HK1184181B - Polyetheramines, compositions including polyetheramines, and methods of making - Google Patents

Abstract

Embodiments of the present disclosure includepolyetheramines, methods of making polyetheramine, methods of using polyetheramine, and the like.

Description

Polyetheramines, compositions containing polyetheramines, and methods of making the same

Cross Reference to Related Applications

The present application claims priority from U.S. provisional application entitled "POLYETHERAMINES AND METHODs" filed on 9/10/2010 AND having serial No. 61/381,453, which is incorporated herein by reference in its entirety.

Background

Others have involved amine-terminated Ethylene Oxide (EO) Tetrahydrofuran (THF) block copolymers, or block polyetheramines, prepared by ammonia displacement of the chlorine end groups on block α, ω -dichloropolyalkylene oxides. However, this technique has significant disadvantages because the preparation uses expensive reagents in the chlorination reaction, produces chlorinated feed materials and produces HCl as a byproduct, which requires special handling, processing equipment made of expensive building materials, and special processing steps for byproduct disposal. The technology also includes the use of polyetheramines in the formation of block copolymers with adipic acid and hexamethylenediamine and subsequent formation of polyamide fibers.

Other techniques mention the presence of greater than 3% secondary amine end groups in copolymers used in optical fiber applications.

Yet another technology relates to poly (butylene oxide) poly (ethylene oxide) diamine compounds, and their use as additives to vehicle motor fuels. Under some conditions, the use of 1, 2-butylene oxide as a starting material may provide branched segments in the copolymer backbone after the amination step.

There remains a need for techniques that overcome and/or provide other benefits not present in the previously disclosed techniques.

SUMMARY

Embodiments of the present disclosure include polyetheramines, methods of making polyetheramines, methods of using polyetheramines, and the like.

One embodiment of the present disclosure includes an alpha, omega-diamino poly (ethylene oxide-co-tetramethylene oxide ether) random copolymer composition having from about 25 to about 75 mole percent ethylene oxide units and the like.

Wherein one embodiment of the composition comprises a polyetheramine composition according to formula II:

-((OCH₂CH₂)_a(OCH₂CH₂CH₂CH₂)_b)_cNH₂，

wherein: a and b are each an integer equal to or greater than 1; a/b ratio of about 0.33 to about 3.0; c is an integer equal to or greater than 2; and c has an average value of about 4 to about 26.

Among other things, one embodiment of a method of making an α, ω -diamino poly (ethylene oxide-co-tetramethylene oxide ether) random copolymer composition comprises reductive amination of poly (ethylene oxide-co-tetramethylene oxide ether) glycol in the presence of ammonia, hydrogen, and a reductive amination catalyst at elevated temperature and elevated total pressure.

Wherein one embodiment of a method of making an α, ω -diamino poly (ethylene oxide-co-tetramethylene oxide ether) random copolymer composition comprises: hydrogenating a poly (ethylene oxide-co-tetrahydrofuran ether) glycol to an alpha-omega-diamino poly (ethylene oxide-co-tetramethylene oxide ether) random copolymer at a temperature of about 150 ℃ to about 300 ℃ and a total pressure of about 1500psig to about 4000psig (about 10,400kPa to about 27,700kPa) in the presence of a molar ratio of ammonia to poly (ethylene oxide-co-tetramethylene oxide ether) glycol of about 10: 1 to about 150: 1 and a reductive amination catalyst; and recovering the alpha, omega-monoaminopoly (oxyethylene-co-tetrahydrofuranyl ether) random copolymer.

Among other things, one embodiment of an epoxy resin curing agent includes an alpha, omega-diamino poly (ethylene oxide-co-tetrahydrofuran ether) random copolymer composition described herein.

Among other things, one embodiment of curing an epoxy resin curing agent includes contacting an epoxy resin with a polyetheramine described herein.

Among other things, one embodiment of a curing process for preparing polyureas includes contacting a polyisocyanate with a polyetheramine as described herein.

Detailed description of the invention

Unless defined otherwise, all technical and scientific terms used have the same meaning as commonly understood by one of ordinary skill in the art to which this disclosure belongs. Although any methods and materials similar or equivalent to those described can also be used in the practice or testing of the present disclosure, the preferred methods and materials are now described.

All publications and patents cited in this specification are herein incorporated by reference as if each individual publication or patent were specifically and individually indicated to be incorporated by reference and were incorporated herein by reference to disclose and describe the methods and/or materials in connection with which the publications were cited. The citation of any publication is for its disclosure prior to the filing date of the present application and should not be construed as an admission that the present invention is not entitled to antedate such publication by virtue of prior disclosure. Further, the dates of publication provided may be different from the actual publication dates which may need to be independently confirmed.

