Method for preparing a solventless thermoset polymeric composition

Abstract: Solventless polymeric compositions suitable for coatings and moldings are formed by the addition reaction product of a first component comprising mono, di or polyamines, or an adduct of mono, di or polyamines with mono, di or polyfunctional acrylates and/or epoxides and a second component comprising mono, di or polyacrylates or mixtures with mono, di or polyepoxides.

Description: The present invention relates to a method of preparing a thermoset polymeric composition and, more particularly, to generally liquid, low viscosity polymeric compositions which polymerize by means of an addition reaction mechanism. Many different types of liquid polymeric materials are known in the prior art and are used in numerous applications. For example, liquid polymeric compositions can be used for points, coatings and films, or can be poured into molds or substrates to make coatings. However, the various physical properties of these polymeric compositions present certain problems in many applications. For example, compositions having generally high viscosities or rapid reaction rates are difficult to apply as films or coatings without the use of solvents to dilute or dissolve the components. This normally creates pollution problems, however, when the solvent evaporates. Additionally, as the solvents evaporate they can leave voids or blisters in the polymeric material. The French Patent No. 2.200.297 refers to a tertiary amine which may be hardened by ultraviolet radiation and which is characterized by being the reaction product of a Michael addition of an mine with at least one hydrogen atom in the amino group and a stoichiometric surplus of an ethylenic material comprising polyacrylate. The U.K. Patent No. 2.029.433 refers to a printing ink comprising a binder system containing to a total of 100% by weight, from 30 to 90% by weight of a liquid photopolymerizable binder comprising one or more polyethylenically unsaturated photopolymerizable monomers and, optionally, one or more monoethylenically unsaturated monomers; and from 70 to 10% by weight of one or more epoxy resins soluble in said photopolymerizable binder; a photoinitiator for the photopolymerizable binder; a cold curing catalyst or curing agent for the epoxy resin(s); and a colorant. Accordingly, there exists a need in the art for solventless liquid polymeric compositions which can be used in paints and coatings, and which can be poured into molds to make castings. As used herein, the term "solventless" means the absence of any solvent in the components utilized to make the polymeric composition which does not take part in the reaction. Thus, upon mixing the various components, there is no solvent to be evaporated or entrapped into the resulting thermosetting polymeric materials. In other words, the whole system is 100% active and there is no waste through solvent evaporation. Under such solventless conditions, compact films or parts are formed which are void free, since there are no solvent losses through evaporation or solvent entrapments to cause porosity and blistering. Furthermore, the absence of solvents eliminates environmental pollution caused by solvent loss. In this respect, solventless systems are oven better than water-borne polymeric materials because the latter contain small quantities of ammonia, amines and solvents used as water emulsifiers, solubilizers and stabilizers. Conventional solution polymeric materials used for coatings and paints contain substantial amounts of solvents or water which are lost by evaporation to the environment. Solventless systems have no evaporation problems and provide economy with their efficiency. Based on the same weight and thickness of a coating, solventless polymeric systems provide considerably more surface coverage than solution systems because the solventless systems are 100% active. In addition, solventless systems are more compact with respect to production capacity, storage room, transportation room, and are safer, with less attendant health and fire hazards. The best solventless compositions are thermoset through an addition polymerization mechanism. This simply means that component A reacts with component B by adding to it without the formation of any volatile by-products which could cause voids, blisters or entrapments in the film or part. These polymers can include ladder-like type polymers wherein the components are cross-linked spacially in the form of a ladder. For example, two linear parallel polymeric chains are intersected at their repeated reaction sites by components which form the steps of the spacial ladder. The few ladder polymers which are known generally in the art have exceptionally good chemical resistance. However, these compositions are generally solids and are insoluble in organic solvents. Additionally, these ladder-type polymers generally have to be heated above 180°C to effect curing. Thus, it is extremely difficult to use a ladder-type composition as a paint or coating. It would also be advantageous to have a solventless polymeric composition in which the various components are liquids with relatively low viscosities at ambient temperatures. Such systems would be advantageous because they could be conveniently applied as coatings by spraying, dipping, brushing, rolling, or the like. Additionally, liquid, solventless compositions can be more easily mixed together with pigments, pigment extenders, dyes, fillers, carbon, glass or organic fibers without the necessity of dilution with solvents. Low viscosities greatly facilitate any grinding process and the absence of solvents reduces the fire hazard caused by the heat of friction in the presence of volatile and flammable organic solvents. Thus, the systems can readily be utilized to make paints and coatings. Conventionally known polymeric materials used in coatings and paints have typically been of one or two component systems. The one component systems are generally always water borne and comprise solution or emulsion type materials in organic solvents such as oil alkyds, epoxy esters, urethane oils, and latexes. Two component systems generally include: (a) solid or liquid epoxides and polyamines, or amine terminated polyamides; (b) isocyanate terminated polyurethanes and di or polyols, hydroxyl terminated polyurethanes and/or p,p'methylene,o,o', chloro dianiline; (c) unsaturated polyesters; and (d) photoprepolymers. Presently available one component liquid polymeric systems have several distinct disadvantages. For example, the compositions can only be applied in thin coats so that the solvent can evaporate. Additionally, as the solvent evaporates, it can leave voids or blisters. The two component systems also have certain disadvantages. For example, these systems which include epoxides have required a solvent to dissolve the epoxides such that they can be easily applied. Even the normally liquid diepoxides such as those based on Bisphenol A and epichlorohydrin exemplified by EPON-826® and EPON-828®. When these liquid epoxides are cured with polyamines such as triethylene tetramine (TETA), or liquid amine-terminated polyamides such as the Versamides produced by General Mills Company, additional solvents must be used to reduce the viscosity. This is because when the epoxide and amines are mixed together, there is no viscosity decrease, but rather a rapid increase due to the high reactivity and functionality of TETA with the epoxides. Both isocyanate and hydroxyl-terminated polyether- or esterurethanes such as Adiprene L-100®, Adiprene L-150®, Multrathene-2680®, Desmophene® and Desmodurs® have viscosities in excess of 18 N.s./m² or are solids at ambient temperature. Therefore, these compounds cannot be used as components of a liquid, solventless system. Unsaturated polyesters such as the condensation product