Novel foraming compositions and methods for making and using the composition

Abstract
A low-temperature foam compositions and that are produced from an epoxy compound and an acid source can be substantially free of polyurethane or isocyanate chemistry. The disclosed compositions and precursors thereof reduce, if not eliminate, the presence of conventional undesirable compounds and by-products thereof.
Description


FIELD OF THE INVENTION

[0004] The invention relates to foam compositions, precursors thereof and methods for making foam compositions and foam containing articles.



BACKGROUND OF THE INVENTION

[0005] Foams are employed in a wide range of commercial applications including applications requiring thermal and sound insulation such as automotive and construction environments, among others. In the automotive industry, foams are typically formed in situ, and can be used to fill cavities such as pillars and rocke panels, and to dampen sound transmission. In situ foam formation has typically been accomplished by using a polyurethane foam based on isocyanate chemistry. Certain polyurethane foam components and by-products thereof are believed to have an undesirable environmental impact. Consequently, there is a need in this art for low-temperature foam which is cost-effective and substantially free of undesirable materials.



SUMMARY OF THE INVENTION

[0006] The invention is capable of solving problems associated with conventional foam formulations by providing foam compositions and precursors thereto which do not require the use of isocyanates. The inventive compositions and precursors can thereof reduce, if not eliminate, the presence of conventional undesirable compounds and by-products thereof while providing benefits associated with conventional foams, e.g, sound/vibration dampening, thermal insulation, structure reinforcement, floatation, energy dissipation, among other benefits. In addition, the inventive foam has a reduced cured and tack time in comparison to conventional polyurethane foams. These properties in turn improve the efficiency of manufacturing processes that employ foam.


[0007] One aspect of the invention relates to a method of reacting an epoxy compound and a hydrogen donor or acid compound at ambient conditions to produce a foam. This reaction can produce a relatively large exotherm. The heat released by the exothermic reaction can be sufficient to drive an endothermic blowing agent, thus creating a foam virtually instantaneously. In fact, the exothermic reaction can be sufficiently large to cause a blowing agent entrapped within, for example, thermoplastic powders to expand thereby forming a foam.


[0008] Another aspect of the invention relates to a method of containing the foam during expansion by expanding the foam within a containment or control means. The control means confines the expanding foam and determines the direction of expansion. While any suitable control means can be employed, a polymeric bag or sack is desirable. If desired, the polymer bag comprises an adhesive material, e.g., the bag adhesive is activated by the exothermic foam reaction and affixes the resultant foam to a substrate. The polymeric bag can be fabricated from a virtually unlimited array of materials and configured into any desirable shape, e.g., a honeycomb structure, replicating an automotive cavity, etc.


[0009] The inventive foam can be employed in a wide array of end-uses. Examples of such uses include thermal insulation such as appliances, e.g., refrigerators, hot water heaters, etc; aircraft; commercial or residential construction such as spray or rigid insulation for walls, doors, cavity/widow sealant, acoustical control, etc.; packing material, e.g., foam-in-place; marine foams; environmental control, e.g., spill containment footware; furniture; toy and consumer goods; protective equipment such as pads, helmets, etc.; fluid filtration; transportation industry uses, e.g., sound dampeners, structural supporting material, etc. for cars, trucks and heavy duty vehicles; vehicle repair; gasketing material; medical uses such as casts, emergency immobilization, etc.; artistic medium such as decorative brick/block, figures, etc.; among others.







BRIEF DESCRIPTION OF THE DRAWINGS

[0010]
FIG. 1 is a graphical representation of the foam reaction rate and temperature as a function of percent acid.


[0011]
FIGS. 2A and 2B are a schematic drawings of assemblies that can be employed for dispensing the inventive foam within a defined cavity or area.







DETAILED DESCRIPTION

[0012] The invention is based, at least in part, on the surprising discovery that superior foam compositions can be produced from epoxy compounds and acids or hydrogen donor compounds, and in particular, a reaction of the epoxy compounds with the acid source.


[0013] Moreover, the inventive compositions can be polyurethane and/or isocyanate free. By “free” it is meant that the inventive compositions before or after foaming contain less than about 10 wt. % polyurethane and/or isocyanurates, isocyanate, and in most cases 0 wt. %. While the presence of such compounds does not adversely affect the reaction described below in greater detail, these materials can be obviated by employing the inventive formulations. The instant invention, therefore, provides a foam which can be used with or instead of urethane/isocyanate based foams and foaming systems.


[0014] The inventive foam composition is typically obtained from the reaction of one or more foam precursors. The precursor(s) comprise (i) at least one epoxy compound, and (ii) at least one acid source, i.e., a hydrogen donor or an acid, e.g., phosphoric acid, or a compound such as a photoinitiator which can upon activation provide a hydrogen donor or an acid, and (iii) at least one expansion or blowing agent, among other components. An exothermic reaction between the epoxy and hydrogen donor or acid can activate the expansion or blowing agent thereby producing a foam.


[0015] The foam precursor(s) can comprise a single phase system that is activated in response to a source of energy, e.g., heat, UV or electron beam or laser radiation, among other energy sources, or a two component system (an A side precursor and a B side precursor) that are contacted together to produce a foam. When a two component system is employed the epoxy and acid source are provided in separate “side” components.


[0016] Alternatively, the foam precursor(s) can comprise a two component system that is activated in response to a source of, e.g., heat, UV or electron beam or laser radiation, among other energy sources. The two component system can include an acid source as well as a photoinitiator.


[0017] The first component of the precursor(s), an epoxy compound, comprises about 10 to about 80 wt % of the precursor(s). Examples of suitable epoxy compounds include bis-phenol A epoxy, bis-F epoxy, epoxy-modified elastomers, epoxy-modified polybutene, epoxy-modified polybutadiene, epoxy-modified ethylene-propylene-diene rubber (EPDM), cycloaliphatic epoxy, novolac compounds, and mixtures thereof, among others. When a two component system is employed, the epoxy is located on the A-side, or otherwise prevented from prematurely reacting with the acid or other precursors.


[0018] The first component of the precursor can be tailored by adding one or more modifiers. For best results, the modifier is solublized by the epoxy or miscible with the epoxy. Examples of suitable modifiers can comprise at least one member selected from the group consisting of styrene and co-polymers thereof, vinyls and co-polymers thereof, elastomers such as nitrile, ethylene acrylic rubber, mixtures thereof, among others compounds that do not adversely impact the exothermic reaction. Some commercially available materials that can be employed as a modifier comprise Kraton® (Shell Chemical), Varnac® (DuPont), Piccolastic® (Herculcs), Phenoxy® (Paphen), SAA® (styrene-allyl-alcohol copolymer (ARCO), G-Cryl® (Henkel), Rohagum® (Rhomtech), acrylate modified acidic adhesion promoting agent (acid functional oligomer, RadCure®), mixtures thereof, among others. Normally, the epoxy modifier comprises about 2 to about 50 wt. % of the composition prior to foaming.


[0019] A second component of the precursor(s) is the acid source. When a two component precursor system is employed, the acid source is present in the “B side” of the foam precursors. The hydrogen donor or acid usually comprises about 1% to about 30 wt. % of the precursor, and in particular, about 3% to about 15% of precursor B-side precursors. Examples of suitable acid sources include Lewis acids such as sulfonic acids, phosphoric acid, citric acid, carboxylic acid, glycolic, tannic, 1,2,4,5-Benzenenetracarboxylic acid, citraconic acid, L-(+)-Citrulline, fumaric, maleic, azelaic, oxalic acids, and mixtures thereof, among others. Particularly desirable results have been achieved by employing at least one of sulfonic, phosphoric acids and other acid functional compounds, e.g., acid functional acrylics. Depending upon the desired reaction rate and resultant foam characteristics, a relatively concentrated acid can be employed. An example of such a concentrated acid comprises a phosphoric acid that is substantially free of water. By “substantially free” it is meant that the acid contains less than about 10 wt. % and normally less than about 5 wt. % water. Substantially water free acid can be obtained by distilling commercially available acids, e.g., 75% phosphoric acid can be concentrated by distillation. In the case of phosphoric acid, concentration by distillation permits obtaining at least one of meta, ortho and pyro-phosphoric acids. At least one of ortho or pyro-phosphoric acid and mixtures thereof are effective as an acid source when a relatively strong and rigid foam is desired, e.g., an acid source comprising about 50 to greater than 90 wt. % ortho-phosphoric acid. If desired, the acid can comprise an acid functionally equivalent to the hydrogen donor released by a UV photoinitiator, e.g., replace a portion of the photoinitiator with its corresponding acid.


[0020] In one aspect of the invention, an acid substantially free of water is employed to obtain a foam precurso that generates foam having improved structural properties, e.g., foam having a flexural strength about 20 to 100% greater than many conventional materials such as wooden particle board. By employing a substantially water free acid as a foam precursor, the resultant foam has a lower expansion and water absorption, and greate structural strength and adhesion, e.g., to a painted or primed metal surface, wood, particle board, corrugated paper such as honeycomb, ABS, Formica®, Masonite®, thermoplastics such as polystyrene, among other surfaces. Substantially water free acids can also permit using a wider range of precursors, e.g., non-polyol carriers.


[0021] The adhesion of the foam to certain substrates, e.g., ABS, can be improved by pre-treating or priming the substrate surface. An example of a suitable primer comprises applying a silane coating (e.g., Z6040 supplied by Dow Chemical) onto the surface. The silane forms a coating to which the foam can adhere. Adhesion can also be improved by embossing or roughening the surface of the substrate.


[0022] A mechanical fastener can be attached to or incorporated within the substrate such that the foam embeds the fastener. The fastener can comprise a plurality of protrusions, studs or mechanical fastening means having any desirable shape can be located within a cavity to be filled with foam and/or attached to the substrate that contacts the foam. When studs are employed, the studs can be welded, e.g., sonically welded to a thermoplastic, within a cavity to be filled with foam. Protrusions can also be affixed within the cavity or upon the surface by a suitable adhesive, or by mechanical attachment. The height and specific configuration of the protrusions depends upon the application. These protrusions can be fabricated from any suitable material such as thermoplastics such as nylon, metal, among other materials. When introduced into the cavity, the inventive foam composition or precursors thereof embeds the protrusions, fills the cavity and embeds the protrusions thereby affixing the foam within the cavity or onto a substrate.


[0023] In another aspect of the invention, the hydrogen donor comprises a photo-initiator that becomes active when exposed to a source of energy. While any photoinitiator capable of becoming a hydrogen donor upon activation can be employed, specific examples of a suitable photoinitiators include a UV catalyst such as UVI 6974 (Union Carbide) that is described in greater detail in the aforementioned copending and commonly assigned U.S. Non-Provisional Patent Application Serial Nos. 09/081,966, filed on May 20, 1998 and Ser. No. 09/197,107, filed Nov. 20, 1999, both filed in the name of Jeffrey Pachl et al., and entitled “Curable Sealant Composition”. Alternatively, free radical photoinitiators can be employed. An example of a free radical photo-initiator comprises 2-hydroxy-2-methyl-1-phenyl-propan-1-one, e.g., DAROCUR® 1173 (Ciba-Giegy). Free radical photoinitiators can be employed in systems comprising at least one of monomers and oligomers such as acrylated oligomers, urethane acrylates, acrylated epoxies, acrylated acrylics, acrylated polyesters, acrylated polybutadiene, methacrylated counterparts thereof, among others. When such initiators are employed, the foam precursors can be utilized in a single or multi-phase system.


[0024] For example, such a single phase system can be dispensed, exposed to a UV light source or other suitable source of energy that causes the UV catalyst to generate an acid thereby permitting the epoxy or free-radical reaction to occur. The heat released by the exothermic reaction in turn activates an expansion or blowing agent, e.g., a hydrocarbon encapsulated within a thermoplastic, thereby producing a foam. While any suitable single or two phase system can be employed, normally a single phase system produces a foam that is thin relative to a two phase system. Similar to other foam precursors, the radiation activated precursors can be modified for controlling the properties of the precursors or resultant foam, e.g., about 1 to about 20 wt. % polystyrene is added to the epoxy component.


[0025] The blowing agent can comprise one or more of the blowing agents recognized in the foam-forming field. Example of suitable blowing agents include water, hydrazide, diphenyloxide-4,4-disulphohydrazide, carbonamide, azocarbonamide, hexamethylene diamine carbamate, sodium bicarbonate, dimethyl ether, methylene chloride, carbon dioxide, fluorocarbons such as difluoroethane, tetrafluoroethane, BFC-4310, azeotropes and isomers thereof, among others; and hydrocarbons such as isobutane, butane, propane, pentane, isopentane, alcohol, isomers thereof; mixtures thereof, among other known blowing agents. Normally, the expansion or blowing agent comprises about 1 to about 40 wt. % of the foam precursor(s). The blowing agent can be present in either the A or B side of a two component system, although the B-side precursor is preferred.


[0026] The foam precursor(s) can also include at least one carrier component, e.g., a polyol, and optional components such as thermoplastics. A carrier usually comprises about 1 to about 40 wt. % of the precursor, e.g., preferably about 10-30 wt. %. The carrier typically serves to deliver a component, e.g., an acid, expanding agent, catalyst, mixtures thereof, among others for contact with the epoxy. Examples of suitable carriers comprise at least one member selected from the group of polyols including polyester, polyether, polycarbonate and caprolactone; alcohol, polyvinyl alcohol, synthetic or natural oils such as castor, soy, linseed, glycerin and glycols; water, among other carriers that are preferably miscible with the epoxy and mixtures thereof. When a two component precursor system is employed, these carrier materials are typically added to the acid side or “B side” component of the foam precursors


[0027] In addition to the aforementioned epoxy modifiers, the components of the precursor can be tailored by adding one or more modifiers in order to control viscosity, improve stability, physical properties, reaction rates, color, odor, among other characteristics. For best results, the modifier is solublized by the carrier or miscible with a carrier. Examples of suitable modifiers can comprise at least one member selected from the group consisting of natural and synthetic oils such as at least one of castor, soy, canola, linseed, polybutene, epoxidized counterparts thereof, among other oils. Epoxized natural oils such as epoxized castor oil can be employed as a Part A component. The addition of castor oil can also produce a foam having an exterior glaze or skin. Normally, the carrier modifier is used about 2 wt. % to about 50 wt. % of the composition prior to foaming.


[0028] Moreover, the density, moisture and temperature resistance among other physical properties of the final foam product can be modified or tailored by adding a thermoplastic, theromset, plastic or resinous material to the epoxy-containing precursor. While any suitable modifying material can be employed, examples of such modifying materials include dicyandiamide (Dicy (Amicure CG 1400)), ethylene vinyl acetate, polypropylene, polyethylene, rubber, phenoxy resin, phenolics, powdered wax, solid epoxy such as bis-A epoxy or modified epoxy.novalac compound, mixtures thereof, among others. For example, dependign upon the relative concentration of the components of the precursor, polyvinyl alcohol, hydroscopic polyolefin such as modified polypropylene (as well as other suitable materials) can be employed as modifiers and for absorbing steam or water generated by or during the exothermic reaction. About 1 to about 60 wt. % of modifying material can be added relative to the epoxy, e.g., about 2 wt. % of the precursor(s). The modifying material will normally comprise a powder having a particle size less than about 20 microns and a melting point from about 150 to about 400 F. The modifying material will become fluid and normally melt when exposed to the exothermic reaction temperature. When a two component precursor system is employed, these materials are normally, but not necessarily, combined with the epoxy or “A side”.


[0029] The foam precursors can also include a thermoplastic component that can function to modify the properties of the resultant foam, reduce material cost, increase precursor shelf life, among other desirable results. The thermoplastic component of the foam precursor(s) can comprise at least one member selected from the group consisting of acrylonitrile, polyethylene, phenolic, wax, EVA, polypropylene, GMA, acid modified polyethylene, polybutadiene, modified polyethylene blend (such as Bynel® supplied by DuPont Company), SIS or SBS or SEBS blocked copolymers (such Kraton® supplied by Shell Chemical), oligomers, polyolefin, hydroxyl or epoxy functional compounds, among other thermoplastic materials that can be dispersed in a foam precursor and have a melting point less than about the aforementioned exothermic reaction and mixtures thereof. Normally, the thermoplastic component of the precursor will comprise about 1% to about 60 wt. % of the precursor. The thermoplastic component can possess any desirable configuration or particle size. In some cases, the thermoplastic component can form a film or skin upon an exterior surface of the foam thereby improving the resistance of the foam to fluids, e.g., water, gasoline, among other fluids.


[0030] In an aspect of the invention, the flame resistance of the foam can be improved by adding an effective amount of at least one member selected from the group consisting of halogenated epoxy as a component of the epoxy (brominated epoxy Erisys® GE-29), aluminum trihydrates, zinc borate, among other commercially available flame retardants. If desired, a halogenated epoxy can replace a portion of the Part A epoxy. Normally, the flame retardant comprises about 0.5 to about 15 wt. % of the unexpanded foam composition.


