Patent Grant
10189939
This invention relates generally to a polyamine compound useful in epoxy-based coating compositions and thermosetting composites.
Typically, formulating epoxy resins with highly functional curing agents (hardeners) leads to short working lives, high formulation viscosity and brittle parts after curing. These negative effects are all driven by the high functionality of the curing agent. It is well known that in step growth polymerization, the degree of polymerization, Xn, and the critical extent of reaction (gel point−pc) are directly linked to the functionality of the polymerizing system: Xn=2/(2−pfavg) where p is the extent of reaction and favg is the average functionality and pc=2/favg. Thus systems with a high average functionality will reach high molecular weights and gel at a lower degree of polymerization than those with a low average functionality. U.S. Pat. No. 4,293,682 discloses use of tetra- and penta-functional amines as curing agents.
While low functionality curing agents will provide longer pot lives, these lead to final cured networks with low crosslink densities and poor thermal and mechanical properties. This inverse relationship between highly functional monomers needed for final part properties and low functionality monomers for enhanced working time requires a compromise in formulating epoxies. Anything that can be done to enhance working time without adversely affecting the final part properties would be advantageous.
The present invention is directed to a method for curing an epoxy resin by adding to the epoxy resin a curing agent comprising a compound having formula (I)
wherein X is a difunctional group selected from the group consisting of C2-C20 alkyl, C5-C20 cycloalkyl, C6-C10 aryl, C8-C20 aryl alkyl, C4-C20 heteroalkyl or C10-C20 aryl heteroalkyl.
All percentages are weight percentages (“wt %”) and temperatures in ° C., unless otherwise indicated. Concentrations in parts per million (“ppm”) are calculated on a weight/volume basis. An “alkyl” group is a hydrocarbon substituent group having from one to twenty carbon atoms, unless otherwise specified, in a linear or branched arrangement. Alkyl groups optionally have one or more double or triple bonds. Substitution on alkyl groups of one or more hydroxy or alkoxy groups is permitted. Preferably, alkyl groups are saturated and unsubstituted. A “cycloalkyl” group is an alkyl group containing at least one saturated ring. A “heteroalkyl” group is an alkyl group in which at least one carbon has been replaced by O, NR, or S, wherein R is hydrogen, alkyl, aryl or aralkyl; e.g., —CH2CHR′(OCH2CHR′)n— where R′ is hydrogen, methyl or ethyl and n is from one to nine, or an upper limit determined by the maximum size of the heteroalkyl group and the identity of R′. The carbon number of a heteroalkyl group is the actual number of carbon atoms in the heteroalkyl group, and does not include incorporated heteroatoms. Preferably, a heteroalkyl group has only oxygen heteroatoms. Preferably, the ratio of carbon atoms to oxygen atoms is from 5:1 to 2:1, alternatively from 4:1 to 2.5:1. Preferably, a heteroalkyl group is attached through carbon atoms at either end of the chain. An “aryl” group is a substituent derived from an aromatic hydrocarbon compound. An aryl group has a total of from six to twenty ring atoms, unless otherwise specified, and has one or more rings which are separate or fused. An “aralkyl” group is an “alkyl” group substituted by an “aryl” group. An “aryl alkyl” group is a difunctional group in which a difunctional aryl group is inserted into an alkyl group, e.g., —(CH2)xC6H4(CH2)y—, where C6H4 is o-, m- or p-phenylene and x and y may be the same or different, preferably the same, and have values consistent with the overall size of the aryl alkyl group and the identity of the inserted aryl group. An “aryl heteroalkyl” group is a difunctional group in which a difunctional aryl group is inserted into a heteroalkyl group. Substitution on aryl groups of one or more of the following groups: halo, cyano, nitro, hydroxy, alkoxy, alkyl, heteroalkyl, alkanoyl, amino, or amino substituted by one or more of alkyl, aryl, aralkyl, heteroalkyl or alkanoyl is permitted, with substitution by one or more halo groups being possible on alkyl, heteroalkyl, alkanoyl or alkoxy groups. Preferably, aryl groups do not contain halogen atoms. In one preferred embodiment of the invention, aryl groups are unsubstituted or substituted only by alkyl groups. A difunctional group is a substituent group having two points of attachment, e.g., one example of a difunctional alkyl group would be —(CH2)x—, where x could be from two to twenty.
