CC BY
39
Hybrid epoxy-amine hydroxyurethane-grafted polymer O. Figovsky, O. Birukov, A. Leykin, L. Shapovalov
Polymate Ltd. - International Nanotechnology Research Center, MigdalHaEmek, Israel
Abstract: Cured hybrid epoxy-amine hydroxyurethane-grafted polymer by novel structure with lengthy epoxy-amine chains, pendulous hydroxyurethane units and a controlled number of crosslinks was prepared. 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.
Keywords: linear epoxy-amine chains, hybrid hydroxyurethane-grafted polymers, synthetic nonisocyanate leather.
1. INTRODUCTION
Preparing of polymers with a specific topological structure of polymerchains is a perspective way of creating materials with needed properties. Conventional epoxy-amine formulations are used as precursors for three-dimensional cross-linked networks [1, 2]. Chemical formation of resin-hardenernetworks used in case of bifunctional epoxy resins and tetrafunctional aminehardeners and the structures of the obtained networks are shown in Fig. 1 [2, p. 721].
— CH—Ob \ /
—CH—CH, + NibRNII, -— CHCH2—NHRNH—CH2CH— .....................-.............-
о он OH
]
CH—OH !
CH, ]
—снсн,—nrn-ch2ch— I I I
OH CH2 OH
[ -
CH—OH
I
Fig. 1. Scheme of epoxy resin - amine interaction.
Structural Schemes of resin formation-hardener networks for epoxyaminethermoset polymersare shown in Fig. 2 [2, P. 749]:
N
2 л.............л + 1 :с;
Fig. 2. Structural scheme of epoxy amine network.
Thermoplastic resins based on epoxy and amine monomers are alsoknown in the art. For example, patent [3] 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 to250oC. or in a solution at a temperature of up to 200oC.
Patents [4, 5] disclose thermoplastic polyetheramines (TPEA) having aromatic ether/amine repeating units in their backbones and pendant hydroxy lmoieties. Such polyetheramines are prepared by reacting diglycidyl ethers of dihydricaromatic compounds such as the diglycidyl ether of bisphenol-A (DGEBA),hydroquinone, or resorcinol with amines having no more than two amine hydrogenatoms 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 flexuralstrength and modulus. The disadvantage of these products is that they can beprocessed or melted at temperatures of 150 to 200°C. by using only specialequipment, or solutions in high-boiling toxic solvents. A fragment of a TPEA polymerchain is shown belowin Fig. 3 [2, P. 697].
It is known in the art to use hydroxyurethanes for improving some properties of thick cross-linked epoxy polymer networks. For example, patent [6] describes certain polyhydroxyurethane networks that are produced based on reactions between oligomers comprising terminalcyclocarbonate groups and oligomers comprising terminal primary amine groups.
Il
СН
Мл +
4 ' СН'з ч~'
Nib
OIT on
Fig. 3. Elementary unit of the TPEA polymer chain on the base of DGEBA and MEA.
Oligomers comprising terminal cyclocarbonate groups are the products of epoxyresins reacting with carbon dioxide in the presence of a catalyst, the conversion ofepoxy groups into cyclocarbonate groups being 85 to 95%.
Pat. Application [7] discloses a liquid cross-linkable oligomer composition thatcontains a hydroxyurethane-amine adduct and a liquid-reacting oligomer. Thehydroxyurethane-amine adduct is a product of an epoxy-amine adduct reacting with acompound having one or more terminal cyclocarbonate groups.
Patent [8] describes amethod and an apparatus for synthesis of oligomeric cyclocarbonates and their use inmaking a star-shaped structure of the polymer network.
Patent [9] discloses three-dimensionalepoxy-amine polymer networks modified by a hydroxyalkyl urethane,which is obtained as a result of a reaction between a primary amine (one equivalent ofthe primary amine groups) and a monocyclic carbonate (one equivalent of the cycliccarbonate groups). Such hydroxyalkyl urethane modifier is not bound chemically to themain polymer networkand is represented by the following formula (1):
(1),
wherein R is a residue of the primary amine, R2 and R3 are the same ordifferent and are selected from the group consisting of H, alkyl, and hydroxyalkyl, and n satisfies the following condition: n > 2.
