WO1999055766A1 - Novel polymer additives for forming objects - Google Patents
Novel polymer additives for forming objects Download PDFInfo
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- WO1999055766A1 WO1999055766A1 PCT/US1999/009327 US9909327W WO9955766A1 WO 1999055766 A1 WO1999055766 A1 WO 1999055766A1 US 9909327 W US9909327 W US 9909327W WO 9955766 A1 WO9955766 A1 WO 9955766A1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/67—Unsaturated compounds having active hydrogen
- C08G18/68—Unsaturated polyesters
- C08G18/683—Unsaturated polyesters containing cyclic groups
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B26/00—Compositions of mortars, concrete or artificial stone, containing only organic binders, e.g. polymer or resin concrete
- C04B26/02—Macromolecular compounds
- C04B26/10—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- C04B26/16—Polyurethanes
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/36—Hydroxylated esters of higher fatty acids
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/14—Peroxides
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
- C04B2111/20—Resistance against chemical, physical or biological attack
- C04B2111/28—Fire resistance, i.e. materials resistant to accidental fires or high temperatures
Definitions
- the present invention comp ⁇ ses 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
- 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
- thermosetting matenals or thermosets
- thermoplastic matenals 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.
- 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
- 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 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.
- 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.
- thermoplastic 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.
- 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)
- 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.
- 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
- 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
- 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 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.
- 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.
- 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
- thermoplastics have had a substantial molding cost advantage over thermosets
- 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.
- 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.
- 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.
- 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 plastic category Plastic matenals included in the thermosetting plastic category are alkyds, diallyl phthalates, epoxies, melamines, phenohcs, polyesters, sihcones, and ureas
- unfilled thermosetting plastics tend to be harder, more bnttle, and not as tough as thermoplastics
- fillers it is common practice to add fillers to thermosetting matenals
- a wide vanety of fillers can be used for varying product properties
- 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
- filler form and filler surface treatment can also be major vanables
- fillers along with the thermosetting matenal especially for molded products
- Other product forms may be filled or unfilled, depending on requirements.
- 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
- Diallyl phthalates 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
- diallyl phthalate resins 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
- these matenals are expensive, have high mold shnnkage, and have a strong, flexible flash that is extremely difficult to remove from the parts
- 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
- novolacs particularly the epoxy cresols and the epoxy phenol novolacs
- a novolac resin usually formed by the reaction of ocresol or phenol and formaldehyde with epichlorohydnn
- 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
- 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
- cross-linking agents hardeners
- 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.
- 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.
- 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
- 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
- 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.
- epoxies 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 are polymers which are formed by condensation reactions and do give off by-products
- 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
- 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
- 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
- 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
- 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
- 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
- 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 t ⁇ methyl 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 bar ⁇ ers for television tubes
- 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
- 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
- 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
- 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
- the silicon atoms will have one or more organic side groups attached to them, generally phenyl (C5H5 — ), methyl (CH3 — ), or vmyl
- 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
- silicone polymers 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,
- 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
- 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
- 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
- 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
- non-shnnkmg formulations is a mixture compnsing an aldehyde, a glycol, a perchlorate and a metal chloride.
- 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.
- 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.
- CMC carboxymethylcellulose
- 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
- 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.
- 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
- 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.
- 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.
- 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
- 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.
- the present invention may be used to place a protective coating around or on the surface of many of these objects.
- 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
- structural integnty may be preserved for a longer penod of time before replacement is necessary.
- 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.
- 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.
- compositions and methods of the present invention including cookware, plates, utensils, glasses, and baking devices
- 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
- 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-d ⁇ methylan ⁇ hne, and 3,5-d ⁇ methylan ⁇ lme, 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,
- 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.
- 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, DACRONTM, 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.
- 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.
- 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.
- 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.
- 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.
- the reactant fillers are uniformly distributed in the above-described resins.
