CA1238447A - Diethyl toluene diamine hardener systems - Google Patents
Diethyl toluene diamine hardener systemsInfo
- Publication number
- CA1238447A CA1238447A CA000491211A CA491211A CA1238447A CA 1238447 A CA1238447 A CA 1238447A CA 000491211 A CA000491211 A CA 000491211A CA 491211 A CA491211 A CA 491211A CA 1238447 A CA1238447 A CA 1238447A
- Authority
- CA
- Canada
- Prior art keywords
- hardener
- polyepoxide
- bis
- diamine
- epoxy
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
Classifications
-
- 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
- C08G59/182—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 using pre-adducts of epoxy compounds with curing agents
- C08G59/184—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 using pre-adducts of epoxy compounds with curing agents with amines
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D303/00—Compounds containing three-membered rings having one oxygen atom as the only ring hetero atom
- C07D303/02—Compounds containing oxirane rings
- C07D303/12—Compounds containing oxirane rings with hydrocarbon radicals, substituted by singly or doubly bound oxygen atoms
- C07D303/18—Compounds containing oxirane rings with hydrocarbon radicals, substituted by singly or doubly bound oxygen atoms by etherified hydroxyl radicals
- C07D303/20—Ethers with hydroxy compounds containing no oxirane rings
- C07D303/24—Ethers with hydroxy compounds containing no oxirane rings with polyhydroxy compounds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D303/00—Compounds containing three-membered rings having one oxygen atom as the only ring hetero atom
- C07D303/02—Compounds containing oxirane rings
- C07D303/12—Compounds containing oxirane rings with hydrocarbon radicals, substituted by singly or doubly bound oxygen atoms
- C07D303/18—Compounds containing oxirane rings with hydrocarbon radicals, substituted by singly or doubly bound oxygen atoms by etherified hydroxyl radicals
- C07D303/28—Ethers with hydroxy compounds containing oxirane rings
-
- 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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
-
- 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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/64—Macromolecular compounds not provided for by groups C08G18/42 - C08G18/63
- C08G18/6415—Macromolecular compounds not provided for by groups C08G18/42 - C08G18/63 having nitrogen
- C08G18/643—Reaction products of epoxy resins with at least equivalent amounts of amines
Abstract
Diethyl toluene diamine hardener systems Abstract of the Disclosure A resinous hardener system comprising the reaction product of diethyl toluene diamine and an epoxide having a functionality of at least two, the hardener being capable of incorporation into a variety of epoxy and urethane resins.
Description
3-15081i=/CGC 1096 Deathly Tulane Damon hardener systems Adduces from smins3 and moo- and diepoxides have long been Tad in industry a curing agents for epoxy resin. The advantages no the formation of such adduces include tower volatility, lower irritation potential or reduced tendency to blush and exude. Such adequate and the advantageff thereof are discussed in Lee and Seville, Handbook of Epoxy Resins, McGraw Hill ~1967). It it to be noted, Hoover that such adduces may not exhibit significant improvement Lo chemical resistance over that of their free amine counterpart.
More specifically, such adduces have been prepared from diethylen-thiamine with diglycidylether6 of bisphenol A of varying molecular weight. These epoxy resins have all exhibited a functionality of not more than two end have exhibited various improved performance characteri~ticss As previously noted, however, they have been deficient in the important characteristic of resistance to chemical attack, and primarily to solvent attack Likewise, ethylene dianiline-diglycidyl ether bi~phenol A it a preferred curing agent for heat r33istant epoxy resin compounds.
However, ethylene dianilin~ it conaldered a carcinogen by the environmental Protection Agency.
For example, U.S. Patent No. 3,655,624, 3,?04,281 and 3,~96,186 disclose adduces of triglycidyl i30cyanurate and Amy. Those adequate are solid in form, are noted for use -in molding maternal and are generally lnfer:Lo~ in terms of solvent ruttiness. Thus, these materials would have limited value as protective coatings.
I
Additionally, U.S. Patent JOB. 3,538,184, 3,625,918 and 3,629,181 disclose amine adduces which are based on epoxy resins of the bisphenol A Kyle or are alicyclic epoxy resin. While such adduces exhibit improved handling and mechanical properties, it it to be noted that the resins used therein have a functionality of not more than two and that the adduces are again deficl0nt in the important characteristic of resistance to chemical attack.
Other corresponding systems are disclosed in U.S. Patent Nos.
3,996,175 and 4,348,505.
It is the primary object of this invention to prepare novel liquid adduces of dlethyl Tulane dlamine and do- and polyepoxides.
It is a further object to provide adduces for use as curing agents for epoxy and urethane resins.
It is still B further object to provide sunk curing agents which overcome the disadvantages of prior art curing agents when said curing agent are combined with a wide variety of epoxy and urethane resins.
It has now been surprisingly discovered that the preparation of deathly Tulane Damon adduce curing agents with epoxldes of functionality of at least two or urethanes enhances the performance characteristics of the cured epoxy and urethane product. Relative to epoxy resin, in contrast to thy free amine counterpart which requires an excessively long time to cure to a B-stage at room temperature because of it limited reactivity with epoxy resins, the instant adduce substantially shortens thy cure time without a significant reduction in physical properties. Formulated hardeners can be prepared from these adduces to cure At room temperature or to cure to a "B stage" at room temperature and reflow at elevated temperatures. Hardeners formulated from these adduces are specially useful in making heat cured laminate where a reflow Yates aide in obtaining optimum properties. Thy reflow hardener of this invention will cure to a semi-solid B stage at room temperature and the return to a liquid at an elevated temperature. When used in a laminate a reflow system allows the resin to thoroughly penetrate the fiber and avoid air pockets. The absence of air pocket allows the laminate to be used at higher temperatures with increased stability.
Additionally, such adduces are not viewed as carcinogens, sr0 non-staining and are liquid at room temperature.
Deathly Tulane Damon corresponding to the formula Ho SHEA I-\ /C2Hs Q
Ho ~2~5 is the dominant Damon component. It is to be noted, however, that other positional isomers such a 2-methyl-~,6-diethyl-1,3-benzene dlamine may be prevent in combination with the above noted isomer a the applicable Damon component for purposes of this invention.
Commercially available dominoes will generally comprise about 75 %
of the deathly Lamar and about I % of deathly isomer with the remainder consulting of other related component.
There it, for example, available a diethyltoluen0 Damon mixture consisting of 7S,5 % 3,5-diethyltoluene-2,4-diamine, 21,0 % 3,5-diethyltolu0ne-2,6 dlamlne, 3,3 % dialkylated m-phenylenediamine, 0,4 % other trialkylat2d m-phenylene Damon and Owl % other compounds (quantities refer to percent by weight).
