Patent Publication Number: US-2016244563-A1

Title: Hybrid epoxy-amine hydroxyurethane-grafted polymer

Description:
BACKGROUND OF THE INVENTION 
     1. Field of the Invention 
     The disclosed embodiments relate to hybrid epoxy-amine-hydroxyurethane network polymers with lengthy epoxy-amine chains and pendulous hydroxyurethane units. These hybrid polymers combine increased flexibility with well balanced physical-mechanical and physical-chemical properties of conventional epoxy-amine systems and may be used, for example, for manufacturing of synthetic/artificial leather and sport monolithic floorings. 
     2. Description of the Related Art 
     Preparing of polymers with a specific topological structure of polymer chains is a perspective way of creating materials with needed properties. 
     Conventional epoxy-amine formulations are used as precursors for three-dimensional cross-linked networks. Chemical formation of resin-hardener networks used in case of bifunctional epoxy resins and tetrafunctional amine hardeners and the structures of the obtained networks are described in H. Q. Pham, M. J. Marks. Epoxy resins. In the book: Encyclopedia of Polymer Science and Technology. Copyright John Wiley &amp; Sons, Inc., 3 rd  ed., 2004, Vol. 9, pp. 678-804_P. 721 
     
       
         
         
             
             
         
       
     
     Structural Schemes of resin formation—hardener networks for epoxy-amine thermoset polymers are shown in Scheme 2 [H. Q. Pham, M. J. Marks. Epoxy resins. In the book: Encyclopedia of Polymer Science and Technology. Copyright John Wiley &amp; Sons, Inc., 3 rd  ed., 2004, Vol. 9, pp. 678-804_P. 749]: 
     
       
         
         
             
             
         
       
     
     Thermoplastic resins based on epoxy and amine monomers are also known in the art. For example, U.S. Pat. No. 3,317,471 issued in 1967 to Johnson et al. discloses polymers based on diglycidyl ethers of polyhydric phenols and compounds such as alkanolamines and anilines having two amino hydrogen atoms per molecule. The process is carried out at extremely conditions: in a melt at a temperature of up to 250° C. or in a solution at a temperature of up to 200° C. 
     U.S. Pat. No. 5,275,853 issued in 1994 and U.S. Pat. No. 5,464,924 issued in 1995, both to Silvis, et al. disclose thermoplastic polyetheramines (TPEA) having aromatic ether/amine repeating units in their backbones and pendant hydroxyl moieties. Such polyetheramines are prepared by reacting diglycidyl ethers of dihydric aromatic compounds such as the diglycidyl ether of bisphenol-A (DGEBA), hydroquinone, or resorcinol with amines having no more than two amine hydrogen atoms per molecule, such as piperazine, monoethanolamine (MEA), and mono-amine-functionalized poly(alkylene oxide). These polyetheramines are thermoplastic polymers and have an improved barrier to oxygen and a relatively high flexural strength and modulus. The disadvantage of these products is that they can be processed or melted at temperatures of 150 to 200° C. by using only special equipment, or solutions in high-boiling toxic solvents. A fragment of a TPEA polymer chain is shown below by Scheme 3. 
     
       
         
         
             
             
         
       
     