- 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)
- the fillers are further treated with the dispersant formulation descnbed in Example 5
- 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
- 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 chlon
- 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
- 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
- the non-shnnkmg formulation compnses an admixture of benzoyl peroxide, methyl methacrylate and N- methylpyrro dmone.
- benzoyl peroxide, methyl methacrylate and NMP are present m a weight ratio of approximately
- the present mvention further compnses a non-crackmg additive containing N-butyl mercaptan and a halogenated compound, such as tetraethylammonium bromide (TEAB)
- TEAB tetraethylammonium bromide
- 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 iso
- This additive may be combined with one or more of the other additives disclosed above in the practice of the present invention.
- 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.
- 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.
- butanethiol 0.25%
- 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.
- 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.
- 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
- CMC carboxymethylcellulose
- 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,sammlungls, 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
- flexible objects with high tensile strength may be made by forming a strong, fibrous and flexible resin in the following manner
- a polyanilme is employed
- 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
- about 12 gm of ammonium persulfate is dissolved in 200 ml of 1 M
- 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
- 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
- NMP N-methylpyrrohdinone
- 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
- NMP N-methylpyrrohdinone
- 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 descn
- hard resin mixes can be made with the following ranges of reagents- vinylester resin, 400 - 450 gm, N,N-d ⁇ methylan ⁇ lme, 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
- 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.
- resins descnbed in the present application may be used instead of polyester resm, including, but not limited to, vinyl esters and epoxy resins.
- 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.
- 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.
- 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
- 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
- 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
- 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,
- 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
- 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
- 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
- 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)
- 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-d ⁇ methylan ⁇ lme, 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.
- a polar solvent or mixed in dilute polar polymer such as slightly acidic water, alcohol, or about 10 wt% carboxymethylcellulose in slightly acidic water
- 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.
- dodecylbenzene sulfonic acid sodium
- 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 CaC ⁇ 3 and approximately 504 gm of T1O2 were mixed and then treated with about 10 -
- 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.
- 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.
- 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
- 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-d ⁇ methylan ⁇ lme 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
- 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
- This example descnbes a hardener solution that can be used to make an inexpensive, clear and strong resm
- 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
- 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
- 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
- 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.
- 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
- a conventional resm such as a polyester resm
- a 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
- 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.
- 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.
- 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
- 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.
- Example 7 Example 7
- any CMC or polar polymer or any polymer that will swell m water may be used m the practice of the present invention.
- about 300 ml of GEL COAT resin Neste Co , Atlanta, GA
- 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.
- 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
- 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.
- a conventional resin such as a polyester resm
- 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.
- 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
- 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.
- 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
- 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
- polyacryhc acid solution was made by wetting 1 gm of polyacryhc acid with ethanol followed by addition of about 50 ml of water.
- 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
- 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.
- 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
- 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 %
- Methyl ethyl ketone peroxide 99% Hydrogen peroxide (30% stock solution) 1%
- Dodecylbenzenesulfomc acid (sodium salt) 20.0 g p-toluene sulfonic acid (0.1M) 10.0 g Hydrochlonc acid (0.1M) 1 0 ml
- Solution A (0.5% solution of CMC) Water 100 g
- Component 1 was made as follows.
- Surfactant B Component 2 20 g
- Component 2 was made as follows:
- 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.
- 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.
- 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.
- 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-d ⁇ methylan ⁇ hne and cobalt naphthenate were added and mixed thoroughly.
- Solution 4(B) from Example 16 were combined and mixed thoroughly. About 1 ml of 3,5-d ⁇ methylan ⁇ hne, 0.5 ml of polyethylene glycol 400 dimethacrylate,
- 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.
- a mixture 1 was made according to the following formula:
- a mixture 1 was made according to the following formula
- 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.
- 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'-azob ⁇ s ⁇ sobutyron ⁇ tnle (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.
- AIBN 2,2'-azob ⁇ s ⁇ sobutyron ⁇ tnle
- 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 ⁇ -picohne, and 0.3 gm 2,2'-azob ⁇ s ⁇ sobutyron ⁇ tnle (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.