The multi~unctional epoxide component can be selected from broad rang ox al~pbatic and aromatic epoxies having a functionality of at least two. Typical material include diglycidyl ether of bus-phenol A, epoxy phenol novolacs, l,4-butane dill diglycidyl ether, epoxy crossly novolaca, triglycidyl pyromania phenol, triglycidyl tria(p-hydroxyphenyl)methane, tetraglycidyl-1,1,2,2 tetrak~ B
Lo 7 (p-hydroxyphenyl~ethane~ vinyl cyclohexene d~oxlde, NtN,NI,Nl-tatraglycidyl-4,41 ethylene bi3-benzeneamine, N,N,Nl,NI-tetra-glycidyl meta-xylene Damon, diglycidyl aniline, resorcinol diglycidyl ether, the diglycidyl ethers of catcall or hydra-quinine, diglycidyl ortho-toluidine, diglycidyl i~ophthalate, bisphenol P and S epoxy resin, and N,N,Nl,NI-tetraglycidyl 1,3 bis-amlno-methylcyclohexane. The various ethers may by substituted on thy respective phenol rings by such non-reactive substituents a alkyd or halogen.
Preferred components correspond to a) Chic z 1O-CHz-C ~-C~2 0-CHz-C~Iz Jo \. Jo ! *-SHEA -I *-SHEA \.
n wherein R it hydrogen or methyl, and n it 0,2-3,4. These components are exemplified by the epoxidation products of cry novolac~ and phenol novolacs of varying molecular wright. The preparation of aura materials it well Known in the art;
(b) diglycidyl ethers of bisphenol3 corresponding to the formula _ / X \ _ Jo couch I
-C-CHz-C~-~I2 wherein m is 0-50 and X it -SHEA-, Ho I
or US-.
These represent, respectively, biQphenol~ F, A and S;
(c) 1,4-butanediol diglycidyl ether.
Especially preferred as multi functional epoxide components are glycidylised nGvolaks of type pa), wherein the group R it in ortho-position to the glycidyl ether group.
The new adduces of this invention are generally prepared by charging the amine to the reaction vessel and heating to a temperature of 80 to 100C. The polyepoxlde, preferably preheated, 18 thin added over a period of from 60 to 180 minutia, allowing a maximum exotherm up to about 125C. At the conclusion of the p~lyepoxide feed, the reaction mixture is generally heated to 80 to 125C for a period of about 2 to 6 hours 9 to ensure completeness of the reaction. The progress of the reaction can be followed by titration of the epoxide groups using samples taken during the reaction, completion being indicated by the absence of epoxy groups. The adequate are liquid at room temperature with medium viscosity.
With regard to the relative concentrations of the component, the dlamine it prevent in excess in the preparations of the adequate.
Thus, mole ratios of from about 2 to 20, preferably from about 2 to 10, moles of dlamine per mole of polyapoxlde are utilized with 4 to 8 moles of Damon per mole of polyepoxide being proofread and 6 mole of Damon per mole of polyepoxide being particularly preferred.
Other amine may be optionally added to the adduces in order to provide hardeners which yield specifically desired properties in the cured resin.
A suitable amine, there may be mentioned aliphatic, cycloaliphatic or aromatic primary and secondary amine, with the aliphatic and cycloallphatic amine being preferred. Typical amine include monoethanolamine, N-aminoethyl ethanol amine, ethylenediamine, hexamethylene-diamine, trimethylhexamethylenediamine, diethylene-tslamlne, triethylenetetsamlne, tetraethylenepentamine, NUN-dimethylpropylenedlamine-1,3, N,N-diethylpropylenediamine-1,3, bis(4-amino-3-methylcyclohexyl~methane, bis~p-amlnocyclohexyl)-methane, 2,2-bls(4-aminocyclohexyl)-propane, 3,5,5-trimethyl- 9-(amlnomethyl)-cyclohexylamine, N-aminoethyl-piperazine, m-phenylene-diamlne, p-phenylenediamine, bis-(p-aminophenyl)methane, wisp aminophenyl)-sulfone, m-xylylenedlamine, Tulane Damon, 1,2-diaminocyclohexane, 1,4-diaminocyclohexane, 1,3-bis(aminomethyl)-cyclohexane, 1,4-bis(aminomethyl)cyclcohexane, isophorone Damon and l-methyl-imidazole.
Preferred amine include diethyleDetriamine, triethylenetetramine, tetraethylenepentamine, 1,2-diaminocyclohexane, bus (p-amino-cyclohexyl)methane, m-xylylenediamine, isophorone Damon, 1,4-bis(aminomethyl)cyclohexane~ N-aminoethyl-piperazine, 1,3-bin-(amino methyl) cyclohexane, bin(p-aminophenyl~methane and loathly imidazole.
These amine are prevent in maximum concentrations of about 75 %, by weight of the total hardener composition, and preferably on a maximum concentration of 55 %, by weight.
As previously noted, the modified hardener systems can be processed with a wide variety of epoxy resins. Included among such resins are epoxide resins Bud on polyhydrlc phenols such an those based on bisphenol A, F, and S, epoxldation product of cranial novGlacs, and epoxidation products of phenol novolacs; hydantlon epoxide rosins;
polyglycidyl ester; glycidylated aromatic amlne3; glycidylated amino phenols; and certain cycloaliphatic epoxy resins. In adhesive, coating and filament winding applications, resin boned on the diglycldyl ether of boisphenol A is widely used. The modified hardener is utilized in stoichiomatric amounts * 50 % relative to the epoxy resin, preferably the modified hardens is utilized in stoichlometric amounts + 15 % relative to the epoxy rosin.
I
Apart from the above areas of utility, the adults of this invention are useful a curing agent for a wide variety of epoxy in various heat cured application. When combined with dip and polyepoxides, at generally stoichlometric amounts, and cured at elevated tempera-lures, a network of high cro~slink density occurs. Accordingly, the expression "cure" as used herein, denote the conversion of the above adduces and epoxide material into insoluble and infusible cross linked productfl, with simultaneous shaping to give shaped articles such as castings, pressings or laminate, or to give two-dimen~ional structures such as coatings, enamel or adhesive bond. The modified hardener system it particularly advantageous for the formation of coatings because of the improved compatibility with resins and the improved toughness of the resulting cured coatings.
The adduces prepared according to the invention and admixed with other polyepoxide compounds can furthermore be mixed, at any stage before cure, with usual modifiers such as extenders, filler, and reinforcing agents, pigments, distaffs, organic solvent plastic-iris, tacklfiers, rubbers, accelerator or delineate.
A extenders, reinforcing agent, filler and pigment which can be employed in the curable mixture according to the invention there may be mentioned, for example: coal tar bitumen, glass fibers, boron fibers, carbon buyers, cellulose, polysthylane powder, polypropylene powder, mica, asbestos, quartz powder gypsum, antimony trioxides Ben tones, talc silica argyle ("Arousal"), lithopone, Burt, calcium carbonate, titanium dioxide, carbon black, graphite, iron oxide, or metal powders such a aluminum powder or iron powder. It 18 alto possible to add other usual additive, for example, flame proofing agents, agents for conferring thixotropy, flow control agent such as silicone cellulose acetate bitterroot, polyvinyl bitterly, waxes or Stewart (which are in part also used as newlywed release agents to the curable mixtures.
The accelerators, when utilized, function to speed the curing operation in the preparation of thin films, i.e. films of a maximum of 200 em thickness per coat. Typical accelerators include aromatic colds such as benzoic and sallcylic acids; phenols such as phenol, p-tert.butyl phenol, bisphenol A and nonyl phenol; and aromatic alcohols such as bouncily alcohol.
The solvents modify the curable blends, particularly Mervin to control Yiscositiy. Applicable solvents include ether alcohols such as ethylene glycol monomethylether, -mono-athylether, -monobutyl-ether, and the diethylene glycol analogs; aromatic hydrocarbons such as zillion and Tulane.