Preferably, X is a difunctional group selected from the group consisting of C2-C12 alkyl, C5-C10 cycloalkyl, C6-C8 aryl, C8-C12 aryl alkyl, C4-C20 heteroalkyl and C10-C20 aryl heteroalkyl; preferably C3-C10 alkyl and C4-C20 heteroalkyl; preferably C4-C10 alkyl and C6-C15 heteroalkyl; preferably C6-C15 heteroalkyl.
Compounds of formula (I) may be prepared by the methods disclosed in US20120196963A1.
Preferably, compound (I) is made from a diamine, H2N—X—NH2, consisting of polymerized units, e.g., two-six units, of alkylene oxides, e.g., ethylene oxide, propylene oxide and butylene oxide, capped with aminoalkyl groups, e.g., C2-C4 aminoalkyl groups. Preferably, X represents a mixture of groups having the average formula —CH(CH3)CH2(OCH2CH(CH3))n—, where n is from 2 to 4, preferably about 2.7. The mixture having n=2.7 contains at least the species having n equal to 2, 3 and 4, which correspond to X being a C9, C12 or C15 heteroalkyl group, respectively. Preferably, X is a C6-C9 heteroalkyl group having two oxygen atoms.
Preferably, the epoxy resin is a condensate of epichlorohydrin and a diol. Preferably, the epoxy resin is an aromatic epoxy resin, preferably a bisphenol A resin or a novolac epoxy resin, preferably a bisphenol A resin. Preferably, the epoxy resin is a condensate of an aromatic diol (e.g., bisphenol A) and epichlorohydrin. Preferably, the molecular weight of the epoxy resin is no greater than 1000, preferably no greater than 800, preferably no greater than 600, preferably no greater than 400.
The compound of formula (I) may be added to the epoxy resin as part of a mixture with other curing agents to allow fine control of cure time and cured resin properties. Preferably, the curing agent comprises at least 40 wt % of at least one compound of formula (I), preferably at least 50 wt %, preferably at least 60 wt %, preferably at least 70 wt %, preferably at least 80 wt %, preferably at least 90 wt %. Preferably, the ratio of total equivalents of NH in the curing agent to equivalents of epoxide is from 0.5:1 to 1.5:1, preferably from 0.7:1 to 1.3:1, preferably from 0.8:1 to 1.2:1, preferably from 0.9:1 to 1.1:1. The present invention is also directed to a two-component epoxy formulation in which one component comprises a curing agent comprising at least one compound of formula (I) and the other component comprises an epoxy resin.
DER-331 epoxy resin (bisphenol A-epichlorohydrin adduct), DETA and PRIMENE MD amine were obtained from the Dow Chemical Company.
Viscosity Measurements
Using the ratios given in Table 1, fifteen grams of epoxy resin/hardener mixture was prepared for each test. The formulations were prepared by mixing the amine hardener and resin thoroughly with an overhead stirrer. Each viscosity measurement series was started immediately following mixing. Viscosity measurements were performed using a Brookfield Programmable RVDV-II+Viscometer with a YDX-1/SP1-UC-Y type D spindle extension and an SC4-18/13R Spindle. Two series of measurements were run for each resin/hardener mixture, one at 25° C. and a second at 40° C. The temperature, viscosity, torque, spindle speed, and time were recorded for each series to document the change in viscosity over time. Measurements were recorded for 8 hours or until the viscosity exceeded 50000 cps.
