EP1080128A1 - Novel polymer additives for forming objects - Google Patents

Abstract

The present invention relates to novel methods and compositions related to polymer concrete comprising conventional resins with novel additives to prevent shrinking and cracking of the resin, to accelerate curing and to treat fillers. These compositions and methods can be employed to form large objects and objects of irregular shapes. These compositions and methods provide lightweight materials some of which are hard and inflexible, while others are hard and flexible.

Description

NOVEL POLYMER ADDITIVES FOR FORMING OBJECTS

TECFLNICAL FIELD

The present invention compπses generally high flash point resms that can be molded mto a vanety of different objects The present invention also compnses objects that are both hard and flexible More particularly, the present invention relates to polymer concrete that is particularly useful m rapidly casting large objects including poured marble

BACKGROUND OF THE INVENTION

A plastic is an organic polymer, available as a resm. These resms can be liquid or paste and can be used for embedding, coating, and adhesive bonding, or they can be molded, laminated, or formed into desired shapes, including sheet, film, or larger mass bulk shapes

The number of basic plastic matenals is large and the list is increasing In addition, the number of vanations and modifications to these basic plastic matenals is also quite large Taken together, the resultant quantity of matenals available is too large to be completely understood and correctly applied by anyone other than those whose day-to-day work puts them m direct contact with a diverse selection of matenals The practice of mixing brand names, trade names, and chemical names of vanous plastics only makes the problem of understanding these matenals more troublesome. Another vanable that makes it difficult for those not versed m plastics to understand and properly design with plastics is the large number of processes by which plastics can be fabncated Fortunately, there is an organized pattern on which an orderly presentation of these vanables can be based. While there are numerous minor classifications for polymers, depending on how one wishes to categonze them, nearly all can be placed into one of two major classifications — thermosetting matenals (or thermosets) and thermoplastic matenals. Likewise, foams, adhesives, embedding resins, elastomers, and so on, can be subdivided into the thermoplastic and thermosetting classifications. Thermosetting plastics are cured, set, or hardened into a permanent shape. Cunng is an irreversible chemical reaction known as cross-linking, which usually occurs under heat. For some thermosetting matenals, cunng is initiated or completed at room temperature. Even here, however, it is often the heat of the reaction, or the exotherm, which actually cures the plastic matenal Such is the case, for instance, with a room-temperature-cunng epoxy or polyester compound. The cross-linking that occurs in the cunng reaction is brought about by the linking of atoms between or across two linear polymers, resulting in a three-dimensional ngid chemical structure Although the cured part can be softened by heat, it cannot be remelted or restored to the flowable state that existed before cunng Continued heating for long times leads to degradation or decomposition

Thermoplastics differ from thermosets in that they do not cure or set under heat as do thermosets Thermoplastics merely soften, or melt when heated, to a flowable state, and under pressure they can be forced or transferred from a heated cavity into a cool mold Upon cooling in a mold, thermoplastics harden and take the shape of the mold Since thermoplastics do not cure or set, they can be remelted and then rehardened by cooling Thermal aging, brought about by repeated exposure to the high temperatures required for melting, causes eventual degradation of the matenal and so limits the number of reheat cycles.

All polymers are formed by the creation of chemical linkages between relatively small molecules, or monomers, to form very large molecules, or polymers. As mentioned, if the chemical linkages form a ngid, cross-linked molecular structure, a thermosetting plastic results. If a somewhat flexible molecular structure with minimal or no cross-linking is formed, either linear or branched, a thermoplastic results.

Polymenzation Reactions

Polymenzation reactions may occur in a number of ways, with four common techniques being bulk, solution, suspension, and emulsion polymenzation. Bulk polymenzation involves the reaction of monomers or reactants among themselves, without placing them in some form of extraneous media, as is done in the other types of polymenzation.

Solution polymenzation is similar to bulk polymenzation, except that whereas the solvent for the forming polymer in bulk polymenzation is the monomer, the solvent in solution polymenzation is usually a chemically inert medium. The solvents used may be complete, partial, or nonsolvents for the growing polymer chains. Suspension polymenzation normally is used only for catalyst-initiated or free radical addition polymenzations. The monomer is dispersed mechanically m a liquid, usually water, which is a nonsolvent for the monomer as well as for all sizes of polymer molecules which form dunng the reaction The catalyst initiator is dissolved in the monomer, and it is preferable that it does not dissolve in the water so that it remains with the monomer. The monomer and the polymer being formed from it stay within the beads of organic matenal dispersed in the phase Actually, suspension polymenzation is essentially a finely divided form of bulk polymenzation The mam advantage of suspension polymenzation over bulk is that it allows cooling of the exothermic polymenzation reaction and maintains closer control over the cham-building process By controlling the degree of agitation, monomer-to-water ratios, and other vanables it is also possible to control the particle size of the finished polymer, thus eliminating the need to reform the matenal into pellets from a melt, as is usually necessary with bulk polymenzation Emulsion polymenzation is a technique in which addition polymenzations are earned out in a water medium containing an emulsifier (a soap) and a water-soluble initiator. Emulsion polymenzation is much more rapid than bulk or solution polymenzation at the same temperatures and produces polymers with molecular weights much greater than those obtained at the same rate m bulk polymenzations.

In emulsion polymenzation, the monomer diffuses into micelles, which are small spheres of soap film. Polymenzation occurs within the micelles. Soap concentration, overall reaction-mass recipe, and reaction conditions can be vaned to provide control of the reaction rate and yield. The usual sequence of processmg a thermoplastic is to heat the matenal so that it softens and flows, force the matenal in the desired shape through a die or in a mold, and chill the melt into its final shape. By companson, a thermoset is typically processed by starting out with partially polymenzed matenal, which is softened and activated by heating (either or out of the mold), forcing it into the desired shape by pressure, and holding it at the cunng temperature until final polymenzation reaches the point where the part hardens and stiffens sufficiently to keep its shape when demolded.

Plastic-Fabncation Processes and Forms There are many plastic-fabncation processes, and a wide vanety of plastics can be processed by each of these processes or techniques. Fabncation processes can be broadly divided into pressure processes and pressureless or low-pressure processes Pressureless or low-pressure processes include potting, casting, impregnating, encapsulating, and coating. Pressure processes are usually either thermoplastic-matenals processes (such as injection molding, extrusion, and thermoformmg) or thermosetting processes (such as compression molding, transfer molding, and laminating)

Compression Molding and Transfer Molding

Compression molding and transfer molding are the two major processes used for forming molded parts from thermosetting raw matenals. The two can be earned out in the same type of molding press, but different types of molds are used The thermosetting matenals are normally molded by the compression or transfer process, but it is also possible to mold thermoplastics by these processes since the heated thermoplastics will flow to conform to the mold- cavity shape under suitable pressure. These processes are usually impractical for thermoplastic molding, however, since after the mold cavity is filled to its final shape, the heated mold would have to be cooled to solidify the thermoplastic part. Since repeated heating and cooling of this large mass of metal and the resultant long cycle time per part produced are both objectionable, injection molding is commonly used to process thermoplastics.

Compression Molding

In compression molding, the open mold is placed between the heated platens of the molding press, filled with a given quantity of molding matenal, and closed under pressure, causing the matenal to flow into the shape of the mold cavity The actual pressure required depends on the molding matenal being used and the geometry of the mold. The mold is kept closed until the plastic matenal is suitably cured. Then the mold is opened, the part ejected, and the cycle repeated. The mold is usually made of steel with a polished or plated cavity. The simplest form of compression molding involves the use of a separate self-contained mold or die that is designed for manual handling by the operator. It is loaded on the bench, capped, placed in the press, closed, cured, and then removed for opening under an arbor press. The same mold in most instances (and with some structural modifications) can be mounted permanently into the press and opened and closed as the press itself opens and closes. The press must have a positive up-and down movement under pressure instead of the usual gravity drop found in the standard hand press

Transfer Molding

The molding matenal is first placed in a heated pot, separate from the mold cavity The hot plastic matenal is then transferred under pressure from the pot through the runners into the closed cavity of the mold

The advantage of transfer molding lies in the fact that the mold proper is closed at the time the matenal enters Parting lines that might give trouble m finishing are held to a minimum Inserts are positioned and delicate steel parts of the mold are not subject to movement Vertical dimensions are more stable than in straight compression. Also, delicate inserts can often be molded by transfer molding, especially with the low-pressure molding compounds

Injection Molding Injection molding is the most practical process for molding thermoplastic matenals. The operating pnnciple is simple, but the equipment is not.

A matenal with thermoplastic qualities — ■ one that is viscous at some elevated temperature and stable at room temperature without appreciable detenoration dunng the cycle — is maintained in a heated reservoir. This hot, soft matenal is forced from the reservoir into a cool mold. The mold is opened as soon as the matenal has cooled enough to hold its shape on demoldmg. The cycle speed is determined by the rapidity with which the temperature of the matenal used can be reduced, which in turn depends on the thermal conductivity of that matenal. Acrylics are slow performers, and styrenes are among the fastest.

The machine itself is usually a honzontal cylinder whose bore determines the capacity. Within the bore is a piston which, when retracted, opens a hole in the top of the cylinder through which new matenal can be added to replace the charge shot into the mold. The cylinder is heated by electnc bands which permit temperature vanation along its length. Inside the exit end of the cylinder is a torpedo over which the hot matenal is forced just before coming out of the nozzle mto the channels leading to the cavities. This gives the matenal a final churning and ensures thorough heating. The mold opens and closes automatically, and the whole cycle is controlled by timers. Thermoset Ingestion Molding

Because of the chemical nature of the plastic matenals, injection molding has traditionally been the pnmary molding method for thermoplastics, and compression and transfer molding have been the pnmary molding methods for thermosetting plastics Because of the greater molding cycle speeds and lower molding costs m injection molding, thermoplastics have had a substantial molding cost advantage over thermosets As a result, advances in equipment and in thermosetting molding compounds have resulted in a rapid transition to screw-mjection, m-hne molding This has been especially prominent with phenohcs, but other thermosets are also included to varying degrees The growth in screw-injection molding of phenohcs has been extremely rapid The development of this technique allows the molder to automate further, reduce labor costs, improve quality, reduce rejects, and gam substantially overall molding cycle efficiency.

Extrusion and Protrusion

The process of extrusion consists basically of forcing heated, melted plastic continuously through a die, which has an opening shaped to produce a desired finished cross section. Normally it is used for processmg thermoplastic matenals, but it can also be used for processing thermosetting matenals. The mam application of extrusion is the production of continuous lengths of film, sheeting, pipe, filaments, wire jacketing, and other useful forms and cross sections. After the plastic melt has been extruded through the die, the extruded matenal is hardened by cooling, usually by air or water.

Extruded thermosetting matenals are used increasingly in wire and cable coverings. The main object here is the production of shapes, parts, and tolerances not obtainable m compression or transfer molding. Pultrusion is a special, increasingly used technique for pulling resin soaked fibers through an onfice, as it offers significant strength improvements Any thermoset, granular molding compound can be extruded and almost any type of filler may be added to the compound. In fiber-filled compounds, the length of fiber is limited only by the cross-sectional thickness of the extruded piece.

A metered volume of molding compound is fed into the die feed zone, where it is slightly warmed. As the ram forces the compound through the die, the compound is heated gradually until it becomes semi-fluid. Before leaving the die, the extruded part is cured by controlling the time it takes to travel through a zone of increasing temperature The cured matenal exits from the die at temperatures of 300 to 350°F and at vanable rates

Thermosetting Plastics

Plastic matenals included in the thermosetting plastic category are alkyds, diallyl phthalates, epoxies, melamines, phenohcs, polyesters, sihcones, and ureas In general, unfilled thermosetting plastics tend to be harder, more bnttle, and not as tough as thermoplastics Thus, it is common practice to add fillers to thermosetting matenals A wide vanety of fillers can be used for varying product properties For molded products, usually compression or transfer molding, mineral or cellulose fillers are often used as lower-cost, general-purpose fillers, and glass fiber fillers are often used for optimum strength or dimensional stability It should be added that filler form and filler surface treatment can also be major vanables Thus it is important to consider fillers along with the thermosetting matenal, especially for molded products Other product forms may be filled or unfilled, depending on requirements.

Alkyds

Alkyds are available in granular, rope, and putty form, some suitable for molding at relatively low pressures, and at temperatures in the range of 300 to 400°F They are formulated from polyester-type resms Other possible monomers, aside from styrene, are diallyl phthalate and methyl methacrylate Alkyd compounds are chemically similar to the polyester compounds but make use of higher-viscosity, or dry, monomers. Alkyd compounds often contain glass-fiber filler but may, for example, include clay, calcium carbonate, or alumina

These unsaturated resms are produced through the reaction of an organic alcohol with an organic acid. The selection of suitable polyfunctional alcohols and acids permits selection of a large vanation of repeating units Formulating can provide resins that demonstrate a wide range of charactenstics involving flexibility, heat resistance, chemical resistance, and electncal properties.

Diallyl Phthalates (Allyls)

Diallyl phthalates, or allyls, are among the best of the thermosetting plastics with respect to high insulation resistance and low electncal losses, which are maintained up to 400°F or higher, and in the presence of high humidity environments Also, diallyl phthalate resins are easily molded and fabncated

There are several chemical vanations of diallyl phthalate resins, but the two most commonly used are diallyl phthalate (DAP) and diallyl isophthalate (DAIP) The pnmary application difference is that DAIP will withstand somewhat higher temperatures than will DAP

DAPs are extremely stable, having very low after-shnnkage, on the order of 0 1 percent The ultimate in electncal properties is obtained by the use of the synthetic-fiber fillers However, these matenals are expensive, have high mold shnnkage, and have a strong, flexible flash that is extremely difficult to remove from the parts

Epoxies

Epoxy resins are charactenzed by the epoxide group (oxirane rings) The most widely used resins are diglycidyl ethers of bisphenol A These are made by reacting epichlorohydnn with bisphenol A in the presence of an alkaline catalyst By controlling operating conditions and varying the ratio of epichlorohydnn to bisphenol A, products of different molecular weights can be made

Another class of epoxy resins is the novolacs, particularly the epoxy cresols and the epoxy phenol novolacs These are produced by reacting a novolac resin, usually formed by the reaction of ocresol or phenol and formaldehyde with epichlorohydnn These highly functional matenals are particularly recommended for transfer-molding powders, electncal laminates, and parts where supenor thermal properties, high resistance to solvents and chemicals, and high reactivity with hardeners are needed

Another group of epoxy resms, the cycloahphatics, is particularly important when supenor arc-track and weathenng resistance are necessary requirements A distinguishing feature of cycloaliphatic resms is the location of the epoxy group(s) on a nng structure rather than on, the aliphatic chain Cycloahphatics can be produced by the peracetic epoxidation of cyclic olefins and by the condensation of an acid such as tetrahydrophtha c anhydnde with epichlorohydnn, followed by dehydrohalogenation

Epoxy res s must be cured with cross-linking agents (hardeners) or catalysts to develop desirable properties The epoxy and hydroxyl groups are the reaction sites through which cross-linking occurs Useful agents include amines, anhydndes, aldehyde condensation products, and Lewis acid catalysts Careful selection of the proper cunng agent is required to achieve a balance of application properties and initial handling charactenstics

Aliphatic amine cunng agents produce a resm-cunng agent mixture which has a relatively short working life, but which cures at room temperature or at low baking temperatures in relatively short time Resins cured with aliphatic amines usually develop the highest exothermic temperatures dunng the cunng reaction; thus the amount of matenal which can be cured at one time is limited because of possible cracking, crazing, or even charnng of the resm system if too large a mass is mixed and cured. Also, physical and electncal properties of epoxy resms cured with aliphatic amines tend to degrade as the operating temperature increases Epoxies cured with aliphatic amines find their greatest usefulness where small masses can be used, where room-temperature cunng is desirable, and where the operating temperature required is below 100°C

Epoxies cured with aromatic amines have a considerably longer working life than do those cured with aliphatic amines, but they require cunng at 100°C or higher. Resins cured with aromatic amines can operate at a temperature considerably above the temperature necessary for those cured with aliphatic amines. However, aromatic amines are not so easy to work with as aliphatic amines, because of the solid nature of the cunng agents and that some (such as metaphenylene diarmne) sublime when heated, causing stains and residue deposition.

Catalytic cunng agents also have longer working lives than the aliphatic amine matenals, and like the aromatic amines, catalytic cunng agents normally require cunng of the epoxy system at 100°C or above. Resins cured with these systems have good high-temperature properties as compared with epoxies cured with aliphatic amines. With some of the catalytic cunng agents, the exothermic reaction becomes high as the mass of the resm mixture increases.

Acid anhydnde cunng agents are particularly important for epoxy resms, especially the liquid anhydndes. The high-temperature properties of resin systems cured with these matenals are better than those of resm systems cured with aromatic amines. Some anhydnde-cured epoxy-resm systems retain most electncal properties to 150°C and higher, and are not affected physically, even after prolonged heat aging at 200°C. In addition, the liquid anhydndes are extremely easy to work with in that they blend easily with the resms and reduce the viscosity of the resin system Also, the working life of the liquid acid anhydnde systems is comparable with that of mixtures of aliphatic amine and resm. and odors are slight. Amine promoters such as benzyl dimethylamine

(BDMA) oi DMP-30 are used to promote the curing of mixtures of acid anhydnde and epoxy resm

Epoxies are among the most versatile and most widely used plastics in the electronics field This is pnmanly because of the wide vanety of formulations possible, and the ease with which these formulations can be made and utilized with minimal equipment requirements. Formulations range from flexible to ngid in the cured state, and from th liquids to thick pastes and molding powders in the uncured state. Conversion from uncured to cured state is made by use of hardeners or heat, or both The largest application of epoxies is m embedding applications (potting, casting, encapsulating, and impregnating) in molded parts, and in laminated constructions such as metal-clad laminates for pnnted circuits and unclad laminates for vanous types of insulating and terminal boards Molded parts have excellent dimensional stability.

Melamines and Ureas (Aminos)

As compared with alkyds. diallyl phthalates, and epoxies, which are polymers created by addition reactions and hence have no reaction byproducts, melamines and ureas (also commonly referred to as aminos) are polymers which are formed by condensation reactions and do give off by-products Another example of this type of reaction is the polymenzation reaction, which produces phenohcs. Melamines and ureas are a reaction product of formaldehyde with ammo compounds containing NH2 groups Hence they are often also referred to a melamine formaldehydes and urea formaldehydes.

Amino resms have found applications in the fields of industrial and decorative laminating, adhesives, protective coatings, textile treatment, paper manufacture, and molding compounds. Their clanty permits products to be fabncated in virtually any color. Finished products having an amino-resm surface exhibit excellent resistance to moisture, greases, oils, and solvents; are tasteless and odorless; are self-extinguishing, offer excellent electncal properties; and resist scratching and marnng. The melamine resins offer better chemical, heat, and moisture resistance than do the ureas.