     Scheme 3 is described in “Elementary unit of the TPEA polymer chain on the base of DGEBA and MEA.” [Ha. Q. Pham, Maurice J. Marks. Epoxy resins. In the book: Encyclopedia of Polymer Science and Technology. Copyright John Wiley &amp; Sons, Inc., 3 rd  ed., 2004, Vol. 9, P. 697]. 
     It is known in the art to use hydroxyurethanes for improving some properties of thick cross-linked epoxy polymer networks. For example, U.S. Pat. No. 6,120,905 issued in 2000 to Figovsky describes certain polyhydroxyurethane networks that are produced based on reactions between oligomers comprising terminal cyclocarbonate groups and oligomers comprising terminal primary amine groups. Oligomers comprising terminal cyclocarbonate groups are the products of epoxy resins reacting with carbon dioxide in the presence of a catalyst, the conversion of epoxy groups into cyclocarbonate groups being 85 to 95%. 
     U.S. Pat. Application Publication No. 20100144966 published in 2010 (inventors: Birukov, et al.) discloses a liquid cross-linkable oligomer composition that contains a hydroxyurethane-amine adduct and a liquid-reacting oligomer. The hydroxyurethane-amine adduct is a product of an epoxy-amine adduct reacting with a compound having one or more terminal cyclocarbonate groups. 
     U.S. Pat. No. 7,232,877 issued in 2007 to Figovsky, et al. describes a method and an apparatus for synthesis of oligomeric cyclocarbonates and their use in making a star-shaped structure of the polymer network. 
     U.S. Pat. No. 7,989,553 issued in 2011 to Birukov, et al. discloses three-dimensional epoxy-amine polymer networks modified by a hydroxyalkyl urethane, which is obtained as a result of a reaction between a primary amine (one equivalent of the primary amine groups) and a monocyclic carbonate (one equivalent of the cyclic carbonate groups). Such hydroxyalkyl urethane modifier is not bound chemically to the main polymer network and is represented by the following formula (1): 
     
       
         
         
             
             
         
       
     
     wherein R 1  is a residue of the primary amine, R 2  and R 3  are the same or different and are selected from the group consisting of H, alkyl, and hydroxyalkyl, and n satisfies the following condition: n≧2. 
     U.S. Pat. No. 5,235,007 issued in 1993 to Alexander, et al. describes an epoxy resin composition that comprises a cured reaction product of an epoxy base resin and a curing agent mixture. The curing agent mixture comprises a di-primary amine or polyamine and an aminohydroxyurethane (aminocarbamate) which is the reaction product of the amine and a cyclic carbonate and is represented by the following formula (2): 
     
       
         
         
             
             
         
       
     
     where R 1  is a residue of the di-primary amine or polyamine that may consist additional free amine hydrogen atoms, R 2  and R 3  are selected from the group consisting of H and alkyl, and at least one of R 2  and R 3  is hydrogen. The amine has a molecular weight of 60 to 400. Preferred carbonates are ethylene carbonate and propylene carbonate. A preferred curative comprises a mixture of amine and aminocarbamate used in a molar ratio of 1:1 to 2:1. 
     Thus, although the hardener comprises the aminohydroxyurethane, a pure amine is an indispensible main component of this hardener, and the final polymer has a thermoset cross-linked structure. 
     Thick cross-linked networks are also typical for epoxy-amino-hydroxyurethane compositions described in U.S. Pat. No. 5,677,006 issued in 1997; U.S. Pat. No. 5,707,741 issued in 1998; U.S. Pat. No. 5,855,961 issued in 1999; and U.S. Pat. No. 5,935,710 issued, in 1993, all to Hoenel, et al., all of which are incorporated by reference. 
     A method of obtaining urethane-modified amines is presented by G. Rokicki and R.  aziński in “Polyamines Containing β-Hydroxyurethane Linkages as Curing Agents for Epoxy Resin”,  Die Angewandte Makromolekulare Chemie,  1989, Vol. 170, No. 1, 211 to 225 (Nr. 2816). 
     Triethylene tetramine (TETA) was modified by different mono- and di-cyclic carbonates at mole ratios TETA:carbonate from 1:1 to 4:1 and temperature 50-60° C. for 2-12 hours, thus aminohydroxyurethanes were obtained. The results of physical and mechanical investigations of an epoxy resin crosslinked with the aminohydroxyurethanes show increase of strength features of the cured systems. However flexible materials were not obtained, and values of elongation at break were not more than 8%. 
     A detailed review of polyhydroxyurethane networks and methods of preparation thereof are presented by O. Figovsky and L. Shapovalov in “Cyclocarbonate-based Polymers Including Non-Isocyanate Polyurethane Adhesives and Coatings”,  Encyclopedia of Surface and Colloid Science , Somasundaran. P. (Ed), V. 3, 1633 to 1653, New York, Taylor &amp; Francis, 2006 and by O. Figovsky, L. Shapovalov, A. Leykin, O. Birukova, R. Potashnikova in “Advances in the field of nonisocyanate polyurethanes based on cyclic carbonates.  Chemistry  &amp;  Chemical Technology,  2013, V. 7, No. 1, P. 79-87. 
     A new polysiloxane-modified polyhydroxy polyurethane resin derived from a reaction between a 5-membered cyclic carbonate compound and an amine-modified polysiloxane compound is disclosed in U.S. Pat. No. 8,703,648 issued in 2014 to Hanada, et al. The production process and resin compositions for thermal recording medium, imitation leather, thermoplastic polyolefin resin skin material, weather strip material, and weather strip also have been described. 
     Such polymers have in their backbones only hydroxyurethane units but not epoxy-amine. A disadvantage of the disclosed method is an inconvenience in preparation of a polyhydroxy polyurethane resin, namely the long-time use (30 hours for first stage and 10 hours for second stage) of a toxic solvent (N-methylpyrrolidone) at 80-90° C. and subsequent separation of the product from the solvent. Another disadvantage is the use of toxic polyisocyanates for crosslinking of resins. 
     Different variations of the aforementioned composition and method are also disclosed in other patent publications of Hanada, et al. (US Pat. Application Publication 20140024274 published in 2014; US Pat. Application Publication 20130171896 published in 2013; US Pat. Application Publication 20120232289 published in 2012; and US Pat. Application Publication 20120231184 published in 2012). 
     SUMMARY OF THE INVENTION 
     An object of the present invention is to provide a novel structure of a cured epoxy-amine hydroxyurethane-grafted polymer which contains main backbone of the following formula (3): 
     