Preparation of Molded Bars
Resin and hardener were mixed for 1 minute in a disposable cup using an overhead stirrer. The resin mixture was poured into a nine cavity (each cavity is 3″×½″× 3/16″) (7.6 cm×1.3 cm×4.8 mm) pre-heated (65° C.) silicone rubber mold and de-gassed in a 65° C. vacuum oven. The mold was placed in a pre-heated forced air, programmable oven and covered with an aluminum pan to minimize turbulence. The cure schedule used was 65° C./2 hours, ramp to 150° C. over 30 minutes, hold 150° C./2 hours, ramp to 200° C. over 30 minutes, hold 200° C./1 hour, then cool to 65° C. at 2° C./minute. Fluoropolymer-based mold release was used to facilitate the specimen removal from the mold. Upon de-molding, the bars had surface roughness and flashing. Each specimen was sanded to approximately 0.10 inch (2.54 mm) thickness using an orbital sander and a stainless steel part jig. Once near the desired thickness, a fine grit sandpaper was used to give the parts a smooth, scratch-free surface. This process eliminated any surface defects and gave parts with a uniform thickness.
3-Point Flex Testing
Three point flex testing was performed on an INSTRON model 5567 using Blue Hill 2 Software Version 2.24.787 according to ASTM D790-03. A 2 inch support span and a crosshead speed of 0.050 in/min was used for all measurements. Three point flex testing was replicated on six bars of each epoxy/hardener formula and the results are reported as an average value after excluding any statistically outlying data points
Post Cure Differential Scanning Calorimetry (DSC) Testing
DSC analyses were performed using a TA Instruments Q100 DSC. Temperature scans were run from 25° C. to 260° C. at 10° C./minute, back to 25° C. at 10° C./min followed by a re-heat scan back to 260° C. at 10° C./min. All analyses were run under a flowing nitrogen atmosphere.
Thermogravimetric Analyses (TGA)
Thermogravimetric analyses were performed using a TA Instruments Q50 TGA. The temperature was ramped from 25° C. to 400° C. at 10° C./min, then 50° C./min to 600° C. with a final hold time of 10 min. All analyses were run under a flowing air atmosphere.
Dynamic Mechanical Analyses (DMA)
Dynamic mechanical analyses were performed using a TA Instruments Q800 DMA. A 3-point flex mode was used with a span of 25 mm. Typical part dimensions were 36 mm×13 mm×2.3 mm. The instrument was run in multi-frequency—strain mode, using a preload force of 0.5N, strain of 0.1% and a frequency of 1 hz. The temperature was ramped from 25° C. to 200° C. at 3° C./min. All analyses were run under air.
The main focus of this work was to assess the pot life and the thermal and mechanical properties of thermoset epoxy systems cured with the hexafunctional hindered amine hardeners and their comparisons with commercially available hardeners.
Table 1 contains the amines used in this study, their functionality, amine equivalent weight and formulation ratio for mixing DER-331 assuming a ratio of 1:1 equivalents of amine:equivalents of epoxide. The structures of the amines can be seen in Structure Table 1.
Calculations Using Epoxy Equivalent Weight for DER-331=185.5
DETA is the commercially available comparative example. JeffD-230-bis-AMP (n is ca. 2.7), HD-bis-AMP and EDBDA-bis-AMP are examples of this disclosure. HD-bis-ACyHM is a comparative example from U.S. Pat. No. 2,816,926.
Formulation Viscosity as a Function of Time and Temperature
Initially, small scale formulations were prepared and their viscosities were measured as a function of time both at 25° C. and 40° C. As can be seen in the table, the initial viscosities of the comparative and inventive compositions are similar.
In sharp contrast, the time to exceed either 5000 or 50,000 cps is significantly enhanced for the inventive compounds relative to DETA or HD-bis-ACyHM. This demonstrates the longer time to gellation for the inventive compounds despite their higher functionality.
Three Point Flex Testing
With proven advantages in formulation working life behavior, the demonstration of desirable cured resin properties becomes important. Castings were prepared by pouring resin formulations into a warm silicone rubber mold comprised of nine individual cavities, followed by vacuum degassing to remove trapped air. The mold was then placed in a forced air, programmable oven for curing; the mold was covered with a loose fitting lid to minimize turbulence. A minimum of 5 test specimens were used to generate the summary data. The reduced flex data are collected in Table 3.