Patent [10] describes anepoxy resin composition that comprises a cured reaction product of an epoxy baseresin and a curing agent mixture. The curing agent mixture comprises a di-primaryamine or polyamine and an aminohydroxyurethane (aminocarbamate) which is there action product of the amine and a cyclic carbonate and is represented by theformula (2):
HtN-R'-N-C-O-C^'HjH-R3
where R1 is a residue of the di-primary amine or polyamine that mayconsist additional free amine hydrogen atoms, R2 and R3 are selected from the groupconsisting of H and alkyl, and at least one of R2 and R3 is hydrogen. The amine has amolecular weight of 60 to 400. Preferred carbonates are ethylene carbonate andpropylene carbonate. A preferred curative comprises a mixture of amine andaminocarbamate used in a molar ratio of 1:1 to 2:1.
Thus, although the hardener comprises the aminohydroxyurethane, apure amine is an indispensible main component of this hardener, and the final polymerhas a thermoset cross-linked structure.
Thick cross-linked networks are also typical for epoxy-aminohydroxyurethane compositions described in U.S. patents [11].
A method of obtaining urethane-modified amines is presented by G.Rokicki and R. Lazinski [12]. Triethylenetetramine (TETA) was modified by different mono-and dicycliccarbonates 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 ofphysical and mechanical investigations of an epoxy resin cross linked
with aminohydroxyurethanes show increase of strength features of the cured systems.However flexible materials were not obtained, and values of elongation at break werenot more than 8 %.
A detailed review of polyhydroxyurethane networks and methods ofpreparation thereof are presented by O. Figovsky and L. Shapovalov [13] and by O. Figovsky, L.Shapovalov, A. Leykin, O. Birukova, R. Potashnikova [14].
A new polysiloxane-modified polyhydroxy polyurethane resin derivedfrom a reaction between a 5-membered cyclic carbonate compound and an aminemodifiedpolysiloxane compound are disclosed in US Patents [15]. The production process and resin compositions for thermal recordingmedium, imitation leather, thermoplastic polyolefin resin skin material, weather stripmaterial, and weather strip also have been described.Such polymers have in their backbones only hydroxyurethane units butnot epoxy-amine. A disadvantage of the disclosed method is an inconvenience in preparation of a polyhydroxy polyurethane resin, namely the long-time use (30 hoursfor first stage and 10 hours for second stage) of a toxic solvent (N-methylpyrrolidone)at 80-90oC. and subsequent separation of the product from the solvent. Anotherdisadvantage is the use of toxic polyisocyanates for cross linking of resins.
Different variations of the aforementioned composition and method arealso disclosed in these patent publications [15].
OBJECTS AND METHODS
The following commercially available raw materials were used: - epoxy resins and glycidyl ethers: DER® 331 (standard diglycidyl ether of bisphenol A, EEW=187), D.E.N.® 431 (epoxy-novolac resin, EEW=175), Polypox® R11 (diglycidyl ether of cyclohexanedimethanol, EEW=175), Polypox® R14 (diglycidyl
ether of neopentyl glycol, EEW=155) all produced by Dow Chemical Company; epoxy resin ST-3000 (hydrogenated DGEBA, EEW=230) produced by KUKDO Chemical Co.; Heloxy® 48 (triglycidyl ether of trimethylol propane, EEW=145) produced by Momentive Specialty Chemicals Inc.;
- cyclic carbonate: Jeffsol® PC (propylene carbonate, CCEW=102) produced by Huntsman Corp.
-di-primary and polyfunctional amines: Vestamin® TMD [2,2,4(2,4,4)-trimethylhexamethylene diamine] produced by Evonik; Jeffamine® D400 (polyoxypropylene diamine, AEW=230, AHEW=115) and Jeffamine® T403 (polyoxypropylenetriamine, AEW=162, AHEW=81) both produced by Huntsman Corp.; PolyTHF®Amin 350 (polytetrahydrofuranamine, AEW=160.3 AHEW=88) produced by BASF; MXDA (meta-xylylenediamine, AEW=68; AHEW=34) produced by Mitsubishi Gas Chemical Comp.; D.E.H.® 20 (diethylenetriamine, AEW=51.5; AHEW=20.6) produced by Dow Chemical Company.
Abbreviations used:
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 of the components.
Reactions between cyclic carbonate and primary amine groups were monitored by Nicolet 380 FT-IR spectrometer according to cyclic carbonate vC=O band at 1800 cm-1. Dynamic viscosity was determined on Brookfield VN-II+ viscometer. Pot life of compositions was determined according to ASTM D1084 as the time during which the viscosity is doubled.
