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GB2031431A - Novel epoxy curing agent - Google Patents

Novel epoxy curing agent Download PDF

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Publication number
GB2031431A
GB2031431A GB7924094A GB7924094A GB2031431A GB 2031431 A GB2031431 A GB 2031431A GB 7924094 A GB7924094 A GB 7924094A GB 7924094 A GB7924094 A GB 7924094A GB 2031431 A GB2031431 A GB 2031431A
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Prior art keywords
molecular weight
composition
epoxy resin
additive
curing agent
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GB7924094A
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Texaco Development Corp
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Texaco Development Corp
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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
    • C08G59/504—Amines containing an atom other than nitrogen belonging to the amine group, carbon and hydrogen
    • 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

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Epoxy Resins (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

The invention concerns amine- cured epoxy resin compositions. These compositions have an enhanced adhesive strength resulting from the use of an additive which is a polyoxyalkylene polyamine having a molecular weight from 900 to 4000, e.g. having the formula <IMAGE> wherein X = hydrogen, methyl or ethyl, Z is a hydrocarbon radical, r is 2 to 4, n is a positive number, y is 2 or 3, and A and B are each a positive number.i

Description

SPECIFICATION Novel epoxy curing agent This invention relates to curable epoxy resins having increased adhesive strength; and, more particularly, to amine cured epoxy resins.
Epoxy resins constitute a broad class of polymeric materials having a wide range of physical characteristics. The resins are characterized by epoxide groups which are cured by reaction with certain catalysts or curing agents to provide cured epoxy resin compositions with certain desirable properties. One such class of curing agents are generally the amines. The most commonly used amine curing agents are aliphatic amines such as diethylenetriamine, triethylenetetramine and the like and/or polyoxyalkylene polyamines; such as polyoxypropylenediamines and triamines and their amino propyl derivatives.
It has been surprisingly discovered that cured epoxy resins having outstanding adhesive strength can be obtained by using a combination of known low molecular weight curing agents and higher molecular weight materials. The cured epoxy resin compositions of the instant invention are useful as coatings, castings, sealants and especially adhesives.
According to the broad aspect of the instant invention, the adhesive strength of epoxy resins cured with low molecular weight amines is enhanced by the addition of an effective amount of a polyoxyalkylenepolyamine having a molecular weight of from about 900 to about 4000.
A preferred embodiment is a curable epoxy resin composition having superior adhesive strength comprising a diglycidyl ether of 4,4'-isopropylidene bispheno, a curing amount of an imine curing agent of about 350 molecular weight or less and an effective amount of a polyoxyalkylenepolyamine having a molecular weight of from about 900 to about 4000.
According to the instant inventive concept, blends of a polyepoxide, an amine curing agent of about 350 molecular weight or less and a polyoxyalkylenepolyamine of about 900 to 4000 molecular weight and, optionally, an accelerator are thoroughly admixed and cured in accordance with conventional methods to provide cured epoxy resins having unexpectedly superior adhesive strength.
Generally the vicinal polyepoxide containing compositions which are amine cured are organic materials having an average of at least 1.8 reactive 1,2-epoxy groups per molecule. These polyepoxide materials can be monomeric or polymeric, saturated or unsaturated, aliphatic, cycloaliphatic, aromatic or heterocyclic, and may be substituted if desired with other substituents besides the epoxy groups, e.g., hydroxyl groups, ether radicals, aromatic halogen atoms and the like.
Preferred polyepoxides are those of glycidyl ethers prepared by epoxidizing the corresponding allyl ethers or reacting, by known procedures, a molar excess of epichlorohydrin and an aromatic polyhydroxy compound, i.e., isopropylidene bisphenol, novolak, resorcinol, etc. The epoxy derivatives of methylene or isopropylidene bisphenols are especially preferred. The diglycidyl ether of 4,4'-isopropylidene bisphenol was used as the epoxy resin in the Examples which follow.
A widely used class of polyepoxides which are useful according to the instant invention includes the resinous epoxy polyethers obtained by reacting an epihalohydrin, such as epichlorohydrin, and the like, with either a polyhydric phenol or a polyhydric alcohol. Typically the epoxy resins have an average of at least 1.8 reactive, 1,2-epoxy groups per molecule.An illustrative, but by no means exhaustive, listing of suitable dihydric phenols includes 4,4'isopropylidene bisphenol, 2,4'-dihydroxydiphenylethylmethane, 3, 3'-dihydroxydiphenyldiethyl- methane, 3,4'-dihydroxydiphenylmethylpropylmethane, 2,3 '-dihydroxydiphenylethylphenylmeth- ane, 4, 4'-dihydroxydiphenylpropylphenylmethane, 4,4'-dihydroxydiphenylbutylphenylmethane, 2,2'-dihydroxydiphenylditolylmethane, 4,4'-dihydroxydiphenyltolylmethylmethane and the like.