It is also possible in adhesive formulations, for example, to add rubbers such as carboxyl-terminated acrlyonitrile-butadiene rubber, modifying resins such as triglycidyl p-amlnophenol, accelerators such as boron trifluoride monoethylamine complexes or imida~ole complexes, and other additional hardeners such as dlcyandiamide.
The curable mixtures can be manufactured in the usual manner with the aid of known mixing equipment (stirrers, kneaders or rollers).
The curable epoxide resin mixtures are especially useful in the fields of surface protection, the electrical industry, laminating processes and the building industry. They can be used in a forum-lotion which it in each case suited to the particular end use, id the unfilled or filled state, optionally in the form of solutions or emulalons, as paints enamel, sistering powders, compression molding compositions, dipping resins, casting resins, injection molding formulations, impregnating resins and adhesives, as tooling resins, laminating resins, sealing and filling compassion, floor covering compositions and binders or mineral aggregate.
Of primary interest, is their utility in making heat cured laminates wherein the previously noted reflow properties aid in obtaining optimum performance characteristics. Thus, the formulated hardeners Jo . .
~.~93~
_ 9 _ are especially useful in making heat cured laminates where a reflow system aids in obtaining optimum properties. As previously noted, the reflow hardeners of this invention will cure to a ~eml-solid B
state at room temperature and then return to a liquid at an elevated temperature. When used in a laminate, a Roy system allows the resin to thoroughly penetrate the fires and avoid air pockets. The absence of elf pocket allow the laminate to be used at higher temperatures with increased stability.
The adduces of this invention can likewise be readily utilized to cure a wide variety of urethane resin composltons in various heat cured application These hardener can be readily incorporated into urethane resins compositions by known mixing techniques familiar to practitioner skilled in the art.
The polyisocyanates which can be used in the curable polyurethane resin compositions include any of those commonly employed in making polyurethane plflstics or resins such a Tulane dil~ocyanate, 4,4-diphenylmethane diisocyanate, polyaryl polylsocyanates, and hexamethylene diisocyanatQ, or less conventional onus such as phenylindane diisocyAnate. A 18 well known, resins made from sunk polyisocysnates ens brittle so that for most purposes it is pro-furred to use the conventional polyisocyanste prepolymers having an average of more than a jingle isocyanate group per molecule, made by pre-rea&tlng a molecular excess of a doesn't such as one of the foregoing with an Organic material containing at least two hydroxyl groups per molecule and having a molecular weight of at least 300, such as castor oil, a hydroxy-terminated polyether, e.g., a polyp alkaline glycol in which each alkaline group contains from 2 to 6 carbon atoms, a hydrvxy-termlnated polyester, particularly an aliphatic polyester of an alkaline glycol in which each alkaline contains 2 to 6 carbon atoms with an aliphatic polycarboxylic acid which contains in addition to the carboxyl group only hydrocarbon groups, the total numbs of carbon atoms in the acid being prefer-ably from 3 to 10, or a hydroxy-te~minated polybutadlene or butsdiene~acrylonitrlle copolymer. Polyethar~ such as polyethylene - 10- ~23~
glycol, polypropylene glycol and polytetramethylene glycol having molecular weights from 300 to 2,000 and polyesters such as the hydroxy-containing polyesters of any of the polyalkylene glycols, preferably those having 2 to 6 carbon atoms, with polycarboxylic acids containing from 3 to 10 carbon atoms and containing only hydrocarbon groups in addition to carboxyl groups are also pro-furred. Such polyesters have an average equivalent weight (based on hydroxyl groups of 150-1,000 and have 2 to 4 hydroxyl groups per molecule. Prspolymer~ are preferred which are made by reacting at least two molecular proportions of a dli~ocyanate as described above with a polyalkylene glycol as described above to form a p~epolymer having an equivalent weight (based upon isocyanate groups) of 400-1,500, but other prepolymer~ having an equivalent weight (isocyanate) within the same range are also desirable. Partially blocked polyi~ocyanates are alto applicable.
When combined with polyurethane at generally stoichiometric amounts and cured at elevated temperatures, the previously noted network of high crossllnk density for epoxy resins it alto evident with the urethane. These systems can also be mixed with the various optional ingredients noted hereinabove as well as with typical urethane extenders and plasticizers.
The following samples will further ill~stIate the embodiments of the instant invention. In these examples, all part are given by weight unless otherwise noted.
Example 1 This example illustrates the preparation of a typical modified hardener of the instant invention.
An adduce of deathly Tulane Damon and diglycidyl ether of bi~phenol A was made at a molar ratio of 4:1. 531 gym of deathly Tulane Damon (76 % deathly isomer and 19 % deathly isomer- ETHAC~RE~ 100 from Ethyl Corp.) were weighed into a reaction flask equipped with mechanical stirrer, thermometer and healing Jacket. The flask was heated with stirring to 80C. 269 gym of preheated diglycidyl ether of bisphenol A having an epoxide content of 5,1-5,5 equ./kg were added to the flask through a dropping funnel. The temperature way raised to 100C and maintained for one hour with an exotherm to 125C.
There in obtained an adduce having an average molecular weight ranging from 720-740.
Example 2 An adduce of deathly Tulane Damon (the swamp as used in Example 1) and an epoxy phenol novolac resin was made at a molar ratio of 6-1.
680 gym of deathly Tulane dlamine were weighed into a reaction flask equipped with a mechanical stirrer, thermometer and heating jacket.
120 gym of preheated epoxy phenol novolac reloan having an epoxide content of 5,5-5,7 equ./kg were added Wylie with stirring. After the addition way complete the temperature aye maintained at 100C
for 3 hours on order to complete the reaction.
There is obtained an adduce having peaks of maximum ab~orbance in the IT spectrum at: 3370, 2957, 2891, 1625, 1478 and 1451 cm The product ha a softening point of -21~C.
Example 3-4 The procedure of Example 1 was repeated utilizing the fallowing component 8:
Part en 3 Example 4 Diglycidyl ether of blsphenol A I 28.1 --1,4-butanediol dlglycidylether -- 18.5 Deathly Tulane diamlne (as in Example 1)71.9 81.5 1) DORIA 332 from DOW (epoxide content of 5,7 equ./kg) Following data characterize the adequate of example 3 and 4:
Example 3 Example 4 Softening point (C) -15 -20 Maximum IT absorbency (cm ) 3380, 2957, 3370, 2957, 2891, 16259 2091, 1625, 1~78, 1~51 14789 1451 Example 5 Thy following example it directed to the physical and performance characteristics of processed epoxy resins utilizing the hardeners of Examples 1-4.
The resin systemfl were prepared by blending the resin component wit}
the optional ingredients and the hardener at room temperature. The epoxy resin utilized for Formulation A hereinafter was a blend of 65 parts diglycidyl ether of bi3phenol A (DORIA 332), 25 parts of epoxy phenol novolac baa in example 2) and 10 part of 1,4-butane-dill dlglycidyl ether. The epoxy resin utilized for Formula lions B-G hereinafter was an 45 parts iron oxide filled epoxy blend utilizing 47 parts diglycidyl ether of blsph3nol A (DORIA 332) and 3 parts 1,4-butanadiol diglycidyl ether.