of maleic anhydride, phthalic anhydride or isophthalic acid with 15% to 25% molar excess of 1,2 propylene glycol diluted with 30% to 50% by weight of styrene monomer have been used as good, solventless systems when combined with 1% by weight of a ketone hydroperoxide catalyst and 0.3% by weight cobalt naphthoate as an accelerator. However, the volatility of the odorous styrene monomer, the highly critical 100/1/0.03 weight ratio and the very rigid and inflexible thin films which are produced make the styrene diluted unsaturated polyester system unsuitable for coatings or paints. However, these unsaturated polyesters are broadly used in combination with fiberglass to produce reinforced plastics. Perhaps most similar to solventless systems are photoprepolymers composed of di or polyacrylates diluted with monoacrylates containing polymerization inhibitors, photoinitiators (catalysts), and photoaccelerators (tertiary amines). However, these formulated prepolymers have limited storage life and have to be protected from contact with ultraviolet light. Additionally, the curing of these compositions requires strong sources of ultraviolet light or electron beam. These sources are generally accompanied by strong infrared light which causes evaporation of the unpleasantly smelling monoacrylic esters. Additionally, only films of a few mils in thickness can be fully cured. As soon as the surface of the photo prepolymer is exposed to ultraviolet light or electron beam it hardens, thus inhibiting further penetration of the ultraviolet light. This self inhibition problem of photoprepolymers is even more acute if the polymer contains pigments or fillers. Thus, photoprepolymers are generally limited to applications requiring very thin, and preferably clear, films. In view of the foregoing, it is obvious that it would be a significant advancement in the art to provide a solventless polymeric composition which could be used for coatings and paints and also which could be poured into substrates or molds to form castings. It would be still a further advancement if such a solventless system had a liquid consistency of a relatively low viscosity at ambient temperatures. Object of the invention is a method of preparing a thermoset polymeric composition, optionally containing a filler, characterized in that it comprises mixing a di or polyamine of the general structure R n (NH₂) n , wherein R is a n-valent radical of aliphatic, cycloaliphatic, heterocyclic or aromatic structure and n is an integer of at least 2, and/or their adducts with mono-, di or polyacrylates or epoxides prepared in an equivalent ratio of amine to epoxide and acrylate of at least 2 to 1, with a di- or polyacrylate and optionally a monoacrylate and further optionally a mono-, di- or polyfunctional epoxide and in the absence of a solvent, whereby the components are mixed in substantially stoichiometric proportions, optionally a filler, and thermosetting the mixture at a temperature of 4 to 32°C in the absence of a photoinitiator. Further preferred is a method wherein as the amine there is used a diamine selected from the group consisting of hydrazine, ethylene diamine, butylene diamine, hexamethylene diamine, 2-methyl, 1,5 pentane diamine, trimethyl hexamethylene diamine, isophorone diamine, cyclohexamethylene diamine, methylene bis cyclohexamethylene diamine, isomers thereof, and substituted derivatives thereof, the adduct of n moles of the above amines with n or 2n moles of monofunctional acrylates or methyl acrylates or the adducts of n moles of a difunctional acrylate or methyl acrylate or the diamide-amines obtained from the condensation of n moles of dimer fatty acid dodecanedioic acid, sabacic acid or the dimethyl esters thereof with 2n moles of hydrozine or 2n moles of a diamine of above simple diamines with the sulfone, urea or amide imide diamines obtained from the condensation of n moles of sulfuryl chloride, urea, or trimellic anhydride with 2n moles of hexamethylene diamine, methylene bis cyclohexamethylene diamine, polyoxopropylene diamines 230, 400, 600, 800, 1000, 2000; and/or the tri or polyamines selected from the group consisting of diethylene triamine, dipropylene triamine, triethylene tetramine, tetraethylene pentamine, polyoxopropylene triamine-400, condensates thereof with dicarboxylic or tricarboxylic acids or the lower esters thereof with oxalic acid, adipic acid, azelaic acid, sebacic acid, dodecandioic acid, dimer fatty acids, isophthalic and terephthalic acids, trimellitic anhydride, trimesic acid, sulfuryl chloride, or urea at a molar ratio of 2 to 1 of di or tri polyamine to difunctional acid or ester or a molar ratio of 3 to 1 of di or tri polyamine to a trifunctional acid or ester. Further preferred is a method wherein the difunctional acrylates are selected from the group consisting of butane diacrylate, neopentyl diacrylate, 1,6 hexamethylene diacrylate, oxo diethylene diacrylate, oxo triethylene diacrylate, oxo tetraethylene diacrylate, polyoxoethylene diol diacrylates or dimethyl acrylates, and di, tri or poly oxo propylene diol diacrylates or dimethyl acrylates, N,N' methylene bis acrylamide, N,N' methylene bis methyl acrylamide, the adducts of n moles of an amine or an ethanol imine with n moles of a triacrylate; and the tri or polyfunctional acrylates or methyl acrylates are selected from the group consisting of trimethylol propane triacrylate, pentaerythritol triacrylate, the tetra acrylate or methyl acrylate of pentaerythritol; the adducts of n moles of an imine with n moles of pentaerythritol tetracrylate or tetramethyl acrylate; and the adducts of n moles of a diimine or n moles of a primary amine with 2n moles of a di, tri or polyacrylate or methyl acrylate, and the adducts of n moles of primary diamines with 3n or 4n moles of a di, tri or tetra-functional acrylate or methyl acrylate. Further preferred is a method wherein the mono, di or polyfunctional epoxides are selected from the group consisting of ethylene, propylene, butene, styrene, and cyclohexamethylene oxides; aliphatic diepoxides; diglycidyl ether of bisphenol A; aniline, novolac, phenol or cresol containing di or polyepoxides; glycolate or adipates of dicyclohexamethylene and dimethyl cyclohexamethylene diepoxides; the halo and alkyl substituted derivatives, isomers, and higher or lower analogues of the above. Further preferred is a method which additionally comprises 1 to 3 percent hexakis methoxy methylene melamine as a surface tension reducer. Still further preferred is a method wherein as filler there are used 2 to 98% by weight of one of the fillers of the group asphalt, hydrocarbon resins such as alpha polymethylstyrene, polyvinyl carbazole or polyterpenes. In addition, preferred is a method whereby there is contained up to 90% by weight of silicon dioxide alone or in combination with minor quantities of pigments or dyes. Last not least, further preferred is a method which is characterized in that it contains as filler 30 to 75% by weight of fiberglass, fiber cloth or carbon fiber. The first and second components are formulated such that they are both liquids having a relatively low viscosity at ambient temperatures. Thus, the components can be mixed together and can be applied as a coating or paint by spraying, dipping, brushing, or rolling, or they can be poured into substrates or molds to make castings. In one embodiment, the first component comprises a di or polyamine, hydrazine, or an amino-hydrazine terminated derivative and mixtures thereof either alone or in combination with mono-, di- or polyacrylates. In a second embodiment of the present invention, anhydrides are added to the first component which is then mixed with the second component to form a solid or liquid composition which thermosets upon heating. The components of the polymeric composition may be formulated so as to form two liquid