Cycloaliphatic carbonates as reactive diluents in epoxy resins

Abstract

Embodiments of the present invention disclose a method for limiting peak exotherm temperatures in epoxy systems comprising the step of: combining an amine hardener, an epoxy and a diluent to form an epoxy system, wherein the diluent is selected from the group consisting of: ethylene carbonate, propylene carbonate, butylene carbonate, delta-valerolactam, delta-valerolactone, gamma valerolactone, butyrolactam, beta butyrolactone, gamma butyrolactone, and combinations thereof.

Claims

1. A method for limiting peak exotherm temperatures in an epoxy system comprising the steps of: forming an epoxy system consisting of an epoxy resin that is an aromatic glycidyl ether based upon a mixture of bisphenol A and bisphenol F, polyetheramine, a cycloaliphatic amine and 2% by weight up to 10% by weight of a diluent and a reactive agent selected from the group consisting of glycerin carbonate, glycerin and a mixture thereof and optionally an additive selected from the group consisting of: a filler, a stabilizer, and a mixture thereof where the % by weight is based on the total weight of the epoxy system, and wherein the diluent is selected from the group consisting of: ethylene carbonate, propylene carbonate, butylene carbonate and combinations thereof and wherein the epoxy system is substantially free of an aliphatic glycidyl ether.

2. The method of claim 1, wherein the diluent is propylene carbonate.

3. The method of claim 1, wherein the cycloaliphatic amine is isophorone diamine.

4. The method of claim 1, wherein the diluent is present in an amount of 2% by weight to 5% by weight, based on the total weight of the epoxy system.

5. A method to produce a molded epoxy composite article comprising: forming an epoxy system consisting of an epoxy resin that is an aromatic glycidyl ether based upon a mixture of bisphenol A and bisphenol F, polyetheramine, a cycloaliphatic amine and 2% by weight up to 10% by weight of a diluent and a reactive agent selected from the group consisting of glycerin carbonate, glycerin and a mixture thereof and optionally an additive selected from the group consisting of: a filler, a stabilizer, and a mixture thereof where the % by weight is based on the total weight of the epoxy system and wherein the diluent is selected from the group consisting of: ethylene carbonate, propylene carbonate, butylene carbonate and combinations thereof and wherein the epoxy system is substantially free of an aliphatic glycidyl ether; injecting, filling or infusing the epoxy system into a mold; and heating the epoxy system.

6. The method of claim 5, wherein the epoxy composite article comprises a composite blade.

7. The method of claim 5, wherein the peak exotherm temperature of the epoxy system is less than 160° C. during heating.

8. An epoxy composite article produced according to the method of claim 5.

9. The epoxy composite article of claim 8, wherein the epoxy composite article is a wind blade.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

(1) The following FIGURE has been added to further clarify properties of the present invention.

(2) FIG. 1 shows the temperature rise during gel time testing.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

(3) The present invention relates to cycloaliphatic carbonates as reactive diluents in epoxy resins for decreasing the exotherm temperature of cast epoxy formulations, thus allowing an increase in the temperature(s) of the initial components. The ability to increase the initial component temperature(s) while avoiding degradation and other ill-effects caused by too-high exotherm temperature(s) provides a significant further viscosity reduction and the benefits that such a reduction provides. Such a viscosity reduction can also allow a further decrease in the level of reactive diluent, which can provide increases in certain thermal and mechanical properties. This use of these reactive diluents may have the advantages of lower ecotoxicity, less thermal degradation of the material in larger casts and shortened cycle times over epoxy systems that use other diluents.

(4) Embodiments of the present invention disclose a method for limiting peak exotherm temperatures in an epoxy system. The method comprises the step of combining an amine hardener, an epoxy and a diluent to form an epoxy system.