       
         
         
             
             
         
       
     
     where R′ is a residue of a diglycidyl ether (epoxy resin); R 1  is a residue of the di-primary amine; R 2  and R 3  are residues of monocyclic carbonate and are selected from the group consisting of H, alkyl C 1 -C 2 , hydroxymethyl, and at least one of R 2  and R 3  is hydrogen. 
     The schematic structural formula of the novel polymer is the following: 
     
       
         
         
             
             
         
       
     
     where E-R′-E is a residue of a diglycidyl ether, which reacted with amine hydrogens, 
     E is a converted epoxy gro 
     N is a nitrogen atom, 
     A is a residue of a di-primary amine, 
     U(OH) is a hydroxyurethane group, and 
     ═N-A-U(OH) is a residue of aminohydroxyurethane formula 2 with the number of free amine hydrogen atoms equal 2. 
     Another object of the invention is to provide a novel cured epoxy-amine hydroxyurethane-grafted polymer by using a small amount of polyfunctional compounds for creating a controlled number of cross-links, wherein the polyfunctional compounds are selected from the group consisting of polyfunctional epoxy resins, aminohydroxyurethane formula 2 with a number of free amine hydrogen atoms more than 2, and combinations thereof. 
     A schematic structural formula of the novel polymer with the directions of the possible cross-links (shown by arrows) is the following: 
     
       
         
         
             
             
         
       
     
     where 
     
       
         
         
             
             
         
       
     
     is a residue of the polyfunctional epoxy resin, other designations being the same as above. Polyamines with a number of free amine hydrogen atoms more than 2 also may be used for cross-linking. 
    
