WO2011097009A2 - Compositions de résine époxy durcissables - Google Patents

Compositions de résine époxy durcissables Download PDF

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Publication number
WO2011097009A2
WO2011097009A2 PCT/US2011/000162 US2011000162W WO2011097009A2 WO 2011097009 A2 WO2011097009 A2 WO 2011097009A2 US 2011000162 W US2011000162 W US 2011000162W WO 2011097009 A2 WO2011097009 A2 WO 2011097009A2
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composition
epoxy resin
polyol
present
curable
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PCT/US2011/000162
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English (en)
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WO2011097009A3 (fr
Inventor
Ludovic Valette
Jayaraman Krishnamoorthy
Marvin L. Dettloff
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Dow Global Technologies Llc
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Publication of WO2011097009A3 publication Critical patent/WO2011097009A3/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
    • C08G59/50—Amines
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
    • C08G59/62—Alcohols or phenols
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
    • C08L71/02—Polyalkylene oxides

Definitions

  • thermosettable or curable epoxy resin compositions More specifically, this invention relates to a thermosettable epoxy resin composition including at least one polyol wherein the polyol is selected to provide a decrease in the peak exotherm temperature of the thermosettable epoxy resin composition.
  • Epoxy thermoset resins are one of the most widely used engineering resins, and are well-known for their use in adhesives, coatings, castings, laminates and composites. Epoxy resins form a glassy network, exhibit excellent resistance to corrosion and solvents, good adhesion, reasonably high glass transition temperatures, and adequate electrical properties.
  • thermosettable or curable epoxy resin formulation typically uses a curing agent, such as an amine curing agent, for crosslinking the epoxy resin to form a cured product such as a composite, casting or laminate.
  • a curing agent such as an amine curing agent
  • crosslinking the epoxy resin to form a cured product such as a composite, casting or laminate.
  • temperature of the curing formulation can increase to a point that may lead to degradation of the thermoset and/or thermally sensitive materials that may be in contact with the thermoset.
  • Ruetasolv DI mixture of diisopropyl naphthalenes supplied by RKS GmbH.
  • Ruetasolv DI mixture of diisopropyl naphthalenes supplied by RKS GmbH.
  • Ruetasolv DI can be used in modeling resins, resins for electric insulation and casting resins for tools to provide lower exothermic peak temperatures compared to the same system not containing the Ruetasolv DI.
  • the downside of these non-reactive diluents is that the non-reactive diluents act as plasticizers which may significantly reduce the glass transition temperature of the cured formulation compared to the same cured formulation that does not contain the non-reactive diluents.
  • the drop in glass transition temperature may be more than 20 °C compared to a control.
  • U.S. Patent No. 5.350.779 provides another example of how an epoxy-based composition might be formulated to control the heat release.
  • U.S. Patent No. 5.350.779 teaches the use of an epoxy composition cured with an amine mixture consisting of at least one sterically-hindered cycloaliphatic diamine and the balance with at least one sterically-unhindered cycloaliphatic diamine. Limiting the type of amine used in an epoxy resin limits the potential use of the formulation because it limits the range of properties that can be obtained.
  • the present invention discloses a two-component epoxy-based adhesive comprising a resin compound and a curing agent component.
  • the resin component comprises an epoxy resin, a toughener that it preferably a polymer polyol and, optionally, fumed silica.
  • the curing agent comprises a polyoxylakyleneamine, and amine terminated butadiene-acrylonitrile polymer, tertiary amine, polyamide resin, silane and fumed silica.” While exotherm control is generally not needed in adhesives, in some cases this may be important.
  • U.S. Patent No. 6,645,341 does not teach that its particular polyols (or any other polyols) can reduce the peak exotherm temperature of its formulation compared to a control. Further, no disclosure is made in U.S. Patent No. 6,645,341 concerning the effect of these particular polyols (or any other polyols) drops the Tg of this type of formulation compared to a control.