components which have a relatively low viscosity and can be separately stored for a year or more. When the two components are mixed together, they form a liquid composition which thermosets at ambient temperatures within a few hours without having to heat the composition. As used herein, ambient temperatures generally refers to temperatures between about 4°C and 32°C. However, these systems will also set at higher and lower temperatures depending upon their viscosities and reactivities. Because the components and the resulting mixture, for a short period of time, are liquids at ambient temperatures, the composition is easy to work with. Additionally, because the system is solventless, there are no solvents to evaporate and cause pollution or form blisters and voids in the final product. The first liquid component is formed from di or polyamines, or adducts of di or polyamines with mono, di or polyacrylates or epoxides. The amount of acrylate or epoxide that must be added to the amine is dependent upon the actual compounds used. The basic requirement is that the component be a liquid of relatively low viscosity at ambient temperatures and have at least four reactive amine hydrogens so that it can polymerize. Examples of suitable mixtures are more fully discussed hereinafter. The second liquid component is formed from mono, di or polyacrylates, or adducts of mono, di or polyacrylates with mono, di or polyepoxides and/or glycidyl ethers of acrylic acid or methacrylic acid. The amount of acrylates and epoxides in the second component is dependent upon the number of amine hydrogens in the first component. If a fully cured system is desired, the number of acrylic linkages, that is, the number of acrylic C=C double bonds, and epoxides should be equal to the number of amine hydrogens. When n=2 the class of diamines results having the general formula R₂ (NH₂)₂ wherein R₂ is a divalent radical of aliphatic, cycloaliphatic, heterocyclic or aromatic structure and/or various combinations. R₂ can also contain (in addition to carbon and hydrogen atoms), oxygen, sulfur, halogens and their combinations. Accordingly, the term "diamine" is extended, and covers in addition to the simple diamines, the hydroxyl, ether, keto, ester, amide, imide, thiol, thio, sulfono, nitrile and urea diamines, as well as hydrazine and hydrazine-terminated hydrazides. Hydrazine results from the formula R₂(NH₂)₂ when R₂ is nil. The following examples of diamines are given by way of illustration Useful diamines of this invention are: hydrazine; ethylene diamine; 1,4 butylene diamine; 1,6 hexamethylene diamine; 2 methyl 1,5 pentamethylene diamine; 1,2 cyclohexamethylene diamine; p,p' methylene biscyclohexylene diamine PAMC-20®, metaxylylene diamine; isophorone diamine; trimethyl, 1,6 hexamethylene diamine; metaphenylene diamine; 1,7 naphthylene diamine; p,p' methylene dianiline; p,p' methylene, o,o' chloro dianiline; p,p' oxo or sulfono dianiline; polyoxopropylene diamines (Jeffamine®) with molecular weights of 230, 400, 600, 900, 2000; and monododecenylsuccimide of polyoxopropylene triamine (Jeffamine T-403®). The adducts of any of these specific diamines with mono, di or polyacrylates or epoxides by using at least 2 to 1 equivalents of diamine versus epoxide or acrylate bond. For example, the diamines which are obtained by mixing 2.0 moles of 1,6 hexamethylene diamine and 0.5 moles of p,p' isopropylidene diphenol diglycidyl ether or 1.0 mole 1,6 hexamethylene diol dimethyl acrylate. Other illustrative diamines are the condensation products of 1.0 mole oxalic acid, adipic acid, azelaic acid, sebacic acid, dodecanedioic acid, dimer fatty acid, isophthalic or terephthalic acids (or their dimethyl esters) with 2.0 moles of PAMC-20® or polyoxopropylene diamine-400 (Jeffamine D-400®) through the elimination of 2.0 moles of water (or methanol). Other illustrative diamines are N,N' dioxopropylene (Jeffamine D-230®) urea hydrazine, the dihidrazide of dimer fatty acid and the like. When n=3 the class of triamines results having the general formula R₃(NH₂)₃. For n=3,4,5... the generic term of polyamine is used. Wherein R₃ is a tri (or poly) valent radical having an aliphatic, cycloaliphatic, heterocyclic or aromatic structure and their combinations. Simple R₃ groups are composed of carbon and hydrogen atoms, but in the present invention can also include oxygen, halogen, sulfur, nitrogen and their combinations. Tri (or poly) amines can be simple or may contain in their backbone hydroxyl, ether, keto, halogen, ester, amide, imide, thio, thiol, sulfone, urea, hydrazide or their combinations, and include, substituted derivatives, as well as their adducts with either mono, di or polyacrylates or epoxides wherein at least 2/1 molar ratios of tri or poly amine to mono, di or poly functional acrylate or epoxide has been used. The same molar ratios of at least 2/1 are also applicable to the condensation products of a tri (or poly) amine with oxalic acid, malonic acid, adipic acid, azelaic acid, sebacic acid, dimer fatty acid, isophthalic acid, terephthalic acids (or their methyl or ethyl esters), trimellitic anydride and urea. Illustrative examples of tri (or poly) amines are: diethylene triamine, dipropylene triamine, polyoxopropylene triamine (Jeffamine T-403®) triethylene tetramine, tetraethylene pentamine, 2,4-Bis-(p-aminobenzyl) aniline (BABA®) (BHMT®) and bis hexamethylene triamine. Additional tri or poly amines include amines obtained by the reaction of 1.0 mole of melamine with 3.0 moles of a diamine; the adducts obtained from the addition reaction of 2.0 moles of triethylene tetramine with 1.0 mole of p,p'isopropylidene diphenol of diglycidyl ether or 1.0 mole of tetraoxoethylene glycol dimethyl acryla the adduct of 3.0 moles of 1,6 hexamethylene diamine with 1.0 mole of trimethylol propane triacrylate; the condensation reaction product of 1.0 mole dimer fatty acid, adipic acid, oxalic acid, terephthalic acid, or trimellitic anydride with 2.0 moles of polyoxopropylene triamine (Jeffamine T-403® or 1.0 mole urea with 2.0 moles of polyoxopropylene triamine (Jeffamine T-403®) The Acrylates Mono-, di- or polyacrylates useful in this invention are those having aliphatic, cycloaliphatic, or aromatic structures and their combinations. In addition, adducts of acrylates with mono-, di- or polyamines in which an excess of at least 2/1 of di- or polyacrylate per amino hydrogen are also useful in this invention. Illustrative examples of mono functional acrylics are: hydroxyl ethyl acrylate, hydroxyl propyl acrylate, as well as the methyl ester, ethyl ester, butyl ester, 2-ethyl hexyl ester, bornyl ester and stearyl esters of acrylic acid or methyl acrylic acid, crotonic acid, phenyl acrylic acid or phenyl methyl acrylic acid. Additional acrylates include the adducts of 1.0 mole diethanol amine to 1.0 mole of 1,6 hexamethylene diol acrylate, and 1.0 mole aniline to trimethylol propane triacrylate. Illustrative examples of difunctional acrylates are the diacrylates and dimethyl acrylates of: 1,4 butylene diol, neopentyl glycol, oxodiethylene glycol, oxotriethylene glycol, trioxotetraethylene glycol, oxopolyethylene glycols (300, 400, 600) 1,6 hexamethylene diol, oxodipropylene glycol, oxotetra propylene glycol, wherein the terms diol and glycol are synonymous. Also included are the adducts of 1.0 mole of dodecyl amine with 1.0 mole of pentaerythritol tetra acrylate; 1.0 mole of diethanol amine to 1.0 mole of trimethylol ethane triacrylate or trimethylolpropane triacrylate. Illustrative examples of tri- or polyacrylates are: the triesters of acrylic acid, or methyl acrylic acid, with trimethylol ethane, trimethylol propine, and pentaerythritol; the adduct of 1.0 mole mono-ethanol amine to 1.0 mole of pentaerythritol tetra acrylate or penta erythritol tetramethyl acrylate; the adduct of 1.0 mole of dodecyl amine to 2.0 