary diamines of component (i) include, but are not limited to, 3,6-di-n-butyl-l,2-benzenediamine, 4,6-di-n-propyl-l,3-benzenediamine, 2,5-dioctyl-

1 ,4-benzenediamine, 2,3-diethyl-l ,4-benzenediamine, 4,5,6-trihexyl-l ,3-benzenediamine, 2,4,6-triethyl- 1 ,3-benzenediamine, 2,4-diethyl-6-methyl- 1 ,3 -benzenediamine, 4,6-diethyl- 2-methyl- 1 ,3-benzenediamine, 2,4-diisopropyl-6-methyl- 1 ,3-benzenediamine, 2-methyl- 4,6-di-sec-butyl-l,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-l,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-l,4-benzenediamine, and the like. Of these more preferred types of aromatic primary diamines, particularly preferred is a mixture of 2,4-diethyl-6-methyl-l,3- benzenediamine and 4,6-diethyl-2-methyl-l,3-benzenediamine (DETDA, Ethacure 100). [0014] 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 one-ringed aromatic primary diamine in this invention, can be called 2,4-diethyl-6-methyl-l,3-benzenediamine, 2,4-diethyl-6-methyl- 1,3-phenylenediamine, 3,5-diethyl-2,4-diaminotoluene, or 3,5-diethyl-toluene-2,4- diamine. II. Component (ii)

[0015] Aromatic primary diamines of component (ii) are those in which at least one position ortho to an amino group bears a tertiary hydrocarbyl group, and which aromatic primary diamine is in the form of two phenyl rings connected by an alkylene bridge and having one amino group on each ring. The amino groups may be in any position on the rings; preferably, each amino group is meta or para relative to the alkylene bridge. The alkylene bridge 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, i.e., a methylene group. More preferred aromatic primary diamines of component (ii) are those in which both amino groups are para relative to the alkylene bridge. An especially preferred aromatic primary diamine of component (ii) is a compound in which both amino groups are para relative to the alkylene bridge and the alkylene bridge is a methylene group.

[0016] The tertiary group ortho to each amino group has from four to about twenty carbon atoms; preferably, the tertiary hydrocarbyl group has from four to about ten carbon atoms. Suitable tertiary groups include tert-butyl, 2-(2-methyl)butyl, 2-(2-methyl)pentyl, 3-(3-methyl)pentyl, 2-(2-methyl)hexyl, and the like. A preferred tertiary group is tert- butyl. 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. Other hydrocarbyl groups, when present on the phenyl ring(s), are as described above for the hydrocarbyl groups of component (i). When an amino group is not ortho to the alkylene bridge, the other position ortho to the amino group may also have a hydrocarbyl group; this hydrocarbyl group does not have to be tertiary. Hydrocarbyl groups other than those ortho to the amino groups may be present on one or both phenyl rings. [0017] Examples of suitable aromatic primary diamines of component (ii) include 2,2'- methylenebis(6-tert-butyl-benzeneamine), 3,3'-methylenebis{6-[2-(2- methyl)butyl]benzeneamine}, 4,4'-methylenebis(2-tert-butylbenzeneamine), 4,4'-methylenebis(2-methyl-6-tert-butylbenzeneamine), 4,4'-methylenebis(2,6- di-tert-butylbenzeneamine), 4,4'-methylenebis(2-tert-butyl,6-ethylbenzeneamine), 4,4'- methylenebis{2,6-di[3-(3-methyl)pentyl]benzeneamine), and the like. Preferred are 4,4'- methylenebis(2-tert-butylbenzeneamine), 4,4'-methylenebis(2-tert-butyl,6- methylbenzeneamine), and 4,4'-methylenebis(2-tert-butyl,6-ethylbenzeneamine), especially 4,4'-methylenebis(2-tert-butylbenzeneamine). [0018] A particularly preferred chain extender composition in this invention is one in which component (i) is a mixture of 2,4-diethyl-6-methyl-l,3-benzenediamine and 4,6- diethyl-2-methyl-l,3-benzenediamine, and in which component (ii) is 4,4'- methylenebis(2-tert-butylbenzeneamine).

Processes of the Invention [0019] In the processes of the invention, a polymer which is a polyurethane, polyurea, or polyurea-urethane is made by mixing together at least one aromatic 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 polyisocyanate to form a second mixture; this second mixture is allowed to cure. In other processes of this invention, the polyisocyanate 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 polyisocyanate 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 aromatic polyisocyanate and at least one polyol and/or at least one polyetheramine or with a prepolymer or a quasiprepolymer of the polyisocyanate and the polyol or polyetheramine. In the practice of this invention, use of quasiprepolymers is preferred way of producing polyureas. [0020] The aromatic polyisocyanates are organic polyisocyanates having at least two isocyanate groups. Generally, the polyisocyanates 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 polyisocyanates that can be used are also taught in, for example, U.S. 4,595,742.