  • the present invention provides a solution to the problems encountered with the use of prior art diluents in amine-cured epoxy formulations by employing a polyol to reduce the peak exotherm temperature during cure relative to the same composition that does not contain the polyol (referred to herein as the "Control").
  • thermosettable or curable epoxy resin compositions that may be used in applications where the release of heat from the curing of the thermoset due to the mass of the thermoset could result in thermal decomposition of the thermoset or reduction of mechanical properties of structural parts in contact with the thermoset.
  • these applications principally include impregnating formulations used in electrical potting or encapsulation, plastic tooling and fiber reinforced composites.
  • thermosettable or curable epoxy resin formulation or composition wherein the composition includes (a) at least one epoxy resin, (b) at least one amine curing agent, and (c) at least one polyol with a hydroxyl number in the range of about 1 mg KOH/g to about 1000 mg KOH/g; wherein the polyol is selected to provide a decrease in the peak exotherm temperature of the
  • thermosettable epoxy resin composition of at least about 10% relative to the peak exotherm temperature of the Control.
  • the presence of the polyol does not reduce the glass transition temperature of the cured thermoset by more than about 20 °C relative to the Control.
  • the at least one polyol with a hydroxyl number in the range of 1 mg KOH g to 1000 mg KOH/g may be present in the final composition containing epoxy resin, polyol and amine curing agent in a sufficient amount to decrease the peak exotherm temperature of the reaction between the amine curing agent and the epoxy resin in the composition while not reducing the glass transition temperature of the cured thermoset by more than about 20 °C relative to the Control.
  • Another embodiment disclosed herein relates to a process of preparing the above curable epoxy resin composition.
  • Yet another embodiment disclosed herein relates to a process of producing a cured composite product using the above curable epoxy resin composition.
  • Figure 1 is a graphical illustration showing the reduction in the peak exotherm temperature of an amine-cure epoxy formulation without a polyether polyol (Control) and with a polyether polyol. Details are given in Comparative Example A and Example 1.
  • the present invention utilizes a curable epoxy resin composite composition useful for preparing a cured product; wherein the curable composition includes (a) at least one epoxy resin; (b) at least one amine curing agent; and (c) at least one polyol with a hydroxyl number in the range of 1 mg KOH/g to 1000 mg OH/g; wherein the at least one polyol is present in the final composition containing epoxy resin, polyol and amine curing agent in a sufficient amount to reduce the peak exotherm temperature from the reaction between the amine curing agent and the epoxy resin while not reducing the glass transition temperature of the cured thermoset by more than 20 °C relative to the Control.
  • the curable composition includes (a) at least one epoxy resin; (b) at least one amine curing agent; and (c) at least one polyol with a hydroxyl number in the range of 1 mg KOH/g to 1000 mg OH/g; wherein the at least one polyol is present in the final composition containing epoxy resin, polyol
  • One embodiment of the present invention is directed to a formulated composition or system for composite and casting applications. In these end use
  • the present invention composition includes at least one epoxy resin, component (a).
  • Epoxy resins are those compounds containing at least one vicinal epoxy group.
  • the epoxy resin may be saturated or unsaturated, aliphatic, cycloaliphatic, aromatic or heterocyclic and may be substituted.
  • the epoxy resin may also be monomeric or polymeric.
  • the epoxy resins used in embodiments disclosed herein for component (a) of the present invention, may vary and include conventional and commercially available epoxy resins, which may be used alone or in combinations of two or more. In choosing epoxy resins for compositions disclosed herein, consideration should not only be given to properties of the final product, but also to viscosity and other properties that may influence the processing of the resin composition.
  • Particularly suitable epoxy resins known to the skilled worker are based on reaction products of polyfunctional alcohols, phenols, cycloaliphatic carboxylic acids, aromatic amines, or aminophenols with epichlorohydrin.
  • a few non-limiting embodiments include, for example, bisphenol A diglycidyl ether, bisphenol F diglycidyl ether, resorcinol diglycidyl ether, and triglycidyl ethers of para-aminophenols.