As will be apparent to those of skill in the art upon reading this disclosure, each of the individual embodiments described and illustrated has discrete components and features that may be readily separated from or combined with the features of any of the other several embodiments without departing from the scope or spirit of the present disclosure. Any described method may be performed in the order of events described or in any other order that is logically possible.

Unless otherwise indicated, embodiments of the present disclosure employ chemical techniques that are within the skill of the art, and so forth. These techniques are well described in the literature.

Unless otherwise indicated: parts are parts by weight, concentration in% is weight%, temperature is in ° c, and pressure is in atmospheric pressure. The pressures reported as pounds per square inch gauge (psig) comprise one atmosphere (14.7 psig) of pressure. One atmosphere is equivalent to 14.7 psig absolute or 0 psig. The standard temperature and pressure are defined as 25 ℃ and 1 atmosphere.

It is to be understood that this disclosure is not limited to particular materials, reagents, reactive materials, manufacturing processes, etc., as such may, unless otherwise specified, vary. It is also to be understood that the terminology used is for the purpose of describing particular embodiments only, and is not intended to be limiting. It is also possible in the present disclosure that the steps may be performed in a different order, where logically possible.

As used herein, for the purposes of the specification and appended claims, the singular forms "a," "an," and "the" include plural referents unless the context clearly dictates otherwise. Thus, for example, reference to "a vector" includes a plurality of vectors. In this specification and in the claims which follow, reference will be made to a number of terms which shall be defined to have the following meanings unless an intention to the contrary is apparent.

Discussion of the invention

Embodiments of the present disclosure include polyetheramines, methods of making polyetheramines, methods of using polyetheramines, and the like. Embodiments of the present disclosure provide a process for preparing a polyetheramine, i.e., an amine-terminated random copolymer of Ethylene Oxide (EO) and Tetrahydrofuran (THF), by reductive amination of a diol copolymer starting material with hydrogen and ammonia in contact with a suitable catalyst. The polyetheramine may have about 25 to about 75 mole percent EO units and/or may have greater than 90% primary amine end groups. Unlike other technologies, the polyetheramines of the present disclosure have very low amounts of secondary amine end groups (i.e., very high amounts of primary amine end groups) and would be desirable for epoxy curing and for the preparation of polyureas and polyurethanes. In addition, other techniques do not use Tetrahydrofuran (THF), and the use of THF is beneficial because it does not produce unbranched segments in copolymers formed using THF. Furthermore, embodiments of the present disclosure provide a cost effective method for the preparation of the polyetheramines described herein.

One embodiment of the present disclosure includes polyetheramines containing predominantly unblocked primary amine termini that can impart lower viscosity to the curing agent system and increase flexibility and toughness when used in the curing, crosslinking, and hardening of epoxy resins.

In one embodiment, the polyetheramine has from about 25 to about 75 mole percent EO units and greater than 90 percent primary amine end groups. In one embodiment, the polyetheramine may be an alpha, omega-monoamino poly (ethylene oxide-co-tetrahydrofuran ether) random copolymer composition having from about 25 to about 75 mole percent ethylene oxide units.

Embodiments of polyetheramines, or poly (ethylene oxide-co-tetrahydrofuran ether) diamines, may result from the reductive amination of random copolymers of Ethylene Oxide (EO) and Tetrahydrofuran (THF). In one embodiment, the copolymer is a random poly (oxyethylene-co-tetrahydrofuran ether) glycol and may be derived from the random copolymerization of Ethylene Oxide (EO) and Tetrahydrofuran (THF).

In one embodiment, the poly (oxyethylene-co-tetrahydrofurfuryl ether) glycol may be represented in structure by formula I:

H((OCH₂CH₂)_a(OCH₂CH₂CH₂CH₂)_b)_cOH

wherein a and b may each independently be an integer equal to or greater than 1, the ratio of a/b may be about 0.33 to about 3.0, and c may be an integer equal to or greater than 2, and the average value of c may be about 4 to about 26. In one embodiment, the diol of formula I may have a number average molecular weight of from about 500 to about 3000 daltons, from about 1000 to about 2500 daltons, or from about 1500 to about 2500 daltons. In one embodiment, the diol of formula I may have from about 25 to about 75 mole percent ethylene oxide units, from about 30 to about 65 mole percent ethylene oxide units, or from about 40 to about 55 mole percent ethylene oxide units.