The following characteristics were then determined:
Mixed Viscosity - The vacuity of the blended epoxy-hardener system was measured with a Brook field RVF viscometer using spindle 3 at 20 rum at 23-25C. Samples were mixed for two minutes and the viscosity reading taken one minute thereafter.
heat Deflection Temperature - Determined according to ASTM D-648-82.
The liquid material WEBB poured into a shoed mold, cured overnight at room temperature and then at the indicated cure schedule. The test was conducted using a load of 18~2 bar on a sample size of 1~27 cm x 1.21 cm x 1.27 cm.
Pot life - Thy specified quantities of mixed epoxy resin and hardener were reacted in n metal can at room temperature until cured. The time to complete cure was measured. The mixture was considered cured when it became solid at room temperature.
Thin Layer Tack Time - This text is a measure of the time needed to sufficiently aura a mixed system to a solid form such that a finger imprint remains visible on the surface. The test proceeds by depositing a 500 em layer of the epoxy system on a surface, at room temperature, and periodically putting a finger imprint on the surface thereof.
Parts , formulation A B C D E G
__ __ _ .__ _ _ __ Example 1 adduce 45 _ _ _ _ _ Example 2 adduce _ 35 23 85 90 Example 3 adduce _ 50 39 _ _ 50 50 Example 4 adduce _ _ 9 _ 35 Triethylene tetramin 50 _ _ _ _ Deathly Tulane Damon _ _ 9 _ _ 35 m-Xylene Damon _ 15 15 15 10 15 15 l-Methyl imidazole 5 _ _ _ _ _ Ratio of modified epoxy resin to hardener 100/13 100/17 outyell 100/13 100/15 100/16 100/17 I
Formulation A B C D E F G
_ . _ _ __ Mixed Viscosity (CUPS) 1660 _ _ _ _ _ Heat Deflection Temp.* (C)141 146 146 148 152 145 143 Cure Schedule 1 2 2 2 2 2 2 Pot Life (total wt. 175 gym) (min.) 65 _ _ _ _ _ _ . _ _ Pot Life (total wt. 210 gym) (his.) _ _ _ 35 50 _ 20 _ _ _ _ Thin Layer Tack Time (his.) _ _ _ 16 20 _ *) Cure Schedule - 1 2
More specifically, such adduces have been prepared from diethylen-thiamine with diglycidylether6 of bisphenol A of varying molecular weight. These epoxy resins have all exhibited a functionality of not more than two end have exhibited various improved performance characteri~ticss As previously noted, however, they have been deficient in the important characteristic of resistance to chemical attack, and primarily to solvent attack Likewise, ethylene dianiline-diglycidyl ether bi~phenol A it a preferred curing agent for heat r33istant epoxy resin compounds.
However, ethylene dianilin~ it conaldered a carcinogen by the environmental Protection Agency.
For example, U.S. Patent No. 3,655,624, 3,?04,281 and 3,~96,186 disclose adduces of triglycidyl i30cyanurate and Amy. Those adequate are solid in form, are noted for use -in molding maternal and are generally lnfer:Lo~ in terms of solvent ruttiness. Thus, these materials would have limited value as protective coatings.
I
Additionally, U.S. Patent JOB. 3,538,184, 3,625,918 and 3,629,181 disclose amine adduces which are based on epoxy resins of the bisphenol A Kyle or are alicyclic epoxy resin. While such adduces exhibit improved handling and mechanical properties, it it to be noted that the resins used therein have a functionality of not more than two and that the adduces are again deficl0nt in the important characteristic of resistance to chemical attack.
Other corresponding systems are disclosed in U.S. Patent Nos.
3,996,175 and 4,348,505.
It is the primary object of this invention to prepare novel liquid adduces of dlethyl Tulane dlamine and do- and polyepoxides.
It is a further object to provide adduces for use as curing agents for epoxy and urethane resins.
It is still B further object to provide sunk curing agents which overcome the disadvantages of prior art curing agents when said curing agent are combined with a wide variety of epoxy and urethane resins.
It has now been surprisingly discovered that the preparation of deathly Tulane Damon adduce curing agents with epoxldes of functionality of at least two or urethanes enhances the performance characteristics of the cured epoxy and urethane product. Relative to epoxy resin, in contrast to thy free amine counterpart which requires an excessively long time to cure to a B-stage at room temperature because of it limited reactivity with epoxy resins, the instant adduce substantially shortens thy cure time without a significant reduction in physical properties. Formulated hardeners can be prepared from these adduces to cure At room temperature or to cure to a "B stage" at room temperature and reflow at elevated temperatures. Hardeners formulated from these adduces are specially useful in making heat cured laminate where a reflow Yates aide in obtaining optimum properties. Thy reflow hardener of this invention will cure to a semi-solid B stage at room temperature and the return to a liquid at an elevated temperature. When used in a laminate a reflow system allows the resin to thoroughly penetrate the fiber and avoid air pockets. The absence of air pocket allows the laminate to be used at higher temperatures with increased stability.
Additionally, such adduces are not viewed as carcinogens, sr0 non-staining and are liquid at room temperature.
Deathly Tulane Damon corresponding to the formula Ho SHEA I-\ /C2Hs Q
Ho ~2~5 is the dominant Damon component. It is to be noted, however, that other positional isomers such a 2-methyl-~,6-diethyl-1,3-benzene dlamine may be prevent in combination with the above noted isomer a the applicable Damon component for purposes of this invention.
Commercially available dominoes will generally comprise about 75 %
of the deathly Lamar and about I % of deathly isomer with the remainder consulting of other related component.
There it, for example, available a diethyltoluen0 Damon mixture consisting of 7S,5 % 3,5-diethyltoluene-2,4-diamine, 21,0 % 3,5-diethyltolu0ne-2,6 dlamlne, 3,3 % dialkylated m-phenylenediamine, 0,4 % other trialkylat2d m-phenylene Damon and Owl % other compounds (quantities refer to percent by weight).
The multi~unctional epoxide component can be selected from broad rang ox al~pbatic and aromatic epoxies having a functionality of at least two. Typical material include diglycidyl ether of bus-phenol A, epoxy phenol novolacs, l,4-butane dill diglycidyl ether, epoxy crossly novolaca, triglycidyl pyromania phenol, triglycidyl tria(p-hydroxyphenyl)methane, tetraglycidyl-1,1,2,2 tetrak~ B
Lo 7 (p-hydroxyphenyl~ethane~ vinyl cyclohexene d~oxlde, NtN,NI,Nl-tatraglycidyl-4,41 ethylene bi3-benzeneamine, N,N,Nl,NI-tetra-glycidyl meta-xylene Damon, diglycidyl aniline, resorcinol diglycidyl ether, the diglycidyl ethers of catcall or hydra-quinine, diglycidyl ortho-toluidine, diglycidyl i~ophthalate, bisphenol P and S epoxy resin, and N,N,Nl,NI-tetraglycidyl 1,3 bis-amlno-methylcyclohexane. The various ethers may by substituted on thy respective phenol rings by such non-reactive substituents a alkyd or halogen.