Other polyhydric phenols which may also be co-reacted with an epihalohydrin to provide these epoxy polyethers are such compounds as resorcinol, hydroquinone, substituted hydroquinones, e.g., methylhydroquinone, and the like.
Among the polyhydric alcohols which can be co-reacted with an epihalohydrin to provide these resinous epoxy polyethers are such compounds as ethylene glycol, propylene glycols, butylene glycols, pentane diols, bis (4-hydroxycyclohexyl)dimethylmethane, 1,4-dimethylolbenzene, glycerol, 1,2,6-hexanetriol, trimethylolpropane, mannitol, sorbitol, erythritol, pentaerythritol, their dimers, trimers and higher polymers, e.g., polyethylene glycols, polypropylene glycols, triglycerol, dipentaerythritol and the like, polyallyl alcohol, polyhydric thioethers, such as 2,2, ,3,3'-tetrahydroxydipropylsulfide and the like, mercapto alcohols such as monothioglycerol, dithioglycerol, and the like, polyhydric alcohol partial esters, such as monostearin, pentaerythritol monoacetate, and the like, and halogenated polyhydric alcohols such as the monochlorohydrins of glycerol, sorbitol, pentaerythritol and the like.
Another class of polymeric polyepoxides which can be amine cured and are in accordance with the instant invention includes the epoxy novolak resins obtained by reacting, preferably in the presence of a basic catalyst, e.g., sodium or potassium hydroxide, and epihalohydrin, such as epichlorohydrin, with the resinous condensate of an aldehyde, e.g., formaldehyde, and either a monohydric phenol, e.g., phenol itself, or a polyhydric phenol. Further details concerning the nature and preparation of these epoxy novolak resins can be obtained in Lee, H. and Neville, K., Handbook of Epoxy Resins, McGraw Hill Book Co., New York, 1967.
It will be appreciated by those skilled in the art that the polyepoxide compositions which are useful according to the practice of the present invention are not limited to those containing the above described polyepoxides, but that these polyepoxides are to be considered merely as being representative of the class of polyepoxides as a whole.
The amine curing agents of 350 molecular weight or less which can be utilized in accordance with the instant invention are generally any of those amine curing agents which are well known to be useful for the curing of vicinal epoxides. Generally, those curing agents having at least three reactive amino hydrogens are useful.
Exemplary of those low molecular weight amines which can be utilized are alkylene polyamines such as diethylene triamine, triethylene tetramine and the like; oxyalkylene polyamines such as polyoxypropylene, di- and triamine and diamino derivatives of ethylene glycol.
Additionally, aromatic amine curing agents are useful, such as the alkylene-linked polyphenyl amines, phenylene diamines and polycyclic or fused aromatic primary amine compounds.
Additionally the corresponding cycloaliphatic compounds can be used.
Likewise, the polyamide curing agents such as the condensation products of polyamines and polycarboxylic acids are useful. Suitable such amide compounds are, for example, the condensation product of a polyamine and a dimerized fatty acid produced in accordance with U.S.
2,379,413.
Of the amine curing agents known to be effective in curing a vicinal epoxy resin, preferred curing agents in accordance with the instant invention are the polyoxyalkylene containing amine compounds. A preferred class of polyoxyalkylene polyamines is depicted by the formula:
wherein X is hydrogen, a methyl radical or an ethyl radical; Z is a hydrocarbon radical having 2 to 5 carbon atoms forming from 2 to 4 external ether linkages; n is a finite number chosen depending on the molecular weight desired and r is a number from 2 to 4. The most preferred polyoxyalkylene polyamines are the polyoxypropylene diamines wherein X is a methyl radical, n is a number from about 1 to 3, Z is a 1,2-propylene radical and r is about 2. These polyoxyalkylene polyamines can be prepared by known methods as disclosed in U.S.
3,236,895 and U.S. 3,654,370. The most preferred polyoxyalkylene polyamine is a polyoxypropylene diamine having a molecular weight of about 230.
Another preferred class of polyoxyalkylene polyamines can be depicted by the formula:
wherein X, Z, n and r are defined as in Formula I and y is 2 or 3. These poly(aminoalkylamino)polyethers are the hydrogenated product of the cyanoalkylated adduct of a polyoxyalkylene polyamine as above described. The preparation of the cyanoalkylated adducts is described in U.S. 3,666,788 issued to Rowton, May 30, 1972.
The polyoxyalkylenepolyamines of from about 900 to 4000 molecular weight which in combination with the above enumerated known curing agents produce superior adhesive properties in epoxy resins are in particular polyoxyalkylene diamines of the formula:
wherein X is a hydrogen, a methyl radical or an ethyl radical; Z' is a hydrocarbon alkylene radical having from 2 to 5 carbon atoms; and, n is an average number of from about 14 to about 65. Preferred polyoxypropylene diamines wherein X is a methyl radical, n is an average number from 25 to 35, Z is a 1,2-propylene radical. These polyoxyalkylene polyamines can be prepared by known methods as disclosed in U.S. 3,236,895 and U.S. 3,654,370.
Other polyoxyalkylene polyamines of from about 900 to 4000 molecular weight suitable for use in this invention include compounds of the formula:
where A and B are chosen to adjust molecular weight and other properties. For example, in the embodiment where the molecular weight is about 900 A is about eight (8) and B is about one (1). Where the molecular weight is about 2000, A is about twenty-one (21) and B is about one (1).
In accordance with this method, the reactants are simply admixed in correct molar ratios in a suitable reaction vessel and heated, if necessary, until the reaction occurs.
Optionally, the epoxy resin formulations of the instant invention can include an "accelerator" to speed the amine cure of epoxy resin, especially at ambient temperatures. In several applications, such acceleration is beneficial, especially when an epoxy resin is used as an adhesive in flammable environment, thus making elevated temperature cure inconvenient or even hazardous. Lee, H. and Neville, K., Handbook of Epoxy Resins, pp. 7-14 describes the use of certain amine-containing compounds as epoxy curing agent-acc"ierators.
Many accelerators are knowri in the art which can be utilized in accordance with the instant invention. Examples include salts of phenols; salicyclic acid; amine salts of fatty acids such as those disclosed in U.S. 2,681,901; and, tertiary amines such as those disclosed in U.S.
2,839,480. A preferred accelerator in accordance with the instant invention is disclosed in U.S.
3,875,072 issued to G. Waddill, April 1, 1975. The accelerator comprises a combination of piperazine and an alkanol amine in a weight ratio of about 1:8 to 1:1.
According to the method of the instant invention, the adhesion properties of epoxy resins cured with amines of about 350 molecular weight or less are enhanced by the addition of an effective amount of a polyoxyalkylenepolyamine having a molecular weight of from about 900 to about 4000 as hereinbefore described. The amount of additive effective in bringing about the increased adhesive property is somewhat empirical and will depend upon the resin, the amine curing agent, and the use of an accelerator. Generally, the additive can be utilized in amounts from about 2 to about 50 parts by weight based on one hundred parts by weight of the epoxy resin constituent.
The preferred resins comprise polyglycidyl ethers of a polyhydric phenol cured by incorporating therein a curing amount of a polyoxyalkylenepolyamine of molecular weight from about 200 to 350, a polyoxyalklenepolyamine of from about 900 to 4000 and, optionally, an accelerator combination of piperazine and an alkanolamine, the combination having a combined weight ratio of between about 1:8 to 1:1.
The amine cured resins having superior adhesion in accordance with the instant invention are prepared in a conventional manner. The low and high molecular weight amine curing agents are admixed with the polyepoxide composition in amounts according to the amine equivalent weight of the curing agents employed. Generally the number of equivalents of amine groups is from about 0.8 to about 1.2 times the number of epoxide equivalents present in the curable epoxy resin composition, with a stoichiometric amount being preferred. When using an accelerator, amounts from 1 to about 10 parts by weight based on 100 parts by weight of the resin are generally satisfactory. The exact amount of constituents in accordance with the above general requirements will depend primarily on the application for which the cured resin is intended.
The curing agents and other additives are incorporated into the uncured resin by admixing.
Preferably, the high molecular weight polyoxyalkylenepolyamine is first admixed with the low molecular weight curing agent and/or the accelerator prior to addition to the resin. The constituents forming the curable material are then intimately admixed by standard methods and degassed in the presence of a commercial defoamer and minute amounts of silicone oils to prevent voids and bubbles.
Although all of the epoxy resins disclosed herein are generally useful in accordance with the instant inventive concept, those based on aliphatic compounds are preferably not used exclusively. The presence of resins containing polyglycidyl ethers of polyhydric phenols in amounts greater than 50% by weight of the resin constituent, and more preferably 80% by weight and more preferably 100% by weight has been shown to greatly enhance the desirable properties of the cured material, especially the adhesive strength.
It will further be realized that various conveniently employed additives can be admixed with the polyepoxide containing composition of the instant invention prior to final cure. For example, in certain instances it may be desired to add minor amounts of other polyalkyleneamine cocatalysts as herein described, or hardeners along with varjous other accelerators and curing agent systems well known in the art.