Amino molding compounds can be fabncated by economical molding methods. They are hard, ngid, and abrasion-resistant, and they have high resistance to deformation under load. These matenals can be exposed to subzero temperatures without embnttlement. Under tropical conditions, the melamines do not support fungus growth Ammo matenals are self-extinguishing and have excellent electncal insulation characteristics They are unaffected by common organic solvents, greases and oils, and weak acids and alkalies Melamines are supenor to ureas in resistance to acids, alkalies, heat, and boiling water, and are preferred for applications involving cycling between wet and dry conditions or rough handling Aminos do not impart taste or odor to foods

Addition of alpha cellulose filler, the most commonly used filler for aminos, produces an unlimited range of light-stable colors and high degrees of translucency Colors are obtamed without sacnfice of basic matenal properties Shnnkage charactenstics with cellulose filler aie a major problem Melamines and ureas provide excellent heat insulation, temperatures up to the destruction point will not cause parts to lose their shape Amino resms exhibit relatively high mold shrinkage, and also shnnk on aging Cracks develop in urea moldings subjected to severe cycling between dry and wet conditions Prolonged exposure to high temperature affects the color of both uiea and melamine products

A loss of certain strength charactenstics also occurs when amino moldings are subjected to prolonged elevated temperatures Some electncal charactenstics are also adversely affected, the arc resistance of some mdustnal types, however, remains unaffected after exposure at 500°F Ureas are unsuitable for outdoor exposure Melamines expenence little degradation m electncal or physical properties after outdoor exposure, but color changes may occur

Phenohcs Like melamines and ureas, phenolic resm precursors are formed by a condensation reaction Phenohcs are among the oldest, best-known general- purpose molding matenals They are also among the lowest m cost and the easiest to mold An extremely large number of phenolic matenals are available, based on the many resm and filler combinations, and they can be classified m many ways One common way of classifying them is by type of application or grade In addition to molding matenals, phenohcs are used to bond fnction matenals for automotive brake linings, clutch parts, and transmission bands They serve as binders for wood-particle board used in building panels and core matenal for furniture, as the water-resistant adhesive for extenor-grade plywood, and as the bonding agent for converting both organic and inorganic fibers into acoustical- and thermal insulation pads, batts, or cushioning for home, industrial, and automotive applications They are used to impregnate paper for electncal or decorative laminates and as special additives to tackify, plasticize, reinforce, or harden a vanety of elastomers

Although it is possible to obtain vanous molding grades of phenohcs for vanous applications, as discussed, phenohcs, generally speaking, are not equivalent to diallyl phthalates and epoxies in resistance to humidity and retention of electncal properties in extreme environments Phenohcs are, however, quite adequate for a large percentage of electncal applications Grades have been developed which yield considerable improvements m humid environments and at higher temperatures The glass-filled, heat-resistant grades are outstanding in thermal stability up to 400°F and higher, with some being useful up to 500°F Shnnkage in heat agmg vanes over a fairly wide range, depending on the filler used

Pohbutadienes Polybutadiene polymers that vary in 1,2 microstructure from 60 to 90 percent offer potential as moldings, laminating resms, coatings, and cast liquid and formed-sheet products. These matenals, being essentially pure hydrocarbon, have outstanding electncal and thermal stability properties

Polybutadienes are cured by peroxide catalysts, which produce carbon- to carbon bonds at the double bonds in the vinyl groups The final product is

100 percent hydrocarbon except where the starting polymer is the — OH or — COOH terminated vanety. The nature of the resultant product may be more readily understood if the structure is regarded as polyethylene with a cross-link at every other carbon m the main chain Use of the high-temperature peroxides maximizes the opportunity for thermoplastic-like processmg, because even the higher-molecular-weight forms become quite fluid at temperatures well below the cure temperature. Compounds can be injection-molded in an in-line machine with a thermoplastic screw

Polxesters (Thermosetting)

Unsaturated, thermosetting polyesters are produced by addition polymenzation reactions. Polyester resms can be formulated to have a range of physical properties from bnttle and hard to tough and resistant to soft and flexible Viscosities at room temperature may range from 50 to more than 25,000 centipoise (cP). Polyesters can be used to fabncate a mynad of products by many techmques, including but not limited to, open-mold casting, hand lay- up, spray-up, vacuum-bag molding, matched-metal-die molding, filament winding, pultrusion, encapsulation, centnfugal casting, and injection molding

By the appropnate choice of ingredients, particularly to form the linear polyester resm, special properties can be imparted Fire retardance can be achieved through the use of one or more of the following chlorendic anhydnde, aluminum tnhydnte, tetrabromophtha c anhydnde, tetrachlorophtha c anhydnde, dibromoneopentyl glycol, and chlorostyrene Chemical resistance is obtained by using neopentyl glycol, lsophthahc acid, hydrogenated bisphenol A, and tπmethyl pentanediol Weathenng resistance can be enhanced by the use of neopentyl glycol and methyl methacrylate Appropnate thermoplastic polymers can be added to reduce or eliminate shnnkage dunng cunng and thereby minimize one of the disadvantages histoncally inherent in polyester systems

Thermosetting polyesters are widely used for moldings, laminated or reinforced structures, surface gel coatings, liquid castings, furniture products, fiberglass parts, and structures such as boats, including but not limited to sailboats, motor boats, and fishing boats, other motor vehicles such as automobiles, trains, motorcycles, trucks, and airplanes, gliders, sleds, and bathroom and kitchen components Cast products include furniture, bowling balls, simulated marble, gaskets for vitnfied-clay sewer pipe, pistol grips, pearlescent shirt buttons, and implosion barπers for television tubes

By lay-up and spray-up techniques large- and short-run items are fabncated Examples include boats of all kinds, such as pleasure sailboats and powered yachts, commercial fishing boats and shnmp trawlers, small military vessels, dune buggies, all-tenain vehicles, custom auto bodies, truck cabs, horse trailers, motor homes, housing modules, concrete forms, and playground equipment

Molding is also performed with premix compounds, which are doughlike matenals generally prepared by the molder shortly before they are to be molded by combining the premix constituents in a sigma-blade mixer or similar equipment Premix, usmg conventional polyester resms, is used to mold automotive-heater housings and air-conditioner components Low-shnnkage resin systems permit the fabncation of extenor automotive components such as fender extensions, lamp housings, hood scoops, and trim rails

Wet molding of glass mats or preforms is used to fabncate such items as snack-table tops, food trays, tote boxes, and stackable chairs Corrugated and flat paneling for room dividers, roofing and sidmg, awnings, skylights, fences, and the like is a very important outlet for polyesters

Pultrusion techniques are used to make fishing-rod stock and profiles from which slatted benches and ladders can be fabncated Chemical storage tanks are made by filament winding

Sύicones

Si cones are a family of unique synthetic polymers, which are partly organic and partly inorganic They have a quartzlike polymer structure, being made up of alternating silicon and oxygen atoms rather than the carbon-to- carbon backbone, which is a charactenstic of the organic polymers Sihcones have outstanding thermal stability

Typically, the silicon atoms will have one or more organic side groups attached to them, generally phenyl (C5H5 — ), methyl (CH3 — ), or vmyl

(CH2=CH — ) units Other alkyd aryl, and reactive organic groups on the silicon atom are also possible These groups impart charactenstics such as solvent resistance, lubncity and compatibility, and reactivity with organic chemicals and polymers

Silicone polymers may be filled or unfilled, depending on properties desired and application They can be cured by several mechanisms, either at room temperature [by room-temperature vulcanization (RTV)] or at elevated temperatures Their final form may be fluid, gel, elastomenc, or ngid

Some of the properties which distinguish silicone polymers from their organic counterparts are (1) relatively uniform properties over a wide temperature range, (2) low surface tension, (3) high degree of slip or lubncity, (4) excellent release properties, (5) extreme water repellency, (6) excellent electncal properties over a wide range of temperatures and frequencies, (7) inertness and compatibility, both physiologically and in electronic applications,

(8) chemical inertness, and (9) weather resistance

Flexible two-part, solvent-free silicone resins are available in filled and unfilled forms Their viscosities range from 3000 cP to viscous thixotropic fluids of greater than 50,000 cP The polymer base for these resms is pnmanly dimethylpolysiloxane. Some vmyl and hydrogen groups attached to silicon are also present as part of the polymer

These products are cured at room or slightly elevated temperatures Dunng cure there is little if any exotherm, and there are no by-products from the cure The flexible resins have Shore A hardness values of 0 to 60 and Bashore resiliencies of 0 to 80 Flexibility can be retained from -55°C or lower to 250°C or higher

Flexible resms find extensive use in electncal and electronic applications where stable dielectnc properties and resistance to harsh environments are important They are also used many mdustnes to make rubber molds and patterns

Rigid silicone resins exist as solvent solutions or as solvent-free solids The most significant uses of these resins are as paint intermediates to upgrade thermal and weathenng charactenstics of organic coatings, as electncal varnishes, glass tape, and circuit-board coatings Glass cloth, asbestos, and mica laminates are prepared with silicone resms for a vanety of electncal applications Laminated parts can be molded under high or low pressures, vacuum-bag-molded, or filament-wound

Thermosetting molding compounds made with silicone resins as the binder are finding wide application in the electronic industry as encapsulants for semiconductor devices Inertness toward devices, stable electncal and thermal properties, and self-extmguishing charactenstics are important reasons for their use

Similar molding compounds, containing refractory fillers, can be molded on conventional thermoset equipment Molded parts are then fired to yield a ceramic article High-impact, long-glass-fiber-filled molding compounds are also available for use in high-temperature structural applications

In general, silicone resins and composites made with silicone resms exhibit outstanding long-term thermal stabilities at temperatures approaching 300°C, and excellent moisture resistance and electncal properties All of the conventional plastics shnnk and/or crack to some degree when molded into large objects To avoid these problems, elaborate cunng schemes often have to be implemented which, in some cases, takes time and specialized equipment What is needed is an additive or additives that will inhibit cracking and shnnkage and allow the rapid casting of large objects from a vanety of pnor art resins What is also needed are additives that will strengthen objects made from conventional and gel coat resms without significantly increasing their weight

SUMMARY OF THE INVENTION The present invention compnses novel resin polymer additives which can be used to cast large objects in a short time with substantially no shnnkage or cracking, and without the use of specialized equipment or special cunng environments such as heating The additives of the present invention can be used in a wide variety of conventional resms and also with gel coat resins

The present invention compnses additives that impart non-shnnkmg properties and non-crack g properties to a wide vanety of conventional resms The additives can be added to resins and by adjusting the concentration of certain components of the additives, the rate of cunng can be controlled without accompanying side effects such as shnnkage or cracking

One of the non-shnnkmg formulations is a mixture compnsing an aldehyde, a glycol, a perchlorate and a metal chloride. In one preferred embodiment, this non-shnnkmg formulation is a mixture compnsmg formaldehyde, ethylene glycol, copper perchlorate and copper chlonde.

A second, non-shnnkmg formulation is an admixture compnsing a peroxide or an azo compound, a methacrylate or acrylate monomer, and N- methylpyrrohdmone. In one preferred embodiment, this second, non-shnnkmg formulation is an admixture compnsing benzoyl peroxide, methyl methacrylate and N-methylpyrrohdmone.

The present invention further compnses a non-crackmg formulation containing N-butyl mercaptan and a halogenated compound, such as tetraethylammonium bromide, or vanous chain extenders. The present invention further compnses another additive compnsing a formulation which is a hardener solution that may be added to conventional resins and to gel coat resins to increase the strength of the objects made from these resins The hardener solution is made by dissolving dibenzoyl peroxide to saturation in about 50 ml of methylmethacrylate on a cold water bath. An equal volume of styrene is added and mixed. Other monomers containing styrene, and other strong peroxides may be used in the practice of this invention Optionally, butanethiol (0.25%), preferably 1-butanethιol, may be added to the mix Other methacrylate monomers and acrylate monomers such as those in Table I may also be used in the practice of this invention. The present invention further compnses another formulation which may be used to increase the strength of conventional resins and gel coat resins through the addition of different amounts of a solution of carboxymethylcellulose (CMC) solution made by first saturating CMC powder in methanol followed by the addition of water and other ingredients. By increasing the amount of CMC solution added to conventional resms and gel coat resins, the strength of the object made form these resins increases without significant increases in the weight of the object

The vanous formulations can be used combination or singly depending upon the resm and filler to which the formulations are to be added Preferably, all three formulations are added to the resm before casting the large object

The present invention also compnses a filler in the form of binders and polar polymer gels that are treated with a polar solvent.

The present invention also compnses a method of pretreatmg glass fiber before it is incorporated into a polymer resin to add strength to the resin The pretreated glass fiber compnses conventional fiberglass that has been treated with a surfactant or dispersant formulation such as dodecyl benzene sulfonic acid or any other ionic surfactant The dodecyl benzene sulfonic acid is dissolved in water and then the volume is increased with ethylene glycol at a ratio of approximately 10% to 90% ethylene glycol to approximately 10% to 90% of the aqueous solution of dodecyl benzene sulfonic acid.

Another embodiment of the present invention provides a substantially non-flammable prepolymer resin that can be used to cast objects.

Accordingly, it is an object of the present mvention to provide additives to conventional resms which impart the desirable charactenstics of non- shnnkage and non-cracking when casting the resin, with the addition of treated fillers as descnbed above.

It is another object of the present invention to provide novel additives and resm compositions that can rapidly be cast mto objects including large objects without shnnking or cracking It is another object of the present invention to provide novel additives that may be used to increase the strength of objects made from conventional resins and gel coat resins without significantly increasing the weight of the objects.

It is yet another object of the present mvention to provide a novel method of pounng or casting large objects from polymer resms.

It is yet another object of the present invention to provide a novel method of manufactunng large objects from polymer resins that are fire- resistant

Another object of the present invention is to provide methods and compositions that can be used in the construction industry. It is another object of the present invention to provide a method and composition for casting cultured marble

It is another object of the present invention to provide a prepolymer solution that is substantially non-flammable

Another object of the present invention is to provide additives for use m casting cultured marble which impart the desirable charactenstics of non- shnnkage and non-crackmg when casting the marble, and significantly accelerate the process of casting the marble

Another object of the present invention is to provide methods and matenals for rapidly casting objects that are hard, exhibit high resistance to breakage, and are flexible.

These and other objects, features and advantages of the present invention will become apparent after a review of the following detailed descnption of the disclosed embodiments

DETAILED DESCRIPTION OF THE INVENTION

The present invention compnses a polymer resm that can be rapidly cast with substantially no shnnkage or cracking The polymer resin of the present invention can be cast into a vanety of objects, including large objects, without special cunng conditions. The polymer resm is especially useful in casting large building elements such as blocks, pavers, shingles, roofs, floors, sidmg, stairs, bricks, pilings, bridges, sea retaining walls, piers, docks, foundations, beams, walls, including structural walls and sound walls, and the like. The present invention may also be used to cast modular units such as apartments, houses, portable homes, jail cells, rooms, basements, storage sheds, classrooms, portable schools, portable offices, and hazardous matenals and hazardous chemicals storage cabinets and buildings The present invention may also be used to cast toys, playgrounds, swing sets, jungle gyms, and other items used by children

The methods and compositions of the present invention may be used to make objects used in the construction industry. For example, foundations, pilings, walls, floors, tiles, wall tiles, floor tiles, paneling, sinks, kitchen counter tops, cabinets, laboratory counter and bench tops, table tops, basins, pedestal wash basins, bidets, toilets, unnals, showers, shower stalls, tubs, bathtubs, Jacuzzis, hot tubs, whirlpools, vanity tops, wall surrounds, decorator mirror frames, soap dishes, and towel bars may all be made as well as other hard surfaces Plumbing matenals including, but not limited to, pipes, sewer pipes, manholes, manhole covers, storage tanks, couplings, joints, fixtures, knobs, showerheads, faucets, drains, water pipes, water mams, and fountains may all be manufactured with the present mvention Houses may be constructed rapidly and at reduced cost in geographic areas deficient in traditional building matenals such as timber. Apartment units may be cast rapidly in modular form and assembled quickly into buildings

Drainage systems, culverts, driveways, curbs, walkways, sidewalks, and many other objects typically made from concrete may be made with the methods and compositions of the present invention Components of bndges and other reinforced structures may be constructed from the present invention due to the strength of these novel matenals. Railroad ties, poles for streetlights, poles for traffic lights, poles for street signs, telephone poles, poles and structural elements for transmission systems, electncal manholes, high voltage lines, communication towers, docks, decks, piers, sea retaining walls, breakwaters, jetties, and other objects made from timber, concrete and/or steel may be made more economically and rapidly with the methods and matenals of the present invention.

In addition to forming many of the objects listed above, it is to be understood that the present invention may be used to place a protective coating around or on the surface of many of these objects. For example, one embodiment of the present invention, existing shipping pilings may be encapsulated or coated with the composition of the present invention to mcrease strength and longevity, and to decrease the need for routine maintenance such as painting By encapsulating or coating the surfaces of structural elements of objects, structural integnty may be preserved for a longer penod of time before replacement is necessary. For example, in another embodiment of the present mvention, steel and/or concrete components of bndges may be coated with the compositions of the present invention in order to retard corrosion from sources such as environmental pollutants and salt water, thereby extending the useful life of the bndge Since the compositions of the present invention are corrosion resistant and may be colored consistently throughout, coating an object such as a bndge would decrease or eliminate the need for expensive, labonous and lengthy routine maintenance and painting. Other objects that may receive coatings of the present invention include, but are not limited to, sidmg, shingles, slate, tile, sound walls, sea walls, docks, jetties, breakwaters, tunnels, ship hulls, poles including telephone poles and light poles, transmission towers for communication and power lines, as well as other objects mentioned elsewhere in the present application.

A wide vanety of cooking and kitchen objects may be made with the compositions and methods of the present invention including cookware, plates, utensils, glasses, and baking devices The present inventions include novel compositions compnsing conventional resins, including, but not limited to, epoxies, polyesters, polyurethanes, flexible sihcones, ngid sihcones, polybutadienes, polysulfides, depolymenzed rubber and allyhc resms Polyesters that can be used in the present invention mclude polyesters containing one or more monomers including, but are not limited to, alpha methyl styrene, methyl methacrylate, vmyl toluene, diallyl phthalate, tnallyl cyanurate, divinyl benzene, and chlorostyrene

Initiators for cunng the resins include, but are not limited to, peroxides such as benzoyl peroxide, methyl ethyl ketone peroxide (also called 2-butanone peroxide), hydrogen peroxide, and dibenzoyl peroxide Other initiators that may be used in the present invention include azo compounds. Polyani ne in N- methylpyrro dmone may also be used as an initiator in some formulations.

Catalysts include, but are not limited to, cobalt II acetate, cobalt II naphthenate, methylene II acetate, chromium II acetate, copper II acetate, calcium oxide, N,N-dιmethylanιhne, and 3,5-dιmethylanιlme, can be used in the present invention. Diethylamines, tnethylammes and other amine-contammg catalysts may also be used in the present invention. Catalysts are dissolved in any suitable solvent including, but not limited to, solvents such as styrene, water, or alcohol. The catalysts that can be used in the present invention are well known to those of ordinary skill in the art. (See Handbook of Plastics,

Elastomers and Composites, Harper, C.A., editor, McGraw-Hill, 1992 which is incorporated by reference).

Fillers can be used with the present invention in the form of powders, fibers, flakes, and liquids, for example, tar. Fillers are used to modify viscosity, increase pot life, reduce exotherm, modify density, improve heat resistance, modify thermal conductivity (usually to increase thermal conductivity), increase strength, improve machmeabi ty, increase hardness and wear resistance, modify electncal properties, increase chemical and solvent resistance, modify fnction charactenstics, improve thermal shock resistance, improve adhesion, and impart color. Generally the fillers should be low in cost, reproducible in composition, particle size, and shape, easy to disperse in the compound, and low in density, and they should not increase the viscosity of the mixture excessively. The filler should stay in suspension or be able to be resuspended with a minimum of stirring. Fillers that can be used in the present invention include, but are not limited to, silica, calcium carbonate, clays, aluminum hydroxide, titanium dioxide, calcium silicate, aluminum trihydride, glass spheres, hollow spheres, fibers including glass, asbestos, DACRON™, cotton, and nylon, metal powders and particles, powders, sand, soil, fly ash, pigments, carpet and fragments thereof, saw dust, crushed stone, pea gravel, and stone. In one embodiment of the present invention, a polymeric resin is combined with one or more fillers and one or more initiators and/or catalysts. The resulting polymer composition cures quickly and exhibits superior structural properties. Desirably, the polymer resin is a polyester resin and the filler is a concrete mix, such as Sakrete or a combination of Portland cement, sand and aggregates. Suitable initiators and catalysts include, but are not limited to, the initiators and catalysts described above. The amount of polymer resin, filler, initiators and catalysts may vary. Desirably, the polymer resin comprises from about 5 to about 90 weight percent and the filler comprises from about 95 to about 10 weight percent based on the total weight of the mixture. More desirably, the polymer resin comprises from about 5 to about 50 weight percent and the filler comprises from about 95 to about 50 weight percent based on the total weight of the mixture. Even more desirably, the polymer resin comprises from about 5 to about 30 weight percent and the filler comprises from about 95 to about 70 weight percent based on the total weight of the mixture. Desirably, the amount of additives, such as initiators and/or catalysts, is up to about 5 weight percent based on the total weight of the mixture. More desirably, the amount of additives, such as initiators and/or catalysts, is up to about 3 weight percent based on the total weight of the mixture. Even more desirably, the amount of additives, such as initiators and/or catalysts, is up to about 1 weight percent based on the total weight of the mixture.