One embodiment of the polyetheramine is structurally represented by formula II:

-((OCH₂CH₂)_a(OCH₂CH₂CH₂CH₂)_b)_cNH₂

wherein a and b are each integers equal to or greater than 1, the ratio of a/b is from about 0.33 to about 3.0, and c is an integer equal to or greater than 2, and the average value of c is from about 4 to about 26.

In one embodiment, the polyetheramine diamine (polyetheramine of formula II or an α, ω -diamino poly (ethylene oxide-co-tetrahydrofuran ether) random copolymer composition) may have a number average molecular weight of about 500 to about 3000 daltons or about 1000 to about 2500 daltons.

In one embodiment, the polyetheramine diamine (polyetheramine of formula II or an α, ω -diamino poly (ethylene oxide-co-tetrahydrofuran ether) random copolymer composition) may have from about 25 to about 75 mole%, from about 30 to about 65 mole%, or from about 40 to about 55 mole% of ethylene oxide units.

In one embodiment, the amine end groups of the polyetheramine diamine (polyetheramine of formula II or an α, ω -diamino poly (ethylene oxide-co-tetrahydrofuran ether) random copolymer composition) may have greater than about 85% primary amine groups, greater than about 90% primary amine groups, or greater than about 95% primary amine groups.

In one embodiment, the amine end groups of polyetheramine diamines (polyetheramine of formula II or alpha, omega-diamino poly (ethylene oxide-co-tetrahydrofuran ether) random copolymer compositions) may have such amine end groups: less than about 15% secondary amine groups, less than about 10% secondary amine groups, or less than about 5% secondary amine groups.

In one embodiment, the polyetheramine diamine (polyetheramine of formula II or an α, ω -diamino poly (ethylene oxide-co-tetrahydrofuran ether) random copolymer composition) may have a polydispersity index of about 1.5 to about 2.5 or about 1.8 to about 2.3 for the random copolymer.

In one embodiment, the polyetheramine diamine (polyetheramine of formula II or an α, ω -diamino poly (ethylene oxide-co-tetrahydrofuran ether) random copolymer composition) can have a combination of the features described above (e.g., number average molecular weight, mole% ethylene oxide units, primary amine groups, amine end groups, and polydispersity index of the random copolymer).

In some examples of the disclosure, the diol of formula I may be converted to a polyetheramine (polyetheramine of formula II or an α, ω -diamino poly (ethylene oxide-co-tetrahydrofuran ether) random copolymer composition) by reductive amination in the presence of ammonia, hydrogen, and a catalyst at elevated temperature and pressure.

In one embodiment, the α, ω -diamino poly (ethylene oxide-co-tetrahydrofuran ether) random copolymer composition may be prepared by reductive amination of poly (ethylene oxide-co-tetrahydrofuran ether) glycol in the presence of ammonia, hydrogen, and a reductive amination catalyst at elevated temperature and elevated total pressure. In one embodiment, the molar ratio of ammonia to poly (oxyethylene-co-tetrahydrofurfuryl ether) glycol may be greater than the stoichiometric amount of ammonia required to complete the hydroxyl-terminal to amine-terminal conversion.

The reductive amination process is effectively carried out in a slurry catalyst system or in a fixed bed system, wherein the latter can be operated in trickle bed or submerged bed mode.

The reductive amination catalyst may comprise a cobalt or nickel catalyst, which may be present as a supported catalyst, and the support material may be silica, alumina or silicaAlumina, or as a mixture ofCobalt or nickel catalysts are typically referred to as skeletal metal catalysts. The cobalt or nickel catalyst may also contain other metals, such as copper, chromium or molybdenum, as promoters for the reductive amination reaction.

The source of hydrogen can be molecular hydrogen, a gas stream containing a high concentration of hydrogen (e.g., greater than about 80 mole percent hydrogen), and a gas mixture containing hydrogen and other gaseous compounds that are inert in the reductive amination reaction, such as nitrogen, argon, or helium.

An excess of ammonia (higher than the molar equivalent needed to complete the hydroxyl-to-amine-terminal conversion) is effective to promote high conversion of hydroxyl end groups and high selectivity for primary amine formation. The amount of ammonia can include a molar ratio of ammonia to starting polyether diol of greater than 10: 1, such as from about 30: 1 to about 150: 1, from about 30: 1 to about 100: 1, or from about 30: 1 to about 60: 1.