[0031] In one particularly useful aspect of the invention, a liquid or gaseous blowing agent is combined with or encapsulated within a thermoplastic particle or powder, e.g., a hydrocarbon encapsulated within an acrylonitrile shell as in Expancel® that is supplied by Expancel Tnc., a division of Akzo Nobel Industries. When a two component precursor system is employed, the shells are normally combined on the B side along with the carrier. These shells can, however, be combined with the A side or in a single phase system so long as the composition of the shells is not substantially affected by the epoxy, e.g, the acrylonitrile or vinylidene chloride shells may be soluble within the epoxy. For example, the shells can be fabricated from polyolefins such polyethylene and polypropylene; vinyls, EVA, nylon, acrylics, among other materials not soluble in the epoxy component, and mixtures thereof could be present in the epoxy component of a two phase precursor system. The shells are selected to melt, soften, expand, rupture or retain their physical configuration depending upon whether or not an open or closed cell foam is desired. The shells can also comprise a distribution of differing particle sizes, composition and activation temperatures, e.g., a foam precursor comprising at least two different particle sizes and activation temperatures. A foam comprising particles having a range of sizes and compositions is especially desirable when producing an acoustical foam. The acoustical properties of a foam can also be improved by employing particles encapsulating blowing agents of more than one composition, e.g., employing shells encapsulating differing blowing agents. Specific examples of suitable encapsulated blowing agents comprise at least one member selected from the group of hydrocarbons such as isobutane and isopentane; fluorocarbons such as 1-1-dichloroethene, HFC-134a, HEC-152a; and nitrogen releasing chemical blowing agents such as those supplied as Celogen® by UniRoyal that are encapsulated within any suitable thermoplastic, e.g., 2-methyl 2-propenioc acid methyl ester polymer with 2-propenenitrile and vinylidene chloride polymer and polyvinylidene fluoride. These materials are supplied commercially by Expancel, Inc. a division of Akzo Nobel as Expancels® 051WU, 051DU, 091DU80, 820WU, 820DU, 642WU, 551WU, 551WU80, 461DU or Micropearl® F30D supplied by Pierce and Stevens. These materials can be supplied in either dry or wet form. These materials can also be coated with any suitable material for controlling the activation temperature of the encapsulated blowing agents. An example of a coating comprises an acrylated materials, waxes, among other materials. When the A and B sides are contacted (or in the case of a single phase system exposed to an energy source), the epoxy reacts with the hydrogen or acid thereby releasing heat and causing the expansion agent within the shells to foam. The foam can be characterized by a composite wherein the epoxy reaction product (including of the aforementioned modifying materials) forms a matrix that embeds the expanded shells. Depending upon the physical characteristics desired in the foam, the shells can be open or closed cells.


[0032] In a further aspect of the invention, the encapsulated foam precursor can comprise at least one member selected from the group consisting of an acid source, a curing agent, surfactants, epoxy accelerators, among other foam precursors. By curing agent it is intended to mean one or more compositions, other than an acid source, that causes an epoxy functional material to react, exotherm, and cross-link. Examples of curing agents comprise at least one member selected from the group consisting of imidazoles, amines, amides, derivatives thereof, among others. If desired an encapsulated or unencapsulated acid source can be employed in conjunction with an encapsulated curing agent. An example of an encapsulated or polymer bound curing agent comprises those supplied by Landec as Intelimer® 7001, 7002, 7004, 7024 and mixtures thereof. By employing one or more encapsulated or polymer bound foam precursors, it is possible to produce a foam by a multiple stage reaction method wherein the resultant foam has enhanced physical properties, e.g., density, water absorption, hardness and strength.


[0033] The foam characteristics can also be modified by adding one or more filler materials to the precursor(s). Conventionally used filler materials comprise at least one of talc, mica, magnesium silicate, oxidized polyethylene, sodium silicate, alcohols, petroleum jelly, aromatic acid methacrylate-mixed half esters, methacrylated polybutadiene, concrete mix (supplied commercially as Quickrete®), arylalkoxy silane, hollow ceramic spheres, inorganic microspheres, dispersants, conventional blowing/expansion agents, flame retardants such as phosphates, borates and halogenated compounds; plasticizers, diluents, pigments, colorants, metal or ceramic powders, soybean hulls, pecan hulls, rice hull, antimicrobial agents such as fungicides, fumed silica, abrasive materials, magnetic materials, anti-static or conductive materials, mixtures thereof, among others. If desired calcium carbonate can be added to the foam precursor for increasing the hardness and density of the resultant foam. When included the filler comprises about 1 to about 60 wt. % of the foam precursors.


[0034] The inventive foam can be matrix that embeds or contacts other materials in order to obtain a composite structure. The compositing materials can comprise the aforementioned filler materials, previously formed preform or structures, e.g., honeycomb, fibrous mat, shaped particulate member, honeycomb structures, syntactic materials such as described in U.S. Pat. No. 4,568,603 hereby incorporated by reference; among others. The compositing material can be added to a foam precursor and/or introduced when foaming the precursors. In one aspect, the compositing material comprises styrene pellets, e.g., recycled packaging material, that is ground and added to the previously described carrier. These pellets function to reduce weight and cost of the resultant foam. In another aspect, the compositing material comprises a material for improving the compressive strength of the foam and/or spacers for limiting the degree to which the foam can be compressed, e.g., nylon, polyolefins, polyethylene, among other materials. The compressive strength improving materials can be of any suitable form such as cubes, beads, mixtures thereof, among other shapes.


[0035] In one aspect of the invention, one or more foam precursors interact to form an intermediate foam precursor. The intermediate foam precursor can correspond to a Part A and/or Part B. The intermediate foam precursor can be contacted with another precursor or another intermediate foam precursor in order to obtain a foam. A carrier such as a polyol, e.g., a polyester polyol, can interact with at least one member selected from the group of an acid source, e.g, phosphoric acid; a modifier, e.g., styrene; among other precursor components. An epoxy can interact with at least one member selected from the group of an acid source, e.g., phosphoric acid; a modifier, e.g., styrene; among other precursors that are miscible with the epoxy. If desired the aforementioned carrier containing intermediate product is contacted with the aforementioned epoxy containing intermediate product to obtain a foam. The intermediate precursor can be self-supporting. The combined intermediate products can produce a gel-like product that in turn is converted to a foam, e.g, the intermediate product can comprise a gel that can be shaped prior to onset of foam formation.


[0036] The precursor(s) and/or intermediate products thereof can be pre-blended and stored in separate containers prior to use. To this end, an A-side or first precursor mixture is typically obtained by combining the epoxy and modifying material, e.g, polyvinyl alcohol and polypropylene, and a B-side or second precursor mixture can be obtained by combining the carrier, e.g., a polyol, hydrogen donor/acid and thermoplastic, e.g., encapsulated blowing agent.


[0037] The precursor(s) can be produced using any suitable apparatus that imparts an amount of shear sufficient to obtain a substantially homogenous precursor. Examples of suitable apparatus comprise hand mixing, static tube mixtures, the structures described illustrated by FIGS. 2A and 2B (described below in greater detail), impingement spraying precursors, extrusion, e.g., a twin screw extruder, among other conventional apparatus. Normally, the samples are mixed for about 1 to about 40 seconds depending upon the composition and mixing environment, e.g., a 1:1 A:B composition can be mixed for about 1 to about 10 seconds in a static tube mixer.


[0038] The inventive method involves contacting the epoxy compound and acid or hydrogen donor under conditions effective to provide an exothermic reaction. The heat produced from the reaction can then cause the blowing agent(s) to expand in forming the desired foam. For example, where two precursors, A and B are employed, the two compositions can be combined- to obtain a foam by using conventional foam manufacturing equipment. For example, A-side and B-side can be contacted as two high pressure streams within a mixing chamber of an external mix-head. While heat can be added to the precursors, the reaction between “A” and “B” can occur at ambient conditions, e.g., to control viscosity, adjust reaction rate, etc. The ratio of A-side to B-side normally ranges from about 1:1 to about 10:1 or 1:10.


[0039] An example of a combined A and B side precursor composition is set forth in the following Table.
1TABLEChemicalTradeNameNameSupplierWt. %EquivalentCycloaliphaticUvacureUCB1-80Sartomer-Epoxy1500RadcureSARCAT ® K126CaparolactoneTone 0301Union0-70CarbidePhosphoricPhos. AcidJ. T.1-20commodityAcidBakerThemoplasticExpancelNobel1-50Pierce & Stevens-IndustriesMicropearls ®


[0040] The pH of the A-side component (containing the epoxy compound(s)) is normally about 6 to at least about 8. The pH of the B side of the foam precursor comprising an acid and a carrier is normally about 0.5 to about 4, e.g., the pH of phosphoric acid when mixed with polyol. Normally, the pH prior to reaction with A-side precursors is about 1.6. The composition and concentration of the foam precursors can be modified to achieve a predetermined reaction rate e.g., by tailoring the concentration of the acid. The affects of the pH or acid concentration of the B side are better understood by reference to FIG. 1 which illustrates the affects upon the composition demonstrated in Example 9.


[0041] Referring now to FIG. 1, FIG. 1 is a graphical representation of % acid in the precursor versus foam reaction time and temperature. FIG. 1 illustrates that as the acid concentration increases the reaction temperature increases and the reaction time decreases. FIG. 1 also illustrates that the precursor can be selected to a predetermined reaction time/temperature. For example, by selecting a higher reaction temperature (higher acid concentration) a wider range of modifying materials can be employed whereas by selecting a slower reaction time (lower acid concentration) the foam has easier handling characteristics.


[0042] The viscosity of a foam precursor can be tailored to enhance the resultant foam characteristics. The viscosity of the “A-side” or epoxy component of the foam precursor is normally controlled, for example, so that a modifying material, e.g., a plastic powder, becomes or remains dispersed within the “A-side” precursor. While any suitable viscosity control agent can be employed desirable results can be achieved by using a solid polymer (in particulate form) to produce a foam precursor gel.


[0043] Examples of suitable solid polymers comprise at least one member selected from the group consisting of waxes, polyethylene, EVOH, PVOH, fluoropolymers and dispersions thereof such as polytetrafluoroethylene (supplied as Teflon® by the DuPont Company), among others. The viscosity control agent can range in particle size of about 20 to 50 microns, e.g,. less than 325 mesh. An example of a controlled viscosity composition comprises about 5 to about 10 wt. % solid epoxy, about 5 to about 15 wt. %, powdered polyethylene and about 25 to about 30 wt. % blowing agent. In addition to viscosity, the characteristics of the foam can be tailored by varying the temperature, pressure, foam pH, foam density, among other parameters known to those skilled in this art. Also, the “A-side” of the system can be thickened into a gel by the addition of a surfactant such as any commercially available liquid detergent or titanate such as Kenrich KRTTS, e.g., about 0.1 to about 10 wt. % surfactant. This enables a more complete rheological control, included insuring the homogeneity of the system.


[0044] As discussed above, the foam can be produced from a single-phase system, e.g., only an “A-side” mixture. An example of such a system comprises an epoxy, a polyol, thermoplastic spheres, modifying materials, phenoxy, polypropylene, mixtures thereof, among other components. This one component system can be heat activated. In other words the system expands by being exposed to elevated temperature, e.g., about 125C. If desired the single phase foam system can be initiated by employing a photo-initiator instead of, or in conjunction with, an elevated temperature. Examples of such initiators comprise at least one member selected from the group consisting of Union Carbide UVI 69/74 among others. Normally, the amount of such an initiator corresponds from 0.5 to about 5 wt % of the foam precursor. More details regarding photoinitiators can be found in “Photopolymerization Behavior of Several Cationic Photoiniators in Catatonically Cured Resin Systems” by Edward Jurczak; that is hereby incorporated by reference.


[0045] Single phase systems are especially useful when applied upon a substrate by being sprayed. For example, the single phase system can be sprayed upon an automotive subassembly for reducing the amount of sound transmission to the interior of the car. In a further example, the single phase system can be sprayed upon a first component, e.g., a plastic fascia, exposed to UV to cause foaming and affixed upon a second component, e.g, metal support member, wherein the foam functions to reduce vibrations between the components.


[0046] A composite foam structure can be obtained in accordance with the instant invention. A structural modifier such as fibers, particles, rods, tubes, powders, mixtures thereof, among others, can be incorporated as a component of the foam precursor. The structural modifier can be employed for tailoring the chemical and/or physical properties of the resultant foam. Examples of suitable structural modifiers, normally as chopped fibers, ceramic or glass spheres or powders, can comprise at least one of nylon, carbon, carbonates, polymers such as polyethylene and polypropylene, graphite, Kevlar®, Dyneon, ceramic, fiberglass, mineral fillers, e.g., mica, metals, among other materials. The amount of such structural modifiers normally comprises about 1 to about 60 wt. % of the uncured foam precursor.


[0047] Any suitable commercially available foam production equipment can be employed for mixing and dispensing the inventive foam precursors to obtain the inventive foam. Examples of such equipment comprises DoPag (ECONO-MIX) supplied by Kirkco Corporation, Monroe, N.C; as well as equipment supplied commercially by Jesco Products Company, Inc, Sterling Heights, Mich. Another example comprises using an Econo-Mix pump in combination with an Albion static mix head. The foam precursors can also be mixed by employing a power mix gun such as supplied by Sealant and Equipment Company, Oak Park, Mich. If desired, the inventive foam can be expanded within a cavity, e.g., an automotive A pillar, by employing a dispensing apparatus having a replaceable/disposable static mix head. That is, the static mix head can comprise a replaceable plastic tubing having a center piece with a helix or vortex configuration, that is connected to a pump discharge flange and inserted into the cavity for foaming the precursors.


[0048] In one aspect of the invention, the inventive foam is dispensed through a commercially available dual tube dispenser (e.g., a 4:1 dual tube dispenser supplied by Tah Industries). That is, one of dual tubes is loaded with an inventive Part A composition and the other tube contains an inventive Part B. The Part A and B are dispensed by the dual tube dispenser and pass through a static tube mixer (also known as a motionless mixer). The Part A and B are contacted by the static tube mixer thereby causing the Parts A and B to react and produce a foam. When dispensing the inventive compositions via a dual tube dispenser, the inventive compositions can be employed as replacement for conventional caulks as well as commercial cavity filling foams, e.g., polyurethane foams.


[0049] Another static mix head design has a valve type of arrangement that is illustrated in FIGS. 2A and 2B. Referring now to FIG. 2A, FIG. 2A illustrates a one-way value type of arrangement wherein the foam or precursors thereof are introduced or injected via a one-way valve 1 (commonly known as a zerk) that is positioned within a cap 2. Valve 1 can also include a flap or secondary valve 1A that prevents foam from escaping by reverse flow through valve 1. The cap 2 seals or defines one end of a cavity being filled with foam. The cap 2 can include hooks or locking tabs 3 for securing the position of cap 2, e.g, within the so-called A pillar of an automobile thereby permitting foam to be dispensed within the automotive cavity in a controlled manner. Normally, one end of the valve 1 is connected to a mixing zone 4 such as the aforementioned static mixers having helical vanes 5. After traveling through the valve 1 and static mixer 4, the foam is released into the cavity to be filled with foam. The area and direction into which the foam expands can be control and/or defined by using a containment means such as a polymeric bag 6 (the containment means is described below in greater detail).


[0050] Referring now to FIG. 2B, this type of arrangement provides a longer mixing time for the foam precursors before the foam is released into the cavity to be filled. The arrangement illustrated in FIG. 2B can also be employed as a cap 10 to seal or define one end of the cavity to be sealed. After delivering the foam precursors, a mix head 11 or previously described valves (4 and 5 of FIG. 2A). The foam precursors travel through mix head 11 and are released at the opening defined at 12 as foam. The opening 12 can also be within the aforementioned containment means. The caps 1 and 10 can remain associated with the foam product within the cavity. By using such a replaceable mix head, any problems associated with clogged mix heads are avoided. Two pressure streams can also be employed, to converge in a mix chamber or cavity to be foamed and mix action occurs without use of additional mixing apparatus. In addition to the foregoing, the inventive foam composition and precursors thereof can be injected, extruded, shaped, sprayed, cast, molded, among other conventional processes in order to obtain a desirable foam article. The configuration of the foam article can be virtually any shape including continuous shapes such as films or webs, discrete forms, among other shapes.


[0051] While the above description emphasizes particular foam compositions, the inventive compositions (and precursors thereof) can include additives such as dyes, fillers, surfactants, pigments, nucleating agents, among other conventional employed foam additives. If desired a pH indicator can be added to the precursor in order to provide a visual detection means for a reaction product. An example of a suitable pH indicator comprises at least one member selected from the group consisting of methyl red, methyl blue, chlorophenol red, bromothymol blue. That is, as the foam precursor react, e.g, acid-epoxy, the acid is consumed thereby changing the pH and causing the pH indicator to change color.