moles of trimethylol propane triacrylate or 2.0 moles of penta erythritol tetra acrylate; the adduct of 1.0 mole 1,6 hexamethylene diamine, or Amine-6 with 4.0 moles of 1,6 hexamethylene diol diacrylate. The Epoxides Illustrative examples of mono, di or poly functional epoxides are: ethylene oxide, propylene oxide, butylene oxide, styrene oxides, and RD-4 (Ciba-geigy Co.) Compounds containing one epoxide and one acrylate or methyl acrylate structure in a single molecule are exemplified by the glycidyl ester of acrylic or methacrylic acid. Diepoxides include the diglycidyl ether of isopropylidene diphenol. Other examples include Novolac liquid diepoxides such as DOW-431® and DOW-439® as well as any other liquid or low melting solid mono, di or polyepoxide. Cycloaliphatic diepoxides such as bis-cyclohexane or bismethyl cyclohexane adipate or glycolate diepoxides can also be used in the present invention. It was discovered that the addition polymerization of amines or hydrazine with acrylates are generally exothermic, and take place at ambient temperatures or below with the exception of aromatic amines. The rate of reaction is greater with primary than secondary amines. Also, hydrazine reacts faster than aliphatic primary diamines which in turn react faster than cycloaliphatic diamines, which in turn react faster than aromatic diamines with acrylates which in turn are more reactive than their methyl or alkyl substituted analogues. In fact, while aliphatic, cycloaliphatic, or heterocyclic amines react exothermically with acrylates and methyl acrylates at ambient temperatures, aromatic mono, di or polyamines usually have to be heated from about 100 to 160°C for one to two hours in order to effect their addition polymerization. It was found that the addition of 1 to 6%, or more, by weight to the component B composed of mono, di or poly acrylates, glycidyl esters of acrylic or methyl acrylic acids and/or mono, di or poly epoxides in their clear or pigmented form, of phenols, cresols, xylenols, naphthols, dihydroxy benzenes, dihydroxy naphthalenes, bisphenols and their mono or poly halo, nitro, ether, ester, alkyl, oxo, thio and sulfone substituted derivatives, isomers and homologues, followed by the equivalent mixing of component A and B catalyzes their poly addition reactions and signficantly reduces their thermosetting times. Thus, by using a suitable catalyst it is possible to react aromatic amines with acrylates at ambient temperatures rather than having to heat the mixture. The replacement of a diamine with a primary diamine or hydrazine and their amine or hydrazine terminated diprimary amines or hydrazines rapidly increases their possibilities and their stochiometrical combinations, illustrated by the following examples: III. The case of I (this product is shown in equation I) can be further reacted by diepoxides to form ladder like polymers as follows: Wherein Since mono-, di- or polyacrylates do not react with mono-, di- or polyepoxides, the addition reactions between mono, di or polyamines and mono, di or poly functional acrylates diluted with mono-, di- or polyepoxides predominantly proceeds, at first as an addition of amine hydrogen atoms to acrylate bonds, and then the refining amine and imine hydrogens add to the epoxide rings. Consequently, mono-, di- or polyacrylates can be used as solvents for mono-, di- or polyepoxides to significantly reduce their viscosities and both the solute and solvent enter into the addition polymerization reactions upon mixing with mono, di or poly amines. It was found that primary or secondary amines react faster with mono anydrides or carboxylic acid anhydrides than with diepoxides at ambient temperatures. For example, 2n moles of a diamine represented by the general formula H₂N-R₂-NH₂ and 2n moles of diacrylate represented by the general formula Addition of the above to 4n moles of methyl tetrahydrophthalic anhydride in the presence of 4 to 5 epoxide equivalents results in: (wherein Z₂ is equal to Upon heating at above 150°C the groups adds to oxiran or epoxide rings to form (hydroxy ester) linkages. The addition of phenolic catalysts provides fast thermosetting times for equivalent mixtures of components A and B of the clear or pigmented solventless systems, thus causing a shorter pot life for the mixture. The most practical utilization of these precatalyzed solventless, two component systems is with air less (or air) dual guns which provide minimum mixing times. Liquid, solventless, two component systems of relatively low viscosity, which upon mixing thermoset at ambient temperatures through addition polymerization mechanisms proceeding in a "ladder" type formation yield compact, transparent, glossy and void free films or parts of any desired shape and thickness and are suitable for any applications. The use of air or airless spraying guns equipped with metering devices, ultrasonic mixing devices and pumping systems automatically mix only the specifically recommended ratios needed for spraying. If brushing is chosen with a solventless system as the method of application, the two components, A and B, should be well mixed for at least five minutes and then applied. Since there is no solvent evaporation there are minimal brushing marks resulting from constant changes in viscosity through evaporation of solvents. Additionally, from about one to about three weight percent of a surface tension reducer such as hexakis methoxy methylene melamine can be added to the system It was also found that the clear or the lightly filled form of the system provides 100% active varnishes, lacquers, or sealants of any desired thickness having 92% or better transparency of liquid consistency. The relatively low viscosity and high gloss of the solventless two component systems make them particularly useful in producing solar panels, and in casting optical devices and gyroscopes. Aluminum or copper water conduits also can be readily cast into place as integral parts of a solar panel. Furthermore, the solventless, liquid two component systems of this invention can be applied as paints of various shades and thicknesses. It was found that one coat can provide thicknesses of up to 10 mils while providing outstanding gloss, non-yellowing characteristics and excellent ultraviolet light, salt water and chemical resistance. Suggested applications of such paints are in marine, maintenance, construction, vessel, automotive and aircraft industries. The paints are tough through the combination of pencil hardness greater than H-7 and impact (direct or reverse) resistance greater than 1.3 x 10⁶N/m². When filled with 30 to 75% by weight fiberglass or fiber cloth, or carbon fiber they can replace unsaturated polyesters or epoxides in producing reinforced plastics for boats, tanks, corrugated sheets, bowling balls, bowling alleys, trays and chairs. It was found that the solventless, liquid, two component systems of this invention can be mixed with up to 90% by weight silicon dioxide, alone or in combination with minor quantities of pigments or dyes to produce pliable plaster-like putties which set to ceramic like materials upon curing at ambient temperatures. Suggested applications are water and oil pipes, tiles, prefabricated buildings, highway light reflectors, oil platform coverage, industrial floors, fishing lures, etc. In other words, the solventless, liquid, two component system can be used either as clear pigmented or filled coatings and paints as well as liquid thermosetting polymers for coating or molding objects of any shape, size or dimension. Furthermore, it was found that the liquid solventless, two component systems have outstanding adhesion to glass, bricks, ceramics, all metals including stainless steel, iron, aluminum, copper, titanium, chrome, tin, zinc, all thermosetting and thermoplastic polymers with the exception of polyolefins and