Note: Descriptions are shown in the official language in which they were submitted.
CA 022660~4 1999-03-11
WO 98/11159 PCT/US97/16439
NOVEL POLYMER ADDITIVES FOR FORMING O~JECTS
TEC~NICAL FIELD
The present invention relates to a polymer concrete comprising
conventional resins with certain additives to prevent shrinking and cracking
of the resin. The present invention also comprises additives which
strengthen objects made from conventional and gel coat resins without
significantly increasing their weight. The present invention also comprises
objects that are both hard and flexible. More particularly, the present
invention relates to polymer concrete that is particularly useful in rapidly
casting large objects including poured marble.
BACKGROUND OF THE INVENTION
A plastic is an organic polymer, available as a resin. These resins
can be liquid or paste and can be used for embedding, coating, and adhesive
bonding; or they can be molded, laminated, or formed into desired shapes,
including sheet, film, or larger mass bulk shapes.
The number of basic plastic materials is large and the list is
increasing. In addition, the number of variations and modifications to these
basic plastic materials is also quite large. Taken together, the resultant
quantity of materials available is too large to be completely understood and
correctly applied by anyone other than those whose day-to-day work puts
them in direct contact with a diverse selection of materials. The practice of
mixing brand names, trade names, and chemical names of various plastics
only makes the problem of understanding these materials more troublesome.
Another variable that makes it difficult for those not versed in plastics to
understand and properly design with plastics is the large number of
processes by which plastics can be fabricated. Fortunately, there is an
organized pattern on which an orderly presentation of these variables can be
based. While there are numerous minor classifications for polymers,
CA 022660~4 1999-03-11
WO 98/11159 PCT/US97/16439
depending on how one wishes to categorize them, nearly all can be placed
into one of two major classifications--thermosetting materials (or
thermosets) and thermoplastic materials. Likewise, foams, adhesives,
embedding resins, elastomers, and so on, can be subdivided into the
thermoplastic and thermosetting classifications. Thermosetting plastics are
cured, set, or hardened into a permanent shape.
Curing is an irreversible chemical reaction known as cross-linking,
which usually occurs under heat. For some thermosetting materials, curing
is initiated or completed at room temperature. Even here, however, it is
often the heat of the reaction, or the exotherm, which actually cures the
plastic material. Such is the case, for instance, with a room-temperature-
curing epoxy or polyester compound. The cross-linking that occurs in the
curing reaction is brought about by the linking of atoms between or across
two linear polymers, resulting in a three-dimensional rigid chemical
structure. Although the cured part can be softened by heat, it cannot be
remelted or restored to the flowable state that existed before curing.
Continued heating for long times leads to degradation or decomposition.
Thermoplastics differ from thermosets in that they do not cure or set
under heat as do thermosets. Thermoplastics merely soften, or melt when
heated, to a flowable state, and under pressure they can be forced or
transferred from a heated cavity into a cool mold. Upon cooling in a mold,
thermoplastics harden and take the shape of the mold. Since thermoplastics
do not cure or set, they can be remelted and then rehardened by cooling.
Thermal aging, brought about by repeated exposure to the high temperatures
required for melting, causes eventual degradation of the material and so
limits the number of reheat cycles.
All polymers are formed by the creation of chemical linkages
between relatively small molecules, or monomers, to form very large
molecules, or polymers. As mentioned, if the chemical linkages form a
rigid, cross-linked molecular structure, a thermosetting plastic results. If a
somewhat flexible molecular structure with minimal or no cross-linking is
formed, either linear or branched, a thermoplastic results.
.
Polymerization Reactions
Polymerization reactions may occur in a number of ways, with four
common techniques being bulk, solution, suspension, and emulsion
CA 022660~4 1999-03-11
WO 98/111~9 PCT/US97/16439
polymerization. Bulk polymerization involves the reaction of monomers or
reactants among themselves, without placing them in some form of
extraneous media, as is done in the other types of polymerization.
Solution polymerization is similar to bulk polymerization, except that
whereas the solvent for the forming polymer in bulk polymerization is the
monomer, the solvent in solution polymerization is usually a chemically
inert medium. The solvents used may be complete, partial, or nonsolvents
for the growing polymer chains.
Suspension polymerization normally is used only for catalyst-
l O initiated or free radical addition polymerizations. The monomer is dispersed
mechanically in a liquid, usually water, which is a nonsolvent for the
monomer as well as for all sizes of polymer mo~ecules which form during
the reaction. The catalyst initiator is dissolved in the monomer, and it is
preferable that it does not dissolve in the water so that it remains with the
l S monomer. The monomer and the polymer being formed from it stay within
the beads of organic material dispersed in the phase. Actually, suspension
polymerization is essentially a finely divided fonn of bulk polymerization.
The main advantage of suspension polymerization over bulk is that it allows
cooling of the exothermic polymerization reaction and maintains closer
control over the chain-building process. By controlling the degree of
agitation, monomer-to-water ratios, and other variables it is also possible to
control the particle size of the finished polymer, thus elimin~ting the need to
reform the material into pellets from a melt, as is usually necessary with
bulk polymerization.
Emulsion polymerization is a technique in which addition
polymerizations are carried out in a water medium containing an emulsifier
(a soap) and a water-soluble initiator. Emulsion polymerization is much
more rapid than bulk or solution polymerization at the same temperatures
and produces polymers with molecular weights much greater than those
obtained at the same rate in bulk polymerizations.
In emulsion polymerization, the monomer diffuses into micelles,
which are small spheres of soap film. Polymerization occurs within the
micelles. Soap concentration, overall reaction-mass recipe, and reaction
conditions can be varied to provide control of the reaction rate and yield.