The present invention is also directed to reactant fillers. Desirably, the reactant fillers are uniformly distributed in the above-described resins. Preferably, the reactant fillers are pretreated with (1) a hydroxyl group (e.g., an alcohol such as ethyl alcohol), or diluted polar solvents or polar polymers such as carboxymethylcellulose (CMC), or a compound containing a functional carbonyl group (e.g., an organic acid such as acetic acid) with slightly acidic pH, and (2) a non-cracking additive formulation (see Example 3) More preferably, the fillers are further treated with the dispersant formulation descnbed in Example 5 In one embodiment, the dispersant formulation compnses an ionic surfactant, such as dodecylbenzene sulfonic acid or its sodium salt, mixed with p-toluene sulfonic acid monohydrate in a ratio of about 1 1 This mixture is then added to ethylene glycol at a ratio of approximately 2 parts ethylene glycol to 1 part of the p-toluene sulfonic acid mixture The treated filler is then added to the resm in a conventional manner

The present invention includes additives that can be added to conventional resins, with or without fillers, to impart desired effects of non- shnnkage and non-crackmg to cured objects formed from the resms

One of the additives is a non-shnnking formulation compnsing a mixture of an aldehyde, a glycol, a perchlorate and a metal chlonde Suitable aldehydes that may be used in this formulation include, but are not limited to, formaldehyde, paraformaldehyde, and glutaraldehyde Suitable glycols that may be used in this formulation include, but are not limited to, propylene glycol, ethylene glycol and polymers thereof Suitable perchlorates that may be used m this formulation mclude, but are not limited to, copper perchlorate Suitable metal chlondes that may be used in this formulation include, but are not limited to, copper II chlonde, mercunc chlonde, magnesium chlonde, manganese chlonde, nickel chlonde, feme chlonde, ferrous chlonde, silver chlonde, gold chlonde, zinc chlonde, cadmium chlonde, and aluminum chlonde In one preferred embodiment, the non-shnnkmg formulation compnses a mixture of formaldehyde, ethylene glycol, copper perchlorate and copper chlonde Desirably, the non-shnnkmg additive compnses formaldehyde (approximately 100 parts), ethylene glycol (approximately 100 parts), copper perchlorate (approximately 10 parts), and copper chlonde (approximately 20 parts) Depending upon the resm that is being treated, the composition can vary

Another additive is a second, non-shnnkmg formulation which is an admixture compnsmg a peroxide or an azo compound, a methacrylate or acrylate monomer, and N-methylpyrrohdmone (NMP) Suitable peroxides that may be used in this formulation mclude, but are not limited to, benzoyl peroxide, hydrogen peroxide, dibenzoyl peroxide and methyl ethyl ketone peroxide Alternatively, azo compounds may be used instead of peroxide compounds Suitable methacrylate and acrylate monomers that may be used in this formulation include, but are not limited to, those listed in Table 1 below In one preferred embodiment, the non-shnnkmg formulation compnses an admixture of benzoyl peroxide, methyl methacrylate and N- methylpyrro dmone. In this embodiment, benzoyl peroxide, methyl methacrylate and NMP are present m a weight ratio of approximately 100:50:20.

TABLE I

TABLE I (cont.)

The present mvention further compnses a non-crackmg additive containing N-butyl mercaptan and a halogenated compound, such as tetraethylammonium bromide (TEAB) Alternatively, vanous chain extenders may be used instead of the TEAB. Suitable chain extenders include, but are not limited to, acetic acid, acetone, benzene, n-butyl alcohol, isobutyl alcohol, sec- butyl alcohol, tert-butyl alcohol, n-butyl chlonde, n-butyl iodide, tert-butyl mercaptan, carbon tetrabromide, carbon tetrachlonde, chlorobenzene, chloroform, diethyl ketone, diethyl dithioglycolate, diethyl disulfide, dioxane, diphenyl disulfide, dodecyl mercaptan, ethyl acetate, ethylbenzene, ethylene dibromide, ethylene dichlonde, ethyl thioglycolate, mercaptoethanol, methyl isobutyl ketone, methylcyclohexane, methyl isobutyrate, methylene chlonde, methyl ethyl ketone, pentaphenylethane, propylene chlonde, isopropylbenzene, isopropyl mercaptan, tetrachloroethane, thio-β-naphthol, thiophenol, toluene and tnphenylmethane. In one embodiment, N-butyl mercaptan and TEAB are mixed together at a ratio of approximately 100 parts N-butyl mercaptan to 1 part

TEAB by weight. This additive may be combined with one or more of the other additives disclosed above in the practice of the present invention.

The various formulations can be used in combination or singly depending upon the resin and filler to which the formulations are to be added. In general terms, one embodiment of the present invention provides a preferred method of making objects comprising treating fillers with polar solvents or polar polymers and a dispersant formulation; mixing the treated fillers with resin; adding ethylene glycol and styrene; adding in any order the three additives A, B , and C, described in Examples 1, 2, and 3; adding catalyst and dimethylaniline; and adding initiator.

Typically, additives A, B and C are added at a concentration of between about 0.1 to 4% by weight with a desired concentration of between approximately 0.5% to 2% by weight. It is to be understood that the additives can be used separately or together in the final resin preparation depending upon the desired properties that need to be imparted to the formed object.

The present invention also provides a method for strengthening objects made from resin, and an additive composition which is a hardener solution that may be added to conventional resins and gel coat resins to increase the strength of the objects made from these resins. The hardener solution is made by dissolving dibenzoyl peroxide to saturation in about 50 ml of methylmethacrylate on a cold water bath. An equal volume of styrene is added and mixed. Optionally, butanethiol (0.25%), preferably 1-butanethiol, may be added to the mix. A preferred range of butanethiol that may be used in the present invention is from about 0.02% to 0.25% by weight. Other monomers containing styrene, and other strong peroxides, including, but are not limited to, benzoyl peroxide, hydrogen peroxide, dibenzoyl peroxide, methyl ethyl ketone peroxide, 2,5-di-methyl-2,5-bis(2-ethyl hexyl peroxy)hexane, t-butyl peroxyoctoate, lauroyl peroxide, t-butyl perbenzoate and t-amyl peroxides, may be used in the practice of this invention. Other methacrylate monomers and acrylate monomers, such as those in Table I, may also be used in the practice of this invention.

Another method of the present invention that may be used to increase the strength of conventional resins and gel coat resins is the addition of different amounts of a solution of carboxymethylcellulose (CMC) solution made by first saturating CMC powder in methanol or ethanol followed by the addition of water and other ingredients. Heat may optionally be used to accelerate CMC entenng solution By increasing the amount of CMC solution added to conventional resins and gel coat resms, the strength of objects made from these resms increases without significant increases in their weight Desirable concentration ranges of CMC in aqueous solution are from about 0 1% to 5 0% by weight, with a more preferred concentration range of from 0 25% to 5 0% by weight and a most desired concentration range of from 0 5% to 1% by weight

Polyanilme may also be used to increase the strength of conventional resms and gel coat resms Desirable concentration ranges of polyanilme in aqueous solution are from about 0 1% to 5 0% by weight, with a more desired concentration range of from 0 25% to 5 0% by weight, and a most desired concentration range of from 0 5% to 1% by weight Polyanilme may also be combined with the CMC in solution in a range of polyanilme to CMC from about 10% to 90% by weight

The present invention also includes cultured marble products According to the present invention, cultured marble products can be made without the pnor art requirements of carefully controlling the cunng process to avoid shnnkage and cracking of the final poured product The cultured marble products made with the present invention may be used in a vanety of applications descnbed above Some preferred applications of the present invention are the production of tiles, paneling, sinks, counter tops, basins, sinks, pedestal wash basins, bidets, table tops, toilets, toilet holders, urmals, showers, tubs, bathtubs, Jacuzzis, hot tubs, whirlpools, couplings, joints, fixtures, soap dishes, towel bars, toilet paper dispensers, knobs, showerheads, faucets, drains, fountains, sidmg, and surface application to bncks or stone The present invention also includes methods and compositions for rapidly making strong but flexible objects Strong and flexible objects have many uses a vanety of mdustnes For example, in the transportation industry, bumpers made with one embodiment of the present invention would increase protection to motor vehicles such as automobiles, trucks, and buses Strong and flexible objects would also be useful as bumpers on the sides of boats, such as sailboats, as bumpers for loading docks for trucks and train cars, as crash guards on the highway, as bumpers on loading docks for boats, ships, trucks, and trams, as protective stnps on the sides of motor vehicles, as mud flaps for motor vehicles, as a matenal for use m the construction of dashboards, as a building matenal a geographic area prone to earthquakes, as a building matenal in areas subject to vibrational stress such as near subways, railroads and highways and near bndges, and as a matenal for use in construction of playgrounds and recreational facilities, including surfaces of playgrounds, monkey bars, jungle gyms, and swing sets

In one embodiment of the present invention, flexible objects with high tensile strength may be made by forming a strong, fibrous and flexible resin in the following manner In this method, a polyanilme is employed To produce the polyanilme used in the present invention, a prepolymer solution is prepared by mixing about 21 ml of distilled punfied aniline with about 300 ml of 1 M HC1 The prepolymer solution is then placed in a three necked flask, purged with nitrogen, and cooled to approximately 5° C In a separate container, about 12 gm of ammonium persulfate is dissolved in 200 ml of 1 M

HC1 The container is purged with pure nitrogen The ammonium persulfate solution is cooled to about 5° C and then added to the three necked flask The mixture is cooled to approximately 0° C and stirred for about 20 minutes The temperature of the solution is then raised to from 8° to 10° C for about 15 minutes Next, the solution is cooled to approximately 0° C and stirred for about 45 minutes The polyanilme precipitate is then washed several times by filtration with distilled water The polyanilme precipitate is treated with 1 M potassium hydroxide for about 24 hours after which it is filtered, washed again for 6 to 12 hours in distilled H2O, heated, and dned in a vacuum oven for about 24 hours at 50° C The dned polyanilme is ground into a powder The mixture may be optionally extracted with a soxhlet extraction with acetonitnle for 3 hours until the extract is no longer colored This extraction produces a polyanilme powder The polyanilme is dned in an oven at 50° C for about 6 to 7 hours and then ground to a powder It is then treated with 1 M KOH for about 24 hours after which it is filtered, washed again for 6 to 12 hours in distilled

H2O and dned in a vacuum oven for about 24 hours at approximately 50° C

The polyanilme precipitate is then dissolved in a N-methylpyrrohdinone (NMP) to saturation Different amounts of polyanilme may be added to NMP to achieve a final percentage of from 0 1% by weight of the total mixture to a saturated solution It is to be understood that pyrrohdone and pyrro dmone are synonymous as used throughout the present application Objects made with strong, fibrous and flexible resin may be used in numerous applications requmng supenor strength, including but not limited to, sheathing for cables, wires, power lines, transmission lines, communication cables, and fiber optic cable A resin mix can be made with the following method To about 30 ml of polyester resin is added approximately 4-8 ml of styrene, 0.5 to 1 ml N,N- dimethylanihne, 0.5 to 1 ml of cobalt II naphthenate as catalyst, 0.2 to 0.8 ml of the saturated solution of polyanilme in N-methylpyrrohdinone as descnbed above, and about 0.1 to 0 4 ml of an initiator, methyl ethyl ketone peroxide The resulting resin displays a fibrous matnx which is strong and flexible.

Other hard resin mixes can be made with the following ranges of reagents- vinylester resin, 400 - 450 gm, N,N-dιmethylanιlme, 0.25 - 2 gm, catalyst cobalt II naphthenate, 0.25 - 2 gm; Solution 4A (Example 16), 3 -4 gm, Solution 4B (Example 16), 0 8 - 3 gm, Solution 5C (Example 16), 3 - 4 gm, and calcium oxide, 2 - 3 gm Examples of some of these ranges are presented in Table 5

It is to be understood that other catalysts, as descnbed in the present application, may be used instead of cobalt II naphthenate in the method descnbed above Both diethylamine and tnethylamine may also be used as catalysts, as well as other amine-contammg catalysts. In addition, other resins descnbed in the present application may be used instead of polyester resm, including, but not limited to, vinyl esters and epoxy resins.

In another embodiment of the present mvention for making strong flexible matenals with fibrous resm, the solution of polyanilme in N- methylpyrro dinone as descnbed in the precedmg embodiment is used without methyl ethyl ketone peroxide The polyanilme in N-methylpyrrohdmone acts as a slower initiator than the methyl ethyl ketone peroxide. In this embodiment, the addition of methyl ethyl ketone peroxide, from about 0.1% to 2% by weight, is optional and it may be added to accelerate the reaction. The resulting resm displays a fibrous matnx which is strong and flexible.

The present invention also includes blends of resins and glass fiber which exhibit high tensile strength comparable to glass fiber and do not require the labonous and expensive multiple applications of glass fiber layers with lengthy cunng times. The pretreated fiber glass compnses conventional glass fiber that has been treated with a surfactant or dispersant formulation such as dodecyl benzene sulfonic acid or any other ionic surfactant. The dodecyl benzene sulfonic acid is dissolved in water and then the volume is increased with ethylene glycol at a weight ratio of approximately 10% to 90% ethylene glycol to approximately 10% to 90% of the aqueous solution of dodecyl benzene sulfonic acid. Desirably, glass fiber is pretreated before it is incorporated into a polymer resm to add strength to the resin. After wetting the glass fiber with the surfactant, about 5 gm of pretreated glass fiber and about

400 ml of surfactant are mixed in a high speed blender until single fibers are apparent This embodiment of the present invention produces objects that are strong, lightweight and useful in applications employing glass fiber including, but not limited to, the manufacture of motor vehicles, especially the shell or body of the motor vehicle, including fenders, panels, hoods, trunks and roofs

In another specific embodiment, the present invention may be used to produce hulls and decks of boats and ships, or to coat the surfaces of existing hulls and decks for protection, maintenance and repan Boats including but not limited to, sailboats, catamarans, speedboats, power boats, fishing boats, cabin cruisers, houseboats, and rowboats, may all be made with the present invention

It is to be understood that the objects made through the practice of the present mvention possess special properties such as fire retardance, chemical resistance, weather resistance, biological resistance, including resistance to microbes, resistance to environmental contaminants and pollution, corrosive resistance, resistance to ultraviolet radiation, heat resistance, resistance to cracking and breakage, and electncal properties These properties can be enhanced by altenng the addition of specific chemicals disclosed herein

A further embodiment of the present invention is a polyester resin prepared by the following method Propylene glycol is reacted with one or more monomers selected from the maleic anhydnde, phtha c anhydnde, and fumanc acid Desirably, the reaction takes place in a temperature controlled, nitrogen purged, vacuum conditioned environment The reactants are mixed in a reaction vessel, such as a 3-neck flask, and the reaction vessel is subsequently purged with nitrogen gas The temperature of the reaction mixture is increased to about 80-90°C until the reactants melt The reaction temperature is slowly increased to about 180-190°C and held at this temperature for about 6 hours Desirably, the reaction vessel is vacuum conditioned in order to remove the water produced dunng the polyester ratification reaction It is believed that water is produced in the above-descnbed reaction after about 50 minutes at a temperature of 180-190°C In one embodiment of the present invention, vacuuming of the system takes about 3 to 4 hours after the reaction starts In a further embodiment of the present mvention, one or more polymenzation inhibitors may be added to the reaction vessel to stop the polymenzation reaction Suitable polymenzation inhibitors include, but are not limited to, hydroquinone It is also desirable to use a Dean-Stark trap and a water-cooled condenser for refluxing in order to prevent propylene glycol and phthahc anhydnde from vaponzing and leaving the reaction flask It is desirable to maintain the molar ratio of propylene glycol, maleic anhydnde and maleic anhydnde at a molar ratio of about 1 0 5 0 5 In order to prevent loss of propylene glycol due to its low boiling point, it is desired to increase the amount of propylene glycol in the system to about 5 wt % greater than the above- descnbed molar ratio In an alternative method of making the polyester resm, a portion of the maleic anhydnde is replaced with fumanc acid to obtain a molar ratio of propylene glycol, fumanc acid, phthahc anhydride, and maleic anhydnde of about 1 0 3 0 5 0 2 When fumanc acid is added to the reaction vessel, the reaction mixture is preferably based with a temperature of 150°C foi about 1 hour to improve the solubility of fumanc acid in the reaction mixture

Another embodiment of the present invention is a prepolymer resin that is substantially non-flammable As used herem, non-flammable descnbes a prepolymer composition that has a flash point, as determined by the closed cup flash point determination, of greater than about 150°C, with a preferable flash point of greater than about 170°C with a more preferable flash point of greater than about 190°C, with the most desirable flash point of greater than 212°C The prepolymer resins are prepared generally by mixing ethylene glycol with maleic anhydnde and heating the solution A second solution is prepared by mixing polyethylene glycol with a resm such as a polyester resin This second solution is heated and mixed The two solutions are then mixed and a monomer or low molecular weight polymer such as styrene or ethylene dimethacrylate is added and the mixture is heated This solution is substantially non-flammable and can be used as a prepolymer in prepanng polymers The non-flammable prepolymer solution can be polymenzed in a vanety of ways known to those of ordinary skill in the art

This invention is further illustrated by the following examples, which are not to be construed in any way as imposing limitations upon the scope thereof On the contrary, it is to be clearly understood that resort may be had to vanous other embodiments, modifications, and equivalents thereof which, after reading the descnption herein, may suggest themselves to those skilled in the art without departing from the spint of the present invention For example, it is to be understood that the amounts of reagents used m the following Examples are approximate and that those skilled in the art might vary these amounts and ratios by as much as 30% without departing from the spint of the present invention Example 1

Non- shrinking Additive (A)

A first non-shnnking additive (A) that can be used with conventional resms to inhibit shnnkmg of the resin as it cures is descnbed in this example The formulation compnses the followmg

Additive A (Non-shrinking formulation)

Formaldehyde 100 ml

Ethylene Glycol 100 ml Copper perchlorate 10 mg

Copper chlonde 20 mg

The copper chlonde and copper perchlorate were dissolved into the formaldehyde and the ethylene glycol

Example 2 Non-shrinking Additive (B)

A second non-shnnkmg additive (B) that can be used with conventional resms to inhibit shnnkmg of the resm as it cures is descnbed in this example The formulation compnses the following

Additive B (Non-shrinking formulation)

Benzoyl peroxide 118 mg

Methyl methacrylate 50 ml N-methylpyrrohdinone 20 ml

The benzoyl peroxide was dissolved into the methyl methacrylate and N-methylpyrrohdinone

Example 3

Non- Cracking Additive

A third additive, a non-crackmg formulation that can be used with conventional resms to inhibit shnnkmg of the resm as it cures, is descnbed in this example The formulation compnses the following Additive C (Non-cracking formulation)

N butyl mercaptan 100 mg

Tetraethylammonium bromide 1 mg

Example 4 To a polyester resin was added equal amounts of CaC03 pretreated with a polar solvent or mixed in dilute polar polymer, such as slightly acidic water, alcohol, or about 10 wt% carboxymethylcellulose in slightly acidic water Next approximately 0.2 wt% of additive A, about 1 8 wt% of non- shnnkmg additive B, 1-2 wt% of N,N-dιmethylanιlme, and approximately 2 wt% of the non-crackmg additive C were added Next, an initiator, benzoyl peroxide, and a catalyst, cobalt II acetate, were added at concentrations of about 2 wt% each to polymenze the resm The resin polymenzed with no detectable shnnkage or cracking All percentages in this example are expressed as weight percent (wt%) unless otherwise indicated.