Preferred components correspond to a) Chic z 1O-CHz-C ~-C~2 0-CHz-C~Iz Jo \. Jo ! *-SHEA -I *-SHEA \.
n wherein R it hydrogen or methyl, and n it 0,2-3,4. These components are exemplified by the epoxidation products of cry novolac~ and phenol novolacs of varying molecular wright. The preparation of aura materials it well Known in the art;
(b) diglycidyl ethers of bisphenol3 corresponding to the formula _ / X \ _ Jo couch I
-C-CHz-C~-~I2 wherein m is 0-50 and X it -SHEA-, Ho I
or US-.
These represent, respectively, biQphenol~ F, A and S;
(c) 1,4-butanediol diglycidyl ether.
Especially preferred as multi functional epoxide components are glycidylised nGvolaks of type pa), wherein the group R it in ortho-position to the glycidyl ether group.
The new adduces of this invention are generally prepared by charging the amine to the reaction vessel and heating to a temperature of 80 to 100C. The polyepoxlde, preferably preheated, 18 thin added over a period of from 60 to 180 minutia, allowing a maximum exotherm up to about 125C. At the conclusion of the p~lyepoxide feed, the reaction mixture is generally heated to 80 to 125C for a period of about 2 to 6 hours 9 to ensure completeness of the reaction. The progress of the reaction can be followed by titration of the epoxide groups using samples taken during the reaction, completion being indicated by the absence of epoxy groups. The adequate are liquid at room temperature with medium viscosity.
With regard to the relative concentrations of the component, the dlamine it prevent in excess in the preparations of the adequate.
Thus, mole ratios of from about 2 to 20, preferably from about 2 to 10, moles of dlamine per mole of polyapoxlde are utilized with 4 to 8 moles of Damon per mole of polyepoxide being proofread and 6 mole of Damon per mole of polyepoxide being particularly preferred.
Other amine may be optionally added to the adduces in order to provide hardeners which yield specifically desired properties in the cured resin.
A suitable amine, there may be mentioned aliphatic, cycloaliphatic or aromatic primary and secondary amine, with the aliphatic and cycloallphatic amine being preferred. Typical amine include monoethanolamine, N-aminoethyl ethanol amine, ethylenediamine, hexamethylene-diamine, trimethylhexamethylenediamine, diethylene-tslamlne, triethylenetetsamlne, tetraethylenepentamine, NUN-dimethylpropylenedlamine-1,3, N,N-diethylpropylenediamine-1,3, bis(4-amino-3-methylcyclohexyl~methane, bis~p-amlnocyclohexyl)-methane, 2,2-bls(4-aminocyclohexyl)-propane, 3,5,5-trimethyl- 9-(amlnomethyl)-cyclohexylamine, N-aminoethyl-piperazine, m-phenylene-diamlne, p-phenylenediamine, bis-(p-aminophenyl)methane, wisp aminophenyl)-sulfone, m-xylylenedlamine, Tulane Damon, 1,2-diaminocyclohexane, 1,4-diaminocyclohexane, 1,3-bis(aminomethyl)-cyclohexane, 1,4-bis(aminomethyl)cyclcohexane, isophorone Damon and l-methyl-imidazole.
Preferred amine include diethyleDetriamine, triethylenetetramine, tetraethylenepentamine, 1,2-diaminocyclohexane, bus (p-amino-cyclohexyl)methane, m-xylylenediamine, isophorone Damon, 1,4-bis(aminomethyl)cyclohexane~ N-aminoethyl-piperazine, 1,3-bin-(amino methyl) cyclohexane, bin(p-aminophenyl~methane and loathly imidazole.
These amine are prevent in maximum concentrations of about 75 %, by weight of the total hardener composition, and preferably on a maximum concentration of 55 %, by weight.
As previously noted, the modified hardener systems can be processed with a wide variety of epoxy resins. Included among such resins are epoxide resins Bud on polyhydrlc phenols such an those based on bisphenol A, F, and S, epoxldation product of cranial novGlacs, and epoxidation products of phenol novolacs; hydantlon epoxide rosins;
polyglycidyl ester; glycidylated aromatic amlne3; glycidylated amino phenols; and certain cycloaliphatic epoxy resins. In adhesive, coating and filament winding applications, resin boned on the diglycldyl ether of boisphenol A is widely used. The modified hardener is utilized in stoichiomatric amounts * 50 % relative to the epoxy resin, preferably the modified hardens is utilized in stoichlometric amounts + 15 % relative to the epoxy rosin.
I
Apart from the above areas of utility, the adults of this invention are useful a curing agent for a wide variety of epoxy in various heat cured application. When combined with dip and polyepoxides, at generally stoichlometric amounts, and cured at elevated tempera-lures, a network of high cro~slink density occurs. Accordingly, the expression "cure" as used herein, denote the conversion of the above adduces and epoxide material into insoluble and infusible cross linked productfl, with simultaneous shaping to give shaped articles such as castings, pressings or laminate, or to give two-dimen~ional structures such as coatings, enamel or adhesive bond. The modified hardener system it particularly advantageous for the formation of coatings because of the improved compatibility with resins and the improved toughness of the resulting cured coatings.
The adduces prepared according to the invention and admixed with other polyepoxide compounds can furthermore be mixed, at any stage before cure, with usual modifiers such as extenders, filler, and reinforcing agents, pigments, distaffs, organic solvent plastic-iris, tacklfiers, rubbers, accelerator or delineate.
A extenders, reinforcing agent, filler and pigment which can be employed in the curable mixture according to the invention there may be mentioned, for example: coal tar bitumen, glass fibers, boron fibers, carbon buyers, cellulose, polysthylane powder, polypropylene powder, mica, asbestos, quartz powder gypsum, antimony trioxides Ben tones, talc silica argyle ("Arousal"), lithopone, Burt, calcium carbonate, titanium dioxide, carbon black, graphite, iron oxide, or metal powders such a aluminum powder or iron powder. It 18 alto possible to add other usual additive, for example, flame proofing agents, agents for conferring thixotropy, flow control agent such as silicone cellulose acetate bitterroot, polyvinyl bitterly, waxes or Stewart (which are in part also used as newlywed release agents to the curable mixtures.
The accelerators, when utilized, function to speed the curing operation in the preparation of thin films, i.e. films of a maximum of 200 em thickness per coat. Typical accelerators include aromatic colds such as benzoic and sallcylic acids; phenols such as phenol, p-tert.butyl phenol, bisphenol A and nonyl phenol; and aromatic alcohols such as bouncily alcohol.
The solvents modify the curable blends, particularly Mervin to control Yiscositiy. Applicable solvents include ether alcohols such as ethylene glycol monomethylether, -mono-athylether, -monobutyl-ether, and the diethylene glycol analogs; aromatic hydrocarbons such as zillion and Tulane.
It is also possible in adhesive formulations, for example, to add rubbers such as carboxyl-terminated acrlyonitrile-butadiene rubber, modifying resins such as triglycidyl p-amlnophenol, accelerators such as boron trifluoride monoethylamine complexes or imida~ole complexes, and other additional hardeners such as dlcyandiamide.
The curable mixtures can be manufactured in the usual manner with the aid of known mixing equipment (stirrers, kneaders or rollers).