Conditions for reductive amination can include a temperature of about 150 ℃ to about 300 ℃ (e.g., about 170 ℃ to about 220 ℃ or about 190 ℃ to about 210 ℃) and a total pressure (including vapor pressures of ammonia and hydrogen) of about 1500psig to about 4000psig (about 10,400kPa to about 27,700kPa) or about 2500psig to about 3500psig (about 17,235kPa to about 24,132 kPa).

The amine-terminated EO-THF copolymers or polyetheramines of the present disclosure may be used as curing, crosslinking or hardening agents in the form of pure polyetheramines, as blends with other amines, or as so-called adducts of polyetheramines with epoxy resins, where these amine curing agents are used to cure, crosslink or harden the epoxy resin, including, for example, coatings, adhesives or composites.

Blends of the polyetheramines of the present disclosure with other polyamines, such as amine-terminated polypropylene oxide or triamines prepared, for example, by reaction of propylene oxide with a triol initiator followed by hydroxyl amination of the terminal groups are most suitable because these blends allow a balance between processing and performance parameters in the final cured article.

In one embodiment, the polyetheramines of the present disclosure may contain unhindered di-primary amine groups, which may impart a specific ratio to epoxy resin formulations by using amine-terminated polyoxypropylene glycols, such as amine-terminated polypropylene glycols, e.g., under the trademark POWDERFaster cure is obtained with those sold by the D series amines. Polyetheramines can impart lower viscosity to the curing agent system than that produced by amine-terminated polytetramethylene glycol curing agents, and can also provide a good balance of performance and handling properties, particularly in composite applications, as well as increased flexibility, toughness, and fracture resistance, while reducing crack propagation.

The amine curing agent may be combined with an epoxy resin, which is a polyepoxide containing about 2 or more 1, 2-epoxy groups per molecule. Such Epoxides are described in y.tanaka, "Synthesis and characterization of Epoxides (syntheses and characterization of Epoxides)", edited by c.a.may, Epoxy Resins Chemistry and technology (Marcel Dekker 1988). Examples of commercially available epoxy resins include, but are not limited to,825(Hexion)，826(Hexion)，383(Dow)。

other applications of the polyetheramines of the present disclosure may include their use in the preparation of polyureas and polyurethanes, especially for use in RIM or spray processes, which may be used to prepare castings, coatings, adhesives or sealants.

Another application of the polyetheramines of the present disclosure includes their use in the preparation of copoly (ether-amides), which may be used, for example, to prepare thermoplastic polyamide elastomers suitable for use in forming elastic shaped articles such as fibers with enhanced dyeability.

Poly (oxyalkylene) polyamines (also known as polyetheramines or amine-terminated polyethers) have previously been reported as curing agents (hardeners, crosslinkers) for use in various epoxy resins in applications such as coatings, adhesives and composites. See, for example, the Huntsman Technical Bulletin as a curing agent for epoxy resins used in composite materialsAmine (A), (B), (C) and (C)4mines as CuringAgents for Epoxy Resins in Composites)。

The amine-terminated EO-THF copolymers of the present disclosure can be used as novel curing agents for epoxy resins in the preparation of polyureas and polyurethanes, and in the preparation of copoly (ether-amides).

Test method

The amine-terminated EO-THF copolymers of the present disclosure are prepared by analytical techniques including titration of amine end groups with standardized acids, for example using ASTM test methods D2074-07[ 2007; standard Test Methods for Total, Primary, Secondary and Tertiary amine values of Fatty Amines (Standard Test Methods for Total, Primary, Secondary, and Tertiary amine values of Fatty Amines) by Alternative Indicator Methods.

Use of IR spectroscopy and as required as known to those skilled in the art¹³Method of C NMR spectroscopy.

The reaction products were characterized and analyzed using Gas Chromatography (GC) and proton NMR (nuclear magnetic resonance) in a manner known to those skilled in the art.

All Gas Chromatography (GC) analyses can be performed using an AGILENT TTECHNOLOGIES6890 equipped with an AGILENT DB-5 or DB-1701 column, a helium (He) carrier gas, and a flame ionization detector.

All NMR analyses can be performed using a VARIAN, Inc.500-MR (500MHz magnet) or 600-MR (600MHz magnet) spectrometer and software.

Examples

The following examples are put forth so as to provide those of ordinary skill in the art with a complete disclosure and description of how the disclosed and claimed methods and compositions and compounds are made and used. Efforts have been made to ensure accuracy with respect to numbers (e.g., amounts, temperature, etc.) but some errors and deviations should be accounted for.