Example 5 Dispersant Formulation

A dispersant formulation for pretreating fillers was prepared as follows, about 60 grams of dodecylbenzene sulfonic acid (sodium salt) was dissolved completely m approximately 60 ml of aqueous 0 1 M p-toluene sulfonic acid monohydrate. Then, about 2580 ml of ethylene glycol and about 1200 ml of 0.1 M p-toluene sulfonic acid solution were added. The resulting solution was then thoroughly mixed. Fillers were either added directly to the formulation or were pretreated with an organic alcohol, such as ethyl alcohol or an organic carboxylic acid, such as acetic acid (approximately 0.01 - 0.1 M) at a slightly acidic pH. The fillers to be added to the resin were immersed in the dispersant formulation for a penod of about 0.5 to 2 hours. The fillers were then added to the resm mixture.

Example 6

Cultured Marble

This Example descnbes the production of cultured marble using the additives of the present invention and a filler that is not a polar polymer. The production of cultured marble was in two parts The conventional resm made up the body of the cultured marble object. The gel coat provided a smooth surface for the cultured marble object The surface and the mix are capable of being colored

The basic resin m this Example was about 300 ml of diethyl fumarate trans-2-butene 1,4 diol gel It is to be understood that any resin or polyester resm may be used in the practice of the method disclosed m this Example. The filler was prepared as follows- about 732.5 gm of CaCθ3 and approximately 504 gm of T1O2 were mixed and then treated with about 10 -

20% by weight of ethyl alcohol or slightly acidic water for approximately 1 hour Fillers other than CaCθ3 and T1O2, including, but not limited to, powders, sand, soil, and fly ash, may be used in this mvention The dispersant formulation from Example 5 was then added to the filler preparation at a concentration of about 1.5% by weight. The resm (diethyl fumarate trans-2- butene 1,4 diol gel) was then mixed with the filler in dispersant formulation

Additive A from Example 1, additive B from Example 2 and non-shnnkmg additive C from Example 3 were then added in any order to a final concentration of about 1% by weight of each To this mixture was added about 70 ml of ethylene glycol, 70 ml of styrene, 12 ml of cobalt II acetate and 14 ml of N,N- dimethylani ne. This formulation was thoroughly mixed To polymenze the conventional resin, approximately 10 ml of a 30% solution of benzoyl peroxide was added. This formulation is designated the "basic resm." The gel coat resm was prepared as follows. A first formulation was prepared by mixing about 1008 gm of T1O2 or CaC03 with about 60 ml of 4 wt% diluted dodecyl benzene in water. Approximately 60 ml of the conventional resm without benzoyl peroxide was added along with about 6.5 ml of cobalt II acetate. The first formulation was then thoroughly mixed A second gel coat preparation compnses approximately 300 ml of

GEL COAT resm from Occidental Chemicals mixed with about 105 gm of T1O2. The first preparation and the second gel coat preparation were mixed in a ratio of approximately 2 to 1. Just before use, an initiator such as 10% to 30% methyl ethyl ketone peroxide or 10% to 30% benzoyl peroxide was added at a final concentration of about 2% by volume.

The gel coat preparation was coated on the surface of a form The basic resin formulation was then poured mto the form and allowed to cure. The resin cured to hardness withm approximately 5 minutes and was completely cured within about 1 hour. The resulting object could be removed from the mold after approximately 10 minutes. Example 7

Rapid Casting Method for Gel Coat Preparations and Conventional Resin Formulations

This example descnbes a method for rapid casting that may be employed with both the gel coat preparations, including cultured marble, and conventional resin formulations The method involves two steps which may be practiced at room temperature and involves the use of a polar polymer as the filler The method produces a smooth surface In addition, the resms from

Example 6 may be used in the practice of the method disclosed m this Example

Step 1 First, a carboxymethylcellulose (CMC) gel was formed by saturating about 5g of CMC powder with methanol Next, the CMC was slowly added to approximately 800 ml of water while mixing to make a CMC solution Alternatively, CMC may be saturated with ethanol instead of methanol and mixed with water in a similar manner

Step 2 To each 40 ml of gel coat or resin formulation, was added between approximately 3 ml and 6 ml of the CMC solution Optionally, approximately 10% to 20% by weight of ethylene glycol and/or styrene were added to this mixture The amount of CMC solution was based on the desired strength, appearance, and cost of the final product Next, about 1-2% (vol%) of N,N-dιmethylanιlme was added together with any known catalyst while mixing Catalysts which may be employed at this step include, but are not limited to, methylene II acetate, chromium II acetate, copper II acetate and cobalt

II naphthenate Catalysts were added at approximately 10% (vol %) in solvents such as alcohol, styrene, water, or any suitable solvent for the specific catalyst

The reaction was initiated by adding about 1 - 2% (vol %) of peroxide and mixing into the other ingredients Suitable peroxides include, but are not limited to, methyl ethyl ketone peroxide, hydrogen peroxide, and dibenzoyl peroxide at initial concentrations of about 10% to 30% Other initiators that have been used include other peroxide initiators and azo initiators The cunng rate and heat generated vary depending on the amount of CMC gel and peroxides employed Addition of less gel produced less heat and increased cunng time while addition of more gel resulted in generation of higher amounts of heat and reduced cunng times

The method of this example produced a clear gel coat contrast to many methods taught the art In addition, this method was amenable to pounng the gel coat into a mold, and painting or spraying the gel coat onto a surface Additional examples of this method are provided in Table 8 below

Sample 11 m Table 8 produced excellent results

Example 8

Method of Strengthening Objects Made from Resin Through Addition of a Hardener Solution

This example descnbes a hardener solution that can be used to make an inexpensive, clear and strong resm In addition, inexpensive and strong gel coat resins may be produced by the method of this example Both conventional resms and gel coat resms may be made stronger using the hardener solution of the present example

Step 1 Formulation for a Hardener Solution in a Cold Bath A hardener solution was made by dissolving benzoyl peroxide to saturation in about 50 ml of methylmethacrylate m a beaker maintained in an ice bath An equal volume of styrene was added and mixed Step 2 Formation of Conventional Resins and Gel Coat Resins of

Increased Strength In order to make an inexpensive clear gel coat, between about 1 ml and 5 ml of the CMC solution of Step 1 of Example 7 was slowly mixed with approximately 50 ml of polyester resin It is to be understood that any CMC or polar polymer or any polymer that will swell in water may be used in the practice of the present invention Next, about 50 ml of the gel coat resm of Example 7 was added and slowly mixed Between about 0 1 ml and 1 0 ml of N,N dimethylanihne was added (preferred volume of 0 25 ml) About 0 1 ml to 2 0 ml of a cross-linker, poly(ethyleneglycol-400) dimethacrylate, was added It is to be understood that any ethylene glycol cross-linker or other cross-linker such as divinyl monomers, may be employed Next, about 0 1 ml to 1 5 ml of the catalyst, cobalt II naphthenate, was added A preferred volume of cobalt II naphthenate was approximately 0 25 ml Catalysts which may be employed at this step include, but are not limited, to methylene II acetate, chromium II acetate, copper II acetate and cobalt II acetate Catalysts were added at about 10% (vol %) in solvents such as alcohol, styrene, water, or any suitable solvent for the specific catalyst

The hardener solution (about 0 5 ml) was then added The reaction was initiated by adding from about 0 25 ml to 2 0 ml of the initiator methyl ethyl ketone peroxide A preferred volume of methyl ethyl ketone peroxide was approximately 0 35 ml Other initiators which may have been used include, but are not limited to, methyl ethyl ketone peroxide, hydrogen peroxide, and dibenzoyl peroxide at concentrations of about 10% to 30%, and azo compounds

Example 9

Method of Strengthening Objects Cast from Conventional and Gel Coat Resins by Varying the Amount of CMC Solution

The following example demonstrates a method for increasing the structural strength of objects cast from resms This method may be used to increase the strength of objects cast from conventional resins and gel coat resms As shown in this Example, as the amount of CMC solution of Example 7 was increased in the presence of the proper amounts of catalysts, hardeners and initiators, the strength of the resulting object increased while the weight decreased

To about 100 ml of conventional polyester resm was added between approximately 2 ml and 25 ml of the CMC solution of Example 7 Next, about 100 ml of GEL COAT resm purchased from Neste Co. (Atlanta, GA) was added. To this mixture were added approximately 1 ml of dimethylanihne, 2 ml of the cross-linker of Example 8, poly(ethyleneglycol-400) dimethacrylate, 1 ml of catalyst (cobalt II naphthenate), 2 ml of the hardener solution of Example 8 , and 0.5 ml of the initiator, methyl ethyl ketone peroxide. The initiator, methyl ethyl ketone peroxide, or other initiators that may be used m the present invention are added last, however there is no special order for adding the other ingredients descnbed in this Example. It is to be understood that any ethylene glycol cross-linker or other cross-linker, such as divmyl monomers, may be employed. In addition, the other initiators and catalysts listed in Example 8 have been used in the present invention In this Example, about 2 ml, 5 ml or

10 ml of the CMC solution of Example 7 was used and the resulting object tested These objects were tested to measure the compression strength and flexibility using a device with an upper test limit of 3000 pounds per square inch (psi) The objects made with 2 ml, 5 ml or 10 ml of the CMC solution displayed strength of 2500 psi, 2900 psi, and more than 3000 psi, respectively.

The resm would not break in this machine

Comparative tests of DuPont CORIAN® matenals of comparable thickness at twice the weight of the object of the present Example made with about 10 ml of the CMC solution showed that the CORIAN® samples broke at 2100 psi while the object of the present Example did not break. Therefore, this object had a strength greater than the upper test limit of the test machine (greater

Example 10 Hard Surface Matenal

To approximately 300 ml of a conventional resm, such as a polyester resm, was added about 40 ml of styrene, 20 ml of methylmethacrylate and 5 ml of a dispersant formulation The dispersant formulation was compnsed of about 20 gm dodecylbenzene sulfonic acid (sodium salt) mixed in about 10 ml of aqueous 0 1 M p-toluene sulfonic acid monohydrate, which was then mixed with about 20 ml of ethylene glycol, 10 ml of methylmethacrylate and 10 ml of styrene The resulting solution was then thoroughly mixed and approximately

70 ml of the CMC solution of Example 7 (step 1) was added It is to be understood that any CMC or polar polymer or any polymer that will swell m water may be used m the practice of the present invention

Next, about 300 ml of GEL COAT resm (Neste Co , Atlanta, GA) was added to this solution, followed by the addition of approximately 5% fiberglass

(vol%) which was about 35 ml of compacted fiberglass The compacted fiberglass was first soaked in about 90% ethylene glycol and about 10% of the dispersant formulation descnbed above, mixed briefly in a blender, and pressure was applied until most of the fluid was removed Next approximately 4 ml of N,N-dιmethylanιhne was added followed by about 8 ml of a cross linker solution, for example a cross-linker solution of poly(ethyleneglycol- 400)dιmethacrylate or pentaerythntol tetraacrylate, and about 4 ml of catalyst (cobalt II naphthenate) These three chemicals were added m any order Next 8 ml of the hardener solution of Example 8, Step 1, was added followed by addition of between 3 to 7 ml of a 30% solution of the initiator methyl ethyl ketone peroxide in styrene Other initiators, including peroxide initiators, have been used at solution strengths of approximately 10%-30% in the appropnate solvents Catalysts which could be employed at this step mclude, but are not limited to, methylene II acetate, chromium II acetate, copper II acetate and cobalt II acetate Catalysts were added at about 10% (vol %) in solvents such as alcohol, styrene, water, or any suitable solvent for the specific catalyst

The reaction was initiated by adding from about 3 ml to 7 ml of a 30% solution of the initiator methyl ethyl ketone peroxide A preferred volume of initiator methyl ethyl ketone peroxide was 5 ml Other initiators which have been used were peroxides including, but not limited to, methyl ethyl ketone peroxide, hydrogen peroxide, and dibenzoyl peroxide at concentrations of 10% to 30% in appropnate solvents. Other peroxide initiators and azo initiators may also be used The initiator methyl ethyl ketone peroxide, or other initiators that may be used in the present invention were added last It is to be understood that any ethylene glycol cross-linker or other cross-linker, such as divinyl monomers, may be employed In addition, the other initiators and catalysts listed in Example 8 could be used m the present invention After all reagents were mcluded, the mixture was poured into a mold and placed on a vibrating table to facilitate removal of air bubbles

The object made with the method of the present example was tested to measure the compression strength and flexibility using a device with an upper limit of 3000 pounds per square inch (psi) Comparative tests of DuPont

CORIAN® matenals of comparable thickness at twice the weight of the object of the present Example showed that the CORIAN® samples broke at 2100 psi while the object of the present Example broke at 2200 psi

In the formation of another object using the method of the present example, a volume of about 500 ml of resm and about 100 ml of gel coat were used together with the same volumes of other reagents as reported above The resulting object was very hard but compression tests were not performed In addition, different volumes of about 30, 40, 50, and 90 ml of the CMC solution were used together with the different reagent volumes descnbed above In general, as the amount of CMC in the mixture increased, the flexibility of the formed object increased.

Example 11

Hard Surface Material To approximately 300 ml of a conventional resin, such as a polyester resin, were added about 40 ml of styrene, 30 ml of methylmethacrylate, and 8 ml of the dispersant formulation of Example 10. The dispersant formulation was compnsed of about 20 gm dodecylbenzene sulfonic acid (sodium salt) mixed in approximately 10 ml of aqueous 0.1 M p-toluene sulfonic acid monohydrate, which was then mixed with about 20 ml of ethylene glycol, 10 ml of methylmethacrylate and 10 ml of styrene. The resulting solution was then thoroughly mixed and about 70 ml of the CMC solution of Example 7 (step 1) was added. It is to be understood that any CMC or polar polymer or any polymer that will swell m water may be used m the practice of the present invention. Next, about 300 ml of GEL COAT resin (Neste Co , Atlanta, GA) was added to this solution, followed by addition of approximately 5% fiberglass (vol%) which is about 35 ml of compacted fiberglass The compacted fiberglass was first soaked in about 90% ethylene glycol and 10% dispersant formulation, mixed briefly in a blender, and pressure was apphed until most of the fluid was removed. Next approximately 4 ml of N,N-dιmethylanιhne was added followed by about 8 ml of a cross-linker solution of either poly(ethyleneglycol-400)dιmethacrylate, or pentaerythntol tetraacrylate and 4 ml of catalyst (cobalt II naphthenate) These three chemicals could be added in any order Next, about 8 ml of the hardener solution of Example 8, Step 1, was added followed by about 5 ml of the initiator methyl ethyl ketone peroxide

Catalysts which could be employed at this step include, but are not limited to, methylene II acetate, chromium II acetate, copper II acetate and cobalt II acetate Catalysts were added at 10% (vol %) m solvents such as alcohol, styrene, water, or any suitable solvent for the specific catalyst The reaction was initiated by adding from about 3 ml to 7 ml of the initiator methyl ethyl ketone peroxide A preferred volume of initiator methyl ethyl ketone peroxide was about 5 ml Other initiators which were used were peroxides including, but not limited to, methyl ethyl ketone peroxide, hydrogen peroxide, and dibenzoyl peroxide at concentrations of about 10% to 30% in appropnate solvents Other peroxide initiators and azo initiators may also be used The initiator methyl ethyl ketone peroxide, or other initiators that were used m the present invention were added last It is to be understood that any ethylene glycol cross-linker or other cross-linker, such as divinyl monomers, may be employed In addition, the other initiators and catalysts listed in Example 8 may be used in the present mvention After all reagents were included, the mixture was poured mto a mold and placed on a vibrating table to facilitate removal of air bubbles

The object made with the method of the present example was tested to measure the compression strength and flexibility using a device with an upper limit of 3000 psi Comparative tests of DuPont CORIAN® matenals of comparable thickness at twice the weight of the object of the present Example showed that the CORIAN® samples broke at 2100 psi while the object of the present Example broke at 2400 psi

In the formation of another object using the method of the present example, a volume of about 500 ml of resm and about 100 ml of gel coat were used together with the same volumes of other reagents as reported above The resulting object was very hard but compression tests were not performed

Example 12

Hard Surface Material To about 300 ml of a conventional resin, such as a polyester resm, were added approximately 30 ml of styrene, about 40 ml of polymethylmethacrylate (20% wt/vol), and approximately 15 ml of a dispersant formulation. The dispersant formulation was compnsed of about 20 gm dodecylbenzene sulfonic acid (sodium salt) mixed m approximately 10 ml of aqueous 0.1 M p-toluene sulfonic acid monohydrate, which was then mixed with about 20 ml of ethylene glycol, 10 ml of methylmethacrylate and 10 ml of styrene The resulting solution was then thoroughly mixed and approximately 70 ml of the CMC solution of Example 7 (step 1) was added. It is to be understood that any CMC or polar polymer or any polymer that will swell m water could be used in the practice of the present invention.

Next, about 300 ml of GEL COAT resm (Neste Co., Atlanta, GA) was added to this solution, followed by addition of approximately 5% fiberglass (vol%) which is about 35 ml of compacted fiberglass. The compacted fiberglass was first soaked in about 90% ethylene glycol and about 10% dispersant formulation, mixed bnefly in a blender, and pressure was applied until most of the fluid was removed. Next approximately 5 ml of N,N- dimethylanihne was added followed by about 9 ml of a cross linker solution of either poly(ethyleneglycol-400)dιmethacrylate or pentaerythntol tetraacrylate and 5 ml of catalyst (cobalt II naphthenate) These three chemicals were added in any order. Next, about 9 ml of the hardener solution of Example 8, Step 1, was added followed by 6 ml of the initiator methyl ethyl ketone peroxide. Catalysts which may be employed at this step include, but are not limited to methylene II acetate, chromium II acetate, copper II acetate and cobalt II acetate. Catalysts were added at 10% (vol %) in solvents such as alcohol, styrene, water, or any suitable solvent for the specific catalyst.

The reaction was initiated by adding from about 4 ml to 8 ml of the initiator methyl ethyl ketone peroxide. A preferred volume of initiator methyl ethyl ketone peroxide was 6 ml. Other initiators which have been used were peroxides including methyl ethyl ketone peroxide, hydrogen peroxide, and dibenzoyl peroxide at concentrations of 10% to 30% in appropnate solvents

Other peroxide initiators and azo initiators may also be used. The initiator methyl ethyl ketone peroxide, or other initiators used in the present invention were added last It is to be understood that any ethylene glycol cross-linker or other cross-linker, such as divinyl monomers, may be employed In addition, the other initiators and catalysts listed in Example 8 may be used in the present invention After all reagents are included, the mixture was poured mto a mold and placed on a vibrating table to facilitate removal of air bubbles

The object made with the method of the present example was tested to measure the compression strength and flexibility usmg a device with an upper limit of 3000 psi Comparative tests of DuPont CORIAN® matenals of comparable thickness at twice the weight of the object of the present Example made showed that the CORIAN® samples broke at 2100 psi while the object of the present Example did not break, and therefore had a strength greater than the upper test limit of the test machine (greater than 3000 psi)

In the formation of another object using the method of the present example, a volume of about 500 ml of resin, and about 100 ml of gel coat were used together with the same volumes of other reagents as reported above The resulting object was very hard but compression tests were not performed.

Example 13

Flexible Hard Materials This example presents three methods of making a flexible hard matenal

Mixture A: Mixture A was prepared by mixing the following reagents between about 470 to 530 gm of calcium carbonate; about 65 ml of a solution compnsed of approximately 80% by volume of water, 18% ethyl alcohol and

2% acetone; about 350 ml of gel coat resm or polyester resin; and approximately 10 ml of polyacryhc acid solution. The polyacry c acid solution was made by wetting 1 gm of polyacryhc acid with ethanol followed by addition of about 50 ml of water.

Mixture B: Mixture B was prepared by mixing the followmg reagents between about 470 to 530 gm of calcium carbonate; about 65 ml of a solution compnsed of approximately 80% by volume of water, 18% ethyl alcohol and

2% acetone; about 350 ml of gel coat resm and approximately 30 ml of polyacryhc acid.