[0052] If desired, the inventive composition can be laminated or joined with other articles, e.g., laminated onto metal foil, Mylar, fiberboard, veneer, Formica® etc. In one aspect of the invention, the inventive foam precursors can be applied between two such laminating materials in order to form components that are useful in fabricating furniture. For example, the inventive foam is expanded between two laminating materials, one of which comprises the upper surface (e.g., a wood veneer) and the second the lower surface of a table top. Any excess foam can be removed by conventional methods such as sawing, scraping, etc. The foam imparts structural integrity to the article while reducing weight and fabrication time.


[0053] The inventive composition can also be expanded within a control or containment device or bag having a predetermined shape thereby forming a foamed article that replicates the bag, e.g, refer to U.S. Pat. Nos. 4,269,890 (Breitling), 4,232,788 (Roth), 4,390,333 (Dubois); the disclosure of each of which is hereby incorporated by reference. When expanding the foam into a bag, the previously described valves illustrated in FIGS. 2A and B; those supplied commercially by Inflatable Packaging as part no. IP04, or any other suitable delivery means can be employed at the opening in the bag in order to control introduction of the foam into the bag.


[0054] For example, a bag replicating a cavity such as an automotive cavity or any other desirable configuration unrolls or expands into the cavity as foam is introduced into the bag via the valve. If desired, the bag may comprise or be coated with a heat sensitive adhesive wherein the heat generated by the exothermic foam reaction activates the adhesive. The adhesive can permanently affix the foam containing bag at any desirable location. The bag can also include predetermined areas having weakened seams or perforations that are designed to rupture as the foam expands thereby directing the expanding foam. Similarly, the bag composition can be selected such that the bag melts when exposed to the foam. The melting bag can direct the expanding foam, form a coating upon the foam, and function as an adhesive, among other utilities. Further, a plurality of bags can be employed wherein one bag is surrounded by another bag. The inner and/or outer bag can possess the aforementioned predetermined properties. Furthermore, the bag can comprise areas having distinct chemical and/or physical properties, e.g., a bag comprising one sheet of polyethylene heat sealed around its periphery to a sheet comprising polybutadiene. At least a portion of the bag can be fabricated from one or members selected from the group consisting of polyethylene, polyester, vinyl, nylon, Surlyn®, ethylene vinyl acetate, styrene-isoprene- styrene, styrene- butadiene -styrene or other blocked copolymers, polybutadiene, among other plastic materials with melt points corresponding to temperature range of reaction, polyamide, modified EVA's, modified polyethylene, modified polybutadiene, GMA, SBR, among other plastic materials suitable for bag or bladder construction and seaming capability. The bag or containment means can be utilized with a wide range of foam compositions in addition to the previously described epoxy containing foams. Examples of foams that can be expanded into the previously described containment bags or means comprise at least one of epoxy amine, acrylic, and phenolic among others.


[0055] The foam precursors can be removed from surfaces, equipment, among other articles by employing non-hazardous cleaning materials. An example of suitable cleaning material comprises water, isopropyl alcohol, 2-butoxyethanol and a chelating agent. The cleaning material can be dispensed as an aerosol by using a propellant such as DME, hydrocarbons and carbon dioxide.


[0056] Moreover, the inventive foam can be fabricated to possess a substantially uniform or varying density throughout one or more of its dimensions. The ability to tailor foam density in individual articles as well as throughout an article is a marked improvement in the art. Foams having varying densities can be employed for attenuating or focusing sound, various forms of electromagnetic radiation, radar, etc.


[0057] While the above description emphasizes a reaction between an epoxy containing compound and one or more acid or hydrogen donor, the inventive method can be achieved by employing other polymer systems such as silicones, urethanes, silanes, hydroxyl or caboxyl modified elastomers; hydroxyl, carboxyl or epoxy functional compounds, reactive liquid polymers such as Hycar®, among others. That is, a polymer system is contacted with an acid that generates an exothermic reaction which in turn activates an expansion or foaming agent.


[0058] The following Examples are provided to illustrate not limit the scope of the invention as defined in the appended claims. Unless indicated otherwise, commercially available apparatus and materials were employed in these Examples.



EXAMPLE 1

[0059] A foam product was produced by mixing a 2-part system (A-side precursor and B-side precursor) through a conventional foam production apparatus comprising a static mixer that was manufactured by Albion (Model No. 535-1 or equivalent). The constituents of the foam were maintained in two separate supplies of materials, an A-side precursor and B-side precursor.


[0060] The A-side precursor comprised a blend of the epoxy and the thermoplastic microspheres including a blowing agent, in ratio of 30 parts to 15 (100 parts total). The B-side precursor comprised a blend of the phosphoric acid and the polyol in a 30 part to 50 part ratio (also 100 parts). The feed ratio of A-side precursor to B-side precursor to the mixer head was 1:1. The pH of the B-side precursors was about 1.6 prior to reaction with A-side precursor.


[0061] A pressurized flow through the mixing chamber produced a polymer which rapidly expands and released an amount of exothermic heat sufficient to produce a foam.



EXAMPLE 2

[0062] The process of Example 1 was repeated with the exception that the ratio of epoxy to thermoplastic nicrospheres in A-side precursor was 2:1, and the ratio of phosphoric acid to polyol in B-side precursor was 3:5. The feed ratio of A-side precursor to B-side precursor to the mixer head was 3:1.



EXAMPLE 3

[0063] The process of Example 1 was repeated with the exception that the A-side precursor and B-side precursor components were mixed together by hand (instead of using the static mixer).



EXAMPLE 4

[0064] This example demonstrates the formation of a composite foam. The process of Example 1 was repeated with the exception that about 5 wt. % polytetrafluoroethylene powder (TEFLON® supplied by the DuPont Company) was added to the A-side precursor composition. The A-side precursor and B-side precursor were contacted in the manner described in Example 1. A composite foam was recovered wherein the composite foan had greater flexibility or pliability in comparison the foam obtained by the process of Example 1.



EXAMPLE 5

[0065] A two phase system was used to produce a foam. The A-side precursor was composed of epoxy and microspheres in a 2:1 ratio (67% epoxy, 33.3% microspheres) by weight. (It is noted that for best results, the mix should be used within in 4-8 hours of mixing since certain epoxies can dissolve certain spheres). The A-side precursor was hand-stirred to a smooth consistency.


[0066] The B-side precursor was composed of Polyol (Tone 0301) and Phosphoric acid (10%) by weight). The acid was blended into the polyol. A-side precursor to B-side precursor ratio of 1:1 was contacted in a static tube mixer and produced a foam. The ratio of A to B can be from 1:1 to 4:1 depending on acid concentration.



EXAMPLE 6

[0067] A two phase system was used to produce a foam. The A-side precursor comprised an of epoxy (UCB-Radcure UVACURE 1500). The B-side precursor was comprised of a polyol (50 wt. % —Tone 0301), phosphoric acid diluted with water (approximately 50% acid in a commercially available solution) at 20%, and 30% microspheres. The spheres were hand-stirred into the polyol to a smooth consistency. The acid mixture was blended by hand-stirred into the sphere- polyol mix. An A-side precursor to B-side precursor ratio of 1:1 was contacted in a static tube mixer and produced a foam. The ratio of A to B can be from 1:1 to 4:1 depending on acid concentration.



EXAMPLE 7

[0068] A two phase system was used to produce a foam. The A-side precursor comprised an epoxy (UCB-Radcure UVACurel 500) While the B-side precursor comprised polyol (Tone 0301), polyvinyl alcohol and water blend (PVOH: H20 3:1 blend that corresponded to 20% of the polyol) and microspheres 30% by weight of polyol and acid can be 10% of total ‘B’ mixture. The spheres were hand-stirred into the polyol to a smooth consistency. The PVOH and water are hand-stirred. The PVOH/water solution temperature was 140° F. The PVOH blend was added to the polyol by hand stirring. The acid was hand-stirred into the sphere-PVOH- polyol mix. The A-side precursor to B-side precursor ratio of 1:1 was contacted in a static tube mixer and produced a foam. The ratio of A to B can be from 1:1 to 4:1 depending upon acid concentration.



EXAMPLE 8

[0069] A two phase system was used to produce a foam. The A-side precursor comprised an epoxy (UCB-Radcure UVACure 1500) and a phenoxy resin (Paphen PKHP-200 that corresponded to 25% of A-side precursors, epoxy is 75% of A-side precursors). The B-side precursor comprised 45% polyol (Tone 0301), 23.5% polyvinyl alcohol (Airvol 203S) and 23.5% microspheres. Phosphoric acid was 10% by wt. of the B-side precursor. Spheres are hand-stirred into the polyol to a smooth consistency. The PVOH, microspheres, and polyol are blended by hand stirring. The phosphoric acid was hand-stirred into the sphere-PVOH- polyol mix. An A-side precursor to B-side precursor ratio of 1:1 was used contacted in a static tube mixer to produce a foam. The A to B ratio can range from 1:1 to 4:1 depending on acid concentration.



EXAMPLE 9A

[0070] A two phase system, namely an A-side precursor and a B-side precursor, was used to produce a foam. The A-side precursor comprised an epoxy (UCB-Radcure UVACure 1500) 60 wt %, polypropylene powder (Equistar FP 800-00) 20 wt %, polyvinyl alcohol (Airvol 203S) 20 wt %. The B-side precursor comprised polyol (Tone 0301) 60 wt % and microspheres 30%. Phosphoric acid was 10%. Spheres are hand-stirred into the polyol until a smooth consistency was obtained. The microspheres and polyol are blended by hand stirring. The phosphoric acid was hand-stirred into the microspheres and polyol mix. An A-side precursor to B-side precursor ratio of 1:1 was used and contacted in a static tube mixer to produce a foam. The A to B ratio can, however, range from 1:1 to 4:1 depending on acid concentration.



EXAMPLE 9B

[0071] This Example employed a two phase system wherein the A-side precursor comprised a gel. A two phase system, namely an A-side precursor and B-side precursor, was used to produce a foam. The A-side precursor comprised an epoxy (UCB-Radcure UVACure 1500) 59 wt %, polypropylene powder (Equistar FP 800-00) 20 wt %, polyvinyl alcohol (Airvol 203S) 20 wt % and surfactant (gelling agent) at 1 wt %. The B-side precursor comprised polyol (Tone 0301) 60 wt % and microspheres 30%. Phosphoric acid was 10%. Spheres are hand-stirred into the polyol until a smooth consistency was obtained. The microspheres and polyol are blended by hand stirring. The phosphoric acid was hand-stirred into the microspheres and polyol mix. An A-side precursor to B-side precursor ratio of 1:1 was used and contacted in a static tube mixer to produce a foam. The A to B ratio can, however, range from 1:1 to 4:1 depending on acid concentration.



EXAMPLE 10

[0072] A bag or containment device approximately 8×8 inches in size and having a one-way valve located on one end of the bag was constructed from two sheets of high density polyethylene film. The seams of the bag were designed to rupture at specific locations, which directs foam expansion into cavity area adjacent to weak seams. The sheets were joined by heating on a TEW Electric Heating Company Ltd sealing apparatus. The seams were selectively reinforced by double sealing or weakened to provide multiple points for foam direction from the same bag. The foam composition demonstrated by Example 9 was introduced into this bag. As the foam expanded, the foam escaped from the bag through the relatively weak seams.



EXAMPLE 11

[0073] A bag or bladder composed of each of polyethylene, ethylene vinyl acetate, polybutadiene were fabricated by using the apparatus described in Example 10. The foam of Example 9 was introduced into these bags. The bags, having a melting point less than the exothermic reaction temperature of the foam, failed and released the foam.



EXAMPLE 12

[0074] A bag or bladder composed of each of modified EVA (Bynel®), modified polyethylene (Primacor® supplied by Dow Chemical Company), modified butadiene, glycidal methacrylate (GMA) were fabricated by using the apparatus of Example 10. The foam of Example 9 was introduced into these bags. The heat released from the exothermic reaction of the foam caused the bags to melt. The melting bag material adhered to the foam thereby modifying the surface of the foam. The melting bag also adhered the foam to any surrounding surfaces or articles.



EXAMPLE 13

[0075] A bag or bladder composed of each of polypropylene, polyethylene, woven nylon mesh, aluminized fiberglass mesh was fabricated by using the apparatus of Example 10. Each of the bags was further processed to possess multiple perforations (25-100 holes/in.). The foam of Example 9 was introduced into each of these bags. The perforations allowed the foam to escape in controlled quantities while also generally retaining the shape of the bag.



EXAMPLE 14

[0076] Two bags or bladders, namely an inner and outer bag were fabricated by using the apparatus of Example 10. The inner bag comprised modified butadiene and the outer bag comprised high density polyethylene. The inner bag was placed within the outer bag and the outer bag was sealed. The foam of Example 9 was introduced into the inner bag. Inner bag or bladder melted during the foam reaction. The inner bag was of sufficient size to contain the required amount of mixed foam precursors to fill the out bag. Outer bag construction was of material and size to contain reaction within the cavity.



EXAMPLE 15

[0077] The insertion loss or sound dampening characteristics of the foam produced in accordance with Example 9A was tested in accordance with Society of Automotive Engineers (SAE) J1400. The sample size was 3×3×10 inches and placed within an E-coated metal channel. An increase in insertion loss corresponds to an increase in sound dampening properties that in turn corresponds to less noise within the passenger compartment of an automobile.
2FREQ. (Hz)INSERTION LOSS (dB)12512.516010.620011.425012.031524.540035.450046.863038.480040.1100045.7125045.1160049.6200049.2250050.1315050.9400055.5500058.7630059.2800064.2


[0078] These data illustrate the desirable sound absorbing characteristics of the inventive foam compositions.



EXAMPLE 16

[0079] The viscosity of the Part A foam precursor fabricated in accordance with Example 9A was tested in accordance with conventional methods and apparatus (Brookfield Viscometer, Spindle 27, Thermal-Cell). The of temperature is listed below.
3RPMTemp 75 F.Temp 110 F.Temp 150 F.0.513,000 8,0003,000110,500 5,5002,5002.58,1603,4001,60056,6802,3001,100105,7001,800800204,8301,480600503,9001,2504681003,2801,100404


[0080] The viscosity of the Part B foam precursor fabricated in accordance with Example 9A was tested in accordance with conventional methods and apparatus (Brookfield Viscometer, Spindle 27, Thermal-Cell). The function of temperature is listed below.
4RPMTemp 75 F.Temp 110 F.Temp 150 F.0.522,00013,000 4,000120,00010,000 2,5002.518,6007,0001,600517,8005,3201,3001017,3004,5001,100204,000975503,7008801003,580860



EXAMPLE 17

[0081] This Example illustrates foam formation as a result of being activated by exposure to an energy source, e.g, UV light. A radiation curable foam having the following components was prepared:
5COMPONENTTRADE NAMESUPPLIERAMOUNTCycloaliphatic epoxyUVACURE 1500Radcure50wt. %Caprolactone polyolTone 0301Union Carbide40Blowing agentExpancel DU551Expancel Inc.9Sulfonium saltUVI-6974Union Carbide1


[0082] The above components were combined as follows. The Uvacure and polyol were added together in a mixing vessel and mixed until the solution was clear. The UVI 6974 was added to the mixture, and mixed until substantially completely dispersed (about 2 minutes). The Expancels spheres were added to the mixture and mixed until substantially lump free. For best results, the minimum amount of mixing time, and shear were


[0083] The foam precursors were placed onto a conveyor and exposed to a source of UV light. The method for precursors to UV light is described in the previously identified U.S. patent application Ser. No. 09/197,107, filed Nov. 20, 1999, both filed in the name of Jeffrey Pachl et al., and entitled “Curable Selant Composition”.


[0084] This UV activated foam was modified by adding an acrylic monomer or acrylated oligomer. This modified UV activated foam was prepared as described above and comprised:
6COMPONENTTRADE NAMESUPPLIERAMOUNTAcrylatedIRR 84UCB RADCURE93.5wt. %oligomerAcid functionalOligomerEbecryl 170UCB RADCURE0.9PhotoinitiatorDarocure 1173Ciba-Giegy0.9Blowing AgentF30D-MicropearlsPierce & Stevens4.7


[0085] The resultant foam possessed a pressure sensitive adhesive characteristic. The tacky pressure sensitive characteristic was removed by adding an acrylate compound. A tack-free formulation comprised:
7COMPONENTTRADE NAMESUPPLIERAMOUNTAcrylatedIRR 84UCB RADCURE92.6wt. %oligomerAcid functionalOligomerEbecure 170UCB RADCURE0.9PhotoinitiatorDarocure 1173Ciba-Giegy0.9Blowing AgentF30D-MicropearlsPierce & Stevens4.7AcrylateSartomer 444Sartomer0.9


[0086] The later two formulations were also activated by being exposed to natural light.