The curable epoxide resin mixtures are especially useful in the fields of surface protection, the electrical industry, laminating processes and the building industry. They can be used in a forum-lotion which it in each case suited to the particular end use, id the unfilled or filled state, optionally in the form of solutions or emulalons, as paints enamel, sistering powders, compression molding compositions, dipping resins, casting resins, injection molding formulations, impregnating resins and adhesives, as tooling resins, laminating resins, sealing and filling compassion, floor covering compositions and binders or mineral aggregate.
Of primary interest, is their utility in making heat cured laminates wherein the previously noted reflow properties aid in obtaining optimum performance characteristics. Thus, the formulated hardeners Jo . .
~.~93~
_ 9 _ are especially useful in making heat cured laminates where a reflow system aids in obtaining optimum properties. As previously noted, the reflow hardeners of this invention will cure to a ~eml-solid B
state at room temperature and then return to a liquid at an elevated temperature. When used in a laminate, a Roy system allows the resin to thoroughly penetrate the fires and avoid air pockets. The absence of elf pocket allow the laminate to be used at higher temperatures with increased stability.
The adduces of this invention can likewise be readily utilized to cure a wide variety of urethane resin composltons in various heat cured application These hardener can be readily incorporated into urethane resins compositions by known mixing techniques familiar to practitioner skilled in the art.
The polyisocyanates which can be used in the curable polyurethane resin compositions include any of those commonly employed in making polyurethane plflstics or resins such a Tulane dil~ocyanate, 4,4-diphenylmethane diisocyanate, polyaryl polylsocyanates, and hexamethylene diisocyanatQ, or less conventional onus such as phenylindane diisocyAnate. A 18 well known, resins made from sunk polyisocysnates ens brittle so that for most purposes it is pro-furred to use the conventional polyisocyanste prepolymers having an average of more than a jingle isocyanate group per molecule, made by pre-rea&tlng a molecular excess of a doesn't such as one of the foregoing with an Organic material containing at least two hydroxyl groups per molecule and having a molecular weight of at least 300, such as castor oil, a hydroxy-terminated polyether, e.g., a polyp alkaline glycol in which each alkaline group contains from 2 to 6 carbon atoms, a hydrvxy-termlnated polyester, particularly an aliphatic polyester of an alkaline glycol in which each alkaline contains 2 to 6 carbon atoms with an aliphatic polycarboxylic acid which contains in addition to the carboxyl group only hydrocarbon groups, the total numbs of carbon atoms in the acid being prefer-ably from 3 to 10, or a hydroxy-te~minated polybutadlene or butsdiene~acrylonitrlle copolymer. Polyethar~ such as polyethylene - 10- ~23~
glycol, polypropylene glycol and polytetramethylene glycol having molecular weights from 300 to 2,000 and polyesters such as the hydroxy-containing polyesters of any of the polyalkylene glycols, preferably those having 2 to 6 carbon atoms, with polycarboxylic acids containing from 3 to 10 carbon atoms and containing only hydrocarbon groups in addition to carboxyl groups are also pro-furred. Such polyesters have an average equivalent weight (based on hydroxyl groups of 150-1,000 and have 2 to 4 hydroxyl groups per molecule. Prspolymer~ are preferred which are made by reacting at least two molecular proportions of a dli~ocyanate as described above with a polyalkylene glycol as described above to form a p~epolymer having an equivalent weight (based upon isocyanate groups) of 400-1,500, but other prepolymer~ having an equivalent weight (isocyanate) within the same range are also desirable. Partially blocked polyi~ocyanates are alto applicable.
When combined with polyurethane at generally stoichiometric amounts and cured at elevated temperatures, the previously noted network of high crossllnk density for epoxy resins it alto evident with the urethane. These systems can also be mixed with the various optional ingredients noted hereinabove as well as with typical urethane extenders and plasticizers.
The following samples will further ill~stIate the embodiments of the instant invention. In these examples, all part are given by weight unless otherwise noted.
Example 1 This example illustrates the preparation of a typical modified hardener of the instant invention.
An adduce of deathly Tulane Damon and diglycidyl ether of bi~phenol A was made at a molar ratio of 4:1. 531 gym of deathly Tulane Damon (76 % deathly isomer and 19 % deathly isomer- ETHAC~RE~ 100 from Ethyl Corp.) were weighed into a reaction flask equipped with mechanical stirrer, thermometer and healing Jacket. The flask was heated with stirring to 80C. 269 gym of preheated diglycidyl ether of bisphenol A having an epoxide content of 5,1-5,5 equ./kg were added to the flask through a dropping funnel. The temperature way raised to 100C and maintained for one hour with an exotherm to 125C.
There in obtained an adduce having an average molecular weight ranging from 720-740.
Example 2 An adduce of deathly Tulane Damon (the swamp as used in Example 1) and an epoxy phenol novolac resin was made at a molar ratio of 6-1.
680 gym of deathly Tulane dlamine were weighed into a reaction flask equipped with a mechanical stirrer, thermometer and heating jacket.
120 gym of preheated epoxy phenol novolac reloan having an epoxide content of 5,5-5,7 equ./kg were added Wylie with stirring. After the addition way complete the temperature aye maintained at 100C
for 3 hours on order to complete the reaction.
There is obtained an adduce having peaks of maximum ab~orbance in the IT spectrum at: 3370, 2957, 2891, 1625, 1478 and 1451 cm The product ha a softening point of -21~C.
Example 3-4 The procedure of Example 1 was repeated utilizing the fallowing component 8:
Part en 3 Example 4 Diglycidyl ether of blsphenol A I 28.1 --1,4-butanediol dlglycidylether -- 18.5 Deathly Tulane diamlne (as in Example 1)71.9 81.5 1) DORIA 332 from DOW (epoxide content of 5,7 equ./kg) Following data characterize the adequate of example 3 and 4:
Example 3 Example 4 Softening point (C) -15 -20 Maximum IT absorbency (cm ) 3380, 2957, 3370, 2957, 2891, 16259 2091, 1625, 1~78, 1~51 14789 1451 Example 5 Thy following example it directed to the physical and performance characteristics of processed epoxy resins utilizing the hardeners of Examples 1-4.
The resin systemfl were prepared by blending the resin component wit}
the optional ingredients and the hardener at room temperature. The epoxy resin utilized for Formulation A hereinafter was a blend of 65 parts diglycidyl ether of bi3phenol A (DORIA 332), 25 parts of epoxy phenol novolac baa in example 2) and 10 part of 1,4-butane-dill dlglycidyl ether. The epoxy resin utilized for Formula lions B-G hereinafter was an 45 parts iron oxide filled epoxy blend utilizing 47 parts diglycidyl ether of blsph3nol A (DORIA 332) and 3 parts 1,4-butanadiol diglycidyl ether.
The following characteristics were then determined:
Mixed Viscosity - The vacuity of the blended epoxy-hardener system was measured with a Brook field RVF viscometer using spindle 3 at 20 rum at 23-25C. Samples were mixed for two minutes and the viscosity reading taken one minute thereafter.
heat Deflection Temperature - Determined according to ASTM D-648-82.
The liquid material WEBB poured into a shoed mold, cured overnight at room temperature and then at the indicated cure schedule. The test was conducted using a load of 18~2 bar on a sample size of 1~27 cm x 1.21 cm x 1.27 cm.