Method 1: To about 350 ml of mixture A were added sequentially about

200 ml of epoxy resin, approximately 10 ml of the dispersant of Example 12, and about 100 ml of ethylene glycol. Next, about 100 ml of styrene and about

100 ml of polymethylmethacrylate were added in any order Approximately 4 ml of N,N-dιmethylanιlme, about 11 ml of a cross linker solution of poly(ethyleneglycol-400)dιmethacrylate, and 4 ml of catalyst (cobalt II naphthenate) were added Next approximately 11 ml of the hardener solution of Example 8 (Step 1), and about 5 to 9 ml of the initiator methyl ethyl ketone peroxide were added A preferred volume of methyl ethyl ketone peroxide was 7 ml Other initiators which may be used are peroxides including, but not limited to, methyl ethyl ketone peroxide, hydrogen peroxide, and dibenzoyl peroxide at concentrations of 10% to 30% in appropnate solvents Other peroxide initiators and azo initiators may also be used The initiator solution was always added last and was preceded by the hardener solution Method 2 To about 350 ml of mixture A were added approximately 350 ml of epoxy resm, about 100 ml of ethylene glycol, approximately 100 ml of styrene, about 100 ml of methylmethacrylate, about 20 ml of the dispersant of Example 12, approximately 5 ml of N,N-dιmethylanιlme, about 11 ml of cross linker solution of Example 8 (poly(ethyleneglycol-400)dιmethacrylate), approximately 5 ml of catalyst (cobalt II naphthenate), approximately 11 ml of the hardener solution of Example 8 (Step 1), and about 6 to 10 ml of the initiator methyl ethyl ketone peroxide A preferred volume of methyl ethyl ketone peroxide was 8 ml It is to be understood that other initiators as descnbed in Method 1 may be used The object resulting from practice of this method was extremely flexible and did not break at a pressure of 3000 psi

Method 3 To approximately 350 ml of mixture B were added about 350 ml of epoxy resin, approximately 100 ml of ethylene glycol, approximately 100 ml of styrene about 100 ml of polymethylmethacrylate about 20 ml of the dispersant of Example 12, approximately 5 ml of dimethylanihne, approximately 11 ml of the cross linker solution of Example 8

(poly(ethyleneglycol-400)dιmethacrylate), about 5 ml of catalyst (cobalt II naphthenate), approximately 11 ml of the hardener solution of Example 8 (Step 1), and about 6 to 10 ml of the initiator methyl ethyl ketone peroxide A preferred volume of methyl ethyl ketone peroxide was 8 ml It is to be understood that other initiators as descnbed in Method 1 may be used

It should be understood that other initiators, cross-linkers, catalysts and resins descnbed in preceding example 12 may be used in the practice of the invention disclosed in this example Example 14

Flexible Materials with High Tensile Strength

Preparation of Low Molecular Weight Polyaniline used to make the Flexible

Materials with High Tensile Strength

To produce the low molecular weight polyaniline used in the present invention, a prepolymer solution was prepared by mixing about 21 ml of distilled purified aniline with about 300 ml of 1 M HCl. The prepolymer solution was then placed in a three necked flask and purged with nitrogen and cooled to about 5°C. In a separate container, approximately 12 gm ammonium persulfate was dissolved in about 200 ml of 1 M HCl. The container was purged with pure nitrogen. The ammonium persulfate solution was cooled to about 5°C and then added to the 3 necked flask. The mixture was cooled to about 0°C and stirred for approximately 20 minutes. The temperature of the solution was then raised to a temperature between approximately 8° to 10°C for 15 minutes. Next, the solution was cooled to about 0°C and stirred for 45 minutes. The polyaniline precipitate was then washed several times by filtration with distilled water. The polyaniline precipitate was treated with 1 M potassium hydroxide for 24 hours after which it was filtered, washed again for 6 to 12 hours in distilled H2O, heated, and dried in a vacuum oven for about 24 hours at 50°C. The dried polyaniline was ground into a powder. The mixture was optionally extracted with a soxhlet extraction with acetonitrile for 3 hours until the extract was no longer colored. This extraction produced a polyaniline powder. The polyaniline was dried in an oven at about 50° C for 6 to 7 hours and then ground to a powder. It was then treated with 1 M KOH for approximately 24 hours after which it was filtered, washed again for 6 to 12 hours in distilled H2O and dried in a vacuum oven for 24 hours at 50° C. The polyaniline precipitate was then dissolved in a N-methylpyrrolidinone (NMP) to saturation. Different amounts of polyaniline may be added to NMP to achieve a final percentage of from approximately 0.1% by weight of the total mixture to a saturated solution. It is to be understood that pyrrolidone and pyrrolidone are synonymous as used throughout the present application.

A resin mix was made with the following method. To about 30 ml of polyester resin were added in sequence approximately 6 ml of styrene, 0.75 ml N,N-dimethylaniline, 0.75 ml of cobalt II naphthenate as catalyst, 0.5 ml of the saturated solution of polyaniline in N-methylpyrrolidinone as described above, and about 0.25 ml of the initiator methyl ethyl ketone peroxide. The resulting resm displayed a fibrous matnx and was strong and flexible

Example 15

Flexible Matenals with High Tensile Strength In another embodiment of the present invention, the solution of polyanilme in N-methylpyrrohdinone as descnbed in the preceding Example 14, was used and methyl ethyl ketone peroxide was not added to the mixture The polyanilme m N-methylpyrrohdinone acted as a slower initiator than the methyl ethyl ketone peroxide The resulting resin displayed a fibrous matnx and was strong and flexible

Example 16

Polyester Preparations and Compositions The following solutions were used in surfactant formulations listed below and were combined with the polyester preparations and compositions descnbed in subsequent examples Percentages indicate volume %

Solution 1 To 3000 ml of H2O were added acetone and 1 -butanethiol to achieve final volume percentages of approximately 0 2% and 0 04% respectively

Solution 2 - (Final volume percentages are shown)

Methyl ethyl ketone peroxide 99% Hydrogen peroxide (30% stock solution) 1%

Solution 3

Dodecylbenzenesulfomc acid (sodium salt) 20.0 g p-toluene sulfonic acid (0.1M) 10.0 g Hydrochlonc acid (0.1M) 1 0 ml

Methylene chlonde (10% solution) in methanol 1.0 ml

Ethylene glycol 20.0 ml

Methylmethacrylate 10.0 ml

Styrene 10.0 ml Hardener solution (Example 8) 1.0 ml Solution 4

Carboxymethyl cellulose 1 g

Polyacryhc acid 1 g

H₂0 100 ml

Solution 4(A)

Carboxymethyl cellulose 1 g

Polyacryhc acid 1 g

Sodium hydroxide (1M) 50 ml

H₉0 50 ml

Solution 4(B)

Solution 4A 50 ml

Sodium hydroxide 2 g

Solution 5(A)

Solution A (0 5% aqueous solution of CMC) 25 g

Polyacryhc acid 0.5 g

Solution 5(B) Solution A (0.5% aqueous solution of CMC) 25 g

KOH 0.25 g

Polyacryhc acid 0.5 g

Solution 5(C) Solution A (0.5% aqueous solution of CMC) 25 g

NaOH 0.25 g

Polyacryhc acid 0.5 g

Solution A (0.5% solution of CMC) Water 100 g

CMC 0.5 g

*A range of CMC concentrations from 0.25% to 5% has been successfully employed in Solution A. Surfactant A

Component 1 40 ml

Component 1 was made as follows.

5% polyvmyl alcohol solution (aqueous) 30 ml was added to 70 ml ethylene glycol (this solution was heated to about 110°C while stimng, and the volume was reduced to 70 ml total To 40 ml of Component 1 was added

Ethyl alcohol (distilled) 20 gm

Dodecylbenzenesulfonic acid, sodium salt 2.5 g

Surfactant B Component 2 20 g

Component 2 was made as follows:

1) Ethylene glycol 20 g; plus

2) Dodecylbenzenesulfonic acid, sodium salt 2.5 g to 20 g of Component 2 was added Ethyl alcohol (distilled) 5 g

Surfactant C

Polyethylene glycol average molecular weight 200 20 g

Dodecylbenzenesulfonic acid 2.5 g

Heat of 70°C to 80°C was applied either while dissolving dodecylbenzenesulfonic acid in polyethylene glycol or before the dodecylbenzenesulfonic acid was added to the polyethylene glycol.

Surfactant D

Polyethylene glycol average molecular weight 400 20 g

Dodecylbenzenesulfonic acid 2.5 g

Heat of 70°C to 80°C was apphed either while dissolving dodecylbenzenesulfonic acid in polyethylene glycol or before the dodecylbenzenesulfonic acid was added to the polyethylene glycol.

Surfactant E

Polyethylene glycol average molecular weight 600 20 g Dodecylbenzenesulfonic acid 2.5 g

Heat of 70°C to 80°C was applied either while dissolving dodecylbenzenesulfonic acid in polyethylene glycol or before the dodecylbenzenesulfonic acid was added to the polyethylene glycol.

Example 17 Flexible and flame retardant sample

In a container, approximately 250 ml of epoxy resin, about 200 ml of polyester resm, and 3 ml of Solution 4 from Example 16 were thoroughly mixed. In a separate container, about 200 ml of fly ash and approximately 20 ml of Solution 1 from Example 16 were mixed thoroughly to ensure that the liquid was dispersed evenly through the filler matnx. The contents of both containers were combined mto a single container and mixed thoroughly. While mixing, about 2 ml each of N,N-dιmethylanιlme, polyethylene glycol 400 dimethacrylate, cobalt naphthenate and Solution 2 from Example 16 were added. All constituents were mixed until evenly distnbuted. The contents were poured into mold a and ejected when cured.

Example 18 High flexibility sample

Step 1 Mixture: About 20 ml each of polyester resm and methyl methacrylate were combined in a container and mixed thoroughly. In a separate container, about 50 ml of epoxy resin and 1 ml each of polyethylene glycol 400 dimethacrylate and Solution 2 from Example 16 were added and mixed thoroughly. Approximately 1 ml each of N,N-dιmethylanιhne and cobalt naphthenate were added and mixed thoroughly. Next, about 50 ml of vinylester resm, 5 ml of the step 1 mixture and 1 ml of solution 2 were added These reagents were mixed thoroughly Approximately 1 ml each of N,N-dιmethylanιhne, cobalt naphthenate and Solution 2 were added while mixing and then thoroughly mixed The contents were poured into a mold and ejected when cured

Example 19 Flexible, flame retardant sample

In a container, approximately 50 ml of vinylester resin and 0 5 ml of

Solution 4(B) from Example 16 were combined and mixed thoroughly. About 1 ml of 3,5-dιmethylanιhne, 0.5 ml of polyethylene glycol 400 dimethacrylate,

1 ml each of cobalt naphthenate and Solution 2 from Example 16 were added while mixing. The contents were poured into a mold and ejected when cured

Example 20 Flexible sample

Step 1 Mixture: Approximately 20 ml each of polyester resm and methyl methacrylate were combined in a container and mixed thoroughly In a separate container about 50 ml of epoxy resin and about 1 ml each of polyethylene glycol 400 dimethacrylate, Solution 4(B) and Solution 2 from Example 16 were combined and mixed thoroughly Next, about 1.5 ml each of N,N- dimethylani ne and cobalt naphthenate were added and mixed thoroughly.

Next, approximately 50 ml of vinylester resm, 5 ml of the Step 1 Mixture and 1 ml of Solution 2 were added. All ingredients were mixed thoroughly. About 1.5 ml of each of N,N-dιmethylanιhne and cobalt naphthenate were added and mixed thoroughly. The contents were poured into a mold and ejected when cured.

Example 21

Flexible, flame retardant sample with elevated filler content In a container were combined about 50 gm each of polyester resin, epoxy resin and 2.5 gm of Solution 4 from Example 16 and mixed thoroughly In a separate container, were mixed about 120 gm of calcium carbonate and 12 7 gm of Solution 1. Next, the ingredients of both containers were combined. While mixing, about 20 gm of ethylene glycol was added while mixing. Next approximately 0.25 ml each of N,N-dιmethylanιlιne, polyethylene glycol 400 dimethacrylate, cobalt naphthenate and Solution 2 from Example 16 were added while mixing All ingredients were well distnbuted and then poured into a mold and ejected when cured

Example 22

Flexible, flame retardant sample with elevated filler content

In a container were combined about 50 gm each of polyester resm, epoxy resm and 2 5 gm of Solution 4 These ingredients were mixed thoroughly In a separate container were mixed about 120 gm of calcium carbonate and 127 gm of Solution 1 from Example 16 The ingiedients of both containers were combined Approximately 20 gm of ethylene glycol was added and mixed thoroughly Next, about 0 5 ml each of 3,5-dιmethylanιlme and 0 25 gm each of polyethylene glycol 400 dimethacrylate, cobalt naphthenate and Solution 2 were added while mixing When all ingredients were well distnbuted, the mixture was poured into a mold and ejected when cured

Example 23

Flame retardant sample suitable for cable joints

A mixture 1 was made according to the following formula:

(SYLOSIV® ^{1S a} commercially available 300 molecular sieve available from GRACE.)

To prepare the sample for molding, about 56.1 gm of mixture 1 was mixed with 18.3 gm of calcium carbonate (Ultrafme) and mixed thoroughly. To this mixture were added about 22.5 gm of 4,4' diphenylmethane dnsocyanate and 108.5 gm of a filler such as course sand. The mixture gelled in about 20 minutes Example 24

Flame retardant sample suitable for cable joints

To prepare the sample for molding, approximately 55 4 gm of mixture 1 were mixed with 18.1 gm of calcium carbonate (Ultrafine) and thoroughly mixed To this mixture were added approximately 22.5 gm of 4,4' diphenylmethane diisocyanate, 166.3 gm of a filler such as course sand and 3.397 gm of Surfactant A from Example 16 The results showed swelling of the gel

Example 25

Flame retardant sample with 75% filler suitable for cable joints

To prepare the sample for molding, approximately 46.7 gm of mixture 1 was mixed with 19.3 gm of calcium carbonate (Ultrafine) and thoroughly mixed To this mixture were added about 18 7 gm of 4,4' diphenylmethane diisocyanate, 177.4 gm of a filler such as course sand and 3.397 gm of Surfactant A from Example 16 The results showed swelling of the gel.

Example 26

Flame retardant sample suitable for shielding fiber optical cable joints A mixture 1 was made according to the following formula'

The ingredients were added in the order presented and were thoroughly mixed The mixture gelled in approximately 20 min The results showed swelling of the gel. Example 27

Flame retardant sample suitable for cable joints

A mixture 1 was made according to the following formula

To prepare the sample for molding, 55 4 gm of mixture 1 was mixed with approximately 18 1 gm of calcium carbonate (Ultrafine) Mix thoroughly To the mixture 1, were added about 22.2 gm of 4,4' diphenylmethane diisocyanate, 166.3 gm of a filler such as course sand and 3.4 gm of a surfactant. The surfactant used in this example was surfactant A The mixture gelled in about 20 minutes. The results showed some swelling of the gel

Table 2 presents several additional examples of samples made with the indicated amounts of reagents.

Example 28

Method of Making Non-flammable, Liquid, Resin

Method 1. A non-flammable liquid resin was made by a method compnsmg the following steps: about 100 gm methylmethacrylate, 5 gm polymethylmethacrylate (molecular weight about 75,000), 0.5 gm cobalt II naphthenate, 0.2 gm -picolme, and 0.3 gm 2,2'-azobιsιsobutyronιtnle (AIBN) were mixed; the mixture was heated to approximately 50°C until boiling Next, about 1 ml of 1M hydrochlonc acid was added to stop polymenzation Next, powdered styrene was added to this mixture and the mixture was heated to a temperature from about 60°C to 70°C until the styrene dissolved.

Method 2: A non-flammable liquid resm was made by a method compnsmg the following steps: about 100 g of styrene, 0.5 gm cobalt II naphthenate, 0.4 gm α-picohne, and 0.3 gm 2,2'-azobιsιsobutyronιtnle (AIBN) were mixed; the mixture was heated to approximately 80°C until boiling for a penod of about 10 minutes. Next, about 1 ml of 1M hydrochlonc acid was added to stop polymenzation. Method 3 A non-flammable liquid resm is made by a method compnsing the following steps a resm formulation is made by mixing about 98 06 gm of maleic anhydnde and about 62 07 gm of ethylene glycol or propylene glycol while purging with inert gas, such as nitrogen, throughout the entire reaction, in a vacuum oven, heating the mixture to approximately 190°C to 200°C for about 4 hours, then at 215°C for about 3 hours slowly cooling the mixture and next adding ethylene chlonde The mixture is then cooled for 2 hours at about 5°C The resulting polyester powder was then dissolved separately in the solvents of Methods 1 and 2 to produce two non-flammable liquid resin formulations

Example 29 Method of Making Objects With High Strength, Low or No Shrinkage, and Low Flammabihty

Objects were made by mixing GEL COAT resm (Neste Co , Atlanta, GA), HARD SURFACE resm (McWhorter Co , Inc ), polar polymer (an aqueous solution of CMC (0 5%)), polyacryhc acid, methylmethacrylate, N,N- dimethylanihne, cross-linker (polyethylene glycol 400 dimethacrylate), catalyst (cobalt II naphthenate), and Solution 2 from Example 16, in the amounts and in the order indicated in Table 3 The best results are indicated by astensks next to the sample number at the top of the corresponding column

Objects were made by mixing resin (vinyl ester resin), polar polymer (an aqueous solution of CMC (0 5%)), calcium carbonate, Solution 1 from Example 16, ethylene glycol, monomer (styrene), diisocyanate, N,N- dimethylani ne, catalyst (cobalt II naphthenate), hardener solution (Step 1 from Example 8), Solution 2 from Example 16, and cross-linker (polyethylene glycol

400 dimethacrylate), in the amounts and in the order indicated in Table 4 The best results are indicated by astensks next to the sample number at the top of the corresponding column

Objects were made by mixing resm (vinyl ester resm), a basic solution of polar polymer (an aqueous solution of CMC (0 5%)) and polyacryhc acid, in some cases Solution 4 from Example 16, in some cases cross-linker (polyethylene glycol 400 dimethacrylate), N,N-dιmethylanιhne, in some cases dnsocyanate-methylmethacrylate, catalyst (polyethylene glycol 400 dimethacrylate), and Solution 2 from Example 16, in the amounts and in the order indicated in Table 5 Preferred embodiments were obtained in Samples 2 and 3 shown in Table 5 with the most preferred embodiment shown as Sample

4 of Table 5

The objects made with this method demonstrated very low or no shrinkage Tests conducted with up to seven applications of the flame of a propane torch for penods of 30 seconds showed that the objects made with this method did not bum or smoke

Example 30

Method of Making Lightweight, Economical, Non-flammable Objects With High Filler Content Lightweight, non-flammable objects with high fillei content were made according to the following methods These objects are useful m the construction industry and could be used as roofing tiles, among other objects Some of the objects have high epoxy content and exhibit flexibility while othei objects made with low epoxy content were ngid and hard These properties were obtained using a final resin content of about 6 5%. All the formulations are pourable and castable into a desirable shape

Method 1: Objects were made by mixing calcium carbonate, Solution 1 from Example 16, polyester resin, Solution 4 from Example 16, epoxy resm. ethylene glycol, N,N-dιmethylanιhne or 3, 5-dιmethylanιlme, cross-linker (polyethylene glycol 400 dimethacrylate), catalyst (cobalt II naphthenate), and initiator (Solution 2 from Example 16) m the amounts and in the order indicated in Table 6. Preferred embodiments were obtained in Samples 1 and 2 shown in Table 6.

Method 2. Objects were made by mixing polyester resm, Solution 4 from Example 16, styrene, Surfactant E from Example 16, filler (sand, coarse fly ash, or fine fly ash), calcium carbonate, Solution 1 from Example 16, N,N- dimethylanilme, catalyst (cobalt II naphthenate), and initiator (Solution 2 from Example 16) in the amounts and in the order indicated in Table 7. The preferred embodiment is shown as sample 1 in Table 7 which contained about 78% solids and about 6.5% resin.