What is immediately apparent from the data is that the inventive curing agents have higher initial modulus relative to DETA or HD-bis-ACyHM. Also apparent is the higher peak loads for HD-bis-AMP and JD-230-bis-AMP, and higher strain at break for all 3 inventive compounds relative to DETA or HD-bis-ACyHM. Energy at break—a measure of toughness—is between 50 and 100% higher for the inventive compounds as well.
Thermal Analyses of the Cured Bars
DSC and TGA analyses were performed on portions of the cured bars used to generate the flex data. The DSC protocol used was to heat the specimen from room temperature to 260° C., cool back to room temperature and re-heat to 260° C. This re-heat cycle was implemented to demonstrate the ultimate Tg obtainable with each curing agent. While the ultimate Tg values of the inventive compounds, seen in table 4, were slightly lower than DETA all were clearly acceptable. The TGA data indicates that the inventive compounds have stability equivalent to DETA. The loss in Tg of the HD-bis-ACyHM with the re-heat cycle indicates degradation has occurred during the first heating—clearly a detriment to high temperature use.
DMA Analyses
DMA analyses on the cured bars were performed. Three point bending mode with a 1 inch (2.54 cm) span was chosen for the sample geometry, and the results from a single analysis are shown. The Tg values obtained matched well with those from the DSC re-heat scans. The Storage and Loss moduli show the same trend as seen with the Instron generated data; DETA has lower storage and loss moduli as compared to the inventive compounds and HD-bis-ACyHM is substantially worse still.
The preceding examples have clearly demonstrated the much lower reactivity, longer pot life capability of the inventive compounds while providing superior mechanical and equivalent thermal performance.
This application is a 371 National Phase Application of PCT/US2014/049695, filed Aug. 5, 2014, which claims benefit of U.S. Provisional Application Ser. No. 61/863,652, filed Aug. 8, 2013, the disclosures of which are incorporated herein by reference in their entireties.
| Filing Document | Filing Date | Country | Kind |
|---|---|---|---|
| PCT/US2014/049695 | 8/5/2014 | WO | 00 |
| Publishing Document | Publishing Date | Country | Kind |
|---|---|---|---|
| WO2015/021001 | 2/12/2015 | WO | A |
| Number | Name | Date | Kind |
|---|---|---|---|
| 2816926 | Smiley | Dec 1957 | A |
| 4293682 | Kluger et al. | Oct 1981 | A |
| 4698446 | Lai et al. | Oct 1987 | A |
| 4698466 | Beck | Oct 1987 | A |
| 5153296 | Gras | Oct 1992 | A |
| 20080114094 | Shah et al. | May 2008 | A1 |
| 20120035298 | Tomlinson | Feb 2012 | A1 |
| 20120196963 | Swedo | Aug 2012 | A1 |
| 20140107313 | Burckhardt et al. | Apr 2014 | A1 |
| Number | Date | Country |
|---|---|---|
| 2008-169376 | Jul 2008 | JP |
| 2012-525401 | Oct 2012 | JP |
| WO-2011044472 | Apr 2011 | WO |
| WO 2011044472 | Apr 2011 | WO |
| Entry |
|---|
| International Preliminary Report on Patentability for PCT/US2014/049695, dated Feb. 9, 2016. |
| International Search Report and Written Opinion for PCT/US2014/049695, dated Nov. 6, 2014. |
| Notice of Reasons for Rejection issued on Japanese Application 2016-533369, dated Mar. 12, 2018. |
| Decision to grant issued for JP 2016-533369, dated Jul. 25, 2018 (no English translation). |
| Number | Date | Country | |
|---|---|---|---|
| 20160159970 A1 | Jun 2016 | US |
| Number | Date | Country | |
|---|---|---|---|
| 61863652 | Aug 2013 | US |