The following examples are provided to illustrate embodiments of the present disclosure. The examples are not intended to limit the scope of the present disclosure and should not be so interpreted.

Example 1 preparation of polyetheramine by reductive amination of EO-THF copolymer, MW about 2050

A300 cc stirred autoclave was charged with 60.0g of EO-THF (49 mole% EO) random copolymer, MW 2060, and 10.0g of washed (with DI water until the wash water was neutral) and dried2724 cobalt catalyst mixture. The autoclave was purged with nitrogen, sealed, and 25g of ammonia was added to the autoclave. The stirrer was started and run at 1000rpm and hydrogen was added to the autoclave to give an initial internal pressure of about 650psi gauge (psig) at room temperature. The autoclave was heated to 190 ℃ and hydrogen was added until the internal pressure of the autoclave was about 2500 psig. The mixture was stirred and heated for at least 7 hours, after which the autoclave was cooled to room temperature, evacuated to atmospheric pressure, and 200ml THF was added to dissolve the product. The product mixture was filtered to remove the catalyst and the THF filtrate was stripped under vacuum to give the desired polyetheramine product. The polyetheramine product contains > 90% primary amine end groups.

Example 2 preparation of polyetheramine by reductive amination of EO-THF copolymer, MW about 2050

A 300cc stirred autoclave was charged with a mixture of: 50.0g of EO-THF (49 mole% EO) random copolymer, MW 2049, and 10.0g of finely ground Johnson Matthey HTC Co2000 cobalt catalyst containing about 25% cobalt/cobalt oxide and about 75% alumina. The autoclave was purged with nitrogen, sealed, and 25g of ammonia was added to the autoclave. The stirrer was started and run at 1000rpm and hydrogen was added to the autoclave to give an initial internal pressure of about 650psi gauge (psig) at room temperature. The autoclave was heated to 200 ℃ and hydrogen was added until the internal pressure of the autoclave was about 2500 psig. The mixture was stirred and heated for at least 8 hours, after which the autoclave was cooled to room temperature, evacuated to atmospheric pressure, and 200ml THF was added to dissolve the product. The product mixture was filtered to remove the catalyst and the THF filtrate was stripped under vacuum to give the desired polyetheramine product. The polyetheramine product contains > 90% primary amine end groups.

Example 3 preparation of polyetheramines by reductive amination of EO-THF copolymers, MW about 2500

A300 cc stirred autoclave was charged with 60.0g of EO-THF (37 mole% EO) random copolymer, MW 2539, and 10.0g of washed (with DI water until the wash water was neutral) and dried2724 cobalt catalyst mixture. The autoclave was purged with nitrogen, sealed, and 25g of ammonia was added to the autoclave. The stirrer was started and run at 1000rpm and hydrogen was added to the autoclave to give an initial internal pressure of about 650psig at room temperature. Applying high pressureThe kettle was heated to 190 ℃ and hydrogen was added until the internal pressure of the autoclave was about 2500 psig. The mixture was stirred and heated for at least 7 hours, after which the autoclave was cooled to room temperature, evacuated to atmospheric pressure, and 200ml THF was added to dissolve the product. The product mixture was filtered to remove the catalyst and the THF filtrate was stripped under vacuum to give the desired polyetheramine product. The polyetheramine product contains > 90% primary amine end groups.

Example 4-use of the polyetheramine of example 1 with a commercial curing agentT-403 triamine (Huntsman) blended epoxy resin cure

6.2g of polyetheramine (example 1, amine hydrogen equivalent 515) are reacted with 46g of polyetheramineT-403 triamine (amine hydrogen equivalent of 81) was mixed and the amine curing agent blend was mixed with 100g of liquid epoxy resin, epoxide equivalent of 179, cast into a standard "dog bone" test specimen and cured at 80 ℃ for two hours and at 125 ℃ for three hours. And use ofD-2000 diamine andcomparative blends of T-403 triamine curative, test samples prepared by the same procedure, the test samples exhibiting increased flexural strength and increased fracture resistance.

While various aspects and embodiments have been disclosed, other aspects and embodiments will be apparent to those skilled in the art. The disclosure of various aspects and embodiments is for purposes of illustration and is not intended to be limiting, with the true scope and spirit being indicated by the following claims.