EXAMPLES 18-22 AND 25

[0087] The following Table lists the Components, Trade Names and Suppliers for the foam precursors that were employed in Examples 18 through 22 and 25. The foam in Examples 18-22 was prepared by contacting the Part A with the Part B listed in the tables below in a 2.75″ diameter by 1.92″ height ointment can and mixed by hand. Reaction Time and Temperature were determined in accordance with conventional methods. The percent vertical expansion as well as the shrinkage was determined visually. The Shore A test was conducted using a Type A-2 Shore Durometer Hardness test unit that meets ASTM D2240 requirements. The Shore A test was conducted about 4 hours after foam formation. The instantaneous peak reading was recorded.
8Trade NameComponentSupplierEpon 862Bis F/EpichlorohydrinShell Chemical Co.Epoxy ResinExpancelBlowing Agent (thermal)Expancel, Inc091 DU8O(244F)ExpancelBlowing Agent (thermal): 2-methylExpancel, Inc.051DU (223F)2-propenoic acid methyl esterpolymer with 2-propenenitrile andisobutane is the blowing agentExpancelBlowing Agent (thermal): 2-methylExpancel, Inc.054WU (257F)2-propenoic acid methyl esterpolymer with 2-propenenitrile andisopentane is the blowing agentExpancelBlowing Agent (thermal): 2-methylExpancel, Inc.461DU (208F)2-propenoic acid methyl esterpolymer with 1,1-dichloroetheneand 2-propenenitrile and isobutaneis the blowing agentExpancelBlowing Agent (thermal): 2-methylExpancel, Inc.551WU (199F)2-propenoic acid methyl esterpolymer with 1,1-dichloroetheneand 2-propenenitrile and isobutaneis the blowing agentExpancelBlowing Agent (thermal): 2-methylExpancel, Inc.551 WU802-propenoic acid methyl esterpolymer with 1,1-dichloroetheneand 2-propenenitrile and isobutaneis the blowing agentExpancelBlowing Agent (thermal): 2-methylExpancel, Inc.642WU (183F)2-propenoic acid methyl esterpolymer with 1,1-dichloroetheneand 2-propenenitrile and isobutaneis the blowing agentExpancelBlowing Agent (thermal): 2-methylExpancel, Inc.820DU (167F)2-propenoic acid methyl esterpolymer with 1,1-dichloroetheneand 2-propenenitrile and isobutaneis the blowing agentExpancelBlowing Agent (thermal): 2-methylExpancel, Inc.820WU (167F)2-propenoic acid methyl esterpolymer with 1,1-dichloroetheneand 2-propenenitrile and isobutaneis the blowing agentHeloxy 505Epichlorohydrin Castor Oil BasedShell Chemical Co.Epoxy Resin (aliphatic triglyceridetriglycidyl ether)SR 2391,6 Hexanediol DimethacrylateSartomerSR 495Caprolactone AcrylateSartomerVertrel XFBlowing Agent: 2,3-Dihydroper-DuPontfluoropentane (Pentane,1,1,1,2,3,4,4,5,5,5-decafluoro:CF3CHFCHFCF2CF3)MicropearlsBlowing Agent (thermal): iso-HM RoyalF30Dbutane encapsulated in polymer(Pierce & Stevens)vinylidene chlorideEbecryl 170Adhesion Promoter: AcrylateUCB Radcuremodified acidic adhesionpromoting agentAmicureDicyandiamideAir ProductsCG1400Glycolic AcidTechnical grade (70%)DuPont(70% Tech)H3PO4concentrated grade via distillationDeNOVUS(>95% conc.)of the 75% technical grade fromHarcros ChemicalHQ54merchant grade (73%)PCSAmberphos-54merchant grade (75%)PCS(AMMGA)H3PO4 reagent grade (85%)Fischer Scientific(85% Reagent)H3PO4 technical grade (75%)Harcros Chemicals(75% technical)H3PO4 technical grade (85%)FMC/Harcros(85% technical)ChemicalsBTL 71001Elastomer: EVA powderBTLSR ToledoMU 760-00Elastomer: EVA powder: MI = 23:EquistarMP = 187 F.: VA = 19:Particle Size = 35 meshMicrotheneElastomer: HDPE powder:MillenniumFA 700-00MI = 10.5: MP = 273 F.:Particle Size = 20 micronsMicrotheneElastomer: LDPE powder:MillenniumFN 514-00MI = 70: MP = 216 F.:Particle Size = 20 micronsMicrotheneElastomer: Polypropylene powder:EquistarFP 800-00MP = 325 F.: Particle Size = 20micronsLIR 403Elastomer: Rubber: (polyisopreneKuraray Coliquid rubber)Kraton D1107Elastomer: SIS rubber pelletsShell Chemical CoQ325Calcium carbonateJ M Huber CorpQuikreteConcrete mixQuikrete Co.DicaperlHollow ceramic spheresGrefco IncCS-10-200Qcel 650-DInorganic microspheresPQ CorporationSynPro LiLi stearateFerroStearateA-C 6702Oxidized polyethyleneAllied SignalAirvol 203SPolyvinyl Alcohol (PVOH)Air ProductsGSodium silicatePQ CorporationBTL 74001Versatic acid ester/polyvinylBTLSR Toledoacetate esterAZO 77Zinc oxideMorton MeyerIsopropylAlcoholCommercialAlcohol (70%)EthanolAlcohol: Pure Grain AlcoholCommercialIrcosperse 2174DispersantLubrizolCarbopol EZ-1Emulsion ThickenerB F Goodrich#1 Castor OilOilAcme-HardestyLucantOil: Hydrocarbon based syntheticMitsui ChemicalHC-2000oilVasolinePetroleum JellyChesebrough-PondsIndopol L100PolybuteneAmocoUnifilmRheology Control AgentTroy Chemical100HSMZ6040SilaneDow CorningZ6124Silane: Arylalkoxy silaneDow CorningDish SoapSoapCommercialBoraxoSoap: Sodium tetraboraxDial CorpdecahydrateTriton X45SurfactantUnion CarbideTexaphorSurfactant: Anionic SurfactantHenkelSpecialKRTTSTitanateKenrichSantolinkAllyl glycidyl ether alcohol resinSolutia/MonsantoXI-100SB 400Aromatic acid methacrylate-mixedSartomerhalf esterPliolite ACCopolymer: (styrene-acrylate:Goodyearpowder)Pliolite S-5ACopolymer: (styrene-butadiene:Goodyearpowder)CMD 50859Epoxy:Shell Chemical CoCMD 8750Epoxy:Shell Chemical CoPEP 6180Epoxy: (epoxy toughener: hydrog-Pacific Epoxyenated Bis A:)PEP 6210 PAEpoxy: (epoxy toughener: poly-Pacific Epoxyether adduct, epoxy functionality:EEW = 210: visc = 500 cps)Erisys GE-60Epoxy: (sorbitol glycidyl ether -CVC Specialtyaliphatic polyfunctional epoxy):Chemicalsliquid: EEW = 170: visc = 13,000cpsEpalloy 5000Epoxy: Bis A: (epoxidizedCVC Specialtyhydrogenated Bis A resin): EEW =Chemicals220: visc = 1900 cpsDER 317Epoxy: Bis A: liquidDow ChemicalDER 331Epoxy: Bis A: liquidDow ChemicalDER 736Epoxy: Bis A: liquidDow ChemicalEpon 828Epoxy: Bis A: liquidShellUvacure 1500Epoxy: cycloaliphaticUCB RadcureUvacure 1502Epoxy: cycloaliphaticUCB RadcureUvacure 1533Epoxy: cycloaliphaticUCB RadcureCryacure UVREpoxy: cycloaliphaticUnion Carbide6128K126Epoxy: cycloaliphatic:Sartomer(cycloaliphatic diepoxide)Eponex 1510Epoxy: cycloaliphatic:Shell Chemical Co(cycloaliphatic glycidyl ether):(hydrogenated DGEBPA)Erisys GE-22Epoxy: cycloaliphatic:CVC Specialty(difunctional cycloaliphatic):Chemicals(cyclohexanedimethanol diglycidylether): EEW = 155: visc = 60 cpsUvacure 1534Epoxy: cycloaliphatic:UCB Radcurecycloaliphatic epoxypolyol blendErisys GE-35Epoxy: Glycidyl ether of castor oilCVC SpecialtyChemicalsEpon SU2.5Epoxy: NovolacShellEpalloy 8240Epoxy: Novolac: (epoxidizedCVC Specialtyphenol novolac: liquid): EEW =Chemicals170: visc = 6550 cps: fnc = 2.35Epon 58005Epoxy: rubber modified:B F Goodrich(40% CTBN)ErisysEpoxy: rubber modified:CVC SpecialtyEMRM-22(CTBN modified epoxy)ChemicalsTone ECMonomer: Lactone: 2-oxepanoneUnion Carbide(6-hydroxyhexanoic acid-e-lactone)Santicizer 261Plasticizer: Alkyl Benzyl PhthalateSolutiaSanticizer 278Plasticizer: Alkyl Benzyl PhthalateSolutiaSanticizer 160Plasticizer: Butyl Benzyl PhthalateSolutiaSanticizer 97Plasticizer: Dialkyl AdipateSolutiaSanticizer 141Plasticizer: Flame Retardant:Solutia2-ethyl Diphenyl PhosphateCAPA 316PolyolSolvay Interox LtdTone 0201Polyol: (caprolactone-based polyol:Union Carbidediol): Hydroxyl # = 212:Tone 0301Polyol: (caprolactone-based polyol:Union Carbidetriol): Hydroxyl # = 560:visc −225 @ 55 C.Arcol E-351Polyol: (polyether polyol: cappedArco Chemical Codiol): Hydroxyl # = 40: visc =507 CpArcol DP-1022Polyol: (polyether polyol: diol):Arco Chemical CoHydroxyl # = 1200: visc = 175 cPPPG-425Polyol: (polyether polyol: diol):Arco Chemical CoHydroxyl # = 263: visc = 71 cpsAcclaimPolyol: (polyether polyol: monolArco Chemical CoPolyol 4220diol):AcclaimPolyol: (polyether polyol: monolArco Chemical CoPolyol 6300triol): Hydroxyl # = 28: visc =1452 cP: fnc = 2.94: acid value =0.01Arcol LG-650Polyol: (polyether polyol: triol):Arco Chemical CoHydroxyl # = 650: visc = 1059 cPEbecryl 81Polyol: Modified polyester polyolRadcureK-Flex 188Polyol: Polyester Polyol:King IndustriesDesmophenPolyol: Short chained polyol:BayerL-951Hydroxyl # = 265Hycar 1300 ×RubberB F Goodrich40 HycarRubber: (CTBN acrylonitrile liquidB F Goodrich1300 × 13rubber)Nipol 1312Rubber: (liquid nitrile rubber)Zeon ChemicalCN 301Rubber: (methacrylated polybuta-Sartomerdiene)R45HTRubber: (PBD hydroxylElf Atochemterminated)Actipol E-16Rubber: Activated polybutene:Amoco(Epoxidized polybutene): LiquidTrilene M-101Rubber: Epoxidized EPDMUniroyalPBD 605Rubber: Hydroxyl terminated PBDElf AtochemKraton L-2203Rubber: Hydroxyl terminated polyShell Chemical Co(ethylene/butylene) polymer: DiolRicon 100Rubber: Styrene PBD: LiquidRicon ResinsRicon 184Rubber: Styrene PBD: LiquidRicon ResinsSAT 010SilylKanekaSAT 030SilylKanekaSAT 200SilylKanekaVertrel XF2,3-DyhydroperfluoropentaneDuPont(Pentane, 1,1,1,2,3,4,4,5,5,5-decafluoro: CF3CHFCJFCF2CF3)MicropearlsThermal Blowing Agent: isobutaneHM RoyalF30Dencapsulated in polymer vinylidene(Pierce & Stevens)chloride


[0088] The following terms and definitions are referenced in Examples 18-22.


[0089] Tin Ointment Can: Dimensions 2.75″ d×1.92″ h


[0090] Initial R×n Time: Time that initial expansion is observed (includes mix time, does noe include time to pour part A into part B


[0091] Final R×n Time: Time for reaction to go to completion (includes “Initial R×n Time”)


[0092] R×n Temp: The peak temperature observed during the reations


% Ht Expansion: % HE=[(hf−hi)/hi]×100


[0093] Density: Weight of 1 in3 block of the expanded material (g/in3)


[0094] H2O Absorption 1: 100×(W3-W2)/(W2-WC): WC=weight of aluminum coupon only W2=weight of coupon+material before submerging in water W3=weight of coupon+material after submerging in water: Mix material, apply to a 3″×3″ aluminum coupon, allow to cool to room temperature, submerge in water for 24 hrs, wipe off excess and immediately calculate water absorption.


[0095] H2O Absorption 2: Take a 1.5 inner diameter×h Polyvinyl chloride (PVC) pipe: use Daubert #2-76GSM paper as the release liner inside the PVC pipe (use some means to cap the bottom so that material does not exude out): mix part A & B and pour into the pipe and allow to expand and cure: cool to room temperature: cut 1.5″ lenghts so that the sample size is ≈1.5″ D×1.5″ h: sand the edges: submerge in water for 24 hrs: remove the sample, wipe off excess water and immediately calculate % water absorption. % Water Absorption=100 ×(WF−WI)/WI


[0096] H2O Absorption 3: “Open Chunk”: Mix part A & B in a polystyrene plastic cup: allow to expand and cure: cool to room temperature: Cut a “chunk” of foam from the top surface: submerge in water for 24 hrs: remove the sample, wipe off excess water and immediately calculate % water absorption: % Water Absorption=100×(WF−WI)/WI


[0097] Hardness: Shore A: The foam surface may be irregular: Take highest instantaneous reading from top surface after conditioning at room temperature for 4 hrs minimum


[0098] Shrinkage: Rating: 0=none 1=<1 mm from edge 2=1-2 mm from edge 3=2-3 mm from edge 4=3-4 mm from edge 5=4-5 mm from edge 6=5-6 mm from edge (shrinkage is usually not symmetrical: take the largest gap and divide by 2 if it did not shrink equally from the outer perimeter. Other values listed will visually results: Rating 1=very slight, Rating 2=noticeable, Rating 3 & 4=significant, Rating 5 & 6 significant



EXAMPLE 18

[0099]

9














Components
SAMPLE NO












Wt. %
1
2
3
4
5





Part A


Uvacure 1500
30
30
30
30
30


Microthene
10
10
10
10


FP800-00


Airvol 203 S
10
10
10
10
10


(PVOH)


Dicaperl CS-




10


10-200


Part B


Tone 0301
29.65
29.65
29.65
29.65
29.65


(Polyol)


Micropearls
14.85
10
12
16
14.85


F30D


H3PO4
5.5
5.5
5.5
5.5
5.5


(Reagent:85%)


Rxn Time
59 sec
57 sec
56
57 sec
53 sec


Rxn Temp
288 F.
291 F.
289 F.
265 F.
292 F.


% Vertical
487%
413%
434%
468%
482%


Expansion


Hardness -
20
19
20
21
17


Shore A


Shrinkage
None
None
None
None
Very Slight













Components
SAMPLE NO













Wt. %
6
7
8
9







Part A



Uvacure 1500
30
20
30
30



Microthene
10
10
10



FP800-00



Airvol 203 S
10
10
10
10



(PVOH)



Hycar
10



1300 × 13



PEP 6180

10
5



Part B



Tone 0301
29.65
29.65
29.65
29.65



(Polyol)



Micropearls
14.85
14.85
14.85
14.85



F30D



H3PO4
5.5
5.5
5.5
5.5



(Reagent:85%)



Rxn Time
65 sec
64 sec
58 sec
61 sec



Rxn Temp
265 F.
238 F.
289 F.
270 F.



% Vertical
385%
205%
404%
528%



Expansion



Hardness -
22
23
26
18



Shore A



Shrinkage
Noticeable
Noticeable
Very Slight
Very Slight












Components
SAMPLE NO












Wt. %
10
11
12
13
14





Part A


Uvacure 1500
30
30
20
30
30


Microthene


10
10


FP800-00


Airvol 203 S
20
10
10
10
10


(PVOH)


Microthene

10


10


FN514-00


DER317


10


Microthene




10


FA700-00


Part B


Tone 0301
29.65
29.65
29.65
20
29.65


(Polyol)


Micropearls
14.85
14.85
14.85
14.85
14.85


F30D


H3PO4
5.5
5.5
5.5
5.5
5.5


(Reagent:85%)


CN 301



9.65


Rxn Time
55 sec
50 sec
56
40 sec
51 sec


Rxn Temp
276 F.
274 F.
242 F.
268 F.
277 F.