- AIBN 2,2'-azob ⁇ s ⁇ sobutyron ⁇ tnle
- 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
- 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
- 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-d ⁇ methylan ⁇ hne, 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
- 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-d ⁇ methylan ⁇ hne or 3, 5-d ⁇ methylan ⁇ lme, 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.
- 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.
- 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-d ⁇ methyl aniline and
- 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 CaC ⁇ 3 AD, 0.25 g of N,N dimethyl aniline and
- 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 CaC ⁇ 3 (AD), 0.25 g of N,N-d ⁇ methyl 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
- 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.
- Solution MA#3 20.0 g of Solution B 6.0 g of ethylene dimethacrylate
- 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 CaC ⁇ 3 (AD), 0.25 g of N,N-d ⁇ methyl 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
- 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
- the polymer was then allowed to cure.
- the control solution had a flash point of greater than 212°C .
- Solution MA#2 was a substantially non-flammable prepolymer solution.
- the prepolymer mixture was then polymenzed.
- MA#2 15 g of CaCO3 (AD)
- 0.25 g of N,N-d ⁇ methyl aniline and 0.25 g of cobalt II naphthenate was added and mixed.
- 0.25 g of Solution 2 compnsing 99% methylethylketone peroxide and 1% hydrogen peroxide.
- the polymer was then allowed to cure.
- 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-d ⁇ methyl 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.
- 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-d ⁇ methyl 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
- 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-d ⁇ methyl 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
- 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-d ⁇ methyl 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.
- 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-d ⁇ methyl 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-d ⁇ methyl 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
- 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
- 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 H2 ⁇ and 50 wt% of a solution of 0.25 wt% CMC in H2O) and 15 g of
- 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 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.
- PEGDAM polyethylene glycol dimethylacrylate
- 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
- 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
- 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.
- Example 14 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 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 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
- 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
- the mixture gelled in about 2 minutes.
- 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.
- 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
- 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.
- reaction mixture 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.
- 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 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 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 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 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 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.
- 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.
- Example 16 The mixture gelled in about 1 minute.
- 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.
- Example 16 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.
- 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
- 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
- a non-flammable resin was prepared by mixing 60 g of Solution D-l,
- 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
- 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'-d ⁇ am ⁇ nod ⁇ phenyl 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.
- 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'-d ⁇ am ⁇ nod ⁇ phenyl methane, 5 g of calcium carbonate, and 0 5 g of the stock solution of Example 63 The mixture gelled about 6 minutes.
- a non-flammable polyester resm was prepared by mixing 15 g of
- 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'-d ⁇ am ⁇ nod ⁇ phenyl 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'-d ⁇ ammod ⁇ phenyl 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'-d ⁇ ammod ⁇ phenyl methane and 1.5 g of stock solution (Example 63).
- the mixture gelled in about 4 minutes.
- a non-flammable polyester resin was prepared by mixing 50 g of Solution F-l, 10 g of EGD, 5 g of 4,4'-d ⁇ ammod ⁇ phenyl 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'-d ⁇ ammod ⁇ phenyl 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 CaC ⁇ 3, 1.2 g of 4,4'-d ⁇ ammod ⁇ phenyl methane and 3 g of stock solution (Example 63) The reactants were mechanically mixed in a blender.
- 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 CaC ⁇ 3, 1.2 g of 4,4'-d ⁇ ammod ⁇ phenyl methane and 3 g of stock solution (Example 63). The reactants were mechanically mixed in a blender The mixture gelled in about 1 minute.
- 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 CaC ⁇ 3, 1.2 g of 4,4'-d ⁇ ammod ⁇ phenyl 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.
- 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'-d ⁇ am ⁇ nod ⁇ phenyl 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 CaC ⁇ 3, 1.2 g of 4,4'-d ⁇ am ⁇ nod ⁇ phenyl 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
- 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'-d ⁇ ammod ⁇ phenyl methane and 3 g of stock solution (Example 63). The reactants were mechanically mixed in a blender. The mixture gelled in about 1 minute.