    
     DETAILED DESCRIPTION OF THE INVENTION 
     This invention relates mainly to a linear hybrid epoxy-amine hydroxyurethane-grafted polymer with the following structure of the polymer backbone unit: 
     
       
         
         
             
             
         
       
     
     where a is a residue of a diglycidyl ether (epoxy resin); R 1  is a residue of a di-primary amine; R 2  and R 3  are residues of monocyclic carbonate and are selected from the group consisting of H, alkyl C 1 -C 2 , and hydroxymethyl; and at least one of R 2  and R 3  is hydrogen. 
     The schematic structural formula of the novel polymer is the following: 
     
       
         
         
             
             
         
       
     
     where E-R′-E is a residue of the diglycidyl ether, which reacted with amine hydrogens,
         E is a converted epoxy group, i.e., —CH 2 —CH(OH)—CH 2 —O—,   N is a nitrogen atom,   A is a residue of a di-primary amine,   U(OH) is a hydroxyurethane group, i.e., —R 1 —NH—CO—O—CH(R 2 )—CH(OH)—R 3 , and   ═N-A-U(OH) is a residue of aminohydroxyurethane formula 2 with the number of free amine hydrogen atoms equal 2.       

     The diglycidyl ethers used in this process are selected from the group consisting of aliphatic diglycidyl ethers, cycloaliphatic diglycidyl ethers, aromatic diglycidyl ethers, polyoxyalkylene diglycidyl ethers, and combinations thereof. 
     More specifically, the diglycidyl ether may comprise a diglycidyl ether of bisphenol-A or bisphenol-F, hydrogenated diglycidyl ether of bisphenol-A, 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, neopentyl glycol diglycidyl ether, cyclohexanedimethanol diglycidyl ether, polypropylene glycol diglycidyl ether, dipropylene glycol diglycidyl ether, ethylene glycol diglycidyl ether, and combinations of the aforementioned compounds. 
     The primary diamines used in the process are selected from the group consisting of aliphatic primary diamines, cycloaliphatic primary diamines, aromatic-aliphatic primary diamines, polyoxyalkylene primary diamines, and combinations thereof. 
     More specifically, the primary diamine may comprise 2,2,4-(2,4,4)-trimethyl-1,6-hexanediamine, 1,6-hexanediamine, 2-methyl-1,5-pentanediamine, isophorone diamine, cyclohexane diamine, 4,4′-diaminodicyclohexyl-methane, meta-xylylene diamine, polyoxyethylene diamines, polyoxypropylene diamines, polyoxybutylene diamines, and combinations thereof. The monocyclic carbonate used in the process is selected from the group consisting of ethylene carbonate, propylene carbonate, butylene carbonate, glycerine carbonate. 
     The hybrid epoxy-amine hydroxyurethane-grafted polymer of a novel structure is obtained by curing a liquid oligomer composition which consists of diglycidyl ether and aminohydroxyurethane of structural formula (2) with the number of free amine hydrogen atoms equal to 2: 
     
       
         
         
             
             
         
       
     
     wherein R 1  is a residue of the di-primary amine, R 2  and R 3  are residues of monocyclic carbonate and are selected from the group consisting of H, alkyl C 1 -C 2 , hydroxymethyl, wherein at least one of R 2  and R 3  is hydrogen, and wherein the diglycidyl ether and aminohydroxyurethane are at stoichiometric ratio of glycidyl groups and free amine hydrogen atoms. 
     In turn, aminohydroxyurethane is a product of a reaction of di-primary amine and monocyclic carbonate at equimolar ratio, i.e., two primary amine groups are accounted for one cyclic carbonate group. 
     Alternatively, the hybrid epoxy-amine hydroxyurethane-grafted polymer may also have a number of cross-links obtained by introducing into the initial composition some polyfunctional components for controlling the number of cross-links. The polyfunctional components may comprise polyglycidyl compounds with functionality more than 2, aminohydroxyurethanes of formula 2, wherein R 1  is a residue of the polyamine, with number of free amine hydrogen atoms more than 2, and combinations thereof in amounts of no more than 25 eqv. %. 
     More specifically, the polyglycidyl compound may comprise aliphatic polyglycidyl ethers, cycloaliphatic polyglycidyl ethers, aromatic polyglycidyl ethers, polyoxyalkylene polyglycidyl ethers and combinations of the aforementioned compounds. 
     The aminohydroxyurethane with number of free amine hydrogen atoms more than two may comprise monosubstituted hydroxyurethane aliphatic polyamines, monosubstituted hydroxyurethane polyoxyalkylene polyamines and combinations thereof. 
     The schematic structural formula of the novel polymer with the directions of the possible cross-links (shown by arrows) is the following: 
     