% Vertical
494%
396%
226%
361%
388%


Expansion


Hardness -
16
23
22
42
22


Shore A


Shrinkage
None
Very Slight
Very Slight
Very Slight
Very Slight













Components
SAMPLE NO













Wt. %
15
16
17
18







Part A



Uvacure 1500
30
30
30
15



Microthene



10



FP800-00



Airvol 203 S
10
10
10
10



(PVOH)



Equistar MU
10



76000



AC 6702

10



BTL 71001


10



Cryacure UVR



15



6128



Part B



Tone 0301
29.65
29.65
29.65
29.65



(Polyol)



Micropearls
14.85
14.85
14.85
14.85



F30D



H3PO4
5.5
5.5
5.5
5.5



(Reagent:85%)



CN 301



Rxn Time
55 sec
50 sec
49 sec
56 sec



Rxn Temp
271 F.
280 F.
292 F.
259 F.



% Vertical
406%
415%
519%
326%



Expansion



Hardness -
19

19
15



Shore A



Shrinkage
Very Slight
Very Slight
None
Very Slight












Components
SAMPLE NO












Wt. %
19
20
21
22
23





Part A


Uvacure 1500
30
30
30
30
30


Microthene
10
10
10
10
10


FP800-00


Airvol 203 S
10

10
10
10


(PVOH)


Quickrete

20


Concrete Mix


DER 331




10


Part B


Tone 0301
29.65
29.65
29.65
29.65
29.65


(Polyol)


Micropearls

14.85


14.85


F30D


H3PO4
8
5.5
5.5
5.5
5.5


(Reagent:85%)


Expancel
14.85


091DU80


Expancel


14.85
14.85


642WU


Rxn Time

52 sec
55 sec
52 sec
54 sec


Rxn Temp
298 F.
282 F.
289 F.
285 F.
270 F.


% Vertical
183%
282%
460%
450%
378%


Expansion


Hardness -
75
18
10
12
43


Shore A


Shrinkage
None
Very Slight
Very Slight
None
Noticeable













Components
SAMPLE NO













Wt. %
24
25
26
27







Part A



Uvacure 1500
30
20
30
30



Microthene
10
10
10



FP800-00



Airvol 203 S
10
10
10
10



(PVOH)



Epalloy 8240

10



Q325



10



Part B



Tone 0301

29.65
29.65
29.65



(Polyol)



Micropearls
14.85
14.85

14.85



F30D



H3PO4
5.5
5.5
5.5
5.5



(Reagent:85%)



Acclaim 6300
29.65



Expancel


7.5



051DU



Rxn Time
46 sec
55 sec
72 sec
50 sec



Rxn Temp

278 F.
323 F.
274 F.



% Vertical
206%
388%
219%
570%



Expansion



Hardness -
23
39
53
21



Shore A



Shrinkage
None
Noticeable
Very Slight
Noticeable












Components
SAMPLE NO












Wt. %
28
29
30
31
32





Part A


Uvacure 1500

30
30
30
30


Microthene
10
10
10
10


FP800-00


Airvol 203 S
10
10
10
10
10


(PVOH)


Sartomer K126
30


Epon 58005


10


DER736



10


Sodium




10


Silicate


Part B


Tone 0301
29.65
29.65
29.65
29.65
29.65


(Polyol)


Micropearls
14.85

14.85
14.85
14.85


F30D


H3PO4
5.5
5.5
5.5
5.5
5.5


(Reagent:85%)


Expancel

14.85


820DU


Rxn Time
50 sec
50 sec
54 sec
61 sec
58 sec


Rxn Temp
285 F.
296 F.
273 %
271 F.


% Vertical
483%
410%
396%
374%
410%


Expansion


Hardness -
20
32
34
30
10


Shore A


Shrinkage
None
Noticeable
Noticeable
Significant
Significant













Components
SAMPLE NO













Wt. %
33
34
35
36







Part A



Uvacure 1500
30
30
30
30



Microthene

10
10
10



FP800-00



Airvol 203 S
10
10
10
10



(PVOH)



Q Cel 650-D
10



Texaphor

4



Special



Blue Dish


2



Wish Soap



Part B



Tone 0301
29.65
29.65
29.65



(Polyol)



Micropearls
14.85
14.85
14.85
14.85



F30D



H3PO4
5.5
5.5
5.5
5.5



(Reagent:85%)



Expancel



820DU



E-351 Polyol



29.65



Rxn Time
49 sec
68 sec
71 sec
40 sec



Rxn Temp
294 F.

281 F.
295 F.



% Vertical
445%
530%
502%
302%



Expansion



Hardness -
18
13
23
38



Shore A



Shrinkage
None
Very Slight
None
None












Components
SAMPLE NO












Wt. %
37
38
39
40
41





Part A


Uvacure 1500
30
30
30
30
30


Microthene
10
10
10
10
10


FP800-00


Airvol 203 S
10
10
10

10


(PVOH)


Shell CMD


5


50809


Z6124



2


Part B


Tone 0301


29.65
29.65
29.65


(Polyol)


Micropearls
14.85
14.85
14.85
14.85
14.85


F30D


H3PO4
5.5
5.5
5.5
5.5
5.5


(Reagent:85%)


Sartomer SB
29.65


400


LIR 403

14.65


Santolink XI-

15


100


75% Isopropyl




9.65


Alcohol


Rxn Time
37 sec
32 sec
55 sec


Rxn Temp
292 F.

305 F.


% Vertical
345%
188%
462%
561%
638%


Expansion


Hardness -
39
45
32
15
3


Shore A


Shrinkage
Noticeable
None
Very Slight
None
Very Slight













Components
SAMPLE NO













Wt. %
42
43
44
45







Part A



Uvacure 1500

30
30
25



Microthene
10
10
10
10



FP800-00



Airvol 203 S
10
10
10
10



(PVOH)



Uvacure 1502
30



Expancel


14.85



461DU



Epon 1510



5



Part B



Tone 0301
29.65
14.65
29.65
29.65



(Polyol)



Micropearls
14.85
14.85

14.85



F30D



H3PO4
5.5



(Reagent:85%)



Santolink XI-

15



100



Amberphos-54

6.5
6.5
6.5



Rxn Time
67 sec
45 sec
51 sec
82 sec



Rxn Temp
282 F.

291 F.



% Vertical
450%
440%
340%
334%



Expansion



Hardness -
25
43
35
43



Shore A



Shrinkage
None
Very Slight
None
Noticeable














Components
SAMPLE NO













Wt. %
46
47
48
49







Part A



Uvacure 1500
30
30
30
30



Microthene
10
10



FP800-00



Airvol 203 S
10
10



(PVOH)



Erisys GE-60

10



SAT 200


20



(silyl)



Kraton D1107



5



Part B



Tone 0301
20



(Polyol)



Micropearls
14.85
14.85
14.85
14.85



F30D



Amberphos-54
6.5



#1 Castor Oil
9.65



Arcol LG-650

29.65



HQ54 (73%

6.5
6.5



H3PO4)



Arcol DP-


29.65
29.65



1022



H3PO4 (75%



6.5



technical



grade)



Rxn Time
47 sec
110 sec
101 sec
83 sec



Rxn Temp
287 F.

289 F.



% Vertical
364%
350%
458%
620%



Expansion
364%



Hardness -
32
25
9
7



Shore A



Shrinkage
Very Slight
Very slight
Noticeable
Significant












EXAMPLE 19

[0100]

10















Components
Sample
Sample
Sample
Sample


wt. %
No. 1
No. 2
No. 3
No. 4



















Part A






Uvacure 1500
30
30
30
30


Microthene
10
10
10
10


FP 800-00


Airvol 203 S
10
10
10
10


(PVOH)


Part B


Tone 0301


(Polyol)


Micropearls
14.85
14.85
14.85
14.85


F30D


Amberphos-54
6.5
6.5
6.5
6.5


(AMMGA)


Tone 0201
14.65
20
9.65


Santolink
15
9.65
20


XI-100


Arcol DP-1022



29.65


Initial Rxn
27 sec
24 sec

63 sec


Time


Initial Rxn
204 F.


201 F.


Temp


Rxn Time
42 sec
35 sec

99 sec


Rxn Temp






% Vertical
293%
277%
249%
550%


Expansion


Hardness -
55
59
53
4


Shore A


Shrinkage
Significant
Significant
Noticeable
Noticeable



(>2 mm
(>2 mm
shrinkage
shrinkage



<4 mm
(<4 mm
(>1 mm
(>1 mm



from edge of
from edge of
<2 mm from
<2 mm from



tin cup) after
tin cup) after
edge of tin
edge of tin



cooling to
cooling to
cup) after
cup) after



RT
RT
cooling to
cooling to





RT
RT











EXAMPLE 20

[0101]

11



















Component wt %
Sample No. 1
Sample No. 2
Sample No. 3
Sample No. 4
Sample No. 5
Sample No. 6





Part A


Uvacure 1500
30
30
30
30
40
34.46


Nipol 1312


15
15


Lucant HC-2000
15


Carbopol EZ-1

5


Microthene FP800-00

10


Microthene FN-514-00




20
12.75


Kraton D1107





3.79


Part B


Arcol PPG-425
20

15
10
20


Micropearls F30D
14.85

14.85
14.85
14.85
14.85


75% H3PO4 (tech)
6.5

6.5
6.5
6.5
6.5


Jeff P. Control Part B

50


Arcol DP-1022


5
10


Tone 0301





14.65


Santolink XI-100





15


Initial Rxn Time
40 sec
34 sec
51 sec
50 sec
51 sec
29 sec 31 sec


Final Rxn Time
50 sec
52 sec
65 sec
65 sec
73 sec
70 sec 65 sec


% Ht Expansion
390%
423%
387%
310%
292%
374%


Water Absorption
81% 75%
31% 33%
73% 98%
46% 58%
19% 28%
18% (matl








chunk)


Shore A Hardness
27
28
32
33
62
38


Shrinkage
0
0
≈5.5 mm
≈7 mm
2 mm
2 mm













Sample No.














Component wt %
Sample No. 7
Sample No. 8
Sample No. 9
Sample No. 10
11
Sample No. 12





Part A


Uvacure 1500
30.4
34.46
34.46
50.7
50.7
27.9


Kraton D1107
3.34
3.79
3.79
5.6
5.6
3.1


Microthene FN514-00
11.26
12.75
12.75
18.8
18.8
10.3


Part B


Tone 0301
14.65


Santolink XI-100
15


Micropearls F30D
14.85
14.85
11.6
14.85
14.85
14.85


75% H3PO4 (tech)
6.5
6.5
5.1
6.5
12.5
6.5


Arcol PPG-425





20


Arcol DP-1022

29.65
23.3
29.65
29.65


Initial Rxn Time

83 sec
96 sec
101 sec
28 sec
41 sec


Final Rxn Time

107 sec
132 sec
136 sec
42 sec
58 sec


% Ht Expansion
432%
398%
368%
252%
313%
402%


Density (g/in3)


Water Absorption


Shore A Hardness
36
13
18
28
24
46


Shrinkage
1 mm
1 mm
3 mm
5 mm
1 mm
0.5 mm
















Sample No.
Sample No.
Sample No.

Sample No.













Component wt %
13
14
15
Sample No. 16
17
Sample No. 18





Part A


Uvacure 1500
40.5
40.5
40.5
46.29
46.29
40


Microthene FN-514-00
4.5
4.5
4.5
8.57
8.57


Kraton D1107
15
15
15
5.14
5.14


Nipol 1312





15


Part B


Arcol PPG-425
20
20
20
20
20
20


Micropearls F30D
14.85
24.85
24.85
24.85
24.85
24.85


75% H3PO4 (tech)
6.5
8.5
8.5
8.5
8.5
8.5


Glycolic Acid (70% tech)


6

6


Initial Rxn Time
46 sec
34 sec
33 sec
27 sec
27 sec
32 sec


Final Rxn Time
58 sec
48 sec
49 sec
40 sec
39 sec
46 sec


% Ht Expansion
317%
377%
480%
405%
395%
508%


Density (g/in3)


Water Absorption

115% 142%
116% 174%
59% 131%
443% 409%
131% 160%


Shore A Hardness
63
42
13
29
13
25


Shrinkage
4 mm
0.5 mm
0.5 mm
1.5 mm
1 mm
1 mm

















Sample No.
Sample No.
Sample No.

Sample No.














Component wt %
19
20
21
Sample No. 22
23
Sample No. 24





Part A


Uvacure 1500
40
40
40
40
40
35


Microthene FN-514-00


Kraton D1107


Nipol 1312
15
15
15
15
15
15


Carbopol EZ-1

5
5


Epon CMD 50859





5


Part B


Arcol PPG-425
20
20
20
20
20
20


Micropearls F30D
24.85
24.85
24.85
24.85
24.85
24.85


75% H3PO4 (tech)
8.5
8.5
8.5
8.5
8.5
8.5


Glycolic Acid (70% tech)
6

3


#1 Castor Oil



8


Z6040




1


Initial Rxn Time
30 sec
30 sec
25 sec
33 sec
36 sec
37 sec


Final Rxn Time
42 sec
41 sec
39 sec
59 sec
57 sec
52 sec


% Ht Expansion
382%
402%
417%
421%
455%
432%


Density (g/in3)


Water Absorption

144% 133%
152% 162%
66% 55%
105% 108%
99% 129%








(open chunk:137%)


Shore A Hardness
18
24
17
23
29
23


Shrinkage
3 mm
0 mm
1.5 mm
0 mm
0.5 mm
0 mm

















Sample No.
Sample No.
Sample No.

Sample No.














Component wt %
25
26
27
Sample No. 28
29
Sample No. 30





Part A


Uvacure 1500
40
40
40
40
40
40


Microthene FN-514-00


Kraton D1107


Nipol 1312
15


SAT 030

15
15
15
15


CN 301





15


Part B


Arcol PPG-425

20
20
20
20
20


Micropearls F30D
24.85
24.85
24.85
24.85
24.85
24.85


75% H3PO4 (tech)
8.5
8.5
8.5
8.5
8.5
8.5


Arcol Acclaim 6300
20


#1 Castor Oil


8
15

8


Tone EC Monomer




10


Initial Rxn Time
36 sec
38 sec
50 sec
61 sec
54 sec
42 sec


Final Rxn Time

56 sec
74 sec
95 sec
73 sec
60 sec


% Ht Expansion
150%
555%
492%
370%
467%
445%


Density (g/in3)


1.939


Water Absorption

67% 95%
48% 45%
44% 37%
50% 95%
62% 39%




(open chunk:
(open chunk:

(open chunk:
(open chunk:143%)




260%)
49%)

75%)


Shore A Hardness

18
24
20
25
25


Shrinkage
1.5 mm
0 mm
0 mm
0.5 mm
3 mm
0 mm

















Sample No.
Sample No.
Sample No.

Sample No.














Component wt %
31
32
33
Sample No. 34
35
Sample No. 36





Part A


Uvacure 1500
40
40
40
40
40


CN 301

15

15


Uvacure 1534





40


Part B


Arcol PPG-425
20

20
20
20
20


Micropearls F30D
24.85
24.85
24.85
24.85
24.85
24.85


75% H3PO4 (tech)
8.5
8.5
8.5
8.5
8.5
8.5


#1 Castor Oil
8
8
8
8
8
8


CN 301
15

22

15
15


Ebecryl 81

20


Z6040



1.5


KR TTS




1.5


Initial Rxn Time
41 sec
88 sec
38 sec
39 sec
37 sec
163 sec


Final Rxn Time
59 sec
120 sec
55 sec

54 sec
265 + sec


% Ht Expansion
461%
153%
386%
479%
433%


Density (g/in3)


Water Absorption
99% 66%

37% 45%
45% 34%
294% 243%



(open chunk.

(open chunk
(open chunk. 158%)
(open chunk



160%)

151%)

184%


Shore A Hardness
22
72
22
22
22


Shrinkage
0 mm
1 mm
0 mm
0.5 mm
0 mm

















Sample No.
Sample No.
Sample No.

Sample No.














Component wt %
37
38
39
Sample No. 40
41
Sample No. 42





Part A


Uvacure 1500
40
40
40
40
40
50.91


Ricon 100
15




19.09


SAT 030

25


Ricon 184


15
15


Expancel 461DU



10


Actipol E-16




15


Part B


Arcol PPG-425
20
20
20
20
20
20


Micropearls F30D
24.85
24.85
24.85
14.85
24.85
24.85


75% H3PO4 (tech)
8.5
8.5
8.5
8.5
8.5
8.5


#1 Castor Oil
8
8
8
8
8
8


Initial Rxn Time
39 sec
66 sec
39 sec
31 sec
39 sec
43 sec


Final Rxn Time
64 sec
102 sec
63 sec
50 sec
68 sec
72 sec


% Ht Expansion
504%
348%
470%
345%
395%
432%


Density (g/in3)


Water Absorption
77% 79%
26% 43%
84% 93%
60% 63%
71% 90%
105% 72%



(open chunk
(open chunk.
(open chunk:
(open chunk:166%)
(open chunk.
(open chunk:186%)



119%)
121%)
108%)

101%)


Shore A Hardness
26
22
27
30
32
31


Shrinkage
0 mm
0 mm
0 mm
0 mm
0 mm
0.5 mm

















Sample No.
Sample No.
Sample No.