Pot life - Thy specified quantities of mixed epoxy resin and hardener were reacted in n metal can at room temperature until cured. The time to complete cure was measured. The mixture was considered cured when it became solid at room temperature.
Thin Layer Tack Time - This text is a measure of the time needed to sufficiently aura a mixed system to a solid form such that a finger imprint remains visible on the surface. The test proceeds by depositing a 500 em layer of the epoxy system on a surface, at room temperature, and periodically putting a finger imprint on the surface thereof.
Parts , formulation A B C D E G
__ __ _ .__ _ _ __ Example 1 adduce 45 _ _ _ _ _ Example 2 adduce _ 35 23 85 90 Example 3 adduce _ 50 39 _ _ 50 50 Example 4 adduce _ _ 9 _ 35 Triethylene tetramin 50 _ _ _ _ Deathly Tulane Damon _ _ 9 _ _ 35 m-Xylene Damon _ 15 15 15 10 15 15 l-Methyl imidazole 5 _ _ _ _ _ Ratio of modified epoxy resin to hardener 100/13 100/17 outyell 100/13 100/15 100/16 100/17 I
Formulation A B C D E F G
_ . _ _ __ Mixed Viscosity (CUPS) 1660 _ _ _ _ _ Heat Deflection Temp.* (C)141 146 146 148 152 145 143 Cure Schedule 1 2 2 2 2 2 2 Pot Life (total wt. 175 gym) (min.) 65 _ _ _ _ _ _ . _ _ Pot Life (total wt. 210 gym) (his.) _ _ _ 35 50 _ 20 _ _ _ _ Thin Layer Tack Time (his.) _ _ _ 16 20 _ *) Cure Schedule - 1 2
2 his/ 65C 2 his/ 65C
1 ho J 95C 2 his/ 95C
1 ho /150C 2 hrs/120C
1 ho J 95C 2 his/ 95C
1 ho /150C 2 hrs/120C
3 ho /170C 2 hrs/150C
4 hrs/17QC
Tress data thus illustrate the advantageous characteristic of epoxy rosins containing the resinous hardener systems of the instant invention.
Example 6 A cured polyurethane system was prepared by blending at room temperature 34 parts of the Example 1 adduce, 24 parts of ductile adipate plasticizer and 100 parts of a cyclualiphatic isocyanate urethane system having an isocyanate content of 2,3-2,4 equ./kg.
upon curing at elevated temperatures, the solid urethane exhibited a 90-95 Shore A Hardness Valve.
I
Summarizing, it is seen that this invention provides novel, modified hardens systems for epoxy and urethane resin which exhibit excellent perfor~ancs characterl6tics. Variation may be made in proportions, procedures and materials without departing from the scope of the invention as defined by the following claims.
Tress data thus illustrate the advantageous characteristic of epoxy rosins containing the resinous hardener systems of the instant invention.
Example 6 A cured polyurethane system was prepared by blending at room temperature 34 parts of the Example 1 adduce, 24 parts of ductile adipate plasticizer and 100 parts of a cyclualiphatic isocyanate urethane system having an isocyanate content of 2,3-2,4 equ./kg.
upon curing at elevated temperatures, the solid urethane exhibited a 90-95 Shore A Hardness Valve.
I
Summarizing, it is seen that this invention provides novel, modified hardens systems for epoxy and urethane resin which exhibit excellent perfor~ancs characterl6tics. Variation may be made in proportions, procedures and materials without departing from the scope of the invention as defined by the following claims.
Claims (19)
1. A hardener for epoxy resins and/or urethane resins comprising the adduct obtained from the reaction of diethyl toluene diamine and polyepoxide having a functionality of at least two, said diamine being present in excess relative to said polyapoxide.
2. The hardener of claim 1, wherein said epoxy resin is selected from the group consisting of diglycidyl ether of bisphenol A, epoxy phenol novolacs, 1,4-butanediol diglycidyl ether, epoxy cresol novolacs, triglycidyl para-amino phenol, triglycidyl tris(p-hydroxy-phenyl)methane, tetraglycidyl-1,1,2,2 tetrakis (p-hydroxyphenyl)-ethane, vinyl cyclohexene dioxide, N,N,N1,N1-tetraglycidyl-4,41-methylene bis benzeneamine, N,N,N1,N1-tetraglycidyl meta-xylene diamine, diglycidyl aniline, resorcinol diglycidyl ether, catechol diglycidyl ether, hydroquinone diglycidyl ether, diglycidyl ortho-toluidine, diglycidyl isophthalate, bisphenol F and S epoxy resins, and N,N,N1,N1-tetraglycidyl 1,3 bis-aminomethyl-cyclohexane.
3. The hardener of claim 1, wherein said polyepoxide corresponds to the formula wherein R is hydrogen or methyl, and n is 0,2-3,4.
4. The hardenar of claim 1, wherein said polyepoxide corresponds to the formula wherein m is 0-50 and X is -CH2-, or
5. The hardener of clalm 1, wherein said polyepoxide is 1,4-butanediol diglycidyl ether.
6. The hardener of claim 1, wherein from about 2 to 20 moles of diamine are present per mole of polyepoxide.
7. A curable mixture comprising (a) a polyepoxide compound and (b) a hardener according to claim 1.
8. The curable mixture of claim 7, wherein said polyepoxide compound is selected from the group consisting of epoxide resins based on polyhydric phenols, epoxidation products of cresol novolacs, epoxidation products of phenol novolacs, hydantoin epoxide resins polyglycidyl esters, glycidylated aromatic amines, glycidylated aminophenola and cylcoaliphatic epoxy resins.
9. The curable mixture of claim 7, wherein said hardener and said polyepoxide compound are present in stoichiometric amounts + 50 %.
10. The curable mixture of claim 7 which also contains a maximum of 75 %, by weight of the total hardener composition, of an aliphatic, cycloaliphatic or aromatic primary or secondary amine.
11. The curable mixture of claim 10, wherein said amino is selected from the group consisting of monoethanolamine, N-aminoethyl ethanolamine, ethylenediamine, hexamethylenediamine, trimethyl-hexamethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, N,N-dimethylpropylenediamine-1,3, N,N-di-ethylpropylenediamine-1,3, bis(4-amino-3-methylcyclohexyl)methane, bis(p-aminocyclohexyl)methane, 2,2-bis(4-aminocyclohexyl)-propane, 3,5,5-trimethyl-s-(aminomethyl)-cyclohexylamine, N-aminoethyl-piperazine, m-phenylene-diamine, p-phenylenediamine, bis(p-amino-phenyl)methane, bis(p-aminophenyl)-sulfone, m-xylylenediamine, 1,2-diaminocyclohexane, 1,4-diaminocyclohexane, toluene diamine, 1,3-bis(aminomethyl)cyclohexane, 1,4-bis(aminomethyl)cyclohexane, isophorone diamine and 1-methyl-imidazole.
12. The curable mixtuse of claim 7, wherein in said hardener said polyepoxide corresponds to the formula wherein R is hydrogen or methyl, and n is 0,2-3,4.
13. The curable mixture of claim 7, wherein in said hardener said polyepoxide corresponds to the formula wherein m is 0-50 and X is -CH2-, or
14. The curable mixture of claim 7, wherein 1,4-butanediol diglycidyl ether is the polyepoxide in said hardener.
15. The curable mixture of claim 7, wherein in said hardener from about 2 to 20 moles of diamine are present per mole of polyepoxide.