- 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
- 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 CaC ⁇ 3, 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
- 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 CaC ⁇ 3, 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
- 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
- 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'-d ⁇ am ⁇ nod ⁇ phenyl 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.
- 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'-d ⁇ am ⁇ nod ⁇ phenyl 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 ,
- 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.
- 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.
- 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.
- 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 ,
- Example 92 15 g of diethylene glycol, 85 g of CaC ⁇ 3, 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'-d ⁇ am ⁇ nod ⁇ phenyl methane, 15 g of diethylene glycol, 8.5 g of CaCO3, 3 g of stock solution
- Example 63 Example 63
- 75 g of sand 75 g
- the reactants were mechanically mixed in a blender.
- the mixture gelled in about 2 minutes.
- 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'-d ⁇ am ⁇ nod ⁇ phenyl methane, 15 g of diethylene glycol, 8.5 g of CaC03, 3 g of stock solution
- 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'-d ⁇ am ⁇ nod ⁇ phenyl methane, 15 g of diethylene glycol, 8.5 g of CaCO3, 3 g of stock solution
- 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'-d ⁇ ammod ⁇ phenyl 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.
- 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'-d ⁇ ammod ⁇ phenyl methane, 15 g of diethylene glycol, 12.9 g of CaCO3, 3 g of stock solution
- Example 97 (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'-d ⁇ ammod ⁇ phenyl methane, 15 g of diethylene glycol, 13 9 g of CaC ⁇ 3, 3 g of stock solution
- 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'-d ⁇ am ⁇ nod ⁇ phenyl methane, 15 g of diethylene glycol, 14 9 g of CaC ⁇ 3, 3 g of stock solution
- 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'-d ⁇ am ⁇ nod ⁇ phenyl methane, 15 g of diethylene glycol, 15 g of CaCO3, 3 g of stock solution
- 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'-d ⁇ am ⁇ nod ⁇ phenyl 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.
- HEMA 2- hydroxyethylmethacrylate
- the following polymer is prepared by admixing the following components in the following order and quantities:
- the following polymer is prepared by admixing the following components in the following order and quantities:
- the following polymer is prepared by admixing the followmg components in the following order and quantities:
- the resulting polymer is hard and flexible.
- the following polymer is prepared by admixing the following components in the followmg order and quantities:
- the following polymer is prepared by admixing the following components in the following order and quantities
- the resulting polymer is flexible
- Example 108 The following polymer is prepared by admixing the following components m the following order and quantities-
- Two samples were prepared. In one sample, one layer is prepared. In a second sample, a second layer is poured over a first layer.
- the following polymer is prepared by admixing the followmg components in the following order and quantities:
- Two samples were prepared. In one sample, one layer is prepared. In a second sample, a second layer is poured over a first layer.
- the followmg polymer is prepared by admixing the following components in the following order and quantities:
- the following surfactant is used in several of the following polyurethane formulations:
- each surfactant formulation is admixed over low heat.
- the following polyurethane is prepared by admixing the components in the following order and quantity:
- Example 113 The mixture gels m about 5 minutes at room temperature.
- Example 113 The mixture gels m about 5 minutes at room temperature.
- the following polyurethane is prepared by admixing the components m the following order and quantity:
- the mixture gels m about 5 minutes at room temperature.
- the following polyurethane is prepared by admixing the components m the following order and quantity:
- the mixture gels in about 5 minutes at room temperature.
- the following polyurethane is prepared by admixing the components m the following order and quantity:
- the following polyurethane is prepared by admixing the components in the following order and quantity
- the mixture gels in about 5 minutes at room temperature
- the following polyurethane is prepared by admixing the components in the following order and quantity:
- the mixture gels in about 5 minutes at room temperature.