Additionally, conventional pigments, dyes, fillers, flame retarding agents and the like which are compatible, natural or synthetic resins can be added.
Furthermore, although not preferred, known solvents for polyepoxide materials such as toluene, benzene, xylene, dioxane, ethylene glycol monomethylether and the like can be used.
The polyepoxide resins containing the additives of the instant invention can be used in any of the above applications for which polyepoxides are customarily used. The compositions of the instant invention can be used as impregnants, surface coatings, pottings, capsulating compositions, laminates, and, particularly and most importantly, as adhesives for bonding metallic elements or structures permanently together.
The following examples illustrate the nature of the instant invention but are not intended to be limitative thereof.
Examples I and II indicate that adhesive properties were improved both with ambient and elevated curing when a low molecular weight polyoxypropylenediamine (JEFFAMlNED-230)1 was combined with a polyoxypropylenediamine of molecular weight 2000 (JEFFAMINE&commat;D- 2000).
EXAMPLE I A B C D Formulation Epoxy resin (EEW 185)2 100 100 100 100 JEFFAMINEOD-230 31 30 29 27 JEFFAMINEOD-2000 - 8 20 40 Adhesive Properties:3 Tensile shear strength, psi. 3900 4600 4000 2700 Peel strength, pli. 7.8 14.9 11.9 16.6 1See formula I. JEFFAMINEO products are of a molecular weight corresponding to the number in the name i.e. 230 and 400, 345 and 2000.
2Epoxy resin used in all examples is a diglycidyl ether of 4,4'-isopropylidene bisphenol of 185 epoxy equivalent weight.
3Bond: aluminum-to-aluminum; cure: 1/2 hr., 125"C.
EXAMPLE II A B C D Formulation Epoxy resin (EEW 185) 100 100 100 100 JEFFAMINEOD-230 31 30 29 27 JEFFAMINEO D-2000 - 8 20 40 Accelerator 398 5 5 5 5 Adhesive Properties:' Tensile shear strength, psi. 1200 1500 3100 2400 Peel strength, pli. 6.7 6.5 7.5 18.4 Bond: aluminum-to-aluminum; cure: 7 days, 25"C.
Examples Ill and IV indicate the same inprovement in adhesion properties regardless of type of cure when a more reactive, modified polyoxypropylenepolyamine (JEFFAMlNEA-345)1 was blended with JEFFAMlNED-200O.
EXAMPLE Ill A B C D Formulation Epoxy resin (EEW 185) 100 100 100 100 JEFFAMINE R TA-345 30 29 28 26 JEFFAMINE&commat;D-2000 7 7 19 38 Adhesive Properties:2 Tensile shear strength, psi. 3300 3300 3900 2800 Peel strength, pli. 8.4 11.6 21.5 23.8 'See formula ll.
2Bond: aluminum-to-aluminum; cure: 1/2 hour, 125 C.
EXAMPLE IV A B C D Formulation Epoxy resin (EEW 185) 100 100 100 100 JEFFAMlNETA-345 30 29 28 26 JEFFAMlNED-2000 - 7 19 38 Accelerator 398 5 5 5 5 Adhesive Properties:1 Tensile shear strength, psi. 1400 1600 3500 2900 Peel strength, pli 6.0 5.9 20.3 26.4 'Bond: Aluminum-to-aluminum; cured days, 25 C.
Examples V and VI indicate improved adhesion when JEFFAMINE R D-2000 is incorporated into formulations cured with known polyamine epoxy curatives.
EXAMPLE V A B C D Formulation: Epoxy resin (EEW 185) 100 100 100 100 2-Aminoethylpiperazine 23 22.5 22 20 JEFFAMlNE R D-2000 - 5.5 14 31 Adhesive Properties:' Tensile shear strength, psi. 3300 3700 3800 3700 Peel strength, pli. 8.0 11.5 22.0 26.7 'Bond: aluminum-to-aluminum; cure: 1/2 hour, 125"C.
EXAMPLE VI A B C D Formulation: Epoxy resin (EEW 185) 100 100 100 100 Bis(3-aminopropyl)ethylene diamine 15 15 15 14 JEFFAMINE R D-2000 - 4 9 20.5 Adhesive Properties:' Tensile shear strength, psi. 2300 2200 2400 3000 Peel strength, pli. 4.8 6.8 8.2 12.6 'Bond: aluminum-to-aluminum; cure: 1/2 hour, 125 C.
Example VII shows that adhesive properties are improved when a combination of JEFFA MlNE R TA-345 and JEFFAMINE R ED-900 were used to cure an epoxy resin.
A B C D E Formulation Epoxy resin (EEW 185) 100 100 100 100 100 JEFFAMlNETA-345 30 27 26 24.5 22 JEFFAMlNEED-9001 - 12 17 24.5 34 Accelerator 398 5 5 5 5 5 Adhesive Properties:2 Tensile shear strength, psi. 1400 950 1500 2900 2700 Peel strength, pli 6.0 5.2 5.8 10.5 15.4 'See formula IV 2Cured 7 days, R.T. (~25 C) EXAMPLE VIII This example demonstrates that there is little or no improvement in adhesive properties when the higher molecular weight material is about 400 as opposed to using either of the curing agents alone.
A B C D Formulation: Epoxy resin (EEW 185) 100 100 100 100 JEFFAMlNED-230 30 23 17 - JEFFAMINE R D-400 - 15 26 55 Accelerator 398 5 5 5 5 Adhesive Properties:' Tensile shear strength, psi. 600 700 1300 2900 Peel strength, pli. 0.4 0.3 0.2 1.8 'Bond: aluminum-to-aluminum; cured days, about 25 C Examples IX and X demonstrate that no improvement in adhesive properties is realized when the lower molecular weight curing agent has a molecular weight of about 400.
EXAMPLE IX A B C D Formulation: Epoxy resin (EEW 185) 100 100 100 100 JEFFAMINED-400 57 55.5 54 52 JEFFAMlNED-2O00 - 6.5 13 22 Accelerator 398 10 10 10 10 Adhesion Properties:' Tensile shear strength, psi. 2600 1700 2100 1000 Peel strength, pli. 2.8 4.5 10.4 16.6 'Cured 7 days, R.T. (about 25 C); bond: Al-to-Al EXAMPLE X A B C D E F Formulation: Epoxy resin (EEW 185) 100 100 100 100 100 100 JEFFAMINEOD-400 57 54 52 50 47 43 JEFFAMlNED-2O00 - 13 22 33 47 65 Adhesive Properties' Tensile shear strength, psi. 3700 2200 2700 1 300 900 500 Peel strength, pli. 8.9 15.2 26.7 32.2 25.3 20.5 'Same as Example IX