Example 31

Method of Making Soft, Lightweight, Flexible, Flame-Resistant Objects

To about 21.5 gm of castor oil was added 56.6 gm of polyester resin. These reagents were thoroughly mixed. Next, about 20.5 gm of calcium carbonate (AD grade) was added and mixed thoroughly.. About 65.8 gm of 4,4' diphenylmethane diisocyanate, 1 5 gm of dibutyltin dilaurate, 1 5 ml of tnethylamine, and 4 2 gm of calcium oxide were added and mixed well Next, 1 ml of N,N-dιmethylanιhne, 1 ml of cross-linker (polyethylene glycol 400 dimethacrylate), 1 ml of catalyst (cobalt II naphthenate), and 1 gm of benzoyl peroxide weie added and mixed well The resulting object was soft, lightweight, flexible, flame-resistant and exhibited sufficient low density that it floated in water

Example 32

Method of Making Hard, Lightweight, Flame-Resistant Objects To about 20.5 gm of castor oil was added 56.6 gm of vinylester resm

These reagents were thoroughly mixed Next, about 20 2 gm of calcium carbonate (AD grade) was added and mixed thoroughly About 3.0 gm of benzoyl peroxide mix consisting of 30% benzoyl peroxide in calcium carbonate was added and mixed thoroughly Next, 65.5 gm of 4,4' diphenylmethane diisocyanate, 1.5 ml of dibutyltin dilaurate, 1.5 ml of tnethylamine, and 44 gm of calcium oxide were added and mixed well. Next, 1 ml of N,N- dimethylanilme, 1 ml of cross-linker (polyethylene glycol 400 dimethacrylate), and 1 ml of catalyst (cobalt II naphthenate), were added and mixed well The resulting object was hard, lightweight, flame-resistant and exhibited sufficient low density that it floated in water In a separate expenment, fiberglass was added to reinforce the object made with this method.

Additional expenments were conducted with the following ranges of reagents: castor oil (25 - 26 gm); vinylester resm (25 - 55 gm); calcium carbonate (70 - 90 gm); benzoyl peroxide mix (3 - 3.5 gm); calcium oxide (3.6 - 4.5 gm); 4,4' diphenylmethane diisocyanate (25.1 - 52.1 gm), dibutyltin dilaurate (0.25 - 0.75 ml); tnethylamine (0.25 - 0.75 ml); N,N-dιmethylanιlιne (0.25 - 0.75 ml); cobalt II naphthenate (0.25 - 0.75 ml); polyethylene glycol 400 dimethacrylate (1 ml); and Solution 2 from Example 16 (0.25 - 0.75 ml). These expenments all produced hard, lightweight, flame-resistant objects that exhibited sufficient low density that they floated m water. The initiators were added at the end of the order of the addition of reagents, whereas calcium carbonate, benzoyl peroxide mix, and calcium oxide may be added in any order TABLE 3

*Mix A consisted of the following: 500 ml ca cium carbonate, 65 ml MC solution, 350 ml gel coat, 5 ml polyaniline. ** Indicates best sample. All reagents shown in ml. PMMA in MMA is polymethylmethacrylate in methylmethacrylate.

TABLE 4

All reagents shown in ml. ** Indicates best sample.

TABLE 5

** Indicates best sample. All reagents shown in gm. TABLE 6

All reagents shown in gm.

TABLE 7

*^Λ Indicates best sample. All reagents shown in gm. Example 33

Nonflammable pre-polymer in the liquid phase.

The following formulation is for a prepolymer liquid phase that is nonflammable when it is in the prepolymer liquid phase The prepolymer can then be polymenzed for a vanety of uses The hardener in the following formulations is methyl methacrylate and benzoyl peroxide.

Solution A

100 g of ethylene glycol 100 g of maleic anhydnde Heat to approximately 170° C for approximately 30 minutes

Solution B

100 g of polyethylene glycol 400 50 g of polyester resin powder (Sunnse Corporation) Heat to approximately 95° C for about 30 minutes.

Solution C

15.0 g of low molecular weight polystyrene from Example 14 3.0 g of ethylenediamme

Solution D

15 g of styrene monomers

3.0 g of ethylenediamme

Solution E

100.0 g of ethylene glycol 100.0 g of maleic anhydnde Heat to 170° for 1 hour

Example 34

A non-flammable prepolymer solution was prepared from the solutions in Example 33 by mixing 20.0 grams of Solution A with 9.0 grams of Solution C The resulting mixture was heated to approximately 50°C to 60°C for five to ten minutes. 20.0 g of Solution B was then added to the mixture and thoroughly mixed The resulting prepolymer solution was substantially inflammable The prepolymer mixture was then polymenzed To the prepolymer mixture, 10 g of CaC03 (AD), 0.25 g of N,N-dιmethyl aniline and

0.25 g of cobalt II naphthenate was added and mixed To this solution was added 0.20 g of Solution 2 (Example 16) compnsing 99% methylethylketone peroxide and 1% hydrogen peroxide. The polymer was then allowed to cure

Example 35

A non-flammable prepolymer solution was prepared from the solutions Example 33 by mixing 20.0 grams of Solution A with 36.0 grams of Solution D The resulting mixture was heated to approximately 50°C to 60°C for five to ten minutes. 20.0 g of Solution B was then added to the mixture and thoroughly mixed The resulting prepolymer solution was substantially inflammable The prepolymer mixture was then polymenzed. To the prepolymer mixture, 10 g of CaCθ3 AD, 0.25 g of N,N dimethyl aniline and

0.25 g of cobalt II naphthenate was added and mixed. To this solution was added .20 g of Solution 2 (Example 16) compnsmg 99% methylethylketone peroxide and 1% hydrogen peroxide. The polymer was then allowed to cure.

Example 36

A non-flammable prepolymer solution was prepared from the solutions m Example 33 by mixing 10.0 grams of Solution A with 6.0 grams of styrene. The resulting mixture was heated to approximately 50°C to 60°C for five to ten minutes. 10.0 g of Solution B was then added to the mixture and thoroughly mixed. The resulting prepolymer solution was substantially inflammable. The prepolymer mixture was then polymenzed. To the prepolymer mixture, 10 g of CaCθ3 (AD), 0.25 g of N,N-dιmethyl aniline and 0.25 g of cobalt II naphthenate was added and mixed. To this solution was added 0.20 g of

Solution 2 (Example 16) compnsing 99% methylethylketone peroxide and 1% hydrogen peroxide. The polymer is then allowed to cure.

Example 37 A non-flammable prepolymer solution was prepared from the solutions in Example 33 as follows: Solution MA#1

20.0 g of Solution A 20.0 g of Solution B 6.0 g of ethylene dimethacrylate Mix and heat to 60°C for 5 to 10 minutes. Flash point >212°C

Solution MA#2 40.0 g of Solution B 6 0 g of ethylene dimethacrylate Mix and heat to 60°C for 5 to 10 minutes.

Flash point >212°C

Solution MA#3 20.0 g of Solution B 6.0 g of ethylene dimethacrylate

Flash point >212°C

Solution MA#4

20.0 g of Solution E 20.0 g of Solution B

6.0 g of ethylene dimethacrylate Flash point >212°C

Solution MA#5 10.0 g of Solution E

20.0 g of Solution B 12.0 g of ethylene dimethacrylate Flash point >212°C

Control Solution

20.0 g of Solution A 20.0 g of Solution B Flash point >212°C Example 38

Solution MA#1 was a substantially non-flammable prepolymer solution The prepolymer mixture was then polymenzed. To the prepolymer mixture MA#1, 15 g of CaCθ3 (AD), 0.25 g of N,N-dιmethyl aniline and 0.25 g of cobalt II naphthenate was added and mixed. To this solution was added 0.25 g of Solution 2 (Example 16) compnsing 99% methylethylketone peroxide and

1% hydrogen peroxide. [The flash point in all of the Examples is a closed cup flash determination in which an aliquot of matenal is placed in a sealed vessel

The vessel is equipped with a temperature measunng device such as a thermometer or a thermocouple. The vessel is equipped with an ignition device such as sparker or a glowplug The ignition device is turned on and the vessel temperature is slowly increased until the vapors from the matenal in the vessel are ignited. The temperature at the point of ignition is the flash point value ]

The flash point of the prepolymer mixture in this example was greater than

212°C. The polymer was then allowed to cure. The control solution had a flash point of greater than 212°C .

Example 39

Solution MA#2 was a substantially non-flammable prepolymer solution.

The prepolymer mixture was then polymenzed. To the prepolymer mixture MA#2, 15 g of CaCO3 (AD), 0.25 g of N,N-dιmethyl aniline and 0.25 g of cobalt II naphthenate was added and mixed. To this solution was added 0.25 g of Solution 2 (Example 16) compnsing 99% methylethylketone peroxide and 1% hydrogen peroxide. The polymer was then allowed to cure.

Example 40

Solution MA#2 was a substantially non-flammable prepolymer solution. The prepolymer mixture was then polymenzed. To the prepolymer mixture MA#2, 15.0 g of CaCO3 (AD) and 0.25 g of N,N-dιmethyl aniline. To this solution was added 1.0 g of a mixture compnsing 20% benzoyl peroxide and 80% gypsum. The polymer was then allowed to cure. Example 41

Solution MA#3 was a substantially non-flammable prepolymer solution The prepolymer mixture was then polymenzed. To the prepolymer mixture MA#3, 14.0 g of CaC03 (AD) and 0.1 g of N,N-dιmethyl aniline was added and mixed. To this solution was added 1.0 g of a mixture compnsing 20% benzoyl peroxide and 80% gypsum. The polymer was then allowed to cure

Example 42

Solution MA#4 was a substantially non-flammable prepolymer solution.

The prepolymer mixture was polymenzed by adding to the prepolymer mixture MA#4, 14.0 g of CaC03 (AD) and 0.1 g of N,N-dιmethyl aniline. To this solution was added 1.0 g of a mixture compnsing 20% benzoyl peroxide and 80% gypsum The polymer was then allowed to cure.

Example 43 The following examples (Examples 39 through 42) show the manufacture of flexible polymers. The prepolymer mixture MA#2 was polymenzed by adding to the prepolymer mixture MA#2, 32.2 g of CaCO3

(AD) and 0.12 g of N,N- dimethyl aniline. To this solution was added 1.15 g of a mixture compnsing 20% benzoyl peroxide and 80% gypsum. The polymer was then allowed to cure.

Example 44

The prepolymer mixture MA#3 was polymenzed by adding to the prepolymer mixture MA#3, 36.4 g of CaCO3 (AD) and 0.13 g of N,N-dιmethyl aniline. To this solution was added 1.3 g of a mixture compnsing 20% benzoyl peroxide and 80% gypsum. The polymer was then allowed to cure.

Example 45

The prepolymer mixture MA#4 was polymenzed by adding to the prepolymer mixture MA#4, 32.2 g of CaCO3 (AD) and 0.12 g of N,N-dιmethyl aniline. To this solution was added 1.15 g of a mixture compnsing 20% benzoyl peroxide and 80% gypsum. The polymer was then allowed to cure.

Example 46 The prepolymer mixture MA#5 was polymenzed by adding to the prepolymer mixture MA#5, 36.4 g of CaCO3 (AD) and 0.13 g of N,N-dιmethyl aniline To this solution was added 1.3 g of a mixture compnsing 20% benzoyl peroxide and 80% gypsum The polymer was then allowed to cure

Example 47

A non-flammable prepolymer resin was prepared by mixing 15 g of Solution B, 6 g of ethylenedimethacrylate (EDM), 6 g of Solution A and 10 g of a polyv yl alcohol solution The mixture was split mto two equal batches. To one half of the mixture was added 0.25 millihters of N'N-dimethyl aniline The mixture gelled while mixing To the remaining half of the mixture was added 0 25 millihters of N'N-dimethyl aniline and 1.5 millihters of a 5 wt. % borax solution in water The mixture gelled while mixing

Example 48

A non-flammable prepolymer resin was prepared by mixing 15 g of

Solution A, 3.6 g of a PV A/CMC solution (50 wt% of a solution of 10 wt% PVA in H2θ and 50 wt% of a solution of 0.25 wt% CMC in H2O) and 15 g of

Solution B. Heat was applied.

Example 49

A non-flammable prepolymer resm was prepared by mixing 15 g of Solution B, 6 g of ethylene glycol dimethylacrylate (EGD), and 15 g of Solution

A Heat was applied. The mixture was split into two equal batches

To the first batch mixture was added 0.25 millihters of cobalt II naphthenate, 0.25 millihters of N'N-dimethyl aniline, 0.25 millihters of Solution 2 (Example 16) and 5 g of calcium carbonate (CaCO3). The mixture gelled in about 3 minutes.

To the second batch mixture was added 0.25 millihters of cobalt II naphthenate, 0.25 millihters of N'N-dimethyl aniline and 0.25 millihters of Solution 2. The mixture gelled in about 3 minutes.

Example 50

A non-flammable prepolymer resm was prepared by mixing 15 g of Solution B, 6 g of polyethylene glycol dimethylacrylate (PEGDAM) and 15 g of Solution A. Heat was applied. The mixture was split mto two equal batches.

To the first batch of mixture was added 5 g of CaCO3, 0.25 millihters of cobalt II naphthenate, 0.25 millihters of N'N-dimethyl aniline and 0.25 millihters of Solution 2 (Example 16). The mixture gelled in about 2 minutes To the second batch of mixture was added 3 g of EGD, 0 25 mil liters of cobalt II naphthenate, 0 25 millihters of N'N-dimethyl aniline, 0 25 millihters of Solution 2 (Example 16) and 5 g of CaCθ3 The mixture gelled m about 1 minute

Example 51

A non-flammable prepolymer resin was prepared by mixing 15 g of Solution B, 6 g of diethylene glycol and 15 g of Solution A Heat was applied The mixture gelled in about 3 minutes

Example 52

A non-flammable prepolymer resm was prepared by mixing 15 g of Solution B, 6 g of PEG-400-DMA and 15 g of Solution A Heat was applied The mixture was split mto two equal batches

To the first batch mixture was added 5 g of EGD, 5 g of CaCθ3, 0 25 millihters of cobalt II naphthenate, 0.25 millihters of N'N-dimethyl aniline and

0.25 millihters of Solution 2 (Example 16) The mixture gelled in about 1 minute

To the second batch mixture was added 5 g of EGD, 0 6 g of pentaerythntol tetraacrylate (PENTA) cross-linker, 0.25 millihters of cobalt II naphthenate, 0.25 milhliters N'N-dimethyl aniline, 0.25 millihters of Solution 2

(Example 16) and 5 g of CaCO3. The mixture gelled in about 1 minute

Example 53

A non-flammable prepolymer resm was prepared by mixing 15 g of Solution B, 6 g of DEG, and 15 g of Solution A Heat was applied The mixture was split into two equal batches.

To the first batch mixture was added 5 g of EGD, 5 g of CaCO3, 0.25 millihters of cobalt II naphthenate, 0.25 millihters of N'N-dimethyl aniline and 0.25 millihters of Solution 2 (Example 16) The mixture gelled in about 2 minutes

To the second batch mixture was added 5 g of EGD, 0.6 g of PENTA cross-lmker, 5 g of CaCO3, 0.25 millihters of cobalt II naphthenate, 0.25 mil liters of N'N-dimethyl aniline and 0.25 mil liters of Solution 2 (Example 16) The mixture gelled in about 2 minutes. Example 54

A non-flammable prepolymer resm was prepared by mixing 15 g of Solution B, 6 g of diallyl phthalate and 15 g of Solution A Heat was applied The mixture was split into two equal batches

To the first batch mixture was added 5 g of EGD, 5 g of CaC03, 0.25 milhliters of cobalt II naphthenate, 0.25 milhhters N'N-dimethyl aniline and

0 25 milh ters of Solution 2 (Example 16) The mixture gelled in about 2 minutes

To the second batch mixture was added 5 g of EGD, 0.6 g of PENTA cross-linker, 5 g of CaCθ3, 0.25 milh ters of cobalt II naphthenate, 0 25 mil hters N'N-dimethyl aniline and 0 25 milhhters of Solution 2 (Example 16)

The mixture gelled in about 2 minutes.

Example 55

A first polyester resin was prepared by the following procedure The following reactants were added to a three-neck reaction flask: 152.2 g (2.0 moles) of propylene glycol, 70.0 g (0.6 mole) of fumanc acid, 39.12 g (0.4 moles) of maleic anhydnde and 148.12 g (1.0 mole) of phthahc anhydnde The three necked flask was fitted with a thermometer, a nitrogen gas input and a vacuum pump. The reaction flask was purged with N2 and heated slowly until the temperature reached about 80 to 90°C. The reaction mixture was heated to a temperature of about 180 to 190°C and maintained at this temperature for about 6 hours. To prevent the loss of propylene glycol and phthahc anhydnde (B P 187°C and 140°C respectively) from the reaction mixture, vacuuming to remove water was initiated about 3 hours after starting the reaction. This resulted in an equi bnum shift in the reaction in the direction towards producing a high molecular weight polyester

To further prevent the loss of propylene glycol and phthahc anhydnde, a Dean-Stark trap and water-cooled condenser was used in combination with the vacuum pump This allowed polypropylene glycol and phthahc anhydnde vapors to condensate at the bottom of the condenser and flow back into the reaction flask In a separate tnal, the amount of propylene glycol added to the reaction vessel was increased by about 5 wt.% to offset any loss of propylene glycol due to loss of propylene glycol monomer.

After about 6 hours at a temperature of between about 182 -193°C the reaction mixture was reduced to a temperature of 140°C and maintained at this temperature for approximately 30 minutes. The reaction mixture was then cooled to room temperature and removed from the reaction flask into a collection flask. The reaction produced approximately 10 to 15 millihters of material, about 90 g of resin. The resin material was mixed with a 35% by weight solution of styrene in hydroquinone (50 g of styrene treated with 0.015 g of hydroquinone). This resin mixture was labeled as our standard castable formulation, SCF1.

A polyester resin was prepared by admixing the following ingredients: A second high flash point polyester resin was prepared as follows. Under nitrogen, the following components were combined at the indicated molarity in a flask that was heated.

To prepare the high flash point polyester, the following steps were carried out:

1. Heat the flask and maintain the temperature at 150°C for about one hour until all components are dissolved.

2. Raise the temperature to 180° C and maintain temperature for 3 hours. Remove the water produced during the reaction through a Dean Stark trap.

3. Place the reaction system under a vacuum and raise the temperature to 190°C for an additional 3 hours.

4. After heating for 3 hours, 2-hydroxyethylmethacrylate (Aldrich) is added at a 50:50 ratio. This mixture was identified as Solution SF-1.

Example 56

Three solutions, C-l, D-l and F-l, were produced as follows.

Solution C-l

Solution C-l was prepared by mixing 100 g of PEG-400 and 100 g of maleic anhydride. The mixture was heated to approximately 175°C for about 1 hour.

Solution D-l

Solution D-l was prepared by mixing 100 g of ethylene glycol and 100 g of fumaric acid. The mixture was heated to approximately 170°C for about 30 minutes. Solution F-l

Solution F-l was prepared by mixing 100 g of "the polyester resm from Example 55" and 100 g of PEG-400 The mixture was heated until the polyester resm dissolved in the PEG-400.

Example 57

A non-flammable prepolymer resm was prepared by mixing 15 g of Solution B, 6 g of PEG-400-DMA, and 15 g of Solution C-l. Heat was applied. The mixture was split mto two equal batches.

To the first batch mixture was added 5 g of EGD, 0.6 g of PENTA cross-linker, 3 g of PEG-400-DMA, 5 g of calcium carbonate, 0.25 mil liters of cobalt II naphthenate, 0.25 mil hters of N'N-dimethyl aniline, and 0.25 milhhters of Solution 2 (Example 16) The mixture gelled in about 1 mmute.

To the second batch mixture was added 5 g of EGD, 0.6 g of PENTA cross-linker, 5 g of calcium carbonate, 0.25 mil hters of cobalt II naphthenate, 0.25 milhhters of N'N-dimethyl aniline and 0.25 milhhters of Solution 2

(Example 16). The mixture gelled in about 1 minute.