       
         
         
             
             
         
       
     
     where 
     
       
         
         
             
             
         
       
     
     is a residue of the polyfunctional epoxy resin, other designations being the same as above. 
     Polyamines that have more than two free amine hydrogen atoms also can be used for cross-linking the polymer of the invention. 
     The following commercially available raw materials are used in the subsequent description: 
     
       
         
           
               
             
               
                 TABLE 1 
               
             
            
               
                   
               
               
                 List of raw materials 
               
            
           
           
               
               
               
               
            
               
                   
                   
                   
                 Abbrevi- 
               
               
                 Name 
                 Manufacturer 
                 Description 
                 ation 
               
               
                   
               
               
                 Epoxy resin 
                 Dow Chemical 
                 Diglycidyl 
                 DER 331 
               
               
                 D.E.R. ® 331 
                 Company, 
                 ether of 
               
               
                 EEW = 187 
                 MI, USA 
                 Bisphenol A 
               
               
                 Epoxy resin 
                 Dow Chemical 
                 Epoxy- 
                 DEN 431 
               
               
                 D.E.N. ® 431 
                 Company, 
                 novolac 
               
               
                 EEW = 175 
                 MI, USA 
                 resin 
               
               
                 Epoxy resin 
                 KUKDO Chemical 
                 Hydrogenated 
                 ST-3000 
               
               
                 ST-3000 
                 Co., Korea 
                 DGEBA 
               
               
                 EEW = 230 
               
               
                 Polypox ® R11 
                 Dow Chemical, 
                 Diglycidyl 
                 R11 
               
               
                 EEW = 175 
                 Germany 
                 ether of 
               
               
                   
                   
                 cyclohexane- 
               
               
                   
                   
                 dimethanol 
               
               
                 Polypox ® R14 
                 Dow Chemical, 
                 Diglycidyl 
                 R14 
               
               
                 EEW = 155 
                 Germany 
                 ether of 
               
               
                   
                   
                 neopentyl 
               
               
                   
                   
                 glycol 
               
               
                 Heloxy ® 48 
                 Momentive 
                 Triglycidyl 
                 H48 
               
               
                 EEW = 145 
                 Specialty 
                 ether of 
               
               
                   
                 Chemicals 
                 trimethylol 
               
               
                   
                 Inc., OH, US 
                 propane 
               
               
                 Jeffsol ® PC 
                 Huntsman Corp., 
                 Propylene 
                 PC 
               
               
                 CCEW = 102 
                 TX, USA 
                 carbonate 
               
               
                 Vestamin ® TMD 
                 Evonik, Germany 
                 2,2,4-(2,4,4)- 
                 TMD 
               
               
                 AEW = 79; 
                   
                 Trimethyl- 
               
               
                 AHEW = 39.5 
                   
                 1,6-hexane- 
               
               
                   
                   
                 diamine 
               
               
                 Jeffamine ® 
                 Huntsman Corp., 
                 Polyoxy- 
                 D-400 
               
               
                 D400, 
                 TX, USA 
                 propylene 
               
               
                 AEW = 230; 
                   
                 diamine 
               
               
                 AHEW = 115 
               
               
                 Jeffamine ® 
                 Huntsman Corp., 
                 Polyoxy- 
                 T-403 
               
               
                 T403 
                 TX, USA 
                 propylene 
               
               
                 AEW = 162; 
                   
                 triamine 
               
               
                 AHEW = 81 
               
               
                 PolyTHF ®Amin 
                 BASF, Germany 
                 Polytetra- 
                 PTHFA 350 
               
               
                 350 
                   
                 hydrofuran 
               
               
                 AEW = 160.3 
                   
                 amine 
               
               
                 AHEW = 88 
               
               
                 MXDA 
                 Mitsubishi Gas 
                 Meta- 
                 MXDA 
               