  • Other suitable epoxy resins known to the skilled worker include reaction products of epichlorohydrin with o-cresol and, respectively, phenol novolacs. It is also possible to use a mixture of two or more epoxy resins.
  • the epoxy resins, component (a), useful in the present invention for the preparation of the curable compositions may be selected from commercially available products.
  • the epoxy resin component (a) may be a liquid epoxy resin, D.E.R.® 383 (DGEBPA) having an epoxide equivalent weight of 175-1 85, a viscosity of 9.5 Pa-s and a density of 1.16 gms/cc.
  • D.E.R. 330, D.E.R. 354, or D.E.R. 332 D.E.R. 330, D.E.R. 354, or D.E.R. 332.
  • the amount of epoxy resin in the final composition containing epoxy resin, polyol and amine curing agent may include from about 40 weight percent (wt %) to about 92 wt % epoxy resin. In one embodiment, the composition may include from about 45 wt % to about 87 wt % epoxy resin; and in another embodiment, the composition may include from about 50 wt % to about 82 wt % epoxy resin.
  • the epoxy resin composition of the present invention includes at least one amine curing agent, component (b), which can include for example an aliphatic, a cycloaliphatic, or aromatic amine curing agent.
  • the amine curing agent also referred to as a hardener or cross-linking agent
  • the amine curing agent may be any well known amine curing agent useful for curing or crosslinking the epoxy resin (a).
  • the amine hardener or curing agent that may be used in the final composition containing epoxy resin, polyol and amine curing agent of the present invention to promote crosslinking of the epoxy resin composition to form a polymer composition may include any compound having an amine active group being reactive with the epoxy group of the epoxy resin.
  • the amine curing agents may be used individually, or as a mixture of two or more amine curing agents.
  • the amine curing agent may be selected from any generally known to those skilled in the art as being effective to open the epoxide ring to enable polymerization and crosslinking.
  • Examples of the amine curing agent useful in the present invention include amines, alkanolamines, combinations thereof, and the like.
  • amine curing agent may include primary and secondary polyamines and their adducts; and polyamides.
  • polyfunctional amines may include aliphatic amine compounds such as diethylene triamine (D.E.H. 20, available from The Dow Chemical Company), triethylene tetramine (D.E.H. 24, available from The Dow Chemical Company), tetraethylene pentamine (D.E.H. 26, available from The Dow Chemical Company), as well as adducts of the above amines with epoxy resins, diluents, or other amine-reactive compounds.
  • Aromatic amines such as metaphenylene diamine and diamine diphenyl sulfone, aliphatic polyamines, such as
  • N-aminoethylpiperazine and polyethylene polyamine and aromatic polyamines, such as metaphenylene diamine, diamino diphenyl sulfone, and diethyltoluene diamine, may also be used as the amine curing agent.
  • Preferred amine curing agents contain a sterically hindered amine group wherein an alkyl, cycloalkyl or aralkyl group is in close proximity to the amine group so that the amine group is reacts more slowly than in the case where the alkyl, cycloalkyl or aralkyl group is absent.
  • Some products containing hindered amine groups are polyetheramines (for example, Jeffamine D-230 from Huntsman Chemical), isophorone diamine (for example, Vestamin IPD from Evonik), menthanediamine (for example, Primene MD from Dow Chemical), bis(4-amino-3-methylcyclohexyl)methane (for example, Laromin C-260 from BASF), and combinations thereof.
  • polyetheramines for example, Jeffamine D-230 from Huntsman Chemical
  • isophorone diamine for example, Vestamin IPD from Evonik
  • menthanediamine for example, Primene MD from Dow Chemical
  • bis(4-amino-3-methylcyclohexyl)methane for example, Laromin C-260 from BASF
  • the amount of amine curing agent in the final composition containing epoxy resin, polyol and amine curing agent may include from about 3 weight percent (wt %) to about 42 wt % amine curing agent.
  • the composition may include from about 5 wt % to about 38 wt % amine curing agent; and in another embodiment, the composition may include from about 7 wt % to about 33 wt % amine curing agent.