polytetrafluorines. These latter polymers can be used as molds for the two component system of the present invention. Furthermore, since the solventless, two component systems of this invention are compatible (act as solvents) for liquid or solid asphalts, they can be used to form solventless polyacrylate epoxide tars containing from 2 to 98% by weight asphalt for clear, pigmented or filled systems. In addition to asphalts, other hydrocarbon resins such as alpha polymethylstyrene, polyvinyl carbazole, and polyterpenes can be used with the liquid solventless system of this invention. Other applications involve solventless adhesives for wood, Formica, glass, metals, polyvinyl chloride pipes, polystyrene, ABS plastics, ceramics, leathers, fabrics, metals, paper and their combinations. Other applications will become apparent by the specific illustrative examples given below. EXAMPLES EXAMPLE 1 In an 800 ml. glass beaker were placed 2.0 moles (420 grams) of p,p'methylene bis cyclohexylene diamine (PAMC-20®) and 16 grams of hexakis methoxy, methylene melamine (HMMM) (CYMEL-301®). To this mixture were slowly added over a period of 15 minutes 0.442 moles (100 grams) of 1,6 hexamethylene diol diacrylate under continuous mixing, and water cooling, which continued for an additional 30 minutes. The resulting product was an adduct of p,p'methylene bis cyclohexylene diamine (PAMC-20®) and 1,6 hexamethylene diol diacrylate, diluted with (PAMC-20® and HMMM, (CYMEL 301® consisting of 0.442 moles of adduct, 1.116 moles of PAMC® and 16 grams of CYMEL-301®. The adduct comprises the 2/1 molar addition to the acrylic double bonds of 1,6 hexamethylene diol diacrylate and proceeds exothermically at ambient or lower temperatures. Separately, in another 2000 ml. glass beaker were mixed 720 grams (4.0 epoxide equivalents) of EPON-826® with 1.558 moles (352 grams) of 1,6 hexamethylene diol diacrylate. The first mixture had a viscosity of about 0.23 N.s./m²at ambient temperature and for convenience was called component A, while the second mixture had a viscosity of 0.19 N.s./m² at ambient temperature and was named for convenience component B. The total weight of component A was equal to 420 + 16 + 100 = 536 grams, while the weight of component B was equal to 720 + 352 = 1072. The individual components A and B are stable in storage at ambient temperatures for periods in excess of one year without any significant change in viscosity. The mixing stochiometrical weight ratio of component A to component B is equal to 536/1072 = 1/2. The mixing of 10 grams of component A with 20 grams of component B results in a liquid having an initial viscosity of about 0.2 N.s./m² which rapidly increases with time. However, this particular formulation has 50 to 60 minutes of pot life at ambient temperatures. Upon mixing component A with component B at a weight ratio of 1/2, the resulting mixture increases in viscosity as a function of time and finally solidifies within a few hours to a highly transparent, colorless, glossy, tough and void free film or part. The solidification process is a function of time and temperature and independent of thickness or size. Increased temperatures rapidly accellerate solidification, while decreased temperatures lower the rate of the mixture's solidification. The involved chemical reactions proceed exothermically and apparently in the following order. First, the poly addition of the 2n moles of PAMC® and its adduct with the 2n moles of the diacrylate of 1,6 hexamethylene diol to form a polymeric imine-acrylate. Second, the polymeric imine-acrylate enters into another addition polymerization reaction with the 4n epoxide equivalents, resulting in a ladder like type formation. The steps can be described schematically as follows: Wherein R₂, R'₂ and Z₂ are divalent radicals corresponding in Step 1 and Step 2 to the specific structures of: R₂ equals R'₂ equals -(CH₂)₆-and Z₂₁ equals The CYMEL-301® is 1% by weight of the total weights of components A and B and does not participate in any reaction, but it was found to significantly reduce surface tension and improve film characteristics. Thicker films have much less surface tension and do not require HMMM. EXAMPLE 2 In an 800 ml. glass beaker were placed 1.5 moles (174 grams) of 1,6 hexamethylene diamine and through a dropping funnel were added to it, under stirring and cooling 1.5 moles (381 grams) of 1,6 hexamethylene diol dimethyl acrylate to form a viscous polyimine-dimethylacrylate, designated component A. Separately component B was formed by simply mixing 1.5 moles (453 grams) of tetraoxoethylene glycol diacrylate and 10 grams of CYMEL-301®. Component B had a viscosity of about 90 cps at ambient temperatures. The mixing ratio of component A to component B by weight is equal to A/B = 555/463 = 1.2/1.0. To 12 grams of component A were added 10 grams of component B and mixed for five minutes, then 146 grams of silicon dioxide (sand flour) and 3 grams of chrome green oxide were added to this mixture under continuous mixing. The pliable, plastic semisolid product was placed in aluminum cups and became solidified at ambient temperature within 4 hours. The final product was a hard, solid, green, glossy and smooth composite containing 87% by weight silicon dioxide. When this composite was exposed to an open flame it did not burn due to the 87% silicon dioxide content. It is believed that such composites based on components A and B of most of the following examples containing silicon dioxide, magnesium oxide, aluminum oxide, antimony oxides, and their like, are stronger than cement, and can be used in prefabricated houses or buildings. Such composites also allow reinforcement with steel, and offer a variety of color choices, as well as heat and water insulation. Additionally, they do not shrink or expand significantly, and therefore do not crack. At less than 1/8 of the equivalent concrete thickness, they have excellent impact resistance and elminate the need for plastering, painting, insulation, water proofing and maintenance. Water, oil and gas piping of any diameter or wall thickness can also be made from these compositions. EXAMPLE 3 In an 800ml. glass beaker were placed 2.0 moles (420 grams) of PAMC-20®, 1.0 mole (136 grams) of metaxylene diamine, 1.0 mole (185 grams) of lauryl (or dodecyl) amine and 29.0 grams of CYMEL-20® and mixed for 10 minutes to form component A. Separately in another glass beaker were placed 7.0 epoxide equivalents (1260 grams) of EPON-828®, 2,0 moles (424 grams) of neopentyl glycol diacrylate and 1.0 mole (296 grams) of trimethylolpropane triacrylate, mixed for about 10 minutes and labeled component B. The stochiometrical weight ratio of component A and B in this case is A/B = 770/1980 = 1/2.57. In a high speed blender were placed 100 grams of component A, 305 grams titanium dioxide (Rutile type), 0.5 grams ultramarine blue and grinded for 15 minutes. Then 257 grams of component B were added and mixed for an additional 5 minutes. The resulting mixture was sprayed to bonderized steel panels in layers having thicknesses varying from 0.075 to 7.5 mm. The panels dried to touch within 3 hours and dried hard after 6 hours. Gloss was greater than 90% at a 60 degree angle. Direct and reverse impact resistance was greater than 1.31 x 10⁶ N/m². These steel panels were found to have excellent resistance to nitric acid, seawater and ultraviolet light, as well as outstanding gloss retention, all of which is attributed to the polyacrylate structure. In another experiment, castings were made in metallic molds coated with carnauba wax or polyethylene boxes. These castings were more thin 5.08 cm thick and solidified within 6 hours at ambient temperature or within 10 minutes at 130°C. These castings were highly transparent and tough. EXAMPLE 4 In a 1500 ml. glass beaker were placed 30 grams CYMEL-301® 1.0 mole (152 