Sample No.














Component wt %
43
44
45
Sample No. 46
47
Sample No. 48





Part A


Uvacure 1500
40
40
40
40
40
40


SAT 030
15

15
15
15
15


Kraton L-2203

15


Erisys GE-35





10


Part B


Arcol PPG-425
20
20
20


20


Micropearls F30D
24.85
24.85
24.85
24.85
24.85
24.85


75% H3PO4 (tech)
8.5
8.5
8.5
8.5
8.5
8.5


#1 Castor Oil
8
8
8
8
8
8


CN 301
15


Santolink XI-100


10


Tone 0301



20
29.65


Initial Rxn Time
52 sec
39 sec
53 sec
31 sec
36 sec
48 sec


Final Rxn Time
84 sec
65 sec
83 sec
49 sec
53 sec
77 sec


% Ht Expansion
275%
431%
350%
480%
502%
395%


Density (g/in3)


Water Absorption
34% 36%
79% 61%
26% 40%
159% 220%
102% 102%
96% 75%



(open chunk:
(open chunk 62
(open chunk:
(open chunk:212%)
(open chunk:
(open chunk. 135%)



119%)
%)
117%)

205%


Shore A Hardness
30
26
27
17
16
25


Shrinkage
0 mm
0 mm
0.5 mm
0 mm
0 mm
0 mm

















Sample No.
Sample No.
Sample No.

Sample No.














Component wt %
49
50
51
Sample No. 52
53
Sample No. 54





Part A


Uvacure 1500
40
40
40
40
40
40


SAT 030
15
15
15
15
15
15


Erisys GE-35
10


Part B


Arcol PPG-425
20
20

20
20
20


Micropearls F30D
24.85
24.85
24.85
24.85
24.85
24.85


75% H3PO4 (tech)
12
8.5
8.5
8.5
8.5
8.5


#1 Castor Oil
8
8
8
8

8


Kraton L-2203

15


Tone 0201


20


Santicizer 261



10
15


Z6124





2


Z6040





1


Initial Rxn Time
29 sec
59 sec
27 sec
51 sec
53 sec
45 sec


Final Rxn Time
50 sec
118 sec
36 sec
67 sec
63 sec
78 sec


% Ht Expansion
410%
317%
422%
263%
225%
458%


Density (g/in3)
1.826


Water Absorption
74% (open
29% 44%
104% 138%
19% 22%
41% 54%
22% 24%



chunk:53% &
(open chunk:
(open chunk
(open chunk:75%)
(open chunk
(open chunk. 180%)



64%)
86%)
133%)

137%)


Shore A Hardness
12
34
30
44
50
23


Shrinkage
0 mm
0.5 mm
2 mm
0 mm
0 mm
0.5 mm

















Sample No.
Sample No.
Sample No.

Sample No.














Component wt %
55
56
57
Sample No. 58
59
Sample No. 60





Part A


Uvacure 1500
40
40
40
40
40
40


SAT 030



15


SAT 010
15


SAT 200

15


PBD 605


15

15
15


Part B


Arcol PPG-425
20
20
20
20
20
15


Micropearls F30D
24.85
24.85
24.85
24.85
24.85
24.85


75% H3PO4 (tech)
8.5
8.5
8.5
8.5
8.5
8.5


#1 Castor Oil
8
8
8
8
8
8


Santicizer 261



5
5
10


Z6124



2
2
2


Z6040



1
1
1


Initial Rxn Time
58 sec
50 sec
40 sec
51 sec
40 sec
29 sec


Final Rxn Time
83 sec
76 sec
80 sec
85 sec
69 sec
39 sec


% Ht Expansion
444%
435%
536%
388%
433%
320%


Density (g/in3)


Water Absorption
44% 60%
96% 105%
25% 27%
65% 53%
32% 33%
115% 105%



(open chunk
(open chunk
(open chunk:
(open chunk:85%)
(open chunk.
(open chunk 197%)



191%)
131%)
34%)

54%)


Shore A Hardness
25
20
24
22
23
19


Shrinkage
0 mm
0 mm
0 mm
0 mm
0.5 mm
0.5 mm

















Sample No.
Sample No.
Sample No.

Sample No.














Component wt %
60
61
62
Sample No. 63
64
Sample No. 65





Part A


Uvacure 1500
40
40
40
40
40
40


PBD 605
15
20
25
15
15
15


Part B


Arcol PPG-425
20
20
20
20
25
20


Micropearls F30D
24.85
24.85
24.85
24.85
24.85
14.85


75% H3PO4 (tech)
8.5
8.5
8.5
8.5
8.5
6.5


#1 Castor Oil
6
6
6
3
8


Santicizer 261
7
7
7
5


Z6124
2
2
2


Z6040
1
1
1


Initial Rxn Time
37 sec
43 sec
43 sec
42 sec
46 sec
48 sec 42 sec


Final Rxn Time
62 sec
74 sec
72 sec
71 sec
86 sec
77 sec 60 sec


% Ht Expansion
411%
357%
337%
493%
423%
475% 486%


Density (g/in3)





2.17


Water Absorption
28% 26%
17% 25%
56% 34%
43% 49%
29% 26%
17% 15%



(open chunk.
(open chunk.
(open chunk
(open chunk 134%)
(open chunk:
(open chunk 14%)



119%)
126%)
121%)

71%)


Shore A Hardness
23
22
18
20
20
29 30


Shrinkage
0.5 mm
0.5 mm
0.5 mm
0.5 mm
0.5 mm
0.8 mm















Component wt %
Sample No. 66
Sample No. 67
Sample No. 68







Part A



Uvacure 1500
40
40
40



PBD 605
15
15
15



Z6040


1



Part B



Arcol PPG-425
20
20
20



Micropearls F30D
24.85
24.85
24.85



75% H3PO4 (tech)
8.5
8.5
8.5



#1 Castor Oil
3
3
3



Santicizer 261
7
7
7



Z6124

2
2



Initial Rxn Time
39 sec
38 sec
41 sec



Final Rxn Time
65 sec
55 sec
56 sec



% Ht Expansion
455%
403%
439%



Water Absorption
57% 72%
131% 130%
107% 88%




(open chunk = 153%)
(open chunk = 160%)
(open chunk = 156%)



Shore A Hardness
28
25
28



Shrinkage
0.5 mm
0.5 mm
1 mm












EXAMPLE 21

[0102]

12


















Sample No.














Component wt %
1
Sample No. 2
Sample No. 3
Sample No. 4
Sample No. 5
Sample No. 6





Part A


Uvacure 1500
32.7
36.4
43.6
40
40
40


PBD 605
12.3
13.6
16.4
20
25
15


Part B


Arcol PPG-425
20
20
20
20
20
20


Micropearls F30D
14.85
14.85
14.85
14.85
14.85
14.85


75% H3PO4 (tech)
6.5
6.5
6.5
6.5
6.5
6.5


Santicizer 160





4


Initial Rxn Time
47 sec
47 sec
50 sec
51 sec
54 sec
49 sec


Final Rxn Time
75 sec
70 sec
78 sec

104
67 sec


% Ht Expansion
564%
454%
430%
427%
387%
426%


Density (g/in3)


H2O Absorption 1


H2O Absorption 2


H2O Absorption 3
37%
31%
14%
28% 30%
42% 31%
74%


Shore A Hardness
28
31
32
33
33
38


Shrinkage
0 mm
0.3 mm
1.5 mm
0.8 mm
0.5 mm
3 mm















Sample No.

Sample No.














Component wt %
7
Sample No. 8
Sample No. 9
Sample No. 10
11
Sample No. 12





Part A


Uvacure 1500
40
40
40
40
40
40


PBD 605
15
15
15
10
15
15


Part B


Arcol PPG-425
20
20
20
20
20
20


Micropearls F30D
14.85
14.85
14.85
14.85
14.85
14.85


75% H3PO4 (tech)
6.5
6.5
6.5
6.5
8
9.5


Santicizer 160
8


Santicizer 278

4
8


Initial Rxn Time
51 sec
54 sec
55 sec
42 sec
32 sec
27 sec


Final Rxn Time
71 sec
80 sec
83 sec
57 sec

38 sec


% Ht Expansion
332%
395%
338%
529%
567%
500%


Density (g/in3)


H2O Absorption 1

44% 23%
26% 26%
61% 90%
25% 33%
56% 65%


H2O Absorption 2


H2O Absorption 3
106%
63%
87%
126%
34%
92% 83%


Shore A Hardness
43
24
32
30
29
28


Shrinkage
4 mm
2 mm
2 mm
0 mm (had
0.5 mm (had
0.75 mm (had






radial shrinkage)
radial
radial shrinkage)







shrinkage)















Sample No.

Sample No.














Component wt %
13
Sample No. 14
Sample No. 15
Sample No. 16
17
Sample No. 18





Part A


Uvacure 1500
40
40
40
40
40
40


PBD 605
15
15
15
15
15
15


Epon SU2.5
10


Epon 828



5


Part B


Arcol PPG-425
20

29.98

20
20


Micropearls F30D
14.85
14.85
22.27
14.85
14.85
14.85


75% H3PO4 (tech)
6.5
6.5
9.75
6.5
6.5


CAPA 316

20


Tone 0301



20


Dicy 1400



2
0.26


85% H3PO4 (tech)





6.5


Initial Rxn Time

20 sec
50 sec
74 sec
49 sec
36 sec


Final Rxn Time



99 sec
70 sec
76 sec


% Ht Expansion
414%
430%
445%

451%
433%


Density (g/in3)


H2O Absorption 1


97% 106%


19% 14%


H2O Absorption 2


H2O Absorption 3
40% 56%
69% 65% 57%
128%


22% 13%








17%


Shore A Hardness
53
43
26

30
32


Shrinkage
3 mm
0 mm (had
2.8 mm
very significant
2.6 mm
0 mm




radial shrinkage)















Sample No.

Sample No.














Component wt %
19
Sample No. 20
Sample No. 21
Sample No. 22
23
Sample No. 24





Part A


Uvacure 1500
40
40
35
35
35
40


PBD 605
15
15
15
15
15
15


Epon 828





10


Part B


Arcol PPG-425
20




20


Micropearls F30D
14.85
14.85
14.85
14.85
14.85
14.85


75% H3PO4 (tech)
6.5
6.5
6.5
5
8
6.5


Ebecryl 170
5




15


Desmophen L-951

20
20
20
20


Initial Rxn Time
25 sec
44 sec 50
48 sec 48
72 sec
37 sec 34
18 sec




sec
sec

sec


Final Rxn Time
43 sec
64 sec 67
79 sec 70
100 sec
57 sec 51
35 sec




sec
sec

sec


% Ht Expansion
415%
467% 510%
505% 442%
420%
530% 535%
289%


Density (g/in3)
1.93
2.02


H2O Absorption 1
9% 15%
15% 18%
20% 22%

39% 19%


H2O Absorption 2




36%


H2O Absorption 3
39% 22%
32% 22% 37%
60% 49%

66% 55%
81% 48%





73%

61%


Shore A Hardness
35
38 31
29 32
31
30 27
52


Shrinkage
0.3 mm
1.5 mm 0.8 mm
0.5 mm
3.3 mm
0.5 mm
2 mm





0.75 mm

0.75 mm















Sample No.

Sample No.














Component wt %
25
Sample No. 26
Sample No. 27
Sample No. 28
29
Sample No. 30





Part A


Uvacure 1500
40
30
40
30
40
40


PBD 605
15

15
15
15
7.5


Epon 828



10


SAT 030





7.5


Part B


Arcol PPG-425





20


Micropearls F30D
14.85
14.85
14.85
14.85
14.85
14.85


75% H3PO4 (tech)


6.5
6.5
6.5
6.5


Desmophen L-951
20

10
20


Ebecryl 170
20
30
5
5


Santicizer 261


10


K-Flex 188




20


Initial Rxn Time

<10 sec
21 sec
25 sec
27 sec
48 sec


Final Rxn Time


36 sec
41 sec

61 sec


% Ht Expansion

350%
358%
333%
456%


Density (g/in3)



3.45


H2O Absorption 1



28% 38%


H2O Absorption 2



89%


H2O Absorption 3


94% 95%
84% 83% 85%
32% 28%
19% 22%







30%


Shore A Hardness


39
37
47


Shrinkage

0.5 mm
2.5 mm
2.5 mm
0.9 mm















Sample No.

Sample No.














Component wt %
31
Sample No. 32
Sample No. 33
Sample No. 34
35
Sample No. 36





Part A


Uvacure 1500
40
40
40
40
40
20


PBD 605
7.5

15
15

15


Epon 828


SAT 030
7.5


Trilene M-101

15


Hycar 1300 × 40




15


Uvacure 1533





20


Part B


Arcol PPG-425
20
20
20
20
20
20


Micropearls F30D
14.85
14.85
14.85
14.85
14.85
14.85


75% H3PO4 (tech)
6.5
6.5
6.5
6.5
6.5
6.5


Ebecryl 170
2


#1 Castor Oil


6


Santicizer 141



10


Initial Rxn Time
31 sec
46 sec
49 sec
56 sec
45 sec
47 sec


Final Rxn Time
49 sec
60 sec
68 sec
71 sec
55 sec
78 sec


% Ht Expansion

394%


Density (g/in3)


H2O Absorption 1


H2O Absorption 2


H2O Absorption 3
22% 23%
114% 81% 107%
17% 15%
51% 70%

30% 34%


Shore A Hardness

40


Shrinkage

2.75 mm














Sample No.

Sample No.













Component wt %
37
Sample No. 38
Sample No. 39
Sample No. 40
Sample No. 41
42





Part A


Uvacure 1500
25
40
40
40


PBD 605
15
15
15
15


Epon 828




45
45


Uvacure 1534
15


Part B


Arcol PPG-425
20
20
20
20


Micropearls F30D
14.85
14.85
14.85
14.85
15
15


75% H3PO4 (tech)
6.5


H3PO4 (conc:>95%)

6.5
4.9
4
10
10


Tone EC Monomer




20


#1 Castor Oil





20


Initial Rxn Time
58 sec
28 sec
33 sec
37 sec
58 sec
33 sec


Final Rxn Time
73 sec
37 sec
52 sec
50 sec
93 sec



% Ht Expansion

274%
261%
181%
510%
300%


H2O Absorption 1


H2O Absorption 2


H2O Absorption 3
27% 33%

15% 20%

37% 38%





(72 hrs)

(72 hrs)


Shore A Hardness

62
60
62
48
68


Shrinkage




0 mm
0 mm
















Component wt %
Sample No. 43
Sample No. 44
Sample No. 45
Sample No. 46







Part A



Epon 828
45
45
50
50



Vertel XF



5



Part B



Micropearls F30D
15
15
15
10



H3PO4 (conc:>95%)
10
20
10
10



Santicizer 261
20



Pure Grain Alcohol

20



(EtOH)



Santicizer 97


20
20



Initial Rxn Time
24 sec
108 sec
27 sec
26 sec



Final Rxn Time
72 sec
130 sec





% Ht Expansion
182%
575%
376%
297%



Density (g/in3)

1.37



H2O Absorption 1



H2O Absorption 2



H2O Absorption 3

843% (after 15





mins)



Shore A Hardness
78
4

62



Shrinkage
0.5 mm
0.5 mm

0 mm












EXAMPLE 22

[0103]

13



















Sample No.

Sample No.













Component wt %
1
Sample No. 2
Sample No. 3
Sample No. 4
Sample No. 5
6





Part A


Uvacure 1500
40


PBD 605
15


Epon 828

40
40
35
35
50


Santicizer 97



5
5


Part B


Desmophen L-951
20


H3PO4 (75% tech)
6.5


Micropearls F30D
2
10
10
10
10
10


H3PO4 (>95% conc)

10
10
10
10
10


Arcol PPG-425

20


Santicizer 97


20
20
15
20


#1 Castor Oil




5


Initial Rxn Time
43 sec
263 sec
20 sec
19 sec
24 sec
25 sec


Final Rxn Time
54 sec
299 sec






% Ht Expansion
86%
308%
189%
118%
122%
184%


Density (g/in3)

2.50
6.20

6.93
6.13


H2O Absorption 1
3%


H2O Absorption 2


H2O Absorption 3
3%
27% 23%
8% 10%
18% 22% 18%
11% 12%
5% 6%


Shore A Hardness


88
90
88
88


Shore D Hardness
(32)

27 (30)
30 (32)
27 (30)
28 (30)


(##) = calculated


Shrinkage
2.2 mm
0 mm
0 mm
0 mm
0 mm
0 mm














Sample No.