  • the equivalents ratio of the amine to epoxy groups will most typically be about 1. This means that the number of reactive amine hydrogen atom in the composition is generally equal the number of reactive epoxy groups in the composition. In some cases it may be preferable to use ratios that may range from about 1.1 to about 0.9 to prepare a composition with the best balance of properties for the application. In the case where the equivalent ratio is about 1.1 , this means that the number of reactive amine hydrogen atoms in the composition may be greater than the number of the epoxy groups in the composition. In the case where the equivalent ratio is about 0.9, this means that the number of reactive amine hydrogen atoms in the composition may be less than the number of the epoxy groups in the composition.
  • the final composition containing an epoxy resin, a polyol and an amine curing agent of the present invention includes at least one polyol, component (c) that preferably meets at least one or more of the following criteria: (1) the hydroxyl number (mg OH/g) of the polyol may be generally from 1 to about 1000, preferably from 5 to about 800; more preferably from 1 0 to about 500, most preferably from about 20 to about 400; and/or
  • the polyol does not reduce the glass transition temperature of the cured thermoset by more than about 20 °C relative to the Control; more preferably not more than about 15 °C; and most preferably not less than about 10 °C compared to the Control.
  • the polyol is not necessarily incorporated into the final thermoset network, but can be if desired.
  • the amount of polyol in the final composition containing epoxy resin, polyol and amine curing agent is a sufficient amount to decrease the peak exotherm temperature of the reaction between the amine curing agent and the epoxy resin in the composition while not reducing the glass transition temperature of the cured thermoset by more than about 20 °C relative to the Control.
  • the concentration of the polyol in the composition may include from about 1 weight percent (wt %) to about 40 wt%; and in another embodiment, from about 2 wt % to about 30 wt % polyol.
  • the composition may include from about 2.5 wt % to about 26 wt % polyol; and from about 3 wt % to about 22 wt % polyol in yet another embodiment.
  • the criteria described above are some of the important factors for determining the polyoPs suitability for use in the present invention.
  • Another factor that may need to be considered for each application is the effect the polyol has on the viscosity of the curable composition.
  • composites made by the VARTM method require the use of low viscosity (preferably, less than 500 mPa-s) curable formulations. It is possible that a polyol could meet the criteria described earlier yet lead to a curable composition that has too high a viscosity to be used in the VARTM process. In this case the polyol would not be suitable for use in this particular application.
  • Another factor that may need to be considered for composite applications is the effect the polyol may have on the ability to remove entrained air introduced to the composition during mixing. This process is referred to as degassing.
  • some polyols may act to as surfactants and prolong the degassing time that leads to increased production times. The drop in productivity may render the polyol unsuitable for use in the application.
  • polyether polyols useful in the present invention may be obtained by polymerizing alkylene oxide having from 2 to about 10 carbon atoms.
  • polyethers which can be utilized are those which are produced as by polymerization of tetrahydrofuran or epoxides (such as ethylene oxide, propylene oxide, butylene oxide, styrene oxide, epichlorohydrin, or mixtures thereof), or by addition of epoxide compounds (preferably ethylene oxide, propylene oxide, or mixtures thereof), alone, in a mixture, or in succession, to starting components with reactive hydrogen atoms such as water, polyhydric alcohols, ammonia or polyfunctional amines.
  • Grafted polyether polyols such as those grafted with styrene and/or acrylonitrile can also be utilized.
  • polymers obtained by the polymerization of olefinic monomers can also be used in the present invention.
  • Derivatives of the polymers obtained by chemically modifying the said-polymers can also be used in the present invention.
  • poly(butadiene) obtained by the polymerization of butadiene or by metathesis of 1 ,5 cyclooctadiene can be hydrogenated and used in the above-mentioned application.
  • polymers that can be used in the present invention may be obtained by step growth polymerization. Such polymerization may result in formation of polymers along with or without the formation of other byproducts.
  • the functionalities that may be present in the polymers include ester, urethane, carbonate, amide, imide, urea, siloxanes either in the backbone or in side chains.