grams) N,N', methylene diacrylamide and 2.0 moles (426 grams) of tetradecyl amine and mixed until the exotherm ceased, thus forming a diimine-diamide. Then 2.0 moles (420 grams) of PAMC® 1.0 mole (136 grams) of metaxylene diamine and 1.0 mole (116 grams) of a liquid mixture of C-6 diamines with a molecular weight of 116 were added and mixed for 5 minutes to form component A. Component B was formed in another 3000 ml glass beaker by mixing 8 epoxide equivalents (1440 grams) of EPON-828®, 2.0 moles (424 grams) of neopoentyl glycol diacrylate, and 0.67 moles (198 grams) of trimethylol propane triacrylate. The stochiometrical mixing weight ratio of component A to component B is equal to A/B = 1167/2062 = 1/1.77. When components A and B are mixed together they form polyimine acrylate at first which add to epoxides and form three dimensional polyhydroxyl tertiary amine-epoxy-propionates and N-substituted acrylamides. In another test, 20.62 grams of component B were mixed with 270 grams asphalt having a melting point of about 60°C. To this mixture were added 11.67 grams of component A, mixed for 5 minutes, and then 900 grams of silicon dioxide were added to the mixture, mixed and poured into concrete holes. After 3 hours the final composite was hard, and inspection of it several months later indicated no signs of cracking. EXAMPLE 5 In an 800 ml. glass beaker were placed 0.5 epoxide equivalents (90 grams) of EPON-826® and 2.25 moles (462.5 grams) of PAMC-20® 8.0 grams of CYMEL-301® and mixed for 15 minutes to form component A. In another 1500 ml glass beaker were placed 4 epoxide equivalents (700 grams) of NOVOLAC-431® 2.0 moles (424 grams) of neopentyl glycol diacrylate, and mixed for 10 minutes to form component B. The mixing ratio of this solventless system of component A to component B is Ten grams of component A were mixed with 7.5 grams of zinc oxide and 2.5 grams of red oxide. To this mixture were added 20 grams of component B, mixed for an additional 5 minutes and then the mixture was applied to panels of wood, concrete, steel, aluminum, tin and glass to yield solventless thermosetting, glossy paints at ambient temperatures, even in the absence of titanium dioxide and grinding of the pigments. EXAMPLE 6 In an 800 ml. glass beaker were placed 1.0 mole (403 grams) of Jeffamine T-403® with a molecular weight of 403 and to it were added 1.0 mole (53 grams) of acrylonitrile, under mixing and cooling with water to form component A. Separately in another 1000 ml. glass beaker were placed 3.0 epoxide equivalents (540 grams) of EPON-826®, 1.0 mole (330 grams) of tetraethylene glycol dimethyl acrylate, 13 grams of CYMEL-301® and mixed for 15 minutes to form component B. The mixing weight ratio of A/B = 456/883 = 1/1.94. 10 grams of component A were mixed with 19.4 grams of component B to form an excellent adhesive for glass, steel and wood. EXAMPLE 7 Component A was made by placing in an 800 ml. glass beaker 1.0 mole (403 grams) Jeffamine T-403® 12.5 grams of CYMEL-301® and slowly adding to it 0.25 moles (82.5 grams) of tetraoxoethylene glycol dimethyl acrylate. Component B was made in another beaker by mixing 3.0 epoxide equivalents (540 grams) of EPON-826® and 1.25 moles (272.25 grams) of 1,6 hexamethylene diol diacrylate. The weight ratio of component A to component B of this system is A/B = 1/1.63. Ten grams of component A were mixed with 16.3 grams of component B to form six batches and 11, 24.6, 26.7, 40.5, 55.6, and 106.8 grams of chopped glass fiber or fiber cloth were respectively added to the batches. The resulting mixtures were pressed in polyethylene molds to form castings consisting of 30/70, 40/60, 42/58, 60/40, 70/30 and 80/20 glass to resin ratios. Similar castings were made with general purpose unsaturated polyesters cured with ketone hydroperoxides as well as with EPON-828® and Versamides (amino-terminated polyamides based on dimer fatty acid and triethylene tetra amine condensates). Straight comparisons between all of these specimens measured by impact resistance and resilience suggests that the solventless liquid system of the present invention was better than the epoxide-Versamide 1 and unsaturated polyesters. Based on these findings, as well as in the outstanding adhesion of the solventless system to glass, it will be apparent to those skilled in the art that the solventless systems of this invention are especially adaptable for use as binders for reinforced plastics used in the construction of yachts, storage tanks, pipes, corrugated sheets, fishing lures, bowling balls, etc. Additionally, bridge or construction columns of better strength seem to be feasible. In addition to glass fibers, other filler materials such as graphite, Kevlar® or metallic fibers can also be used. EXAMPLE 8 In an 800 ml. glass beaker were placed 1.0 mole (60 grams) of ethylene diamine, 1.0 mole (216 grams) of azelaic hydrazide, and under mixing and cooling were added 0.8 moles (203.2 grams) of 1,6, N,N' dimethyl hexamethylene diol diacrylate. Two hours later 0.4 moles (28.4 grams) of acrylamide were added and mixed for additional 30 minutes to form component A, having an oligomeric polyimine-hydrazide amide ester structure, and an amine equivalent of 84.6. Component B was formed by using 2 epoxide equivalents (360 grams) of EPON-826® diluted with 2.0 moles (284 grams) of glycidyl ester of methyl acrylic acid and 11 grams of CYMEL-301® . The mixing equivalent weight ratio of component A to B is equal to 507.6/655 = 0.77/1. When 7.7 grams of component A are mixed with 10 grams of component B they form cross-linked polyhydroxyl tertiary (amine and hydrazine) epoxy acrylates. EXAMPLE 9 In a 2000 ml. glass beaker were placed 3.5 moles (406 grams) of AMINE-6 a liquid mixture of C-6 diamines with a molecular weight of 116, 0.5 moles (165 grams) of oxotetraethylene diol dimethyl acrylate, 1.0 mole (152 grams) of N,N'methylene diacrylamide, 23 grams of CYMEL-301® and mixed to form component A. Component B was formed by mixing 2.5 moles (565 grams) of 1,6 hexamethylene diol diacrylate and 6.0 epoxide equivalents (1080 grams) of EPON-828® or simply using 5.0 moles (710 grams) of glycidyl ester of methyl acrylic acid, or 5 moles (1130 grams) of 1,6 hexamethylene diol diacrylate or their combined mixtures. As is shown in this example it is possible to vary the ratios and the ingredients of component B or A to achieve desired viscosities, ratios and properties. EXAMPLE 10 Component A was formed by mixing 0.5 moles (410 grams) of dimer fatty acid condensate (which was formed from the reaction of 1.0 mole (564 grams) dimer fatty acid with 2.0 moles (292 grams) of triethylene tetramine), 2.5 moles (388 grams) of trimethyl 1,6 hexamethylene diamine and 32 grams of CYMEL-301®. Similarly, component B was made by mixing 8 epoxide equivalents (1440 grams) of DOW-431 Novolac, 2.0 moles (452 grams) of 1,6 hexamethylene diol diacrylate and 1.0 mole (302 grams) of oxotetraethylene diacrylate. The equivalent weight ratio of component A and B are A/B = 830/2194 = 1/2.64. When 10 grams of component A are mixed with 26.4 grams of component B they form polyhydroxyl amides-tertiary-amine-epoxy-acrylates. Similarly, component A was made by mixing 1.0 mole (592 grams) of dimer fatty hydrazide, 3.0 moles (630 grams) of PAMC-20® 33 grams CYMEL-301® and 0.5 epoxide equivalent (90 grams) EPON-828® at ambient temperatures. Component B was prepared by mixing 7.5 epoxide equivalents (1350 grams) of EPON-828® dissolved in 4.0 moles (848 grams) of neopentyl glycol diacrylate. The equivalent weight ratio of component A to component B is equal to A/B = 1345/2198 = 1/1.63. Ten grams of component A were mixed with 16.3 grams of component B and a thin layer of this was applied to bond together two pieces of wood. The next day significant force was used to take apart the two wooden pieces, and it was found that all the fibers