Claims (11)

1. A curable epoxy resin composition which comprises: (a) a vicinal polyepoxide having an average of at least 1.8 reactive 1,2-epoxy groups per molecule: (b) a polyamide curing agent having at least 3 reactive amino hydrogens; and, (c) an additive comprising a polyoxyalkylenepolyamine having a molecular weight of from 900 to 4000.
2. A composition as claimed in Claim 1 which comprises an accelerator.
3. A composition as claimed in Claim 1 or 2 wherein the vicinal polyepoxide is the diglycidyl ether of bisphenol A.
4. A composition as claimed in any preceding Claim wherein the polyamine curing agent (b) is a polyoxyalkylene polyamine having a molecular weight from 200 to 350.
5. A composition as claimed in any preceding Claim wherein the additive (c) has the formula
wherein X= hydrogen, methyl or ethyl; Z is a hydrocarbon radical having 2 to 5 carbon atoms and a valence of r ris 2 to 4; and n is a positive number sufficient to provide a molecular weight from 900 to 4000.
6. A composition as claimed in Claim 5 wherein the additive (c) has the formula:
wherein X is hydrogen, methyl or ethyl; Z' is alkylene having from 2 to 5 carbon atoms; and n is a positive number sufficient to provide a molecular weight from 900 to 4000.
7. A composition as claimed in any of Claims 1 to 4 wherein the additive (c) has the formula:
wherein X, Z, n and rhave the meanings given in Claim 5, and yis 2 or 3.
8. A composition as claimed in any of Claims 1 to 4 wherein the additive (c) has the formula:
wherein A and B are each 0 or a positive number sufficient to provide a molecular weight of from 900 to 4000.
9. A cured epoxy resin composition obtained by curing a curable epoxy resin composition as claimed in any of the preceding Claims.
10. A method for increasing the adhesive strength of an epoxy resin composition which is the cured product of a curable mixture comprising which is the cured product of a curable mixture comprising a vicinal polyepoxide having an average of at least 1.8 reactive, 1,2-epoxy groups per molecule; and a polyamine curing agent having at least 3 reactive amino hydrogens, wherein a polyoxyalkylenepolyamine having a molecular weight of from 900 to 4000 is added to the curable mixture.
11. A composition as claimed in Claim I and substantially as hereinbefore described with reference to any of the Examples.
GB7924094A 1978-10-16 1979-07-11 Novel epoxy curing agent Withdrawn GB2031431A (en)