  • the polyol may alternatively have aliphatic and aromatic groups or completely aromatic or completely aliphatic groups in the structure.
  • Polyether polyols such as described in U.S. Patent Application Publication No. 2009/0170974; in U.S. Patent 6,924,321 ; and in Nonionic Surfactants: Polyoxyalkylene Block Copolymers, Nace, V.M., Ed., Marcel Dekker, New York, 1996. These are polymers produced from polymerization reactions involving alkylene oxides typically containing 2-4 carbon atoms (e.g., ethylene oxide, propylene oxide and butylene oxide) with a compound containing one or more alcohol groups. Typical examples of such polyols include for example the VoranolTM product line from The Dow Chemical Company such as for example IP 767, and Voranol 4735.
  • polyols derived from natural oils such as soybean oil include for example SoyolTM from Urethane Soy Systems Co.;
  • Polyester polyols such as those produced by the reaction of a diol such as ethylene glycol and a dicarboxylic acid.
  • a typical example of this class of polyols includes Dynacoll® Copolyesters available from Evonik.
  • capped herein it is meant a hydroxyl group is converted to a group that is substantially chemically inert such an alkyl ether (e.g., methyl ether), ester (e.g., acetate), urethanes and others.
  • Polyols that can be used in the present invention may also include a blend of the above-mentioned types of polyols.
  • the epoxy resin composition of the present invention may also include one or more optional additives conventionally found in epoxy resin systems.
  • the epoxy resin composition of the present invention may contain additives such as nonreactive and reactive diluents; catalysts; other curing agents; other resins; fibers; fillers such as wollastonite, barites, mica, feldspar, talc, silica, crystalline silica, fused silica, fumed silica, glass, metal powders, carbon nanotubes, graphene, and calcium carbonate; aggregates such as glass beads, polytetrafluoroethylene, polyol resins, polyester resins, phenolic resins, graphite, molybdenum disulfide and abrasive pigments; viscosity reducing agents; boron nitride; nucleating agents; dyes; pigments such as titanium dioxide, carbon black, iron oxides, chrome oxide, and organic pigments; coloring agents; thixotropic agents, photo initiators; latent photo initiators
  • the curable resin composition of the present invention may be produced by mixing a "Side A", which contains the epoxy resin and may contain the polyol or other optional additives, with a "Side B” which generally contains the amine hardener and may contain the polyol or other optional additives.
  • a "Side A” which contains the epoxy resin and may contain the polyol or other optional additives
  • a “Side B” which generally contains the amine hardener and may contain the polyol or other optional additives.
  • a preference may be in the design of the volumes of Side A and Side B such that certain predetermined volumes of each side are mixed.
  • the formulation is essentially volatiles free.
  • volatiles free herein it is meant that less than 2 wt% of volatiles remain in the composition as measured at room temperature.
  • composition is also carried out such that the thermal and mechanical properties of the resulting composite upon curing of the epoxy resin composition are maintained.
  • the curable epoxy resin formulation for preparing a cured product such as a composite shaped article may be prepared by admixing the epoxy resin components of the composition as described above. After the epoxy resin composition mixture described above is prepared it may be optionally combined with a reinforcing material, for example when manufacturing a composite. The composition mixture with or without the reinforcing material may then be cured under conventional processing conditions to produce an epoxy resin thermoset material.
  • the curing of the curable epoxy resin composition containing the polyether polyol disclosed herein can be controlled by controlling the exotherm of the reaction.
  • the composition formulation provides a resulting cured product such as a composite which maintains excellent thermal and mechanical properties as described below.
  • composition of the present invention is useful for preparing composites, laminates or castings using conventional methods for the intended use such as described, for example, in Advanced Composite Materials 2001 , 10 (2-3), 99- 106 by Loos, et al; Epoxy Resins, Chemistry and Technology, 2 nd Ed., May, C.A., Ed, Marcel Dekker, N.Y., N.Y., 1988, Chapt.10; Lee, H. and Neville, K., "Handbook of Epoxy Resins," McGraw-Hill Book Company, New York, 1967, Chapters 17 and 22; European Patent No. EP 1074367; and European Patent No. EP 1782935; all of which are incorporated herein by reference.