of the bonded wooden surface were totally removed suggesting that the adhesive bond was much stronger than wood. Similarly impressive results were obtained by adhering tiles, bricks, concrete, steel, glass, polyvinyl chloride, polycarbonate, polyesters, epoxide and polystyrene pieces as individual and combined pieces. The absence of solvents in the present invention provides a compact continuous bond while low viscosity penetrates the substrate thus resulting in outstanding adhesion. EXAMPLE 11 In a 1000 ml. glass beaker were placed 3.0 moles (630 grams) of PAMC-20® and 1.0 mole (213 grams) of tetradecyl amine and 32 grams CYMEL-301® and mixed for 20 minutes to form component A. Separately, in another glass beaker were mixed 7 epoxide equivalents (1260 grams) of EPON-826®, 2.0 moles (424 grams) of 1,6 hexamethylene diol diacrylate, 1.0 mole (296 grams) trimethylol propane triacrylate and 92 grams of ortho cresol to form component B. The mixing ratio of component A to component B was A/B = 875/2100 = 1/2.4 and the ortho cresol catalyst was 4.38% by weight of component B and 3.1% by weight of the combination of components A and B. Upon mixing 10 grams of component A with 24 grams of B a rapid increase in viscosity occurs within 15 minutes and the mixture thermosets to touch free in 40 minutes. In another experiment the ortho cresol was replaced with phenol, chloro phenol, nonyl phenol, ortho dinitro cresol, para dinitro cresol, hydroquinone, dibutyl hydroquinone and p,p'isopropylidene diphenol. It was observed that the thermosetting time of component A and mixtures was decreased as the acidity and the quantity of phenolic compound used increased. Accelleration of thermosetting time at ambient temperatures shortens the pot life of the mixed components A and B and it becomes impractical for brushing applications; however, it is efficient and practical when a dual mixing spray gun is utilized which will limit mixing time of component A and B to a satisfactorily short period of time. EXAMPLE 12 In a 1000 ml. glass beaker were placed 3.0 moles (630 grams) of PAMC-20®, 1.0 mole (213 grams) of tetradecyl amine and 32 grams of CYMEL-301® and mixed for 30 minutes to form component A. Separately, in another glass beaker, were mixed 7 epoxide equivalents (1260 grams) of EPON-828®, 2.0 moles (452 grams) of 1,6 hexamethylene diol diacrylate, 1.0 mole (296 grams) of trimethylol propane triacrylate and 1100 grams of ortho dinitrocresol to form component B. The mixing ratio of component A to B was A/B = 875/3108 = 1/3.55. This was sprayed by using a dual, airless gun to form a fast, thermosetting, yellow, solventless varnish. The same experiment was repeated by using 875 grams of component A which were mixed with 1197 grams titanium dioxide and 3108 grams of component B. This mixture was sprayed by an airless gun to form an antifouling paint which thermoset in less than 50 minutes. EXAMPLE 13 In a two liter resin kettle were placed 2.0 moles (420 grams) of PAMC-20® with 1.0 mole (60 grams) of urea. The mixture was heated to 180°C until 3.0 moles (54 grams) of water were condensed. Urea diamine having a molecular weight of 446 was formed. Also, at ambient temperature to 90°C, 2.0 moles (460 grams) of polyoxopropylene diamine with a molecular weight of 230 (Jeffamine D-230) with 1.0 mole (146 grams) of diethyl oxalate were reacted to form an oxalamide diamine having a molecular weight of 514. Replacement of the 2.0 moles (460 grams) Jeffamine D-230® with 2.0 moles (806 grams) polyoxotriamine-400 (Jeffamine T-403® 1.0 mole diethyl oxalate results in an oxalamide tetramine having a molecular weight of 860. In the same resin kettle were placed 3.0 moles (474 grams) 1,6 trimethyl hexamethylene diamine, and 2.0 moles (376 grams) of azelaic acid and heated up to 200°C until 4.0 moles of water were removed and a diamine terminated oligomeric poly-amide having an average molecular weight of 769 was formed. Similarly, other diamines or polyamine terminated compositions were prepared from the condensation reaction between the following: 1.0 mole of sebacic acid with 2.0 moles of 1,6 hexamethylene diamine, 1.0 mole of adipic acid with 2.0 moles of trimethyl 1,6 hexamethylene diamine, 1.0 mole of azelaic acid with 2.0 moles of diethylene triamine and 1.0 mole of dimer fatty acid with 2.0 moles of triethylene tetraamine. Also, 1.0 mole of sulfonyl chloride was condensed with 2.0 moles of trimethyl, 1,6 hexamethylene diamine, PAMC-20® or polyoxopropylene diamine with a molecular weight of 400 to form amide or sulfonamide diamines. All the amine terminated compounds alone, or as mixtures with simple mono, di or poly amines, can be used as the main ingredient in preparing the component A of the liquid solventless system. EXAMPLE 14 A liquid and low melting mono hydrazide was made by mixing 1.0 mole (242 grams) of the methyl ester of tetradecanoic acid, 1.0 mole (50 grams) of hydrazine monohydrate, and heating the mixture up to 90°C to remove 1.0 mole of methanol and 1.0 mole of water to form the monohydrazide of tetradecanoic acid. Dihydrazides were also ride from the condensation reactions between 1.0 mole of the dimethyl esters of sebacic acid, dodecenedioic acid, or dimer fatty acid and 2.0 moles of hydrazine through the elimination of 2.0 moles of methanol. A trihydrazide was also made from the condensation of 1.0 mole of trimer fatty acid with 3.0 moles of hydrazine. These mono, di or tri hydrazides readily react at ambient temperatures with mono, di or polyacrylates, epoxides, or glycidyl ester of methyl acrylic acid. They can be used alone or with simple amines as the main ingredients to form component A of the solventless system. It was found that hydrazide and oxalamide linkages further enhance the chemical and mechanical performance properties of the thermoset solventless system. EXAMPLE 15 In a two liter resin kettle equipped with a mechanical stirrer, a thermocouple connected to a temperature recorder and a vertical condenser attached to a polyethylene tube ending in a water container were placed 8 moles (928 grams) of 2-methyl, 1,5 pentamethylene diamine and 4.0 moles (240 grams) of urea. This mixture was heated for 5 hours at a temperature between 120°C and 180°C under continuous stirring until 8 moles (136 grams) of gaseous ammonia were evolved. The resulting product was N',N' bis 2-methyl, 1,5 pentamethylene diamine urea having a molecular weight of 258. Component A was formed by mixing 1.0 mole (213 grams) of tetradecyl amine and 1.0 mole (296 grams) of trimethylolpropane triacrylate for about one hour at ambient temperatures to form a tertiary amine linear polyacrylate to which was then added 1.5 moles (387 grams) of N',N' bis 1,5 pentamethylene diamine urea. Components B was formed by mixing three epoxide equivalents (540 grams) of the condensation product of epidilarhydrin and Bisphenol-A of CYMEL 301® 15 grams of orthocresol and 1.0 mole (226 grams) of hexane diol diacrylate. The mixing ratio of component A to component B was A/B = 896/781 = 1.15/1. EXAMPLE 16 In a two liter resin kettle equipped as described in Example 16 were placed 6.0 moles (1260 grams) of PAMC-20® and 3.0 moles (180 grams) of urea. The mixture was heated for five hours under continuous mixing at a temperature of from 120°C to 180°C to eliminate 6.0 moles of gaseous ammonia to form the bis p,p' methylene cyclohexylene symmetrically substituted urea diamino having a molecular weight of 446. Component A was formed by mixing 1.0 mole (213 grams) of tetradecyl amino with 2.0 moles (452 grams) of 1.6 hexane diol diacrylate followed by the addition of 2.0 moles (892 grams) of N,N' p,p' methylene cyclohexylene urea diamine, 1.5 moles (315 grams) of p,p'methylene cyclohexylene damine and 38 grams of CYMEL 301®. The resulting product had a total weight of 1910. Component B was formed by mixing seven epoxide