[0021] 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 are 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.

[0022] In a preferred process of the invention, the chain extender composition has as component (i) a mixture of 2,4-diethyl-6-methyl-l,3-benzenediamine and 4,6-diethyl-2- methyl-l,3-benzenediamine, and has as component (ii) 4,4'-methylenebis(2-tert- butylbenzeneamine) .

Polymers formed by the Invention

[0023] The polymers formed by this invention are polyurethanes, polyureas, and polyurea-urethanes (sometimes called polyurea-polyurethanes). 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, an improvement in the tensile strength and stiffness of the polymers made from chain extender compositions of the invention is observed in comparison to polymers made with only the aromatic primary diamine having one phenyl ring.

[0024] A preferred polymer formed by this invention is formed from a chain extender composition in which component (i) is a mixture of 2,4-diethyl-6-methyl-l,3- benzenediamine and 4,6-diethyl-2-methyl-l,3-benzenediamine, and in which component (ii) is 4,4'-methylenebis(2-tert-butylbenzeneamine). Another preferred polymer of this invention is formed from ingredients comprising 4,4-methylenediphenyl diisocyanate, at least one polyetheramine, and a chain extender composition comprised of (i) an aromatic primary diamine in which at least one position ortho to each 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, in which the amino groups are meta or para relative to each other, and/or with the hydrocarbyl groups being straight chain or branched chain alkyl groups, (ii) an aromatic primary diamine in which at least one position ortho to each amino group bears a tertiary hydrocarbyl group, and which aromatic primary diamine is in the form of two phenyl rings connected by an alkylene bridge and having one amino group on each ring, in which each amino group is meta or para relative to the alkylene bridge and/or the alkylene bridge has from one to about three carbon atoms.

[0025] The following example is presented for purposes of illustration, and is not intended to impose limitations on the scope of this invention.

EXAMPLE 1

[0026] In this Example, the polyisocyanate was 4,4-methylenediphenyl diisocyanate (MDI, 15.2% NCO, Rubinate^R 9480, Huntsman Chemical). Jeffamine^R D-2000 and

(R^")

Jeffamine T-5000 (polyetheramines, Huntsman Chemical) were used to make the

® ® polyureas, with the Jeffamine D-2000 and Jeffamine T-5000 in about an 11 :1 weight ratio. The aromatic primary diamine was a mixture of 2,4-diethyl-6-methyl-l,3-

® benzenediamine and 4,6-diethyl-2-methyl-l,3-benzenediamine (Ethacure 100,

Albemarle Corporation). 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 (Statomiχ^R MS 06-48). ®

[0027] Polyurea formulations containing polyisocyanate, Jeffamine D-2000 and

® ®

Jeffamine T-5000, Ethacure 100, and an aromatic primary diamine were prepared. The

® Ethacure 100 and the aromatic primary diamine were used in a 1 : 1 ratio by equivalents.

® The polyisocyanate was mixed together with a portion of the Jeffamines to form a

® quasiprepolymer. The remainder of the Jeffamines 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. Two polyureas were prepared for comparative purposes. Amounts of the chain extenders relative to each other (in equivalents) are listed in Table 1. The cured polymers were subjected to testing. Properties of the polyureas are summarized in Table 1.

TABLE 1

[0028] In an experiment similar to that of Example 1 , where the aromatic primary

® diamine combined with Ethacure 100 was 4,4'-methylenebis(2-isopropylbenzeneamine), the gel time was too fast, i.e., the curing reaction was finished before the quasiprepolymer

(R^") and the Jeffamines /chain extender mixture were fully mixed.

[0029] It is to be understood that the reactants and components referred to by chemical name or formula anywhere in this document, 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 reactant, a solvent, or etc.). It matters not what preliminary chemical changes, transformations and/or reactions, if any, take place in the resulting mixture or solution or reaction medium as such changes, transformations and/or reactions are the natural result of bringing the specified reactants and/or components together under the conditions called for pursuant to this disclosure.

Thus the reactants and components are identified as ingredients to be brought together in connection with performing a desired chemical operation or reaction or in forming a mixture to be used in conducting a desired operation or reaction. Also, even though an embodiment may refer to substances, components and/or ingredients in the present tense ("is comprised of, "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. [0030] Also, even though the may refer to substances in the present tense (e.g. , "comprises", "is", etc.), the reference is to the substance as it exists at the time just before it is first contacted, blended or mixed with one or more other substances in accordance with the present disclosure.

[0031] 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. [0032] This invention is susceptible to considerable variation in its practice.

Claims

1. A chain extender composition which comprises (i) an aromatic primary diamine in which at least one position ortho to each 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, and

(ii) an aromatic primary diamine in which at least one position ortho to each amino group bears a tertiary hydrocarbyl group, and which aromatic primary diamine is in the form of two phenyl rings connected by an alkylene bridge and having one amino group on each ring.