(5) The amine hardener of the present invention may include any amine hardener suitable for use in epoxy systems. Preferred amine hardeners include aliphatic amines having amine-hydrogen functionality greater than two amine hydrogens per molecule. In some embodiments the amine or amine blend can contain both a polyetheramine and a cycloaliphatic amine. In an embodiment, the amine blend can be of a commercially available polyetheramine such as JEFFAMINE® D-230 amine (commercially available from the Huntsman Corporation, JEFFAMINE is a registered trademark of Huntsman Corporation) and isophorone diamine. One skilled in the art, with the benefit of this disclosure will recognize suitable amine hardeners for use in the present invention.

(6) The epoxy system of the present invention further comprises an epoxy. Common epoxies that are particularly useful are aromatic glycidyl ethers based upon bisphenol A and/or bisphenol F. The bisphenol A based epoxies are particularly economical and reactive enough to provide reasonable curing times with amine hardeners. In a preferred embodiment, the epoxy resins may consist of multifunctional polyglycidyl ethers of dihydric phenols. ARALDITE® PY 302-2 epoxy resin, a blend of Bisphenol A and Bisphenol F based resins, is a commercially available epoxy from the Huntsman Corporation of The Woodlands, Texas (ARALDITE is a registered trademark of Huntsman Corporation). One skilled in the art, with the benefit of this disclosure, will recognize other suitable epoxies for use in this invention.

(7) Epoxy systems of the present invention further comprise a diluent. In an embodiment, the diluent may include ethylene carbonate, propylene carbonate, butylene carbonate, delta-valerolactam, delta-valerolactone, gamma valerolactone, butyrolactam, beta butyrolactone, gamma butyrolactone, and combinations thereof. In an embodiment, the diluent is propylene carbonate. In another embodiment, the diluent may include several other small cyclic compounds such as: butyrolactam (a.k.a. 2-pyrrolidinone), beta-butyrolactone, gamma-butyrolactam, delta-valerolactam, delta-valerolactone, gamma-valerolactone, and combinations thereof.

(8) It is anticipated that in most cases, the preferred levels of diluents will be at levels of less than about thirty weight percent due to their effect in reducing the glass transition temperatures of the cured polymers. On the other hand, sufficient amounts of the compounds must be used in order to have enough to significantly decrease the exotherm temperature, thus it seems likely that levels greater than about two weight percent would be preferred.

(9) Typical diluents used in epoxy systems are glycidyl ethers, such as diglycidyl ether of 1,4-butane diol (aliphatic) or phenyl glycidyl ether (aromatic). The diglycidyl ether of 1,4-butane diol is typically used as a diluent in wind blade applications. Embodiments of the present invention may replace a portion, if not all, of the glycidyl ether diluents with the diluents of the present invention. The use of diluents disclosed herein, in place of epoxy functional diluents, such as the diglycidyl ether of 1,4-butanediol, in composite wind blade formulations may allow a manufacturer to heat the epoxy system a little hotter without exceeding a desired exothermic temperature limit. This may also shorten cycle times for production of items such as wind blades.

(10) In accordance with certain embodiments, the epoxy systems disclosed herein are substantially free of an aliphatic glycidyl ether diluent. As used herein the term “substantially free of an aliphatic glycidyl ether” or “substantially free of 1,4-butane diol” refers to epoxy systems that do not include any aliphatic glycidyl ether in the final composition, but may include minimal amounts of residual aliphatic glycidyl ether that is present in any remaining solvent or residual amounts of aliphatic glycidyl ether that leaches from any containers, molds or glassware used to synthesize and/or store the compositions. In certain examples, “substantially free of an aliphatic glycidyl ether” refers to an aliphatic glycidyl ether content of less than about 0.12% by weight total in the final epoxy system, more particularly less than about 0.09% by weight in the final epoxy system. Though residual amounts of aliphatic glycidyl ether may be present in the final epoxy system, the residual amount does not impart, or retract from, the physical properties, e.g., reduces the maximum exotherm temperature, increases the cured glass transition temperature of the epoxy system, etc. In addition, any residual amounts of aliphatic glycidyl ether that are present do not contribute appreciable amounts of toxic substances to be considered a health hazard.