Sample No.













Component wt %
7
Sample No. 8
Sample No. 9
Sample No. 10
Sample No. 11
12





Part A


Epon 828
40
20
40
40
40
60


CMD 50859

20


Tone EC




2
3


Part B


Santicizer 97

20
20
15
15
15


H3PO4 (>95% conc)
10
10
10
10
10
10


Micropearls F30D
10
10
6
6
4
4


Santicizer 160
20


#1 Castor Oil



5
5
5


Initial Rxn Time
17 sec
22 sec
18 sec
22 sec
22 sec
30 sec


Final Rxn Time








% Ht Expansion
260%
152%
120%
145%
99%
92%


Density (g/in3)

4.20
7.03
6.40
6.94
8.19


H2O Absorption 1


H2O Absorption 2


H2O Absorption 3
40% 32%
50% 34%
13% 12%
13% 11%
15% 10%
3% 2%



39%


Shore A Hardness

80
91
86
93
98


Shore D Hardness

23 (22)
32 (33)
26 (28)
34 (36)
46 (42)


(##) = calculated


Shrinkage
0 mm
0 mm
0 mm
0 mm
0 mm
0 mm














Sample No.

Sample No.













Component wt %
13
Sample No. 14
Sample No. 15
Sample No. 16
Sample No. 17
18





Part A


Epon 828
40
60
80
80
50
50


Santicizer 97
5
7.5
10
10


Vertrel XF



5
10


Part B


Santicizer 97
15
15
15
15
20
20


H3PO4 (>95% conc)
10
10
10
10
10
10


Micropearls F30D
6
6
6
6
5
10


#1 Castor Oil
10
10
10
10

10


Initial Rxn Time


69 sec
66 sec
24 sec
41 sec


Final Rxn Time








% Ht Expansion


60%
61%
238%
123%


Density (g/in3)





4.64-8.38


H2O Absorption 1








H2O Absorption 2








H2O Absorption 3
14%
8% 8%
1% 1%


32% 35%


Shore A Hardness



90

90


Shore D Hardness





29


(##) = calculated



(32)

(32)


Shrinkage


0 mm
0 mm
0 mm
0 mm













Component wt %
Sample No. 19







Part A



Epon 828
65



Santicizer 97
5



Part B



Santicizer 97
15



H3PO4 (>95% conc)
10



Micropearls F30D
10



Initial Rxn Time
25 sec



Final Rxn Time




% Ht Expansion
176%



Density (g/in3)
6.55



H2O Absorption 1



H2O Absorption 2



H2O Absorption 3
4% 4%




(after 48 hrs)



Shore A Hardness
93



Shore D Hardness
(36)



(##) = calculated)



Shrinkage
0 mm












EXAMPLE 23

[0104] This Example illustrates the ability to tailor the inventive foam compositions and obtain foams having a wide range of characteristics. A foam of relatively low density was produced by in accordance with Example 18. The foam was obtained by combining the following foam precursors:
14AMOUNTCOMPONENTTRADE NAMESUPPLIERPart A:18.2gcylcoaliphatic epoxyUvacure 1500Radcure1.8gphenoxy resinPhenoxy PKHP-200Paphen30gbis-A epoxyD.E.R. 736Dow ChemicalPart B29.65g.caprolactone polyolTone 0301Union Carbide14.85g.vinylidene chlorideMicropearls F30DPierce & Stevensencapsulatediso-butane5.5g.phosphoric AcidACROS(85%)


[0105] Each component (Part A & B) was individually mixed by hand using a hand driven paddle in a cup or ointment can. The two were brought together in a single vessel, again mixed by hand, and allowed to react. The foam produced was similar in appearance to other types listed above, but had a final specific gravity 0.16 g/ml.



EXAMPLE 24

[0106] The following Example demonstrates employing the inventive foam as a structural material between two laminates to fabricate furniture. The components listed in the following Table were combined in accordance with Examples 18-22.
15SampleSampleSampleComponents wt. %No. 1Sample No. 2No. 3No. 4AEpon 8287550Santicizer 975Epon 81350Epon 82550BSanticizer 9720202025H3PO4 (>95% conc)10101010Micropearls F30D10101010Initial Rxn Time40 sec33 sec28 sec28 secFinal Rxn Time% H Expansion136%262%225%170%Density 1 (g/in3)Density 2 (g/in3)8.775.705.52H2O Absorption 11% 1% 2%H2O Absorption 2Shore A Hardness9581Shore D Hardness40= calculated(38)(23)Shrinkage0 mm0 mm0 mm0 mmHad significantradial shrinkage


[0107] The following Table list components employed in the above Table for making foam.
16Trade NameComponentSupplier#1 Castor Oil#1 Castor OilCommercialEpon 825Bis A EpoxyShell Chemical Co.Epon 828Bis A EpoxyShell Chemical Co.Epon 813Bis A Epoxy Modified:Shell Chemical Co.(74% Bisphenol Aepichlorohydrin resin &26% Cresyl glycidyl ether)Santicizer 97Dialkyl AdipateSolutiaH3PO4(>95% conc)Phosphoric acid: TookDeNOVUSHarcros 75%Technical Grade & distilledto >90% acid concentrationMicropearls F30DThermal Blowing Agent:HM Royal (Pierceisobutane encapsulated& Stevens)in polymer vinylidenechloride


[0108] Sample No. 1 above was combined and introduced into a mold comprising standard 1″×4″×12″boards and laminating materials comprising wood-grain Formica® and fiber-reinforced paper board that were maintained a defined distance about by wood spacers, i.e., a distance of about ½ inch. The boards and laminating materials were placed into “C” clamps and a vise. The foam composition was prepared and poured between the laminating materials. Once the foam reaction was completed and the foam had cooled to room temperature, the assembly was visually inspected. The foam had adhered to the laminating materials and provided structural support.



EXAMPLE 25

[0109]

17

















Component
Sample No.
Sample No.
Sample No.
Sample No.
Sample No.
Sample No.


Wt. %
1
2
3
4
5
6










Part A













Epon 828
48
23
50
34.5
50
50


Santicizer 97
2


Epon 825

23

9.5


Part B


Santicizer 97
19.8
20
20
18


H3PO4 (>95%
11
10
10
10
10
10


conc)


Micropearls F30D
13.7
12.5
2
12.5
12.5
12.5


Expancel 642DU


2


Expancel 820DU


2


Expancel 551DU


2


Expancel 461DU


2


SR239




20


SR495





20


Initial Rxn Time
28 sec 26
38 sec
38 sec
28 sec 34
41 sec
79 sec



sec


sec


% Ht Expansion
289%
320%
240%
306% 275%
269%
399%


Density 1 (g/in3)

2.41 - 2.75


Density 2 (g/in3)
3.35


H2O Absorption 1
16% 20%
13% 13%


Shore A
50
63


Hardness


Shrinkage
0 mm
0 mm
0 mm
0 mm
0.5 mm
1 mm (had







(had radial
radial shrinkage)







shrinkage)











EXAMPLE 26

[0110] The following Example demonstrates a composition of the instant invention that can be dispensed via a commercially available dual tube caulk gun.
18Product NameChemical NameSupplier% rangePart AEpon 862Bis F epoxy resinShell5-75Cardura E-10glycidyl esterWalsh & Assoc.1-30Polybd ® 605 EpolybutadieneElf Atochem1-60Micropearls F30 DIsobutane encapsulatedHM Royal10-75 in Polymer vinylidenechloridePart BPhosphoric acidphosphoric acidHarcross3-25CD513methacrylateSartomer1-10SR495caprolactone acrylateSartomer1-10


[0111] Parts A and B were prepared separately by being mixed in lab scale beakers. Parts A and B were mixed and dispensed by using a 4:1 TAH Industries motionless mixer tube.



EXAMPLE 27

[0112] The following Table lists the Raw Materials that were employed in Example 27. The foam in Example 27 was prepared and tested in accordance with Examples 18-22 and 25. This Example illustrates foam having desirable flame resistant characteristics. Such foam can be employed in a wide range of applications including aerospace (e.g., aircraft insulation), automotive (e.g., sound abatement and structural support), among other end uses.
19Raw MaterialDescriptionSupplierIntelimer 7004Polymer Bound Imidazole Catalyst:MP = 149FLandecIntelimer 7024Encapsulated 2-Ethyl-4-Methyl Imidazole:LandecMP = 149FIntelimer 7124Polymer Bound Imidazole CatalystLandecPEP 6137Acrylic Monomer Modified Epoxy:EEW = 150:Pacific EpoxyVisc = 950 cPPEP 6138Acrylic Monomer Modified Epoxy:EEW = 150:Pacific EpoxyVisc = 100 cPPEP 6139Acrylic Monomer Modified Epoxy:EEW = 130:Pacific EpoxyVisc = 3000 cPPEP 6264Urethane Modified Epoxy:EEW = 210:Pacific EpoxyVisc = 2000 cPPEP 6431Novolac:EEW = 170:visc = 25,000:fnc = 2.2Pacific EpoxyPEP 6433Novolac:EEW = 170:visc = 8000:fnc = 2.2Pacific EpoxyNPEK-119Bis A Epoxy:EEW = 180-195:Visc = 600-1200Peninsula Polymers/NanYa CorporationEpon 824Bis A / Epichlorohydrin Based Epoxy Resin (85-90%)Walsh & Assoc/Shell& Modified Base Epoxy Resin (10-15%)ChemicalEpon 826Bis A / Epichlorohydrin Based Epoxy Resin:Walsh & Assoc/ShellEEW = 182:Visc = 8000 cPChemicalSR 239DiFunctional:1,6 Hexanediol Dimethacrylate:Sartomervisc = 8:hydrophobic backboneSR 9009TriFunctional:Trifunctional Methacrylate:Sartomervisc = 35CD 9050Monofunctional Acid Ester:AdhesionWalsh &Promoting Monomer:visc = 20Assoc/SartomerCD 9051Trifunctional Acid Ester:Adhesion PromotingWalsh &Monomer:visc = 250Assoc/SartomerSR 444Trifunctional Monomer:PentaerythritolWalsh &Triacrylate:Hydroxyl Pendant Group:Assoc/Sartomervisc = 520 cPCD 513Methacrylate Ester (Propoxylated2 AllylSartomerMethacrylate):Commercially available under5E consentEbecryl 2047Trifunctional Acrylated Diluting Oligomer:UCB Radcurevisc = 400 cP:tensile = 1000 psi:elong = 8%:Tg = 3FEbecryl 3200Acrylated Epoxy:visc = 3000 cP:UCB Radcuretensile = 11,900 psi:elong = 6%:Tg = 118FKronitex TCPTricrecyl Phosphate:Flame RetardantFMC CorpSanticizer 143Modified Triaryl Phosphate EsterSolutiaSanticizer 148Isodecyl Diphenyl PhosphateSolutiaSanticizer 154Triaryl Phosphate Ester:t-ButylphenylSolutiaDiphenyl PhosphateNOVOC RGS-2020DVModified Vinyl Ester:WPE = 300-2800:CompositeVisc = 800 cP:Acid Value = 14-20TechnologyVeova 10Vinyl Ester Of Tertiary Carboxylic acid:Walsh & Assoc/ShellNeodecanoic acid, ethenyl ester:visc ≈ 8 cPComponents Wt. %Sample No. 1234Part AEpon 82860606060BK 5799 (carbon Black)4 g4 g4 g4 gPart BSanticizer 9715151515H3PO4 (conc)7.57.57.57.5Micropearls F30D8888Intelimer 70041.5Intelimer 70241.5Intelimer 71241.5Initial Rxn Time (sec)51 sec64 sec78 sec81 secShrinkage0 mm0 mm0 mm0 mm% Height Expansion221%238%257%234%Density 2 (g/in3) Top4.534.514.724.20Bottom4.874.935.254.76Specific Gravity% H2O Absorption 22.8% 2.0%4.8% 3.06.8% 4.9%7.6% 5.2%Shore A:Initial81 8580 8286 8575 77Shore A - After 24 hr82 8479 7980 7872 71Water SoakComponentsWt. %Sample No. 56789Part AEpon 828603030BK 57994 gEpon 82660603030Z60401Part BSanticizer 971528.4628.4628.46H3PO4 (conc)7.57.513.3413.3413.34Micropearls F30D8814.2314.2314.23CD 51315Initial Rxn Time (sec)92 sec50 sec32 sec31 sec32 secShrinkage0 mm0 mm0 mm0 mm0 mm% Height Expansion383%278%238%209%240%Density 1 (g/in3)Density 2 (g/in3) Top4.753.725.054.50Bottom4.784.154.624.45% H2O Absorption 1% H2O Absorption 254% 71%74% 38%11% 9%15% 13%Shore A:Initial90 8674 7789 8783 80Shore A - After 24 hr78 7545 4770 7357 56Water SoakShore A:% Drop13% ↓ , 13% ↓39% ↓ , 39% ↓21% ↓ , 16% ↓31% ↓ , 30% ↓After 24 hr H2O SoakComponentsWt. %Sample No. 1011121314Part AEpon 8283060603040BK 57994 g)4 gEpon 8263030Z604012.53.52PEP 626420Part BSanticizer 9728.4628.4628.4625.1415.5H3PO4 (conc)1113.3413.3411.797.5Micropearls F30D14.2314.2314.2312.578Initial Rxn Time (sec)45 sec38 sec47 sec44 sec281 secShrinkage0 mm0 mm0.5 mm0.5 mm0.5 mm% Height Expansion178%232%227%233%50%Density 1 (g/in3)Density 2 (g/in3) Top6.114.535.144.13Bottom6.084.134.834.46% H2O Absorption 1% H2O Absorption 224% 26%56% 41%73% 86%27% 20%Shore A:Initial84 8672 6781 7983 80Shore A - After 24 hr67 6830 3144 3850 48Water SoakShore A:% Drop20% ↓ , 21% ↓58% ↓ , 54% ↓46% ↓ , 52% ↓40% ↓ , 40% ↓After 24 hr H2O SoakComponents Wt %Sample No. 15161718Part AEpon 82840404040BK 57994 g4 g4 g4 gPEP 626420PEP 613720PEP 613820PEP 613920Part BSanticizer 97 $1.22/lb15.515.515.515.5H3PO4 (conc) $0.70/lb107.57.57.5Micropearls F30D $8/lb8888Initial Rxn Time (sec)116 sec74 sec81 sec77 secShrinkage0.5 mm0 mm0 mm0 mm% Height Expansion55%210%223%204%Density 1 (g/in3)Density 2 (g/in3) Top11.884.644.274.44Bottom5.244.944.99% H2O Absorption 1% H2O Absorption 220%4% 3%6% 5%5% 3%Shore A:Initial9684 8678 8485 87Shore A - After 24 hr9073 7563 6672 70Water SoakShore A:% Drop6% ↓13% ↓ , 13% ↓19% ↓ , 21% ↓15% ↓ , 20% ↓After 24 hr H2O SoakComponents Wt %Sample No. 19202122Part AEpon 828404550BK 5799 (carbon black)NPEK-1196010DER 73615CD 51310Part BSanticizer 971524.7324.7328.8H3PO4(>85% conc)7.511.611.613.5Micropearls F30D812.3712.3714.4Initial Rxn Time68 sec33 secinstant44 sec% Ht Expansion233%241%190%Density (g/in3) Top4.504.184.01Bot4.284.724.44H2O Absorption25% 12%25% 13%151%Shore A:Initial85 8175 8267 68Shore A:After67 5852 6010 16Water SoakShore A % Drop21% ↓ , 28% ↓27% ↓ , 27% ↓85% ↓ , 77% ↓After Water SoakShrinkage0.2%<2%ComponentsWt. %Sample No. 232425Part AEpon 828503030BK 5799 (carbon black)4 g4 gZ 60402.52Epon 8263030Part BSanticizer 9722.8625.1416.76H3PO4 (>85% conc)11.911.797.86Micropearls F30D12.712.578.38Kraton D11072.54Initial Rxn Time33 sec44 sec 53 sec49 sec% Ht Expansion228%233% 204%210%Density (g/in3) Top4.124.134.53Bot4.474.465.09H2O Absorption(72 hrs:118%27% 20%3% 2%148%)Shore A:Initial78 7183 8085 89Shore A:After(72 hrs:25 26)50 4879 82Water SoakShore A % Drop72 hrs Soak40% ↓ , 40% ↓7% ↓ , 8% ↓After Water Soak68% ↓ , 63% ↓Shrinkage0.2%0.9%0.6%Components Wt %Sample No. 26272829Part AEpon 82830303060BK 5799 (carbon black)4 g4 g4 g4 gEpon 826303030PEP 6210 PA10Cardura E-101010Part BSanticizer 9716.7616.7616.7616.76H3PO4 (>85% conc)7.867.867.867.86Micropearls F30D8.388.388.388.38Initial Rxn Time183 sec44 sec63 sec57 sec ?% Ht Expansion<50%197%257%250%Density (g/in3) Top4.975.195.34Bot5.424.725.33H2O Absorption3% 3%26% 17%9% 4%Shore A:Initial87 8988 8288 84Shore A:After82 8462 5763 56Water SoakShore A % Drop6% ι , 6% ↓30% ↓ , 31% ↓28% ↓ , 33% ↓After Water SoakShrinkage0.2%2.1%2.5%Components Wt %Sample No. 3031Part AEpon 82865.565.5BK 5799 (carbon black)4 g4 gCardura E-103.53.5Part BSantacizer 971717H3PO4 (>85% conc)7.57.5Micropearls F30D8.5Initial Rxn Time8453% Ht Expansion205% 215%0%Density (g/in3) Top5.09Bot5.6018.83H2O Absorption(72 hrs:4% 3%)0.22% (96 hrs)Shore A:Initial90 90>100Shore A:After(72 hrs:87 86)>100 (96 hrs)Water SoakShore A % Drop(72 hrs:3% ↓ ,0% (96 hrs)After Water Soak4% ↓)Shrinkage0.4%3%Compression:1″d (psi)1483 1450Compression:2″d (psi)1113Components Wt %Sample No. 32333435Part AEpon 82865.565.565.565.5BK 5799 (carbon black)4 g4 g4 gCardura E-103.53.53.53.5Expancel 051DU5Part BSanticizer 97178.5H3PO4 (>85% conc)7.57.57.57.5Micropearls F30D8.58.58.5Expancel 051DUVeova 108.57Santolink XI-10017Cardura E-1010Initial Rxn Time120 + sec94 sec232 sec77 sec% Ht Expansion<25%137%258%206%Density (g/in3) Top4.164.68Bot4.195.27H2O Absorption2% 2%1.3% 1%Shore A:Initial73 7579 79Shore A:After61 6470 69Water SoakShore A % Drop16% ↓ , 15% ↓11% ↓ , 13% ↓After Water SoakShrinkage0.7%1%Components Wt %Sample No. 3637383940Part AEpon 82855.59565.565.5Cardura E-103.53.553.53.5Erisys GE-6010Epalloy 824065.5BK 5799 (carbon Black)4 g4 gMicropearls F30D8.5Part BH3PO4 (>85% conc)7.57.5117.57.5Micropearls F30D8.58.58.58.5Cardura E-10121212Veova 1055Santicizer 97175Initial Rxn Time69 sec75 sec63 sec203 sec17 sec% Ht Expansion130%229%166%245%335%Density (g/in3) Top4.635.834.46Bot5.426.114.99H2O Absorption(72 hrs) 5% 3%1% 1%10% 6%(72 hrs)Shore A:Initial74 7494 9576 76Shore A:After(72 hrs) 69 6791 9165 66Water Soak(72 hrs)Shore A % Drop(72hrs)3% ↓ , 4% ↓15% ↓ , 13% ↓After Water Soak7% ↓ , 10% ↓(72 hrs)ShrinkageSlight1%0.4% 0.5%1.1%Compression:1″d (psi)2724 2504Components Wt %Sample No. 4142434445Part AEpon 82865.565.565.565.565.5Cardura E-103.53.53.53.53.5BK 5799 (carbon Black)4 g4 g4 g4 g4 gPart BH3PO4 (>85% conc)7.57.57.57.57.5Micropearls F30D8.58.58.58.58.5Ebecryl 204717Ebecryl 320017CD 905117CD 905017SR 44417Initial Rxn Time81 sec92 sec63 sec82 sec71 sec% Ht Expansion275%275%285%290%300%Density (g/in3) Top4.693.923.673.893.59Bot4.704.754.204.064.12H2O Absorption32% ? 2%3% 27% ?6% 3%29% 42%15% 10%(see 1 below)Shore A:Initial88 8383 8381 8278 8078 78Shore A:After78 7370 7366 6752 5175 75Water SoakShore A % Drop11% ↓ , 12% ↓16% ↓ , 12% ↓19% ↓ , 18% ↓33% ↓ , 36% ↓4% ↓ , 4% ↓After Water SoakShrinkage1.1%0.2%0.3%2%1.2%