N Инженерный вестник Дона, №2 (2016) ivdon.ru/ru/magazine/archive/n2y2016/3625
The polymerized samples were tested with regard to the following mechanical and chemical properties: tensile strength and ultimate elongation were performed on unit Lloyd LR 50K according to ASTM D638M at a speed of 50 mm/min; hardness (Shore D) was determined on durometer CV (SHD0002, Bowers) according toASTM D2240; weight gain at immersion in water (24 h @ 25o C.was determined in accordance with ASTM D570; weight gain at immersion in 20% H2SO4 (24 h @ 25o C.was determinedin accordance with ASTM D543.
RESALTS AND DISCUSSION
Synthesis of hydroxyurethane-amines
Hydroxyurethane-amines(intermediate products) of the formula (2) with the number of free amine hydrogen atoms equal to 2 were synthesized from PC and different amines in a 500 ml glass reactor equipped with a stirrer and a heater (Table 1).
Table 1. Description of the intermediatehydroxyurethane-amines
Name of product Amine AEW/CCEW ratio AHEW of product f Viscosity (25o C.), Pas
HUMA-1 TMD 2 1 130 2 9.15
HUMA-2 MXDA 2 1 119 2 1.48
HUMA-3 D-400 2 1 281 2 0.45
HUMA-4 PTHFA 2 1 226 2 0.7
HUPA-1 T-403 3 1 147 4 3.74
HUPA-2 DETA 2 1 68.3 3 6.7
Synthesis of the hybrid epoxy-amine hydroxyurethane-grafted polymers
The hybrid epoxy-amine hydroxyurethane-grafted polymer of a novel structure is obtained by curing a liquid oligomer composition which consists of diglycidyl ether
N Инженерный вестник Дона, №2 (2016) ivdon.ru/ru/magazine/archive/n2y2016/3625
and aminohydroxyurethane of structural formula (2) with the number of free amine hydrogen atoms equal to 2, wherein the diglycidyl ether and aminohydroxyurethane are at stoichiometric ratio of glycidylgroups and free amine hydrogen atoms. Curing of the grafted polymers (Table 2) were performed at RTfor 7 days.
Table 2. Description of the grafted polymers
Example Intermediatehydroxyurethane- Epoxy resin Cross-linking agents
No. amine amine epoxy
1 HUMA-1 R11 - -
2 HUMA-2 R14 - -
3 HUMA-3 DER 331 - -
4 HUMA-4 ST-3000 - -
5 HUMA-1 DER 331 HUPA-1 H48
6 HUMA-2 R11 HUPA-2 DEN 431
A presumed structure of the main backbone of the novel epoxy-amine hydroxyurethane-grafted polymers can be presented by the following formula (3):
(3),
where R' is a residue of a diglycidyl ether (epoxy resin); R1 is a residue of the di-
2 3
primary amine; R and R are residues of monocyclic carbonate and are selected from
23
the group consisting of H, alkyl C1-C2, hydroxymethyl, and at least one ofR and R is hydrogen.
The schematic structural formula of the novel polymers according to examples 1-4 is the following:
(4),
Il
whereE—R'—E is a residue of a diglycidyl ether, which reacted with amine hydrogens,
E is a converted epoxy group, 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.
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(examples 5-6). The polyfunctional components may comprise polyglycidyl compounds with functionality more than 2, aminohydroxyurethanes of formula 2, wherein R1 is a residue of the polyamine, with number of free amine hydrogen atoms more than 2, and combinations thereof in amounts of 20-25 eqv. %.
A schematic structural formula of the novel polymer according to examples 5-6 with the directions of the possible cross-links (shown by arrows) is the following:
(5),
Е
I
where е—r"—Eis aresidue of the polyflmctional epoxy resin, other designations being the same as above. Polyamines with a number of free amine hydrogen atoms more than 2 also were used for cross-linking.
The results of the tests of the hybrid epoxy-amine hydroxyurethane-grafted polymersare summarized in Table 3 given below.
Table 3.Properties of compositions (examples 1-6).
Measured Characteristics Exampl le No.