Example 58

A non-flammable prepolymer resm was prepared by mixing 15 g of Solution A, 6 g of PEG-400-DMA and 15 g of solution D-l. The above mixture was split into two equal batches.

To the first batch mixture was added 5 g of EGD, 0.7 g of PENTA cross-linker, 5 g of calcium carbonate, 0.25 milhhters of cobalt II naphthenate, 0.25 millihters of N'N-dimethyl aniline, and 0.25 mil hters of Solution 2 (Example 16). The mixture gelled in about 1 mmute.

To the second batch mixture was added 3 g of PEG-400-DMA, 15 g of Solution B, 10 g of EGD, 1.3 g of PENTA cross-linker, 10 g of calcium carbonate, 0.5 milhliters of cobalt II naphthenate, 0.5 millihters of N'N- dimethyl aniline, and 0.5 millihters of Solution 2 (Example 16). The mixture gelled in about 1 minute.

Example 59

A non-flammable prepolymer resm was prepared by mixing 15 g of Solution A, 15 g of Solution D-l, 6 g of PEG-400-DMA, 10 g of EGD and 1.3 g of PENTA cross-linker. The above mixture was split into two equal batches. To the first batch mixture was added 0 6 g of CaO, 5 g of calcium carbonate, 0 125 mil hters of cobalt II naphthenate, 0 125 milh ters of N'N- dimethyl anilme and 0 125 milhhters of Solution 2 (Example 16) The mixture gelled in about 3 minutes

Example 60

A non-flammable prepolymer polyester resm was prepared by mixing 15 g of Solution D-l, 3 g of PEG-400-DMA, 5 g of EGD, 0 7 g of PENTA cross- linker, 5 g of calcium carbonate, 0.25 milhliters of cobalt II naphthenate, 0 25 milhhters of N'N-dimethyl anilme and 0 25 millihters of Solution 2 (Example 16) The mixture gelled m about 2 minutes

Example 61

A non-flammable resin was prepared by mixing 60 g of Solution D-l,

10 g of epoxy resm, 13 g of PEG-400, 21 1 g of EGD, 3 g of PENTA cross- linker, 5 g of calcium carbonate, 0.25 milhhters of cobalt II naphthenate, 0 25 milhhters of N'N-dimethyl aniline and 0.25 mil hters of Solution 2 (Example

16) The mixture gelled in about 1 minute

Example 62 A resm was prepared by mixing 150 g of a polyester resin, 200 g of epoxy resm, 5 milhhters of a 0.25 wt % carboxymethyl cellulose solution, 350 g of aluminum tnhydnde, 10 g of benzyl peroxide, 35 millihters of Solution 1 , 50 g of a 5% wt solution of polymethyl methacrylate methyl methacrylate (PMMA m MMA), 50 g of ethylene glycol, 3 g of PENTA cross-linker, 3 mil hters of N'N-dimethyl anilme, 3 milhhters of cobalt II naphthenate, and 3 milhhters of Solution 2 (Example 16) The mixture gelled in 5 minutes

Example 63

A non-flammable polyester resin was prepared by mixing 15 g of Solution D-l, 3 g of PEG-400-DMA, 5 g of EGD, 0 7 g of PENTA cross- linker, 0 1 g of 4,4'-dιamιnodιphenyl methane, 5 g of calcium carbonate and 10 5 g of a stock solution of 1 g benzyl peroxide mixed with 20 g of PEG-400 The mixture gelled in about 6 minutes. Example 64

A non-flammable polyester resin was prepared by mixing 15 g of Solution D-l, 3 g of PEG-400-DMA, 5 g of EGD, 0.7 g of PENTA cross- linker, 0.3 g of 4,4'-dιamιnodιphenyl methane, 5 g of calcium carbonate, and 0 5 g of the stock solution of Example 63 The mixture gelled about 6 minutes.

Example 65

A non-flammable polyester resm was prepared by mixing 15 g of

Solution D-l, 04 g of tetraethylene glycol (TEG), 3 g of PEG-400-DMA, 5 g of EGD, 0.7 g of PENTA cross-linker, 0.2 g of 4,4'-dιamιnodιphenyl methane. 5 g of CaC03 and 10.5 g of stock solution (Example 63) The mixture gelled in about 4 minutes

Example 66

A non-flammable polyester resm was prepared by mixing 15 g of Solution D-l, 3 g of PEG-400-DMA, 5 g of EGD, 0.7 g of PENTA cross- linker, 0.2 g of 4,4'-dιamιnodιphenyl methane, 20 g of CaCO3 and 10.5 g of stock solution (Example 63). The mixture gelled in about 4 minutes.

Example 67 A non-flammable polyester resin was prepared by mixing 50 g of

Solution D-l, 10 g of EGD, 5 g of 4,4'-dιammodιphenyl methane, 20 g of CaC03 and 20 g of benzyl peroxide. The mixture gelled in about 4 minutes.

Example 68 A non-flammable polyester resin was prepared by mixing 45 g of

Solution F-l, 9 g of PEG-400-DMA, 15 g of EGD, 2.1 g of PENTA cross- linker, 15 g of CaCO3, 0.6 g of 4,4'-dιammodιphenyl methane and 1.5 g of stock solution (Example 63). The mixture gelled in about 4 minutes.

Example 69

A non-flammable polyester resin was prepared by mixing 50 g of Solution F-l, 10 g of EGD, 5 g of 4,4'-dιammodιphenyl methane, 20 g of CaCO3 and 20 g of stock solution (Example 63). The mixture gelled in about 5 minutes. Example 70

A non-flammable polyester resin was prepared by mixing 50 g of Solution F-l, 10 g of EGD, 5 g of 4,4'-dιammodιphenyl methane, 20 g of CaC03 and 20 g of stock solution (Example 63) The reactants were mechanically mixed in a blender The mixture gelled in about 2 minutes.

Example 71 A non-flammable polyester resm was prepared by mixing 45 g of Solution F-l, 9 g of PEG-400-DMA, 1 5 g of EGD, 2.1 g of PENTA cross- linker, 45 g of CaCθ3, 1.2 g of 4,4'-dιammodιphenyl methane and 3 g of stock solution (Example 63) The reactants were mechanically mixed in a blender.

The mixture gelled m about 2 minutes

Example 72

A non-flammable polyester resin was prepared by mixing 45 g of Solution F-l, 9 g of PEG-400-DMA, 15 g of EGD, 2.1 g of PENTA cross- linker, 60 g of CaCθ3, 1.2 g of 4,4'-dιammodιphenyl methane and 3 g of stock solution (Example 63). The reactants were mechanically mixed in a blender The mixture gelled in about 1 minute.

Example 73

A non-flammable polyester resin was prepared by mixing 45 g of Solution F-l, 9 g of PEG-400-DMA, 15 g of EGD, 2.1 g of PENTA cross- linker, 75 g of CaCθ3, 1.2 g of 4,4'-dιammodιphenyl methane and 3 g of stock solution (Example 63) The reactants were mechanically mixed in a blender. The mixture gelled in about 1/2 minutes.

Example 74

A non-flammable polyester resin was prepared by mixing 22.5 g of

Solution F-l, 22.5 g of Solution D-l, 9 g of PEG-400-DMA, 15 g of EGD, 2.1 g of PENTA cross-linker, 75 g of CaCO3, 1.2 g of 4,4'-dιamιnodιphenyl methane and 3 g of stock solution (Example 63). The reactants were mechanically mixed in a blender. The mixture gelled in about 1 minute.

Example 75 A non-flammable polyester resin was prepared by mixing 22.5 g of

Solution F-l, 22.5 g of Solution D-l, 9 g of PEG-400-DMA, 15 g of EGD, 75 g of CaCθ3, 1.2 g of 4,4'-dιamιnodιphenyl methane and 3 g of stock solution

(Example 63) The reactants were mechanically mixed a blender. The mixture gelled in about 1 minute

Example 76 A non-flammable polyester resm was prepared by mixing 45 g of

Solution F-l, 9 g of PEG-400-DMA, 15 g of EGD, 75 g of CaCθ3, 1.2 g of

4,4'-dιamιnodιphenyl methane and 3 g of stock solution (Example 63). The reactants were mechanically mixed in a blender The mixture gelled m about 1/2 minutes

Example 77 A non-flammable polyester resm was prepared by mixing 45 g of Solution F-l, 15 g of EGD, 75 g of CaC03, 1.2 g of 4,4'-dιammodιphenyl methane and 3 g of stock solution (Example 63). The reactants were mechanically mixed in a blender. The mixture gelled in about 1 minute.

Example 78

A non-flammable polyester resin was prepared by mixing 45 g of Solution F-l, 9 g of PEG-400-DMA, 75 g of CaCO3, 1.2 g of 4,4'- diaminodiphenyl methane and 3 g of stock solution (Example 63). The reactants were mechanically mixed m a blender The mixture gelled in about 1 mmute.

Example 79 A non-flammable resin was prepared by mixing 6.4 epoxy resm, 38.6 g of Solution F-l, 9 g of PEG-400-DMA, 15 g of EGD, 75 g of CaCO3, 2.1 g of

4,4'-dιamιnodιphenyl methane and 3 g of stock solution (Example 63). The reactants were mechanically mixed in a blender. The mixture gelled in about 1 minute.

Example 80 A non-flammable resm was prepared by mixing 22.5 g of Solution D-l, 22.5 g of Solution F-l, 9 g of PEG-400-DMA, 75 g of CaCO3, 1.2 g of 4,4'- diaminodiphenyl methane and 3 g of stock solution (Example 63) The reactants were mechanically mixed m a blender. The mixture gelled in about 1 minute Example 81

A non-flammable resm was prepared by mixing 45 g of Solution F-l, 9 g of PEG-400-DMA, 15 g of EGD, 75 g of CaCθ3, 1.2 g of 4,4'- diammodiphenyl methane and 3 g of stock solution (Example 63) and 0 5 g of Surfactant D (Example 16) The reactants were mechanically mixed in a blender The mixture gelled in about 1 mmute

Example 82

A non-flammable resm was prepared by mixing 45 g of Solution F-l, 9 g of PEG-400-DMA, 15 g of EGD, 85 g of CaCθ3, 1.2 g of 4,4'- diam odiphenyl methane, 3 g of stock solution (Example 63) and 0 5 g of Surfactant D (Example 16) The reactants were mechanically mixed in a blender The mixture gelled in about 1/2 minute

Example 83

A non-flammable resin was prepared by mixing 45 g of Solution F-l, 9 g of PEG-400-DMA, 15 g of EGD, 95 g of CaCO3, 1.2 g of 4,4'- diaminodiphenyl methane and 3 g of stock solution (Example 63) and 0.5 g of Surfactant D (Example 16). The reactants were mechanically mixed in a blender The mixture gelled in about 1/2 minute

Example 84

A non-flammable resm was prepared by mixing 47.6 g of Solution F- 1 , 7.5 g of EGD, 79.3 g of CaCO3, 1.3 g of 4,4'-dιamιnodιphenyl methane and 3.2 g of stock solution (Example 63). The reactants were mechanically mixed in a blender. The mixture gelled in about 1/2 mmute.

Example 85

A non-flammable resm was prepared by mixing 52.5 g of Solution F- 1 , 7.5 g of EGD, 75 g of CaCO3, 1.2 g of 4,4'-dιamιnodιphenyl methane and 3.2 g of stock solution (Example 63). The reactants were mechanically mixed in a blender. The mixture gelled in about 1/2 minute.

Example 86 A non-flammable resin was prepared by mixing 52.5 g of Solution F- 1 ,

7.5 g of EGD, 75 g of CaCO3, 1.2 g of 4,4'-dιamιnodιphenyl methane and 3 2 g of stock solution (Example 63). The reactants were mechanically mixed in a blender. The mixture gelled in about 1/2 minute.

Example 87

A non-flammable resin was prepared by mixing 52.5 g of Solution F-l , 7.5 g of EGD, 75 g of CaC03, 1.2 g of 4,4'-diaminodiphenyl methane and 3.2 g of stock solution (Example 63) and 0.47 g of Surfactant D (Example 16). The reactants were mechanically mixed in a blender. The mixture gelled in about 1/2 minute.

Example 88

A non-flammable resin was prepared by mixing 52.5 g of Solution F-l , 3.7 g of EGD, 3.7 g of PEG-400-DMA, 75 g of CaC03, 1.2 g of 4,4'- diaminodiphenyl methane and 3 g of stock solution (Example 63) and 0.47 g of Surfactant D (Example 16). The reactants were mechanically mixed in a blender. The mixture gelled in about 2 minutes.

Example 89

A non-flammable resin was prepared by mixing 45 g of Solution F-l , 15 g of diallyl phthalate, 75 g of CaC03, 1.2 g of 4,4'-diaminodiphenyl methane and 3 g of stock solution (Example 63). The reactants were mechanically mixed in a blender. The mixture gelled in about 2 minutes.

Example 90

A non-flammable resin was prepared by mixing 45 g of Solution F- 1 , 15 g of diethylene glycol, 75 g of CaC03, 1.2 g of 4,4'-diaminodiphenyl methane and 3 g of stock solution (Example 63). The reactants were mechanically mixed in a blender. The mixture gelled in about 2 minutes.

Example 91 A non-flammable resin was prepared by mixing 45 g of Solution F- 1 ,

15 g of diethylene glycol, 85 g of CaCθ3, 1.2 g of 4,4'-diaminodiphenyl methane and 3 g of stock solution (Example 63). The reactants were mechanically mixed in a blender. The mixture gelled in about 2 minutes. Example 92

A non-flammable resm was prepared by mixing 45 g of the first polyester resm descnbed in Example 55, 1.2 g of 4,4'-dιamιnodιphenyl methane, 15 g of diethylene glycol, 8.5 g of CaCO3, 3 g of stock solution

(Example 63) and 75 g of sand. The reactants were mechanically mixed in a blender. The mixture gelled in about 2 minutes.

Example 93

A non-flammable resm was prepared by mixing 45 g of the first polyester resm descnbed in Example 55, 1.2 g of 4,4'-dιamιnodιphenyl methane, 15 g of diethylene glycol, 8.5 g of CaC03, 3 g of stock solution

(Example 63) and 90 g of sand The reactants were mechanically mixed in a blendei . The mixture gelled about 2 minutes

Example 94 A non-flammable resin was prepared by mixing 45 g of the first polyester resin descnbed in Example 55, 1.2 g of 4,4'-dιamιnodιphenyl methane, 15 g of diethylene glycol, 8.5 g of CaCO3, 3 g of stock solution

(Example 63) and 100 g of sand The reactants were mechanically mixed m a blender. The mixture gelled in about 2 minutes.

Example 95 A non-flammable resm was prepared by mixing 45 g of the first polyester resin descnbed in Example 55, 1.2 g of 4,4'-dιammodιphenyl methane, 15 g of diethylene glycol, 12 g of CaCO3, 3 g of stock solution (Example 63) and 107 g of sand. The reactants were mechanically mixed in a blender. The mixture gelled in about 2 minutes.

Example 96

A non-flammable resin was prepared by mixing 45 g of the first polyester resm descnbed in Example 55, 1.2 g of 4,4'-dιammodιphenyl methane, 15 g of diethylene glycol, 12.9 g of CaCO3, 3 g of stock solution

(Example 63) and 116 g of sand. The reactants were mechanically mixed in a blender. The mixture gelled in about 2 minutes. Example 97

A non-flammable resm was prepared by mixing 45 g of the first polyester resm descnbed m Example 55, 1.2 g of 4,4'-dιammodιphenyl methane, 15 g of diethylene glycol, 13 9 g of CaCθ3, 3 g of stock solution

(Example 63) and 125 g of sand The reactants were mechanically mixed in a blender The mixture gelled in about 2 minutes

Example 98

A non-flammable resm was prepared by mixing 45 g of the first polyester resm descnbed in Example 55, 1 2 g of 4,4'-dιamιnodιphenyl methane, 15 g of diethylene glycol, 14 9 g of CaCθ3, 3 g of stock solution

(Example 63) and 134 g of sand The reactants were mechanically mixed in a blender The mixture gelled in about 2 minutes

Example 99 A non-flammable resm was prepared by mixing 45 g of the first polyester resm descnbed in Example 55, 1.2 g of 4,4'-dιamιnodιphenyl methane, 15 g of diethylene glycol, 15 g of CaCO3, 3 g of stock solution

(Example 63) and 144 g of sand. The reactants were mechanically mixed m a blender The mixture gelled in about 2 minutes

Example 100 A high flash point polyester resin was prepared by mixing 100.0 g of the first polyester resm descnbed in Example 55 with 2.0 g of polyethylene glycol 400 dimethylmethacrylate, l.Og tetra(ethylene glycol) dimethylacrylate, 2.4 g 4,4'-dιamιnodιphenyl methane. A second mixture of 30.0 g 2- hydroxyethylmethacrylate (HEMA) and 1.5 g of benzoyl peroxide was prepared. Equal volumes of the two mixtures were admixed and allowed to polymenze.

Example 101

Preparation of a microwave initiator.

20 ml 0.7g polyanilme in 40 ml of N-methyl-pyrnhdinone 80 ml polyvmylalcohol 10% (w/v) m H₂0

25 ml concentrated sulfunc acid

8 ml ethylene glycol

6 ml CuClO₄ saturated solution in THF 139 ml Hydrogen peroxide Add the last two mixtures to the polyaniline preparation and keep the whole solution stirnng in ice bath for 1 hour Then add acrylic acid 50/50 (w%)

Example 102

The following mixtures are used in several of the polymers that follow

Mixture 1

95g Bisphenol A 36g Acrylic Acid

2g Benzyldimethyltetradecvlammonium chlonde dihydrate

0.5 Monohydroxyhydroqumon

Stir 2 hours at 100-110°C. Then add ethylene glycol 50/50 w%

Mixture 2

20% 1-vιnyl 2-pyrrohdιnone

70% ethyl acrylate

10% methacryiic acid mix and stir at 70°C for 3 hours.

Mixture 3

5 ml acrylic acid

5 ml 1 -vinyl 2-pyrrohdmone

20 ml ethyl acrylate 0.5 ml of the microwave initiator of Example 101

Microwave the mixture in a standard 700 watt microwave oven for 30 seconds.

Example 103

The following polymer is prepared by admixing the following components in the following order and quantities:

40 ml Second polyester resin from Example 55

4 ml Mixture 3 from Example 102

4 ml l-Vmyl-2-pyrrohdιnone 0.5 ml Tetra(ethylene glycol) dimethylacrylate or Tetra(ethvlene glvcol) diacrvlate

1/2 ml N,N-dιmethylanιlme

1/2 ml Cobalt naphthenate

1/2 ml Solution 2 from Example 16 Two samples were prepared. In one sample, one layer is prepared. In a second sample, a second layer is poured over a first layer

Example 104

The following polymer is prepared by admixing the following components in the following order and quantities:

40 ml Second polyester resin from Example 55

4 ml Mixture 3 from Example 102

4 ml l-Vιnyl-2-pyrrohdmone 0. 5 ml Pentaerythntol tetraacrylate

1/2 ml N,N-dιmethylanιhne

1/2 ml Cobalt naphthenate

1/2 ml Solution 2 from Example 16 Two samples were prepared. In one sample, one layer is prepared In a second sample, a second layer is poured over a first layer.

Example 105

The following polymer is prepared by admixing the followmg components in the following order and quantities:

10 mil Second polyester resin from Example 55

3.5 ml Mixture 2 from Example 102

0.25 ml N,N dimethylanahne 0.25 ml Cobalt naphthenate

0.25 ml Solution 2 from Example 2

The resulting polymer is hard and flexible.