- the following polyurethane is prepared by admixing the components in the following order and quantity:
- Example 119 The mixture gels in about 5 minutes at room temperature.
- the following polyurethane is prepared by admixing the components in the following order and quantity:
- the mixture gels in about 5 minutes at room temperature
- the following polyurethane is prepared by admixing the components in the following order and quantity
- the mixture gels in about 5 minutes at room temperature.
- the following polyurethane is prepared by admixing the components in the following order and quantity
- the following polyurethane is prepared by admixing the components in the following order and quantity:
- 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.
- the mixture gels in about 5 minutes at room temperature.
- a polymer resin/concrete mixture was prepared having the following ingredients
- the resulting polyester/concrete mixture cured in about 15 minutes.
- a polymer resm/concrete mixture was prepared using the solutions and procedure of Example 125 The mixture had the following ingiedients
- a polymer resm/concrete mixture was prepared using the solutions and procedure of Example 125 The mixture had the following ingredients
- 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.)
- polyester/concrete/fiberglass mixture cured m about 7 minutes.
- a polymer resin/concrete mixture was prepared using the solutions and procedure of Example 125.
- the mixture had the following ingredients:
- the resulting polyester/concrete mixture cured in about 15 to 20 minutes
- a polymer resin/concrete mixture was prepared using the solutions and procedure of Example 125.
- the mixture had the following ingredients:
- a polymer resin/concrete mixture was prepared using the solutions and procedure of Example 125 The mixture had the following ingredients
- 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
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Macromonomer-Based Addition Polymer (AREA)
Abstract
Description
Claims
Priority Applications (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CA002333228A CA2333228A1 (en) | 1998-04-29 | 1999-04-29 | Novel polymer additives for forming objects |
AU35737/99A AU3573799A (en) | 1998-04-29 | 1999-04-29 | Novel polymer additives for forming objects |
EP99917670A EP1080128A1 (en) | 1998-04-29 | 1999-04-29 | Novel polymer additives for forming objects |
Applications Claiming Priority (6)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US09/069,558 | 1998-04-29 | ||
US09/069,558 US6146556A (en) | 1998-04-29 | 1998-04-29 | Polymer additives for forming objects |
US20961598A | 1998-12-11 | 1998-12-11 | |
US09/209,615 | 1998-12-11 | ||
US12253699P | 1999-03-02 | 1999-03-02 | |
US60/122,536 | 1999-03-02 |
Publications (2)
Publication Number | Publication Date |
---|---|
WO1999055766A1 true WO1999055766A1 (en) | 1999-11-04 |
WO1999055766B1 WO1999055766B1 (en) | 1999-12-09 |
Family
ID=27371565
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/US1999/009327 WO1999055766A1 (en) | 1998-04-29 | 1999-04-29 | Novel polymer additives for forming objects |
Country Status (4)
Country | Link |
---|---|
EP (1) | EP1080128A1 (en) |
AU (1) | AU3573799A (en) |
CA (1) | CA2333228A1 (en) |
WO (1) | WO1999055766A1 (en) |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US9630206B2 (en) | 2005-05-12 | 2017-04-25 | Innovatech, Llc | Electrosurgical electrode and method of manufacturing same |
US10294343B2 (en) | 2014-09-24 | 2019-05-21 | The Chemours Company Fc, Llc | Materials with enhanced protection of light sensitive entities |