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FR (1) FR2453872A3 (en)
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Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0087075A1 (en) * 1982-02-18 1983-08-31 Henkel Kommanditgesellschaft auf Aktien Process for the preparation of composite films
EP0109173A1 (en) * 1982-10-15 1984-05-23 Texaco Development Corporation Water based epoxyresin coating composition
EP0397347A3 (en) * 1989-05-12 1992-07-01 Texaco Development Corporation Novel epoxy polyurethane polyurea products
EP1921100A1 (en) * 2006-11-13 2008-05-14 Air Products and Chemicals, Inc. Use of a polyamine stream as curing agent in epoxy adhesive and flooring applications
US7655736B2 (en) 2006-06-09 2010-02-02 Air Products And Chemicals, Inc. Polyamide curative from substituted amine mixture and dimer fatty acid or ester
US7670499B2 (en) * 2004-07-09 2010-03-02 Huntsman Advanced Materials Americas Llc Composition of polyetherdiamine, monoamine, di- or triamine, and alkylphenol
WO2012125240A2 (en) 2011-03-15 2012-09-20 Air Products And Chemicals, Inc. Polyamides and amidoamines from selectively modified amine amines
US8293863B2 (en) 2006-06-09 2012-10-23 Air Products And Chemicals, Inc. Polyamide curative from substituted amine and dimer fatty acid or ester
WO2017136333A1 (en) 2016-02-02 2017-08-10 Evonik Degussa Gmbh Amidoamine and polyamide curing agents, compositions, and methods
WO2018118693A1 (en) 2016-12-19 2018-06-28 Evonik Degussa Gmbh Polyamides and amidoamines derived from hyroxyalkylpolyamines: epoxy curing agents with improved properties
CN111218247A (en) * 2020-03-24 2020-06-02 Tcl华星光电技术有限公司 Frame glue material and liquid crystal display panel
EP3969498A4 (en) * 2019-05-16 2023-01-18 Evonik Specialty Chemicals (Nanjing) Co., Ltd. CURING COMPOSITION