It should be noted that ratios, concentrations, amounts, and other numerical data may be expressed or presented herein in a range format. It is to be understood that such range format is used for convenience and brevity, and thus, should be interpreted in a flexible manner to include not only the numerical values explicitly recited as the limits of the range, but also to include all the individual numerical values or sub-ranges encompassed within that range as if each numerical value and sub-range is explicitly recited. For example, a concentration range of "about 0.1% to about 5%" should be interpreted as: not only are concentrations of about 0.1% to about 5% by weight explicitly recited, but also individual concentrations (e.g., 1%, 2%, 3%, and 4%) and subranges (e.g., 0.5%, 1.1%, 2.2%, 3.3%, and 4.4%) within the indicated range. The term "about" can include ± 1%, ± 2%, ± 3%, ± 4%, ± 5%, ± 8% or ± 10% of the modified value or values. Further, the phrase "about ' x ' to ' y '" includes "about ' x ' to about ' y".

Claims (15)

1. An alpha, omega-diamino poly (ethylene oxide-co-tetrahydrofuran ether) random copolymer composition comprising from 25 to 75 mole percent ethylene oxide units, wherein the amine end groups of the copolymer comprise greater than 90 percent primary amine groups.

2. An α, ω -diamino poly (ethylene oxide-co-tetrahydrofuran ether) random copolymer composition comprising a polyetheramine composition according to formula II:

-((OCH₂CH₂)_a(OCH₂CH₂CH₂CH₂)_b)_cNH₂(formula II)

Wherein:

a and b are each an integer equal to or greater than 1;

b.a/b ratio of 0.33 to 3.0;

c.c is an integer equal to or greater than 2; and is

C has an average value of 4 to 26;

wherein the amine end groups of the polyetheramine composition according to formula II comprise greater than 90% primary amine groups.

3. The composition of claim 1 or 2, wherein the random copolymer has a polydispersity index of 1.5 to 2.5.

4. The composition of any one of claims 1 to 2 having a number average molecular weight of 500 to 3000 daltons.

5. The composition of claim 4 having a number average molecular weight of 1000 to 2500 daltons.

6. A method of making an α, ω -diamino poly (ethylene oxide-co-tetrahydrofuran ether) random copolymer composition wherein the amine end groups of the copolymer comprise greater than 90% primary amine groups, the method comprising reductive amination of poly (ethylene oxide-co-tetrahydrofuran ether) glycol in the presence of ammonia, hydrogen, and a reductive amination catalyst at a temperature of 150 ℃ to 300 ℃ and a total pressure of 1500psig to 4000 psig.

7. The process of claim 6 wherein the amination catalyst comprises cobalt, nickel or a cobalt/nickel mixture.

8. The process of claim 7 wherein the amination catalyst further comprises a metal promoter.

9. The method of any one of claims 6 to 8, wherein the molar ratio of ammonia to poly (oxyethylene-co-tetrahydrofurfuryl ether) glycol is greater than the stoichiometric amount of ammonia required for complete conversion of hydroxyl end to amine end.

10. The method of claim 9, wherein the molar ratio of ammonia to poly (oxyethylene-co-tetrahydrofurfuryl ether) glycol is 10: 1 to 150: 1.

11. The method of claim 10, wherein the molar ratio of ammonia to poly (oxyethylene-co-tetrahydrofurfuryl ether) glycol is 30: 1 to 150: 1.

12. A method of making an α, ω -diamino poly (ethylene oxide-co-tetrahydrofuran ether) random copolymer composition, the method comprising:

a. hydrogenating poly (ethylene oxide-co-tetrahydrofuran ether) glycol at a temperature of 150 ℃ to 300 ℃ and a total pressure of 1500psig to 4000psig in the presence of ammonia to poly (ethylene oxide-co-tetrahydrofuran ether) glycol and a reductive amination catalyst in a molar ratio of 10: 1 to 150: 1 to form an alpha-omega-diamino poly (ethylene oxide-co-tetrahydrofuran ether) random copolymer; and

b. recovering the alpha, omega-diamino poly (ethylene oxide-co-tetrahydrofuran ether) random copolymer.

13. An epoxy resin curing agent comprising the α, ω -diamino poly (ethylene oxide-co-tetrahydrofuran ether) random copolymer composition of any one of claims 1 to 5.

14. A method of curing an epoxy resin, the method comprising contacting the epoxy resin with the epoxy resin curing agent of claim 13.

15. A method of preparing a polyurea comprising contacting a polyisocyanate with the α, ω -diamino poly (ethylene oxide-co-tetrahydrofuran ether) random copolymer composition of any one of claims 1 to 5.