               
                 AEW = 68; 
                 Chemical Comp., 
                 xylylene- 
               
               
                 AHEW = 34 
                 Japan 
                 diamine 
               
               
                 D.E.H. ® 20 
                 Dow Chemical 
                 Diethylene- 
                 DETA 
               
               
                 AEW = 51.5; 
                 Company, 
                 triamine 
               
               
                 AHEW = 20.6 
                 MI, USA 
               
               
                   
               
               
                 Additional abbreviation: 
               
               
                 1) EEW—epoxy equivalent weight; 
               
               
                 2) AEW—primary amine equivalent weight; 
               
               
                 3) AHEW—amine hydrogen equivalent weight; 
               
               
                 4) CCEW—cyclic carbonate equivalent weight; 
               
               
                 5) f—functionality for epoxy compound. 
               
            
           
         
       
     
     The invention will be further described by way of application examples which, however, should not be construed as limiting the scope of the invention application. 
     EXAMPLES 
     The components participated in the reactions shown in the examples were used in the stoichiometric ratios given below. 
     a) Stoichiometric ratio for a reaction of cyclic carbonate with amine is 1 CCEW:1 AEW. 
     b) Stoichiometric ratio for a reaction of epoxy compound with amine is 1 EEW:1 AHEW. 
     The following hydroxyurethane-amine compounds were synthesized for use in the examples as intermediate products 
     Hydroxyurethane-Monoamine HUMA-1 
     158 g (2.0 AEW) of TMD and 102 g (1.0 CCEW) of PC, equivalent ratio 2:1, were put into a 500 ml flask and then the mixture was stirred for 10 min. The reaction mixture was kept in the flask at room temperature during 3 hours and the consumption of the cyclic carbonate groups was controlled by spectrometer FT/IR (wavelength 1800 cm −1 ). 
     Calculated ANEW of HUMA-1 was 130, f=2. 
     Viscosity (25° C.) was 9.15 Pa·s. 
     Hydroxyurethane-Monoamine HUMA-2 
     136 g (2.0 AEW) of MXDA and 102 g (1.0 CCEW) of PC, equivalent ratio 2:1, were put into a 500 ml flask and then the mixture was stirred for 10 min. The reaction mixture was kept in the flask at room temperature during 3 hours and the consumption of the cyclic carbonate groups was controlled by spectrometer FT/IR (wavelength 1800 cm −1 ). 
     Calculated AHEW of HUMA-2 was 119, f=2. 
     Viscosity (50° C.) was 1.48 Pa·s. 
     Hydroxyurethane-Monoamine HUMA-3 
     230 g (1.0 AEW) of D-400 and 51 g (0.5 CCEW) of PC, equivalent ratio 2:1, were put into a 500 ml flask and then the mixture was stirred at room temperature for 10 min. The reaction mixture was kept in the flask at temperature 90° C. during 6 hours and the consumption of the cyclic carbonate groups was controlled by spectrometer FT/IR (wavelength 1800 cm −1 ). 
     Calculated AHEW of HUMA-3 was 281, f=2. 
     Viscosity (25° C.) was 0.45 Pa·s. 
     Hydroxyurethane-Monoamine HUMA-4 
     175 g (1.0 AEW) of PTHFA 350 and 51 g (0.5 CCEW) of PC, equivalent ratio 2:1, were put into a 500 ml flask and then the mixture was stirred at room temperature for 10 min. The reaction mixture was kept in the flask at temperature 90° C. during 3 hours and the consumption of the cyclic carbonate groups was controlled by spectrometer FT/IR (wavelength 1800 cm −1 ). 
     Calculated AHEW of HUMA-4 was 226, f=2. 
     Viscosity (25° C.) was 0.7 Pa·s. 