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AU656917B2 (en) * 1990-10-09 1995-02-23 Mcneil-Ppc, Inc. Epoxy Resin Reaction Products
DE4132982A1 (en) * 1991-10-04 1993-04-08 Grundfos Int Additives improving elasticity and strength of epoxy] resins for stators - comprising polyoxyalkylene amine(s) and opt. also poly:alkylene glycol(s) and/or thermoplastic phenoxy] resins
JP2010116515A (en) * 2008-11-14 2010-05-27 Denki Kagaku Kogyo Kk Epoxy resin composition and sheet

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JPS5923570B2 (en) * 1978-05-18 1984-06-02 三井化学株式会社 epoxy resin composition

Cited By (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0087075A1 (en) * 1982-02-18 1983-08-31 Henkel Kommanditgesellschaft auf Aktien Process for the preparation of composite films
EP0109173A1 (en) * 1982-10-15 1984-05-23 Texaco Development Corporation Water based epoxyresin coating composition
EP0397347A3 (en) * 1989-05-12 1992-07-01 Texaco Development Corporation Novel epoxy polyurethane polyurea products
US7670499B2 (en) * 2004-07-09 2010-03-02 Huntsman Advanced Materials Americas Llc Composition of polyetherdiamine, monoamine, di- or triamine, and alkylphenol
US8293863B2 (en) 2006-06-09 2012-10-23 Air Products And Chemicals, Inc. Polyamide curative from substituted amine and dimer fatty acid or ester
US7655736B2 (en) 2006-06-09 2010-02-02 Air Products And Chemicals, Inc. Polyamide curative from substituted amine mixture and dimer fatty acid or ester
EP1921100A1 (en) * 2006-11-13 2008-05-14 Air Products and Chemicals, Inc. Use of a polyamine stream as curing agent in epoxy adhesive and flooring applications
WO2012125240A2 (en) 2011-03-15 2012-09-20 Air Products And Chemicals, Inc. Polyamides and amidoamines from selectively modified amine amines
US8513376B2 (en) 2011-03-15 2013-08-20 Air Products And Chemicals, Inc. Polyamides and amidoamines from selectively modified amine amines
WO2017136333A1 (en) 2016-02-02 2017-08-10 Evonik Degussa Gmbh Amidoamine and polyamide curing agents, compositions, and methods
US10676564B2 (en) 2016-02-02 2020-06-09 Evonik Operations Gmbh Amidoamine and polyamide curing agents, compositions, and methods
WO2018118693A1 (en) 2016-12-19 2018-06-28 Evonik Degussa Gmbh Polyamides and amidoamines derived from hyroxyalkylpolyamines: epoxy curing agents with improved properties
US11530293B2 (en) 2016-12-19 2022-12-20 Evonik Operations Gmbh Polyamides and amidoamines derived from hydroxyalkylpolyamines: epoxy curing agents with improved properties
EP3969498A4 (en) * 2019-05-16 2023-01-18 Evonik Specialty Chemicals (Nanjing) Co., Ltd. CURING COMPOSITION
CN111218247A (en) * 2020-03-24 2020-06-02 Tcl华星光电技术有限公司 Frame glue material and liquid crystal display panel

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IT1205227B (en) 1989-03-15
IT7926500A0 (en) 1979-10-15

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