  • a composite may be produced with the composition of the present invention using the general process described in the references.
  • a reinforcing material may be used to prepare a composite.
  • glass or carbon fibers may be used as the reinforcing material.
  • fillers may be used as the reinforcing material.
  • thermoset displays excellent thermo-mechanical properties, such as good toughness and mechanical strength, while maintaining high thermal stability.
  • the process to produce the composites or thermoset products of the present invention may be performed by utilizing casting, potting, encapsulation, and impregnation processes such as gravity casting, vacuum casting, automatic pressure gelation (APG), vacuum pressure gelation (VPG), infusion, filament winding, lay up injection, transfer molding, resin injection molding (SCRIMP, VARTM) and the like.
  • APG automatic pressure gelation
  • VPG vacuum pressure gelation
  • SCRIMP resin injection molding
  • the final thermoset of the present invention also maintains its mechanical and thermal properties, and more advantageously, the cured resin of the present invention exhibits a Tg that is sufficient to make the resin useful for making composites and other applications.
  • the polyol used in the epoxy resin curable composition of the present invention advantageously provides a decrease in the peak exotherm temperature of the thermosettable epoxy resin composition of at least about 10% relative to the peak exotherm temperature of the Control.
  • the use of the polyol also advantageously does not reduce the glass transition temperature of the cured thermoset by more than about 20 °C relative to the Control.
  • the cured resin of the present invention i.e.
  • the amine-cured epoxy thermoset which is prepared from the above epoxy resin curable composition containing a polyol has a glass transition temperature that has not been reduced by more than about 20 °C relative to the Control; more preferably not more than about 15 °C; and most preferably not more than about 10 °C compared to the Control.
  • Polypox 760 is an epoxy resin that is commercially available from UPPC, a subsidiary of The Dow Chemical Company, and Polypox 760 has an EEW of 172 g/equivalent; isophoronediamine (1PDA) is an amine curing agent that is commercially available from Evonik, and IPDA has an amine hydrogen equivalent weight of
  • diethyltoluenediamine is and amine curing agent that is commercially available from Albermarle as Ethacure 100, and DETDA has an amine hydrogen equivalent weight of 44.3 g/equivalent
  • IP 767 is a polyether polyol commercially available from The Dow Chemical Company, and it has a hydroxyl number of 35.0-38.0 mg KOH/g
  • Voranol CP 450 is a polyether polyol commercially available from The Dow Chemical Company, and it has a hydroxyl number of 370-396 mg KOH/g.
  • peak exotherm temperature is determined by placing a thermocouple in the curing composition to measure temperature versus time. This will generate a curve such as that shown in Figure 1.
  • a polyol can decrease the peak exotherm temperature relative to the Control. It is important that whatever the curing conditions are used for curing the Control, the same conditions are used for the compositions using the polyol of the present invention because peak exotherm measures are sensitive to changes in the test conditions such as for example the temperature of the surrounding environment.
  • Example and Control data The laboratory method used to generate the Example and Control data was as follows. First, all of the individual components of the composition and the cup that will hold the curable composition are allowed to reach the prevailing starting test temperature for at least one hour. For example, if the test is going to be run at 23 °C, the composition components and the cup that will hold the curable formulation will be held at 23 °C for at least one hour. For example, if test is going to be run at a higher temperature such as 40 °C, the same thing should be done at 40 °C.
  • the appropriate proportions of Side A and Side B as described above should be added to the test cup in the proportions pre-determined before the test to end up with 100 g of total curable composition in the test cup.
  • This composition is hand mixed with a metal spatula for one minute.
  • a thermocouple is inserted into the center of the sample. The thermocouple is attached to a device that records both temperature and time. The device is started as soon as the thermocouple is placed in the sample at the beginning of mixing.