     Hydroxyurethane-Polyamine HUPA-1 
     243 g (1.5 AEW) of T-403 and 51 g (0.5 CCEW) of PC, equivalent ratio 3:1, were put into a 500 ml flask and then the mixture was stirred at room temperature for 10 min. The reaction mixture was kept in the flask at temperature 90° C. during 6 hours and the consumption of the cyclic carbonate groups was controlled by spectrometer FT/IR (wavelength 1800 cm −1 ). 
     Calculated ANEW of HUPA-1 was 147, f=4. 
     Viscosity (25° C.) was 3.74 Pa·s. 
     Hydroxyurethane-Polyamine HUPA-2 
     103 g (2.0 AEW) of DETA and 102 g (1.0 CCEW) of PC were put into a 500 ml flask and then the mixture was stirred at room temperature for 10 min. The reaction mixture was kept in the flask at room temperature during 1 hour and the consumption of the cyclic carbonate groups was controlled by spectrometer FT/IR (wavelength 1800 cm −1 ). 
     Calculated ANEW of HUPA-2 was 68.3, f=3. 
     Viscosity (25° C.) was 6.7 Pa·s. 
     Application Example 1 
     17.5 g (0.1 EEW) of R11 and 13.0 g (0.1 AHEW) of HUMA-1 were mixed at RT for 2 minutes. Then the mixture was poured into standard moulds and cured at RT for 7 days. As a result, hybrid epoxy-amine hydroxyurethane-grafted polymer No. 1 was obtained (see Table 2 below). 
     Application Example 2 
     15.5 g (0.1 EEW) of R14 and 11.9 g (0.1 AHEW) of HUMA-2 were mixed at RT for 2 minutes. Then the mixture was poured into standard moulds and cured at RT for 7 days. As a result, hybrid epoxy-amine hydroxyurethane-grafted polymer No. 2 was obtained (see Table 2 below). 
     Application Example 3 
     18.7 g (0.1 EEW) of DER 331 and 28.1 g (0.1 AHEW) of HUMA-3 were mixed at RT for 2 minutes. Then the mixture was poured into standard moulds and cured at RT for 7 days. As a result, hybrid epoxy-amine hydroxyurethane-grafted polymer No. 3 was obtained (see Table 2 below). 
     Application Example 4 
     23.0 g (0.1 EEW) of ST-3000 and 22.6 g (0.1 AHEW) of HUMA-4 were mixed at RT for 2 minutes. Then the mixture was poured into standard moulds and cured at RT for 7 days. As a result, hybrid epoxy-amine hydroxyurethane-grafted polymer No. 4 was obtained (see Table 2 below). 
     Application Example 5 
     19.64 g (0.105 EEW) of DER 331, 2.9 g H48 (0.02 EEW), 12.35 g (0.095 AHEW) of HUMA-1 and 4.4 g (0.03 AHEW) of HUPA-1 were mixed at RT for 2 minutes. Contents of cross-linking agents 20% (by equivalents). As a result, hybrid epoxy-amine hydroxyurethane-grafted polymer No. 5 was obtained (see Table 2 below). Then the mixture was poured into standard moulds and cured at RT for 7 days. 
     Application Example 6 
     14.0 g (0.08 EEW) of R11, 3.5 g DEN 431 (0.02 EEW), 8.3 g (0.07 AHEW) of HUMA-2 and 2.05 g (0.03 AHEW) of HUPA-2 were mixed at RT for 2 minutes. Contents of cross-linking agents 25% (by equivalents). Then the mixture was poured into standard moulds and cured at RT for 7 days. As a result, hybrid epoxy-amine hydroxyurethane-grafted polymer No. 6 was obtained (see Table 2 below). 
     Testing of the hybrid epoxy-amine hydroxyurethane-grafted polymers obtained in Examples 1 to 6 
     The polymerized samples were tested with regard to the following mechanical and chemical properties: 
     Pot Life (2×viscosity) (in accordance with ASTM D1084) 
     Tensile strength (in accordance with ASTM D638M) 
     Ultimate Elongation (in accordance with ASTM D638M) 
     Hardness (Shore D) (in accordance with ASTM D2240) 
     Weight gain at immersion in water (24 h @ 25° C.) (in accordance with ASTM D570) 
     Weight gain at immersion in 20% H 2 SO 4  (24 h @ 25° C.) (in accordance with ASTM D543) 
     The results of the tests are summarized in Table 2 given below. 
     