2. A composition as in Claim 1 wherein (i) has at least one of the following features: the amino groups are meta or para relative to each other; the hydrocarbyl groups are straight chain or branched chain alkyl groups.

3. A composition as in Claim 2 wherein (i) has at least one of the following features: the amino groups are meta relative to each other; the hydrocarbyl groups have from one to about six carbon atoms.

4. A composition as in Claim 1 wherein in (i), the hydrocarbyl groups are methyl, ethyl, isopropyl, butyl, or mixtures thereof.

5. A composition as in Claim 1 wherein (ii) has at least one of the following features: each amino group is meta or para relative to the alkylene bridge; the alkylene bridge has from one to about three carbon atoms.

6. A composition as in Claim 1 wherein (ii) has at least one of the following features: both amino groups are para relative to the alkylene bridge; the alkylene bridge has one or two carbon atoms; the tertiary hydrocarbyl group is a tert-butyl group.

7. A composition as in Claim 1 wherein (i) has at least one of the following features: the amino groups are meta or para relative to each other; the hydrocarbyl groups are straight chain or branched chain alkyl groups, and wherein (ii) has at least one of the following features: each amino group is meta or para relative to the alkylene bridge; the alkylene bridge has from one to about three carbon atoms.

8. A process for producing a polymer, which process comprises mixing together (A) at least one aromatic polyisocyanate, (B) at least one polyol and/or at least one polyetheramine, and (C) a chain extender comprised of

9. A process as in Claim 8 wherein said polyisocyanate is 4,4- methylenediphenyl diisocyanate.

10. A process as in Claim 8 wherein (B) is at least one polyetheramine.

11. A process as in Claim 8 wherein said polyisocyanate is 4,4- methylenediphenyl diisocyanate, and wherein (B) is at least one polyetheramine.

12. A process as in Claim 8 wherein (i) has at least one of the following features: the amino groups are meta or para relative to each other; the hydrocarbyl groups are straight chain or branched chain alkyl groups.

13. A process as in Claim 12 wherein (i) has at least one of the following features: the amino groups are meta relative to each other; the hydrocarbyl groups have from one to about six carbon atoms.

14. A process as in Claim 8 wherein (ii) has at least one of the following features: each amino group is meta or para relative to the alkylene bridge; the alkylene bridge has from one to about three carbon atoms.

15. A process as in Claim 8 wherein (ii) has at least one of the following features: both amino groups are para relative to the alkylene bridge; the alkylene bridge has one or two carbon atoms; the tertiary hydrocarbyl group is a tert-butyl group.

16. A process as in Claim 8 wherein (i) has at least one of the following features: the amino groups are meta or para relative to each other; the hydrocarbyl groups are straight chain or branched chain alkyl groups, and wherein (ii) has at least one of the following features: each amino group is meta or para relative to the alkylene bridge; the alkylene bridge has from one to about three carbon atoms.

17. A process as in Claim 16 wherein said polyisocyanate is 4,4- methylenediphenyl diisocyanate, and wherein (B) is at least one polyetheramine.

18. A process as in Claim 8 wherein a quasiprepolymer is formed during the process.

19. A process as in Claim 8 wherein a prepolymer is formed during the process.

20. A polymer which is formed from ingredients comprising (A) at least one aromatic polyisocyanate, (B) at least one polyol and/or at least one polyetheramine, and (C) a chain extender comprised of

21. A polymer as in Claim 20 wherein said polyisocyanate is 4,4- methylenediphenyl diisocyanate.

22. A polymer as in Claim 20 wherein (B) is at least one polyetheramine.

23. A polymer as in Claim 20 wherein said polyisocyanate is 4,4- methylenediphenyl diisocyanate, and wherein (B) is at least one polyetheramine.

24. A polymer as in Claim 20 wherein (i) has at least one of the following features: the amino groups are meta or para relative to each other; the hydrocarbyl groups are straight chain or branched chain alkyl groups.

25. A polymer as in Claim 24 wherein (i) has at least one of the following features: the amino groups are meta relative to each other; the hydrocarbyl groups have from one to about six carbon atoms.

26. A polymer as in Claim 20 wherein (ii) has at least one of the following features: each amino group is meta or para relative to the alkylene bridge; the alkylene bridge has from one to about three carbon atoms.

27. A polymer as in Claim 20 wherein (ii) has at least one of the following features: both amino groups are para relative to the alkylene bridge; the alkylene bridge has one or two carbon atoms; the tertiary hydrocarbyl group is a tert-butyl group.

28. A polymer as in Claim 20 wherein (i) has at least one of the following features: the amino groups are meta or para relative to each other; the hydrocarbyl groups are straight chain or branched chain alkyl groups, and wherein (ii) has at least one of the following features: each amino group is meta or para relative to the alkylene bridge; the alkylene bridge has from one to about three carbon atoms.