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 water (24 h @ 25° C.), % 1.1 1.8 0.3 0.3 0.2 0.1
Weight gain at immersion in 10% NaOH(24 h @ 25° C.), % 1.1 1.4 0.6 0.5 0.3 0.1
Testing of Synthetic Leather
The coating formulations for imitation leathers, which contained thecomponents described in Examples 1 to 3, were separately applied onto paper sheetsand cured by drying to form on the paper substrate films of incompletely curedpolymer coating having a thickness of 25 ^m, The coatedproducts were cut into separated pieces, applied onto a fabric substrates (see Table3) and bonded to the substrates under pressure developed by a load. After bonding tothe fabric and solidification of the coating, the paper substrates were peeled off. As aresult, samples A, B, and C of the synthetic leather shown in Table 4 were obtained.
Tensile properties of the samples were determined according to ASTM D638.
N Инженерный вестник Дона, №2 (2016) ivdon.ru/ru/magazine/archive/n2y2016/3625
Cold crack resistance was measured according to CFFA-6 (STANDARDTEST METHODS. CHEMICAL COATED FABRICS AND FILM.Chemical Fabrics &Film Association, Inc. Cleveland, 2011).
Table 4. Main Properties of Synthetic Leather
Sample Fabric type Tensile Elongation, Cold crack
Strength, MPa % resistance, oC.
A non-woven synthetic soft 70 45 -20
B non-woven synthetic hard thin 76 33 -20
C thin synthetic knitwear 24 155 -20
The hybrid epoxy-amine hydroxyurethane-grafted polymer No. 1 wasused as in Sample A, the hybrid epoxy-amine hydroxyurethane-grafted polymer No. 2was used as in Sample B, the hybrid epoxy-amine hydroxyurethane-graftedpolymer No. 3 was used as in Sample C.
CONCLUSION
A method of synthesis of novel polymers with lengthy epoxy-amine chains, pendulous hydroxyurethane units and a controlled number of cross-linkswas proposed. Cured hybrid epoxy-amine hydroxyurethane-grafted polymer withpresumablylinear structure was prepared.
Testings of hybrid polymers demonstrate increased flexibility with well balanced physical-mechanical and physical-chemical properties of conventional epoxy-amine systems. These materials may be used, for example, for manufacturing of synthetic/artificial leather and sport monolithic floorings.
On the subject of hybrid epoxy-amine hydroxyurethane-grafted polymer US patent application was filed [16].
REFERENCES
1. Lee H., Neville K. Handbook of Epoxy Resins. McGraw-Hill, New York, 1967, 922 p.
2. Pham H.Q., Marks M.J. Epoxy resins. In the book: Encyclopedia of Polymer Science and Technology. Copyright John Wiley & Sons, Inc., 3rd ed., 2004, Vol. 9, pp. 678-804.
3. Johnson W.E. et al. US Pat. No. 3,317,471, 1967.
4. Silvis H.C., White J.E. US Pat. No. 5,275,853, 1994.
5. Silvis H.C., Kram S.L. US Pat. No. 5,464,924, 1995.
6. Figovsky O.L. US Pat. No. 6,120,905, 2000.
7. Birukov O., et al.US Pat. Application Publication No. 20100144966, 2010.
8. Figovsky O., et al.US Pat. No. 7,232,877, 2007.
9. Birukov O., et al.US Pat. No. 7,989,553, 2011.
10. Alexander D.C., et al.US Pat. No. 5,235,007, 1993.
11. Hoenel M., et al.US Pat. Nos. 5,677,006, 1997; 5,707,741, 1998; 5,855,961, 1999; and 5,935,710, 1993.
12. Rokicki G. and Lazinski R. Polyamines Containing ß -Hydroxyurethane Linkages as Curing Agents for Epoxy Resin, Die Angewandte Makromolekulare Chemie, 1989, Vol. 170, No. 1, pp. 211-225 (Nr. 2816).
13. Figovsky O. and Shapovalov L. Cyclocarbonate-based Polymers Including Non-Isocyanate Polyurethane Adhesives and Coatings, Encyclopedia of Surface and Colloid Science, Somasundaran. P. (Ed), V. 3, pp. 1633-1652, New York, Taylor & Francis, 2006.
14. Figovsky O., Shapovalov L., Leykin A., Birukova O., Potashnikova R. Advances in the field of nonisocyanate polyurethanes based on cyclic carbonates, Chemistry & Chemical Technology, 2013, V. 7, No. 1, pp. 79-87.
15. Hanada K., et al.US Patents Nos. 8,703,648, 2014; 8,951,933, 2015; 8,975,420, 2015; US Patent Applications Nos. 20140024274, 2014; 20130171896, 2013.
16. Birukov , et al.US Patent Application 14/296,478, 2014.