CN109851746A (en) * | 2018-12-24 | 2019-06-07 | 山东一诺威聚氨酯股份有限公司 | Cellulose modified TPU film material and preparation method thereof |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN110433742B (en) * | 2019-09-11 | 2022-03-01 | 成都工业学院 | Preparation method of microcapsule with double-layer coating structure and microcapsule prepared by preparation method |
Citations (8)
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US3884980A (en) * | 1970-04-06 | 1975-05-20 | Cincinnati Milacron Chem | Aldol condensation using cobalt II halide hydrazine complexes |
US3895149A (en) * | 1973-07-05 | 1975-07-15 | Atlantic Richfield Co | Carpet backed with thixotropic polyurethane adhesive |
US3941855A (en) * | 1973-07-27 | 1976-03-02 | Bayer Aktiengesellschaft | Shaped polyurethane articles and a method for making them |
US4013614A (en) * | 1975-01-29 | 1977-03-22 | H. H. Robertson Company | Method of preparing shaped articles from polymerizable compositions |
US4631206A (en) * | 1984-07-30 | 1986-12-23 | Toyoda Gosei Co., Ltd. | Method for curing polyurethane coating |
US4691045A (en) * | 1984-12-06 | 1987-09-01 | Nippon Shokubai Kagaku Co., Ltd. | Hydroxyl group-containing (meth)acrylate oligomer, prepolymer therefrom, and method for use thereof |
US4822849A (en) * | 1987-08-03 | 1989-04-18 | Reichhold Chemicals, Inc. | Low shrink hybrid resins |
US5284705A (en) * | 1990-09-06 | 1994-02-08 | Garland Floor Co. | Antistatic coating comprising tin-oxide-rich pigments and process and coated substrate |
-
1999
- 1999-04-29 WO PCT/US1999/009327 patent/WO1999055766A1/en not_active Application Discontinuation
- 1999-04-29 EP EP99917670A patent/EP1080128A1/en not_active Withdrawn
- 1999-04-29 AU AU35737/99A patent/AU3573799A/en not_active Abandoned
- 1999-04-29 CA CA002333228A patent/CA2333228A1/en not_active Abandoned
Patent Citations (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3884980A (en) * | 1970-04-06 | 1975-05-20 | Cincinnati Milacron Chem | Aldol condensation using cobalt II halide hydrazine complexes |
US3895149A (en) * | 1973-07-05 | 1975-07-15 | Atlantic Richfield Co | Carpet backed with thixotropic polyurethane adhesive |
US3941855A (en) * | 1973-07-27 | 1976-03-02 | Bayer Aktiengesellschaft | Shaped polyurethane articles and a method for making them |
US4013614A (en) * | 1975-01-29 | 1977-03-22 | H. H. Robertson Company | Method of preparing shaped articles from polymerizable compositions |
US4631206A (en) * | 1984-07-30 | 1986-12-23 | Toyoda Gosei Co., Ltd. | Method for curing polyurethane coating |
US4691045A (en) * | 1984-12-06 | 1987-09-01 | Nippon Shokubai Kagaku Co., Ltd. | Hydroxyl group-containing (meth)acrylate oligomer, prepolymer therefrom, and method for use thereof |
US4822849A (en) * | 1987-08-03 | 1989-04-18 | Reichhold Chemicals, Inc. | Low shrink hybrid resins |
US5284705A (en) * | 1990-09-06 | 1994-02-08 | Garland Floor Co. | Antistatic coating comprising tin-oxide-rich pigments and process and coated substrate |
Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US9630206B2 (en) | 2005-05-12 | 2017-04-25 | Innovatech, Llc | Electrosurgical electrode and method of manufacturing same |
US10463420B2 (en) | 2005-05-12 | 2019-11-05 | Innovatech Llc | Electrosurgical electrode and method of manufacturing same |
US11246645B2 (en) | 2005-05-12 | 2022-02-15 | Innovatech, Llc | Electrosurgical electrode and method of manufacturing same |
US10294343B2 (en) | 2014-09-24 | 2019-05-21 | The Chemours Company Fc, Llc | Materials with enhanced protection of light sensitive entities |
CN109851746A (en) * | 2018-12-24 | 2019-06-07 | 山东一诺威聚氨酯股份有限公司 | Cellulose modified TPU film material and preparation method thereof |
Also Published As
Publication number | Publication date |
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EP1080128A1 (en) | 2001-03-07 |
WO1999055766B1 (en) | 1999-12-09 |
AU3573799A (en) | 1999-11-16 |
CA2333228A1 (en) | 1999-11-04 |
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