[0113]

20

















Components Wt %
Sample No. 46
47
48
49





Part A


Epon 828
65.5
65.5
65.5
55.5


Cardura E-10
3.5
3.5
3.5
3.5


BK 5799 (carbon Black)
4 g
4 g
4 g
4 g


Epalloy 8240



10


Erisys GE-60


Part B


H3PO4 (>85% conc)
7.5
7.5
7.5
7.5


Micropearls F30D
8.5
8.5
8.5
8.5


Santicizer 278
17


SR 9009

17


SR 239


17


Santicizer 97



17


Initial Rxn Time
54 sec
54 sec
79 sec
49 sec


% Ht Expansion
260%
268%
320%
214%


Density (g/in3) Top
4.07
3.99
3.63
4.82


Bot
4.83
4.41
4.20
5.41


H2O Absorption
27% 4% (see 1)
53% 39% (see 1)
12% 9%
3% 2%


Shore A: Initial
80 82
85 85
69 71
86 87


Shore A: After
67 72
77 79
65 67
83 85


Water Soak


Shore A % Drop
16% ↓, 12% ↓
9% ↓, 7% ↓
6% ↓, 6% ↓
4% ↓, 2% ↓


After Water Soak


Shrinkage
0.6%
2%
6%
0.3%





Components Wt %
Sample No. 50
51
52
53





Part A


Epon 828
65.5
55.5
55.5
55.5


Cardura E-10
3.5
3.5
3.5
3.5


BK 5799 (carbon Black)
4 g
4 g
4 g
4 g


Micropearls F30D
8.5


PEP 6433

10


PEP 6431


10


Epalloy 8240



10


Part B


Santicizer 97
17
17
17
17


H3PO4 (>85% conc)
7.5
7.5
7.5
7.5


Micropearls F30D

8.5
8.5
6.5


Initial Rxn Time
56 sec
88 sec
51 sec
52 sec


% Ht Expansion
165%
133%
157%
123%


Density (g/in3) Top
5.39
8.98
5.72
7.15


Bot
5.82
9.59
6.30
7.63


H2O Absorption
2% 1%
36% 29%
0.7% 0.7%
0.5% 0.4%



(72 hrs)


Shore A: Initial
89 90
97 98
91 94
97 97


Shore A: After
85 87
93 94
87 91
95 95


Water Soak
(72 hrs)


Shore A % Drop
5% ↓, 3% ↓
4% ↓, 4% ↓
4% ↓, 3% ↓
2% ↓, 2% ↓


After Water Soak
(72 hrs)


Shrinkage
0.4%
0.2%
0.1%
0.3%


Compression: 1″d (psi)


1886 2090


Compression: 2″d (psi)



2190















Components Wt %
Sample No. 54
55
56
57
58





Part A


Epon 828
50
65.5
55.5
65.5
55


Cardura E-10

3.5
3.5
3.5
3.5


BK 5799 (carbon Black)
4 g
4 g
4 g
4 g
4 g


Epalloy 8240
20


PEP 6431


10


PBD 605




10


Part B


Santicizer 97
17
12
17
20.4
20.4


H3PO4 (>85% conc)
7.5
7.5
7.5
9
9


Micropearls F30D
8.5
3.5
5
2.5
4


Initial Rxn Time
57 sec
51 sec
56 sec
54 sec 51 sec
37 sec


% Ht Expansion
213%
45%
40%
23% 30%
21%


Density (g/in3) Top
5.21
10.77

12.28


Bot
5.87
10.89
9.44
12.41


H2O Absorption
2% 0.9%
0.2%
0.6%
1.1%





(72 hrs)
(5 days)


Shore A: Initial
88 92
100
99
100+


Shore A: After
85 88
99
98
98


Water Soak


(72 hrs)
(5 days)


Shore A % Drop
3% ↓, 5% ↓
1% ↓
1% ↓
2% ↓


After Water Soak


(72 hrs)
(5 days)


Shrinkage
0.1%
1.4%
0.8%
1.9%


Compression: 1″d (psi)
1825 1939
4875 4768
3472 4070
5762 6141
5132 4874













Components Wt %
Sample No. 59
60
61





Part A


Epon 828
150.65
65.5
65.5


Cardura E-10
8.05


BK 5799 (carbon Black)
4 g
4 g
4 g


Veova 10

10


Z 6040


2


Part B


Santicizer 97
17
17
17


H3PO4 (>85% conc)
16
7.5
7.5


Micropearls F30D
5
6.5
6.5


Initial Rxn Time
42 sec 30 sec
54 sec
96 sec


% Ht Expansion
20%
20%
122%


Compression: 1″d (psi)
7212 7201

1955 1940





Components Wt %
Sample No. 62
63
64





Part A


Epon 828
65.5
65.5
65.5


Cardura E-10
3.5

3.5


BK 5799 (carbon black)
4 g
4 g
4 g


Santicizer 97

3.5


Part B


Santicizer 97
20
20.4


H3PO4 (>85% conc)
6.5
9
9


Micropearls F30D
4.5
2.5
2.5


RGS-2020 DV


20.4


Initial Rxn Time
81 sec
58 sec
175 sec


% Ht Expansion
32%
23%
67%


Density (g/in3) Top

11.44
9.54


Bot
11.4
11.38
10.21


H2O Absorption
(72 hrs) 0.4%
0.9
1.3%


Shore A: Initial
100+
100+
98


Shore A: Water Soak
(72 hrs) 100
99
91


Shore A % Drop
(72 hrs) 0% +
1% +
7%


After Water Soak


Salt: % Absorption
0.5%
1.5%


Salt: % Shore A Drop
1% +
16% +


Shrinkage
1.1
1.6%
2.2%


Compression: 1″d (psi)
4116 4452
4382 4933
3784 3786


Heat Age Rating
2
3












Components Wt %
Sample No. 65
66





Part A


Epon 828
42.8
50.4


Erisys GE-29
12.8
4.2


Micropearls F30D
12.8
10.8


BK 5799 (carbon black)
4 g
4 g


Part B


Santicizer 97
17.6
18


Santicizer 154
4.4
4.5


H3PO4 (>85% conc)
13.2
11.2


Initial Rxn Time
25 sec
30 sec


% Ht Expansion
287%
275%


Density (g/in3) Top

3.72


Bot


H2O Absorption
34%


Shore A: Initial
45
71


Shore A: Water Soak
14


Shore A % Drop
69%


After Water Soak


Shrinkage
0.5%
0.2%


Flammability (vert)
Torch
Torch


Flame Time
3 sec
7 sec


Burn Length
0.06-0.19 in
3.75-7 in


Flammability (horiz)
Torch
Torch


Flame Time
5 sec
6 sec


Burn Length
3.25-3.75 in











[0114] A skilled person in this art would understand that these exemplary processes an be modified by manipulating process variables such as time and temperature of each aforementioned mixing step, mixing rate (RPM), time under vacuum, radiation source (e.g., UV light) and length of exposure and distance from source, and level of vacuum (mm Hg) as well as operating a continuous process. While the above Examples illustrate a batch process a skilled person in this art after having reviewed and understood the instant disclosure, would be capable of manipulating the aforementioned process variables to tailor the instant composition for a virtually unlimited array of product applications.


[0115] While the present invention has been described in certain preferred embodiments thereof, it will be apparent that various substitution, omissions, modifications, and other changes which may be made without departing from the spirit of the invention. Thus, the present invention should be limited only by the scope of the following claims including equivalents thereof.


Claims
  • 1. A method for producing a foam comprising: (a) combining at least one halogenated epoxy component with at least one acid source component and at least one blowing agent under conditions sufficient to provide an exothermic reaction wherein at least one foam precursor is encapsulated; and (b) utilizing heat from the exothermic reaction so as to expand the combined components to form a foam.
  • 2. The method according to claim 1 further comprising (c) recovery of the foam.
  • 3. The method according to claim 1 wherein said at least one acid source is substantially water free.
  • 4. The method according to claim 1 wherein the epoxy component is present in a first precursor composition and the acid source is present in a second precursor composition.
  • 5. The method according to claim 4 wherein the first precursor composition further comprises a blowing agent comprising at least one member selected from the group consisting of butane, propane, isobutane, pentane, isopentane and fluorocarbons.
  • 6. The method according to claim 4 wherein the second precursor composition further comprises a carrier material.
  • 7. The method according to claim 1 wherein the epoxy compound and the acid source are present in a single foam precursor composition.
  • 8. The method according to claim 7 wherein the acid source comprises phosphoric acid that is substantially free of water.
  • 9. The method according to claim 1 wherein step (a) occurs at least in part in a containment device.
  • 10. The method according to claim 9 wherein the containment device comprises polyethylene, polyester, vinyl, ethylene vinyl acetate, nylon, ethylene vinyl acetate, styrene-isoprene-styrene, styrene-butadiene-styrene or other blocked copolymers, polybutadiene, polyamide, modified EVA's, modified polyethylene, modified polybutadiene, GMA, SBR or mixtures thereof.
  • 11. The method according to claim 1 wherein the acid source comprises phosphoric acid.
  • 12. A foam composite comprising a foam according to claim 1 which is at least partially in contact with at least one member selected from the group consisting of polyethylene, polyester, vinyl, ethylene vinyl acetate, nylon, ethylene vinyl acetate, styrene-isoprene-styrene block copolymers, styrene-butadiene-styrene block copolymers, polybutadiene, polyamide, modified EVA's, modified polyethylene, modified polybutadiene, GMA, SBR or mixtures thereof.
  • 13. The foam composite of claim 12 further comprising at least one of polyethylene or styrene powders.
  • 14. A foam precursor comprising: (a) an A-side foam precursor composition comprising at least halogenated epoxy functional compound, and a blowing agent, and; (b) a B-side foam precursor composition comprising an acid source and an optional curing agent; wherein at least one of said foam precursors is encapsulated.
  • 15. The foam precursor according to claim 14 wherein (a) further includes a modifying material.
  • 16. The foam precursor according to claim 14 wherein (b) further comprises a carrier material.
  • 17. The foam precursor of claim 14 wherein said blowing agent comprises an encapsulated blowing agent and the encapsulated blowing agent has at least two different activation temperatures.
  • 18. The foam precursor of claim 14 wherein the encapsulated blowing agent comprises a thermoplastic shell that contains at least one of isobutane and isopentane blowing agent.
  • 19. The foam precursor of claim 14 wherein at least one of the A-side precursor and the B-side precursor further comprises castor oil, at least one benzyl phthalate and at least one member selected from the group consisting of Bis A epoxy and Bis F epoxy.
  • 20. The foam precursor of claim 14 wherein said epoxy compound is a bis-A or bis-F epoxy compound; the blowing agent comprises at least one of isopentane and isobutane and the A-side precursor further comprises at least one member selected from the group consisting of polypropylene, polyethylene and polyvinyl alcohol.
CROSS REFERENCE TO RELATED PATENT APPLICATIONS

[0001] This is a continuation-in-part of U.S. patent application Ser. No. 09/344,198, filed on Jun. 24, 1999 as a continuation in part of U.S. Ser. No. 09/300,930, filed on Apr. 28, 1999, that is a continuation in part of Ser. No. 09/197,124, filed on Nov. 20, 1998, that is a continuation-in-part of Ser. No. 09/081,967, filed on May 20, 1998 and entitled “Novel Foaming Compositions and Methods For Making and Using the Composition”. The disclosure of these prior filed patent applications is hereby incorporated by reference. [0002] The subject matter herein claims benefit under 35 U.S.C. 111 (a), 35 U.S.C. 119(e) and 35 U.S.C. 120 of U.S. Provisional Patent Application Serial No. 60/047,273, filed on May 21, 1997, entitled “A Room Temperature Foaming Composition”; and U.S. Provisional Patent Application Serial No. 60/079,205, filed on Mar. 24, 1998, entitled “Novel Foaming Compositions and Methods For Making and Using the Compositions”. The disclosure of the aforementioned Provisional Patent Applications is hereby incorporated by reference. [0003] The subject matter of the instant invention is also related to Non-Provisional Patent Application Serial Nos. 09/081,966, filed on May 20, 1998 and Serial No. 09/197,107, filed Nov. 20, 1999, both filed in the name of Jeffrey Pachl et al., and entitled “Curable Sealant Composition”. The disclosure of these Non-provisional patent applications is hereby incorporated by reference.

Provisional Applications (2)
Number Date Country
60047273 May 1997 US
60079205 Mar 1998 US
Continuation in Parts (4)
Number Date Country
Parent 09344198 Jun 1999 US
Child 09578206 May 2000 US
Parent 09300930 Apr 1999 US
Child 09344198 Jun 1999 US
Parent 09197124 Nov 1998 US
Child 09300930 Apr 1999 US
Parent 09081967 May 1998 US
Child 09197124 Nov 1998 US