Example 106

The following polymer is prepared by admixing the following components in the followmg order and quantities:

10. ml Second polyester resin from Example 55 2nd Mixture 1 from Example 102

0. 12nd N,N dimethylanahne

0. 12nn Cobalt naphthenate

0.12m 1 Solution 2 from Example 2

The resulting polymer is flexible. Example 107

The following polymer is prepared by admixing the following components in the following order and quantities

10 ml Second polyester resm from Example 55 1 ml Mixture 1 from Example 102

1 ml Mixture 2 from Example 102

1 ml Carboxymethvl cellulose

0.12 ml N,N dimethylanahne

0.12 ml Cobalt naphthenate 0 12 ml Solution 2 from Example 2

The resulting polymer is flexible

Example 108 The following polymer is prepared by admixing the following components m the following order and quantities-

40 ml Second polyester resin from Example 55

3.5 ml Mixture 2 from Example 102 0 4 ml 4,4' -diphenylmethane diisocyanate

04 ml Cobalt naphthenate

0.4 ml Solution 2 from Example 2

Two samples were prepared. In one sample, one layer is prepared. In a second sample, a second layer is poured over a first layer.

Example 109

The following polymer is prepared by admixing the followmg components in the following order and quantities:

40 ml Second polyester resin from Example 55

2.0 ml Mixture 2 from Example 102

2.0 ml Mixture 3 from Example 102

0.4 ml 4,4' -diphenylmethane diisocyanate 0.4 ml Cobalt naphthenate

0.4 ml Solution 2 from Example 2

Two samples were prepared. In one sample, one layer is prepared. In a second sample, a second layer is poured over a first layer.

Example 110

The followmg polymer is prepared by admixing the following components in the following order and quantities:

400.0 g Second polyester resin from Example 55

10.0 g polyethylene glycol 400 dimethylmethacrylate

5.0 g Tetra(ethylene glycol) dimethylacrylate lO.O.g 4,4'-dιamιnodιphenyl methane

212.5g 2-hydroxyethylmethacrylate (HEMA)

5.0 g of a mixture of 30 g HEMA and 1.5 g of benzoyl peroxide

Cure the sample under an infrared source for approximately 5 minutes at 60 to 70°C.

Example 111

The following surfactant is used in several of the following polyurethane formulations:

Surfactant # 1

20.0 g Castor oil

2.5 g Antarox 25-R2 surfactant (Rohme-Polanc)

Surfactant #2

20.0 g Lmseed oil

2.5 g Antarox 25-R2 surfactant

Surfactant #3 20.0 g Lmseed oil

2.5 g RHODAFAC RS-710 (Rohm-Polanc)

The components in each surfactant formulation are admixed over low heat.

Example 112

The following polyurethane is prepared by admixing the components in the following order and quantity:

18.4 g Castor oil

18.4 g Linseed oil o.i g Dibutyltin dilaurate

3.9 g Surfactant #1 from Example 111.

2.0.g Sylosiv

21.2 g CaCO,

201.1 g Sand.

14.1 g 4,4' diphenylmethanednsocyanate

The mixture gels m about 5 minutes at room temperature. Example 113

The following polyurethane is prepared by admixing the components m the following order and quantity:

9.2 2 Castor oil

27.6^{^}g Lmseed oil

0.1 2 Dibutyltin dilaurate

3.9 Surfactant #1 from Example 111 2.0.2 Sylosiv 21.2^{^}2 CaCO,

201.1 g Sand

14.1 2 4,4' diphenylmethanediisocyanat

The mixture gels m about 5 minutes at room temperature.

Example 114

The following polyurethane is prepared by admixing the components m the following order and quantity:

9.2 g Castor oil

27.6 g Linseed oil

0.1 g Dibutyltin dilaurate

3.9 g Surfactant #2 from Example 111

2.0.g Sylosiv

21.2 g CaCO₃

201.1 g Sand.

14.1 2 4,4' diphenylmethanediisocyanat

The mixture gels in about 5 minutes at room temperature.

Example 115

The following polyurethane is prepared by admixing the components m the following order and quantity:

18.4 g Castor oil

18.4 g L seed oil

0.1 g Dibutyltin dilaurate

3.9 g Surfactant #2 from Example 111. lO.Og Resin from Example 55

2.0.g Sylosiv

21.2 g CaCo₃

201.1 g Sand.

14.1 g 4,4' diphenylmethanediisocyanate

The mixture gels m about 5 minutes at room temperature. Example 116

The following polyurethane is prepared by admixing the components in the following order and quantity

18.4 g Castor oil

18 4 g Linseed oil o i g Dibutyltin dilaurate

3.9 g Surfactant #2 from Example 111 lO.Og Resin from Example 55

2 0 g Sylosiv

21.2 g CaCo₃

201 l g Sand

14.1 g 4,4' diphenylmethanediisocyanat

The mixture gels in about 5 minutes at room temperature

Example 117

The following polyurethane is prepared by admixing the components in the following order and quantity:

18.4 g Castor oil

18.4 g Linseed oil

0.1 g Dibutyltin dilaurate

3.9 g Surfactant #3 from Example 111.

2.0.g Sylosiv 21.2 g CaCo₃

201.1 g Sand

14.1 g 4,4' diphenylmethanednsocyanate

The mixture gels in about 5 minutes at room temperature.

Example 118

The following polyurethane is prepared by admixing the components in the following order and quantity:

26.3 g Linseed oil

8.8 g Castor oil

0.1 g Dibutyltin dilaurate

3 9 g Surfactant #3 from Example 111.

1.0. g Sylosiv 21.2 g CaCo₃

191.1 g Sand

14.1 g 4,4' diphenylmethanednsocyanate

The mixture gels in about 5 minutes at room temperature. Example 119

The following polyurethane is prepared by admixing the components in the following order and quantity:

9.2 g Linseed oil

27.6 g Castor oil

0.1 g Dibutyltin dilaurate

3.9 g Surfactant #3 from Example 111.

2.0.g Sylosiv

21.2 g CaCo₃

191 1 g Sand

14.1 g 4,4' diphenylmethanednsocyanate

The mixture gels in about 5 minutes at room temperature

Example 120

The following polyurethane is prepared by admixing the components in the following order and quantity

18.4 g Linseed oil

18.4 g Castor oil o.i g Dibutyltin dilaurate

3.9 g Surfactant #3 from Example 111.

2.0.g Sylosiv

21.2 g CaCo,

201.1 g Sand

14.1 g 4,4' diphenylmethanednsocyanate

The mixture gels in about 5 minutes at room temperature.

Example 121

The following polyurethane is prepared by admixing the components in the following order and quantity

18.4 g Linseed oil 18.4 g Castor oil

0.1 g Dibutyltin dilaurate

3.9 g Surfactant #3 from Example 111.

2.0. g Sylosiv

21.2 g CaCo₃ 218.5 g Sand

14.1 g 4,4' diphenylmethanednsocyanate

The mixture gels in about 5 minutes at room temperature. Example 122

The following polyurethane is prepared by admixing the components in the following order and quantity:

36.8 g Linseed oil

36.8 g Castor oil

0.4 g Dibutyltin dilaurate

7.8 g Surfactant #3 from Example 111.

4.0.g Sylosiv

175.0 g CaC0₃

28.2 g 4,4' diphenylmethanednsocyanate

The mixture gels in about 5 minutes at room temperature.

Example 123 The following polyurethane is prepared by admixing the components m the following order and quantity.

36.8 g Lmseed oil

36.8 g Castor oil

0.4 g Dibutyltin dilaurate

7.8 g Surfactant #3 from Example 111.

4.0.g Sylosiv

200.0 g CaCo₃

28.2 g 4,4' diphenylmethanednsocyanate

The mixture gels in about 5 minutes at room temperature.

Example 124

This is an example a flexible matenal that is made with the high flash point resin

Mixture 1 : 100.0 g First polyester resm from Example 55 2.0.g PEG400DMA l.O.g Tetra(ethylene glycol) dimethylacrylate 2.54 g 4,4'-dιamιnodιphenyl methane

Mixture 2:

30.0g 2-hydroxyethylmethacrylate(HEMA)

1.5g Benzoperoxide.

Mix equal parts of Mixture 1 and Mixture 2. Example 125

Preparation of a Fast Cure Polyester/Concrete Mixture The following solutions were prepared

Solution 2(A) N,N-dιmethylanιlme 100 g

Methyl methacrylate 100 g

Solution 2(B)

Cobalt naphthenate 100 g Methyl methacrylate 100 g

Solution 2(C)

Methylethylketone peroxide 100 g

Methyl methacrylate 100 g

Solution 2(D)

Solution 2 (Example 16) 80 g

Benzoyl peroxide 20 g

Solution 2(E)

Solution 2(D) 100 g

Methyl methacrylate 100 g

Solution 2(F) N,N-dιmethylanιhne 100 g

Styrene 100 g

Solution 2(G)

Cobalt naphthenate 100 g Styrene 100 g

Solution 2(H)

Methylethylketone peroxide 100 g

Styrene — 100 g Solution 2(1)

Solution 2(D) 100 g

Styrene 100 g

A polymer resin/concrete mixture was prepared having the following ingredients

Polyester resm 14,400 g

Styrene 1 ,600 g

Sakrete concrete mix 62,000 g Solution 2(A) 90 g

Solution 2(B) 90 g

Solution 2(C) 90 g

The styrene was added to the polyester resin and mixed thoroughly To this mixture was slowly added the Sakrete concrete while mixing Solution

2(A) was added to the mixture and mixed for about 5 minutes Solution 2(B) was then added to the mixture and mixed for about 5 minutes. Solution 2(C) was then added to the mixture and mixed for about 5 minutes. (It should be noted that initiators 2(A), 2(B), and 2(C) may be added to the mixture in any order.)

The resulting polyester/concrete mixture cured in about 15 minutes.

Example 126

Preparation of a Fast Cure Polyester/Concrete Mixture A polymer resin/concrete mixture was prepared using the solutions and procedure of Example 125. The mixture had the following ingredients:

Polyester resm 14,400 g

Styrene 1,600 g

Sakrete concrete mix 62,000 g

Solution 2(A) 90 g

Solution 2(B) 90 g

Solution 2(E) 90 g

The resulting polyester/concrete mixture cured m about 15 to 20 minutes. Example 127

Preparation of a Fast Cure Polyester/Concrete Mixture

A polymer resm/concrete mixture was prepared using the solutions and procedure of Example 125 The mixture had the following ingiedients

Polyester resm 4,120 i

Styrene 560 g

Sakrete concrete mix 21,300

Solution 2(A) 30 g

Solution 2(B) 30 g

Solution 2(E) 30 g

The resulting polyester/concrete mixture cured in about 4 minutes

Example 128 Preparation of a Fast Cure Polyester/Concrete Mixture

A polymer resm/concrete mixture was prepared using the solutions and procedure of Example 125 The mixture had the following ingredients

Polyester resm 4,120 g

Styrene 560 g

Sakrete concrete mix 25,350 g

Solution 2(A) 28 g

Solution 2(B) 28 g

Solution 2(E) 28 g

The resulting polyester/concrete mixture cured in about 7 minutes

Example 129

Preparation of a Fast Cure Polyester/Concrete/Fώerglass Mixture A polymer resin concrete/fiberglass mixture was prepared using the solutions of Example 125 The mixture had the followmg ingredients

Polyester resm 4,120 g

Styrene 560 g Chopped fiberglass 50 cc

Solution SF-1 (Ex 55) 200 cc

Sakrete concrete mix 17,750 g Solution 2(A) 26 g

Solution 2(B) 26 g

Solution 2(E) 26 g

The chopped fiberglass (1/4" to 1/2" m length) was added to the surfactant, SF-1, to wet the fibers The fiber mixture was added to the polyester resm. The styrene was added to the polyester resm and mixed thoroughly To this mixture was slowly added the Sakrete concrete while mixing. Solution 2(A) was added to the mixture and mixed for about 5 minutes. Solution 2(B) was then added to the mixture and mixed for about 5 minutes. Solution 2(C) was then added to the mixture and mixed for about 5 minutes. (It should be noted that initiators 2(A), 2(B), and 2(C) may be added to the mixture m any order.)

The resulting polyester/concrete/fiberglass mixture cured m about 7 minutes.

Example 130

Preparation of a Fast Cure Polyester/Concrete Mixture

A polymer resin/concrete mixture was prepared using the solutions and procedure of Example 125. The mixture had the following ingredients:

Polyester resm 14,400 g

Styrene 1,600 g

Sakrete concrete mix 62,000 g

Solution 2(F) 90 g Solution 2(G) 90 g

Solution 2(1) 90 g

The resulting polyester/concrete mixture cured in about 15 to 20 minutes

Example 131

Preparation of a Fast Cure Polyester/Concrete Mixture

A polymer resin/concrete mixture was prepared using the solutions and procedure of Example 125. The mixture had the following ingredients:

Polyester resin 4,120 g

Styrene 560 g

Sakrete concrete mix 21,300 g Solution 2(F) 30 g

Solution 2(G) 30 g

Solution 2(1) 30 g

The resulting polyester/concrete mixture cured m about 4 minutes

Example 132

Preparation of a Fast Cure Polyester/Concrete Mixture

A polymer resin/concrete mixture was prepared using the solutions and procedure of Example 125 The mixture had the following ingredients

Polyester resm 4,120 g

Styrene 560 g

Sakrete concrete mix 25,350 g

Solution 2(F) 28 g Solution 2(G) 28 g

Solution 2(1) 28 g

The resulting polyester/concrete mixture cured in about 7 minutes

Example 133

Preparation of a Fast Cure Polyester/Concrete/Fiberglass Mixture

A polymer resin concrete/fiberglass mixture was prepared using the solutions of Example 125 and the procedure of Example 129 The mixture had the following ingredients

Polyester resm 4,120 g

Styrene 560 g

Chopped fiberglass 50 cc

Solution SF-1 (Ex 55) 200 cc Sakrete concrete mix 17,750 g

Solution 2(F) 26 g

Solution 2(G) 26 g

Solution 2(1) 26 g

The resulting polyester/concrete mixture cured in about 7 minutes It should be understood, of course, that the foregoing relates only to prefened embodiments of the present invention and that numerous modifications or alterations may be made therein without departing from the spmt and the scope of the invention

Claims

Claims

1 A composition compnsing a high flash point polyester resin, said polyester resin having a flash point of greater than 150┬░C, the composition compnsing at least one oil, dibutyltin dilaurate, at least one molecular sieve, and at least one filler matenal

2 The composition of Claim 1, wherein the at least one oil compnses castor oil, lmseed oil, or a combination thereof

3 The composition of Claim 1, wherein the at least one filler matenal compnses calcium carbonate, sand, or a combmation thereof

4 The composition of Claim 1, further compnsing diphenylmethane diisocyanate, a surfactant, or a combination thereof

5 The composition of Claim 4, wherein the surfactant compnses dodecylbenzenesulfonic acid or a sodium salt thereof

6 The composition of Claim 4, further compnsing benzoperoxide

7 A prepolymer composition compnsing a solution that is capable of undergoing polymenzation and is substantially non-flammable

8 The prepolymer composition of Claim 7, wherein the prepolymer composition has a flash point of greater than approximately 150┬░C

9 The prepolymer composition of Claim 7, wherein the prepolymer composition has a flash point of greater than approximately 190┬░C

10 The prepolymer composition of Claim 7, wherein the prepolymer composition has a flash point of greater than approximately 212┬░C

11 The prepolymer composition of Claim 7, wherein the prepolymer solution is polymenzed to form a solid object

12 The prepolymer composition of Claim 7, wherein the composition compnses polyethylene glycol, and polyester resm powder

13 The prepolymer composition of Claim 12, further comprising ethylene glycol, and maleic anhydnde

14 The prepolymer composition of Claim 13, further compnsing polystyrene, and ethylenediamme

15 The prepolymer composition of Claim 13, further compnsing styrene

16 The prepolymer composition of Claim 15, further compnsing ethylenediamme

17 The prepolymer composition of Claim 12, further compnsing ethylene dimethacrylate

18 The prepolymer composition of Claim 13, further compnsing ethylene dimethacrylate

19 The prepolymer composition of Claim 12, further compnsing N,N-d╬╣methyl anilme, a catalyst, and at least one peroxide

20 The prepolymer composition of Claim 19, wherein the catalyst compnses cobalt naphthenate

21 The prepolymer composition of Claim 19, wherein the at least one peroxide compnses methyl ethyl ketone peroxide, hydrogen peroxide or a combination thereof

22 A prepolymer composition compnsmg propylene glycol, fumanc acid, maleic anhydnde, and phthahc anhydnde

23 The prepolymer composition of Claim 22, furthei compnsing at least one of (a) styrene and hydroquinone, or (b) 2-hydroxymethylmethacrylate

24 The prepolymer composition of Claim 23, further compnsing polyethylene glycol 400 dimethylmethacrylate, tetra(ethylene glycol) dimethylacrylate,

4,4' -diammodiphenyl methane, and a peroxide

25 The prepolymer composition of Claim 23, further compnsmg at least one of (a) cobalt naphthenate, or (b) 1 -vinyl 2-pyrrohdmone

26 The prepolymer composition of Claim 25, further compnsing at least one of (a) acrylic acid, or (b) methacryiic acid

27 The prepolymer composition of Claim 26, further compnsmg ethyl acrylate

28 The prepolymer composition of Claim 27, further compnsmg polyaniline, polyvmylalcohol, sulfunc acid, ethylene glycol, and CuCIO,

29 The prepolymer composition of Claim 28, further compnsing tetra(ethyleneglycol) dimethylacrylate, tetra(ethyleneglycol) or pentaerythntol tetraacrylate.

30. The prepolymer composition of Claim 26, further compnsing- bisphenol A; benzyldimethyltetradecylammomum chlonde dihydrate; and monohydroxyhydroquinon

31 The prepolymer composition of Claim 26, further compnsing carboxymethyl cellulose.

32. The prepolymer composition of Claim 26, further compnsing 4,4-d╬╣phenylmethane dncocyanate, or N, N-dimethylanilme.

33. A polymer produced from the prepolymer composition of Claim

22

34. A high flash point polyester resin produced from the prepolymer composition of Claim 24.

35. A polymer produced from a prepolymer composition compnsing: propylene glycol; fumanc acid; maleic anhydnde; and phthahc anhydnde.

36. The polymer of Claim 35, wherein the prepolymer composition further compnses at least one of (a) styrene and hydroquinone, or (b) 2- hydroxymethylmethacrylate.

37. The polymer of Claim 36, wherein the prepolymer composition further compnses: polyethylene glycol 400 dimethylmethacrylate; tetra(ethylene glycol) dimethylacrylate; 4,4' -diammodiphenyl methane; and a peroxide.

38 The polymer of Claim 36, wherein the prepolymer composition further compnses at least one of (a) cobalt naphthenate, or (b) 1 -vinyl 2- pyrrohdinone

39 The polymer of Claim 38, wherein the prepolymer composition further compnses at least one of (a) acrylic acid, or (b) methacryiic acid.

40 The polymer of Claim 39, wherein the prepolymer composition further compnses ethyl acrylate

41 The polymer of Claim 40, wherein the prepolymer composition further compnses polyanil e, polyvinylalcohol; sulfunc acid; ethylene glycol; and

CuClO₄.

42 The polymer of Claim 41, wherein the prepolymer composition further compnses tetra(ethyleneglycol) dimethylacrylate, tetra(ethyleneglycol) or pentaerythntol tetraacrylate.

43. The polymer of Claim 39, wherein the prepolymer composition further compnses- bisphenol A; benzyldimethyltetradecylammonium chlonde dihydrate, and monohydroxyhydroquinon.

44. The polymer of Claim 39, wherein the prepolymer composition further compnses carboxymethyl cellulose.

45. The polymer of Claim 39, wherein the prepolymer composition further compnses 4,4-diphenylmethane diicocyanate or N, N-dimethylanihne

46 A polyurethane compnsing: at least one oil, dibutylm dilaurate; at least one molecular sieve; at least one filler matenal; and

4, 4' -diphenylmethanednsocyanate.

47 The polyurethane of Claim 46, further compnsing a surfactant

48 The polyurethane of Claim 46, further compnsing the prepolymer composition of Claim 22

49 A polymer produced from the prepolymer composition of Claim 7

50. A polymer produced from the prepolymer composition of Claim 12

51 A polymer produced from the prepolymer composition of Claim 19.