(11) Embodiments of the present invention further comprise the step of heating the epoxy system. The diluent-containing epoxy systems may have reduced exothermicity (i.e. those exhibiting lower peak exotherm temperatures), may be heated to higher initial temperatures, thus allowing for decreased amounts of diluents and/or higher molding temperatures with subsequent improvements in processing or thermal and/or mechanical performance. Any temperature suitable for molding that does not generate sufficient heat to cause problems such as outgassing, charring, discoloration, etc. is acceptable for embodiments of the present invention.

(12) Embodiments of the present invention may further comprise the step of injecting, filling, or infusing the epoxy system into a mold. This mold may be for such articles of manufacture such as a wind blade.

(13) In another embodiment of the present invention, epoxy systems may further comprise one or more reactivity agents. When compared to a system containing a similar level of propylene carbonate, the use of a reactivity agent such as glycerin carbonate adds a particularly short gel time and high exotherm temperature. For this reason, other carbonates, not known for exotherm reduction, such as glycerin carbonate, may also be used in the formulation as a means of adjusting reactivity. Other means of adjusting reactivity, such as addition of glycerin, N-aminoethyl piperazine, or other reactive amines, commonly known to those skilled in the art, may also be used in conjunction with the methods disclosed herein and are herein referred to as “reactivity agents.”

(14) In embodiments of the present invention, epoxy systems may further comprise one or more additives. Additives may comprise various processing aids, fillers, stabilizers, additives, adjuvants, and combinations thereof commonly used in curable epoxy formulations. One skilled in the art, with the benefit of this invention, will recognize other suitable additives for use with the present invention.

(15) Embodiments of the present invention further teach an article of manufacture produced by the method described above. In an embodiment, the article of manufacture is a wind blade.

(16) Embodiments of the present invention further teach the use of the method described above to produce a molded epoxy composite article. In an embodiment, the epoxy composite article is a composite blade used in the generation of electricity, particularly from the wind.

(17) Embodiments of the present invention will be further illustrated by a consideration of the following examples, which are intended to be exemplary of the invention.

EXAMPLES

Example 1

(18) When 200 g masses of an epoxy formulation, having 15% (resin side) of either propylene carbonate or diglycidylether of 1,4-butanediol as a diluent, and an amine curing agent containing a polyetheramine and a cycloaliphatic amine were allowed to react at room temperature, the peak exotherm temperatures measured near the center of the mass were 35° C. and 73° C., respectively. Obviously the use of propylene carbonate as a diluent can limit the exothermic temperature rise compared to the diglycidylether of 1,4-butanediol. In larger masses, such as those used in composite applications, the difference between the two maximum exotherm temperatures is expected to become even larger.

Example 2

(19) FIG. 1 shows the temperature rise during gel time testing (200 g).

(20) Focusing on the four curves on the right side of the FIGURE, they are stoichiometric mixtures of 1) bisphenol A/F epoxy resin, 2) an amine blend (20 wt. % isophorone diamine (IPDA) +80 wt. % polyetheramine (from Huntsman Corporation under the designation XTJ-678) and 3) either propylene carbonate (PC) or diglycidyl ether of 1,4-butanediol diluents (DY-D). The weight percentage diluent levels, based on the diluent plus the epoxy resin, are shown in the boxes in the FIGURE. In particular, the lines with the hollow diamond and hexagonal data points have respectively 10% and 5% by weight PC. The lines with the hollow triangle and square data points have respectively 10% and 5% by weight DY-D. Note that at both usage levels, the peak temperatures of the DY-D containing formulations exceed those of either of the PC containing formulations. The curve at the left with the solid circle data points is of a generally similar formulation except it contains ten weight percent in the resin of glycerin carbonate (GC). The great exotherm temperature is due to the faster reaction caused by catalysis of the epoxide-amine reaction by the hydroxyl group of the glycerin carbonate. Thus this carbonate might be used in admixture with other diluents to speed curing and increase exotherm temperatures when such increases pose no problems.

(21) Although the present invention and its advantages have been described in detail, it should be understood that various changes, substitutions and alterations may be made herein without departing from the spirit and scope of the invention as defined by the appended claims.