16. The product obtained by curing the mixture of claim 7 at elevated temperatures.
17. The product obtained by curing the mixture of claim 10 at elevated temperatures.
18. A curable mixture comprising (a) a urethane resin and (b) a hardener according to claim 1.
19. The product obtained by curing the mixture of claim 18 at elevated temperatures.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US06/653,417 US4540750A (en) | 1984-09-24 | 1984-09-24 | Diethyl toluene diamine hardener systems |
| US653,417 | 1984-09-24 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1238447A true CA1238447A (en) | 1988-06-21 |
Family
ID=24620803
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000491211A Expired CA1238447A (en) | 1984-09-24 | 1985-09-20 | Diethyl toluene diamine hardener systems |
Country Status (5)
| Country | Link |
|---|---|
| US (1) | US4540750A (en) |
| EP (1) | EP0177444B1 (en) |
| JP (1) | JPH0635503B2 (en) |
| CA (1) | CA1238447A (en) |
| DE (1) | DE3579209D1 (en) |
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| DE3703739A1 (en) * | 1987-02-07 | 1988-08-18 | Bayer Ag | METHOD FOR THE PRODUCTION OF MOLDED BODIES, MIXTURES SUITABLE FOR THEM FROM REACTIONABLE COMPOUNDS TO ISOCYANATE GROUPS AND THE MOLDED BODIES OBTAINED BY THE METHOD |
| DE3750166T2 (en) * | 1987-08-26 | 1995-02-23 | Asahi Chemical Ind | Hardener for a curable one-pot epoxy resin system. |
| EP0327039B1 (en) * | 1988-02-04 | 1998-05-13 | Ppg Industries, Inc. | Barrier coatings |
| DE68922416T2 (en) * | 1988-02-04 | 1996-02-01 | Ppg Industries Inc | Ungelled polyamine-polyepoxy resins. |
| US5300541A (en) * | 1988-02-04 | 1994-04-05 | Ppg Industries, Inc. | Polyamine-polyepoxide gas barrier coatings |
| US5006381A (en) * | 1988-02-04 | 1991-04-09 | Ppg Industries, Inc. | Ungelled polyamine-polyepoxide resins |
| JPH02245018A (en) * | 1989-03-17 | 1990-09-28 | Nippon Kayaku Co Ltd | Epoxy resin composition for resin mold and resin mold made thereform |
| US5091574A (en) * | 1990-02-06 | 1992-02-25 | Texaco Chemical Company | Polyoxyethylene diamine derivatives of diglycidyl ethers |
| JPH047382A (en) * | 1990-04-25 | 1992-01-10 | Sunstar Eng Inc | Adhesive for use i lining of water pipe |
| DK0754200T3 (en) * | 1994-03-31 | 2000-08-07 | Ppg Ind Ohio Inc | Epoxy / amine barrier coating |
| DE59609259D1 (en) | 1995-11-29 | 2002-07-04 | Vantico Ag | Core / Shell particles and curable epoxy resin compositions containing them |
| US5840825A (en) * | 1996-12-04 | 1998-11-24 | Ppg Incustries, Inc. | Gas barrier coating compositions containing platelet-type fillers |
| US5728439A (en) * | 1996-12-04 | 1998-03-17 | Ppg Industries, Inc. | Multilayer packaging material for oxygen sensitive food and beverage |
| GB9802950D0 (en) * | 1998-02-11 | 1998-04-08 | Wood Limited E | New coating for pipelines,tanks and structural steelwork |
| US6590011B1 (en) * | 2000-05-01 | 2003-07-08 | Polymeright, Inc. | Radiation initiated epoxy-amine systems |
| GB0019505D0 (en) | 2000-08-08 | 2000-09-27 | Wood Limited E | Coating for drinking water pipelines |
| DE50201239D1 (en) * | 2001-05-21 | 2004-11-11 | Huntsman Adv Mat Switzerland | METHOD FOR PRODUCING COMPONENTS FOR ELECTRONIC DEVICES |
| US20040197472A1 (en) * | 2003-04-04 | 2004-10-07 | Scofield Harry J. | Process and apparatus for sealing freezer enclosures from moisture and contamination |
| TR200705170A2 (en) | 2007-07-25 | 2009-02-23 | Vestel Elektroni̇k Sanayi̇ Ve Ti̇c. A.Ş. | Bus identification circuit. |
| WO2009119467A1 (en) * | 2008-03-25 | 2009-10-01 | 東レ株式会社 | Epoxy resin composition, fiber-reinforced composite material and method for producing the same |
| US9309381B2 (en) | 2011-06-24 | 2016-04-12 | Air Products And Chemicals, Inc. | Epoxy resin compositions using solvated solids |
| JP6272189B2 (en) * | 2014-08-29 | 2018-01-31 | 三菱電機株式会社 | Epoxy resin composition for fiber reinforced composite material, fiber reinforced composite material using the same, and method for producing the same |
| JP2017197679A (en) * | 2016-04-28 | 2017-11-02 | Dic株式会社 | Urethane resin composition, urethane resin molded article and method for producing the same |
| MX2022002241A (en) * | 2019-08-23 | 2022-05-06 | Ppg Ind Ohio Inc | Systems and methods for improved lap shear strength and displacement of two-component structural adhesives. |
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| DE1495705B2 (en) * | 1962-12-28 | 1972-01-13 | Farbenfabriken Bayer Ag, 5090 Lever Kusen | PROCESS FOR THE MANUFACTURING OF HARDENABLE EPOXY MOLDING COMPOUNDS |
| US3631125A (en) * | 1968-01-16 | 1971-12-28 | Union Carbide Corp | Adducts of m-tolylenediamine and curable polyepoxide compositions based on m-tolylenediamine and adducts thereof |
| BE793212A (en) * | 1971-12-24 | 1973-06-22 | Ciba Geigy | HARDENABLE MATERIALS BASED ON EPOXIDIC RESINS |
| US4120913A (en) * | 1976-12-10 | 1978-10-17 | Westinghouse Electric Corp. | Epoxy-amine adhesive compositions |
| JPS55127472A (en) * | 1979-03-26 | 1980-10-02 | Kansai Paint Co Ltd | Resin composition for cation electrodeposition coating |
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- 1984-09-24 US US06/653,417 patent/US4540750A/en not_active Expired - Lifetime
-
1985
- 1985-09-18 DE DE8585810424T patent/DE3579209D1/en not_active Expired - Lifetime
- 1985-09-18 EP EP85810424A patent/EP0177444B1/en not_active Expired - Lifetime
- 1985-09-20 CA CA000491211A patent/CA1238447A/en not_active Expired
- 1985-09-24 JP JP60210900A patent/JPH0635503B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| EP0177444B1 (en) | 1990-08-16 |
| US4540750A (en) | 1985-09-10 |
| JPH0635503B2 (en) | 1994-05-11 |
| JPS6189219A (en) | 1986-05-07 |
| EP0177444A3 (en) | 1987-08-05 |
| EP0177444A2 (en) | 1986-04-09 |
| DE3579209D1 (en) | 1990-09-20 |
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Legal Events
| Date | Code | Title | Description |
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| MKEX | Expiry |