equivalents (1260 grams) of EPON-826®, 1.5 moles (339 grams) of 1,6 hexane diol diacrylate, 1.0 mole (296 grams) of trimethylol propane triacrylate and 15 grams of orthocresol. The weight of this mixture was 1910. The mixing ratio of A/B was 1/1. EXAMPLE 17 In a two liter glass resin kettle equipped with a mechanical stirrer, a thermocouple connected to a temperature recorder, a water trap, a nitrogen tube inlet and a vertical water condenser were placed 10 moles (1160 grams) of 2-methyl 1,5 pentane diamine. Under continuous mixing and cooling 5.0 moles (500 grams) of ethyl acrylate were slowly added over a period of about 2 hours. The temperature was then raised to 160°-180°C and maintained until 5.0 moles (230 grams) of ethyl alcohol were collected. The resulting compound was a triamine-monoamide composed of two primary and one secondary amino groups having a molecular weight of 286 and an amine value of 57.2. The compound is beta 2-methyl 1,5 pentane diamine of propionamido, 2 methyl pentane amine - 1. Additional compounds were formed by replacing 2-methyl 1,5 pentane diamine with 1,6 hexane diamine. Also, ethyl acrylate was replaced with methyl acrylate, acrylic acid, ethyl methyl acrylate, methyl methacrylate or methyl acrylic acid. In the cases of methyl acrylic derivatives, triamines of alpha methyl propionamide were produced. Component A was formed by using 286 grams of the propionamide triamine of 2 methyl 1,5 pentane diamine and 14 grams of CYMEL 301®. Component B was formed by mixing 540 grams EPON-828® 226 grams of 1,6 hexane diol diacrylate and 11 grams of ortho cresol. The mixing weight ratio of A/B=1/2.59. When mixed together, these components produced solventless clear varnishes, adhesives, paints, and composites thermosetting at ambient temperatures. EXAMPLE 18 In the resin kettle equipped as described in the previous Example 13 were placed 4.0 moles (400 grams) of methyl methacrylate and under continuous mixing and cooling, 2.0 moles (232 grams) of 1,6 hexamethylene diamine were slowly added through a dropping funnel over a period of about two hours time. 4.0 moles (464 grams) of 1,6 hexamethylene diamine were then added at once, and the mixture was heated to 160° to 180°C for about two hours until 4.0 moles (128 grams) of methanol were collected. The final composition was a diamide-tetraamine containing two primary, two secondary amino groups and two amide groups. It had a molecular weight of 484, an amine value of 80.66 and was represented by the following structure: Additional compounds were formed by totally or partially replacing 1,6 hexamethylene diamine with 2-methyl 1,5 pentane diamine and by replacing methyl methacrylate with ethyl methacrylate, ethyl acrylate, acrylic acid, methyl acrylic acid or methyl acrylate. The features disclosed in the foregoing description, in the following claims and/or in the accompanying drawings may, both separately and in any combination thereof, be material for realising the invention in diverse forms thereof.

Claims: A method of preparing a thermoset polymeric composition optionally containing a filler, characterized in that it comprises mixing a) a di or polyamine of the general structure R n (NH₂) n , wherein R is a n-valent radical of aliphatic, cycloaliphatic, heterocyclic or aromatic structure and n is an integer of at least 2, and/or their adducts with mono, di or polyacrylates or epoxides prepared in an equivalent ratio of amine to epoxide and acrylate of at least 2 to 1 b) with a di or polyacrylate and optionally a monoacrylate and further optionally a mono, di or polyfunctional epoxide and optionally c) a filler, in the absence of a solvent, whereby the components are mixed in substantially stoichiometric proportions, and thermosetting the mixture at a temperature of 4 to 32° C in the absence of a photoinitiator. A method according to claim 1, wherein as the amine there is used a diamine selected from the group consisting of hydrazine, ethylene diamine, butylene diamine, hexamethylene diamine, 2-methyl, 1,5 pentane diamine, trimethyl hexamethylene diamine, isophorone diamine, cyclohexamethylene diamine, methylene bis cyclohexamethylene diamine, isomers thereof and substituted derivatives thereof, the adduct of n moles of the above amines with n or 2n moles of monofunctional acrylates or methyl acrylates or the adducts of n moles of a difunctional acrylate or methyl acrylate or the diamide-amines obtained from the condensation of n moles of dimer fatty acid, dodecanedioic acid, sebacic acid or the dimethyl esters thereof with 2n moles of hydrazine or 2n moles of the above diamines, the sulfone, urea or amide imide diamines obtained from the condensation of n moles of sulfuryl chloride, urea, or trimellic anhydride with 2n moles of hexamethylene diamine, methylene bis cyclohexamethylene diamine or polyoxypropylene diamines of molecular weight 230, 400, 600, 800, 1000 or 2000; and the tri or polyamines are selected from the group consisting of diethylene triamine, dipropylene triamine, triethylene tetramine, tetraethylene pentamine, polyoxypropylene triamine-400, condensates thereof with dicarboxylic or tricarboxylic acids or the lower esters thereof, such as oxalic acid, adipic acid, azelaic acid, sebacic acid, dodecandioic acid, dimer fatty acids, isophthalic and terephthalic acids, trimellitic anhydride, trimesic acid, or with sulfuryl chloride, or urea at a molar ratio of 2 to 1 of di or tri polyamine to difunctional acid or ester or a molar ratio of 3 to 1 of di or tri polyamine to a trifunctional acid or ester. A method according to one of the preceding claims, wherein the difunctional acrylates are selected from the group consisting of butane diacrylate, neopentyl diacrylate, 1,6 hexamethylene diacrylate, oxo diethylene diacrylate, oxo triethylene diacrylate, oxo tetraethylene diacrylate, polyoxoethylene diol diacrylates or dimethyl acrylates, and di, tri or poly oxo propylene diol diacrylates or dimethyl acrylates, and the tri or polyfunctional acrylates or methyl acrylates are selected from the group consisting of trimethylol propane triacrylate, pentaerythritol triacrylate, the tetra acrylate or methyl acrylate of pentaerythritol; the adducts of n moles of an imine with n moles of pentaerythritol tetraacrylate or tetramethyl acrylate; and the adducts of n moles of a diimine or n moles of a primary amine with 2n moles of a di, tri or polyacrylate or methyl acrylate, and the adducts of n moles of primary diamines with 3n or 4n moles of a di, tri or tetra-functional acrylate or methyl acrylate. A method according to one of the preceding claims, wherein the mono, di or polyfunctional epoxides are selected from the group consisting of ethylene, propylene, butene, styrene, and cyclohexene oxides; aliphatic diepoxides; diglycidyl ether of bisphenol A; di or polyepoxides based on aniline, novolac, phenol or cresol resins; the diepoxides of bis-cyclohexene or bis-methylcyclohexene glycolate or adipate; the halo and alkyl substituted derivatives of the above. A method according to one of the preceding claims, further comprising addition of 1 to 3 percent hexakis methoxy methylene melamine as a surface tension reducer. A method according to one of the preceding claims, wherein as filler there are used 2 to 98% by weight of asphalt or other hydrocarbon resins such as polyalphamethylstyrene, polyvinyl carbazole or polyterpenes. A method according to one of the claims 1 to 5, whereby up to 90% by weight of silicon dioxide alone or in combination with minor quantities of pigments or dyes is added. A method according to any of claims 1 to 5 and 7, characterized in that 30 to 75% by weight of fiberglass, fiber cloth or carbon fiber is added as a filler.

Inventors: NICHOLS GUS, NICHOLS, GUS
Applicants: NICHOLS GUS, NICHOLS, GUS
Application year: 1985
Main classification: C08G59
IPC codes: C08G59