       
         
           
               
             
               
                 TABLE 2 
               
             
            
               
                   
               
               
                 Properties Data of compositions according examples 1-6. 
               
            
           
           
               
               
            
               
                   
                 Application Examples No. 
               
            
           
           
               
               
               
               
               
               
               
            
               
                 Measured Characteristics 
                 1 
                 2 
                 3 
                 4 
                 5 
                 6 
               
               
                   
               
            
           
           
               
               
               
               
               
               
               
            
               
                 Pot life, min 
                 60 
                 40 
                 60 
                 50 
                 25 
                 30 
               
               
                 Hardness, Shore D 
                 15 
                 20 
                 35 
                 20 
                 44 
                 60 
               
               
                 Tensile strength, MPa 
                 1.1 
                 0.9 
                 3.0 
                 2.4 
                 12 
                 10 
               
               
                 Elongation at break, % 
                 147 
                 130 
                 275 
                 183 
                 72 
                 73 
               
               
                 Weight gain at immersion in 
                 1.1 
                 1.8 
                 0.3 
                 0.3 
                 0.2 
                 0.1 
               
               
                 water (24 h @ 25° C.), % 
                   
                   
                   
                   
                   
                   
               
               
                 Weight gain at immersion in 
                 1.1 
                 1.4 
                 0.6 
                 0.5 
                 0.3 
                 0.1 
               
               
                 10% NaOH (24 h @ 25° C.), % 
               
               
                   
               
            
           
         
       
     
     Practical Example 
     Manufacturing of Synthetic Leather 
     The coating formulations for imitation leathers, which contained the components described in Examples 1 to 3, were separately applied onto paper sheets and cured by drying to form on the paper substrate films of incompletely cured polymer coating having a thickness of 25 μm, respectively. The thus-obtained coated products were cut into separated pieces, applied onto a fabric substrates (see Table 3) and bonded to the substrates under pressure developed by a load. After bonding to the fabric and solidification of the coating, the paper substrates were peeled off. As a result, samples A, B, and C of the synthetic leather shown in Table 3 were obtained. 
     Tensile properties of the samples were determined according ASTM D638. 
     Cold crack resistance was measured according to CFFA-6 (STANDARD TEST METHODS. CHEMICAL COATED FABRICS AND FILM. Chemical Fabrics &amp; Film Association, Inc. Cleveland, 2011). 
     
       
         
           
               
             
               
                 TABLE 3 
               
             
            
               
                   
               
               
                 Main Properties of Synthetic Leather 
               
            
           
           
               
               
               
               
               
            
               
                   
                   
                 Tensile 
                   
                 Cold crack 
               
               
                   
                   
                 Strength, 
                 Elonga- 
                 resistance, 
               
               
                 Sample 
                 Fabric type 
                 MPa 
                 tion, % 
                 ° C. 
               
               
                   
               
            
           
           
               
               
               
               
               
            
               
                 A 
                 non-woven synthetic soft 
                 70 
                 45 
                 −20 
               
               
                 B 
                 non-woven synthetic hard 
                 76 
                 33 
                 −20 
               
               
                   
                 thin 
               
               
                 C 
                 thin synthetic knitwear 
                 24 
                 155 
                 −20 
               
               
                   
               
            
           
         
       
     
     The hybrid epoxy-amine hydroxyurethane-grafted polymer No. 1 was used as in Sample A, the hybrid epoxy-amine hydroxyurethane-grafted polymer No. 2 was used as in Sample B, and the hybrid epoxy-amine hydroxyurethane-grafted polymer No. 3 was used as in Sample C. 
     It is to be understood that both the foregoing and the following descriptions are exemplary and explanatory only and are not intended to limit the claimed invention or application thereof in any manner whatsoever.