  • thermocouple to avoid having the thermocouple remain embedded in the cured composition it should be coated with a material such as Teflon (except for the tip) and inserted about 38 mm into a piece of silicon tubing (leaving the tip exposed) prior to placing in the sample. This will allow the thermocouple to more easily be pulled out of the cured composition for further use.
  • a material such as Teflon (except for the tip) and inserted about 38 mm into a piece of silicon tubing (leaving the tip exposed) prior to placing in the sample. This will allow the thermocouple to more easily be pulled out of the cured composition for further use.
  • Example 1 and Comparative Example A demonstrate the reduction in the peak exotherm temperature when a polyol is present in a composition.
  • the components and amounts in Table I were combined in the manner described in the above Exotherm Test procedure. The results are shown in Table I and Figure 1.
  • Comparative Example B was carried out using essentially the same procedure as described in Example 1 . The only difference was the replacement of IP 767 with Voranol CP 450. The sample was cured in the same manner as for Example 1. The Tgl and Tg2 values for Comparative Example B are shown in Table III along with the data for Comparative Example A.

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  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
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  • Polymers & Plastics (AREA)
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Abstract

Cette invention concerne une composition de résine époxy durcissable comprenant au moins une résine époxy ayant en moyenne plus d'un groupe éther glycidylique par molécule; au moins un durcisseur de type amine; et au moins un polyol. Le polyol est présent dans la composition de résine époxy en une quantité suffisante pour abaisser l'exothermie de la réaction de durcissage de la composition tout en maintenant les propriétés thermiques et mécaniques du produit durci obtenu après durcissage de la composition de résine époxy.
PCT/US2011/000162 2010-02-02 2011-01-28 Compositions de résine époxy durcissables WO2011097009A2 (fr)

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Publication number Priority date Publication date Assignee Title
CN105482080A (zh) * 2016-01-12 2016-04-13 雅安市弘利展化工有限公司 一种耐黄变环氧树脂固化剂及其制备方法
WO2016089663A1 (fr) * 2014-12-03 2016-06-09 Dow Global Technologies Llc Composition de résine époxyde durcissable et durcisseur associé
EP3275002B1 (fr) 2015-03-26 2019-06-12 Huntsman Advanced Materials Licensing (Switzerland) GmbH Procédé de préparation de systèmes d'isolation pour des équipements électriques, articles ainsi obtenus et leur utilisation
CN110945074A (zh) * 2017-07-28 2020-03-31 株式会社钟化 环氧树脂组合物

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Cited By (10)

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WO2016089663A1 (fr) * 2014-12-03 2016-06-09 Dow Global Technologies Llc Composition de résine époxyde durcissable et durcisseur associé
CN107041142A (zh) * 2014-12-03 2017-08-11 陶氏环球技术有限责任公司 可固化环氧树脂组合物和用于其的固化剂
EP3275002B1 (fr) 2015-03-26 2019-06-12 Huntsman Advanced Materials Licensing (Switzerland) GmbH Procédé de préparation de systèmes d'isolation pour des équipements électriques, articles ainsi obtenus et leur utilisation
EP3275002B2 (fr) † 2015-03-26 2022-01-19 Huntsman Advanced Materials Licensing (Switzerland) GmbH Procédé de préparation de systèmes d'isolation pour des équipements électriques, et leur utilisation
CN105482080A (zh) * 2016-01-12 2016-04-13 雅安市弘利展化工有限公司 一种耐黄变环氧树脂固化剂及其制备方法
CN110945074A (zh) * 2017-07-28 2020-03-31 株式会社钟化 环氧树脂组合物
JPWO2019021879A1 (ja) * 2017-07-28 2020-06-11 株式会社カネカ エポキシ樹脂組成物
US11236228B2 (en) * 2017-07-28 2022-02-01 Kaneka Corporation Epoxy resin composition
JP7199354B2 (ja) 2017-07-28 2023-01-05 株式会社カネカ エポキシ樹脂組成物
CN110945074B (zh) * 2017-07-28 2023-03-10 株式会社钟化 环氧树脂组合物

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