The usual sequence of processing a thermoplastic is to heat the
material so that it softens and flows, force the material in the desired shape
.. . . .
CA 022660~4 1999-03-ll
WO 98/11159 PCT/US97/16439
through a die or in a mold, and chi]l the melt into its final shape. By
comparison, a thermoset is typically processed by starting out with partially
polymerized material, which is softened and activated by heating (either in
or out of the mold), forcing it into the desired shape by pressure, and
holding it at the curing temperature until final polymerization reaches the
point where the part hardens and stiffens sufficiently to keep its shape when
demolded.
Plas~ic-Fabrication Processes and ~orms
l O There are many plastic-fabrication processes, and a wide variety of
plastics can be processed by each of these processes or techniques.
Fabrication processes can be broadly divided into pressure processes and
pressureless or low-pressure processes. Pressureless or low-pressure
processes include potting, casting, impregnating, encapsulating7 and
coating. Pressure processes are usually either thermoplastic-materials
processes (such as injection molding, extrusion, and thermoforming) or
thermosetting processes (such as compression molding, transfer molding,
and l:lmin~ting).
Compression Molding and ~ransfer Molding
Compression molding and transfer molding are the two major
processes used for forming molded parts from thermosetting raw materials.
The two can be carried out in the same type of molding press, but different
types of molds are used. The thermosetting materials are normally molded
by the compression or transfer process, but it is also possible to mold
thermoplastics by these processes since the heated thermoplastics will flow
to conform to the mold-cavity shape under suitable pressure. These
processes are usually impractical for thermoplastic molding, however, since
after the mold cavity is filled to its final shape, the heated mold would have
to be cooled to solidify the thermoplastic part. Since repeated heating and
cooling of this large mass of metal and the resultant long cycle time per part
produced are both objectionable, injection molding is commonly used to
process thermoplastics.
CA 022660~4 1999-03-11
WO 98/11159 PCT/US97/16439
Compression Molding
In compression molding, the open mold is placed between the heated
platens of the molding press, filled with a given quantity of molding
material, and closed under pressure, causing the material to flow into the
S shape of the mold cavity. The actual pressure required depends on the
mo]ding material being used and the geometry of the mold. The mold is kept
closed until the plastic material is suitably cured. Then the mold is opened,
the part ejected, and the cycle repeated. The mold is usually made of steel
with a polished or plated cavity.
The simplest form of compression molding involves the use of a
separate self-contained mold or die that is designed for manual handling by
the operator. It is loaded on the bench, capped, placed in the press, closed,
cured, and then removed for opening under an arbor press. The same mold
in most instances (and with some structural modifications) can be mounted
permanently into the press and opened and closed as the press itself opens
and closes. The press must have a positive up-and down movement under
pressure instead of the usual gravity drop found in the standard hand press.
Transfer Molding
The molding material is first placed in a heated pot, separate from the
mold cavity. The hot plastic material is then transferred under pressure from
the pot through the runners into the closed cavity of the mold.
The advantage of transfer molding lies in the fact that the mold
proper is closed at the time the material enters. Parting lines that might give
trouble in finishing are held to a minimum. Inserts are positioned and
delicate steel parts of the mold are not subject to movement. Vertical
dimensions are more stable than in straight compression. Also, delicate
inserts can often be molded by transfer molding, especially with the low-
pressure molding compounds.
Injection Molding
Injection molding is the most practical process for molding
thermoplastic materials. The operating principle is simple, but the equipment
is not.
A material with thermoplastic qualities--one that is viscous at some
elevated temperature and stable at room temperature without appreciable
.
CA 022660~4 1999-03-11
WO 98/11159 PCT/US97/16439
deterioration during the cycle--is m~int~in~d in a heated reservoir. This hot,
soft material is forced from the reservoir into a cool mold. The mold is
opened as soon as the material has cooled enough to hold its shape on
demolding. The cycle speed is determined by the rapidity with which the
temperature of the material used can be reduced, which in turn depends on
the thermal conductivity of that material. Acrylics are slow performers, and
styrenes are among the fastest.
The machine itself is usually a horizontal cylinder whose bore
determines the capacity. Within the bore is a piston which, when retracted,
opens a hole in the top of the cylinder through which new material can be
added to replace the charge shot into the mold. The cylinder is heated by
electric bands which permit temperature variation along its length. Inside the
exit end of the cylinder is a torpedo over which the hot material is forced justbefore coming out of the nozzle into the channels leading to the cavities.
This gives the material a final chu}ning and ensures thorough heating. The
mold opens and closes automatically, and the whole cycle is controlled by
timers.
Thermoset Ingestion Molding
Because of the chemical nature of the p]astic materials, injection
molding has traditionally been the primary molding method for
thermoplastics, and compression and transfer molding have been the
primary molding methods for thermosetting plastics. Because of the greater
molding cycle speeds and lower molding costs in injection molding,
thermoplastics have had a substantial molding cost advantage over
thermosets. As a result, advances in equipment and in thermosetting
molding compounds have resulted in a rapid transition to screw-injection,
in-line molding. This has been especially prominent with phenolics, but
other thermosets are also included to varying degrees. The growth in screw-
injection molding of phenolics has been extremely rapid. The development
of this technique allows the molder to automate further, reduce labor costs,
improve quality, reduce rejects, and gain substantially overall molding cycle
efficiency.
CA 022660~4 1999-03-11
WO 98/111~9 PCT/US97/16439
Extr~sion and Protrusion
The process of extrusion consists basically of forcing heated, melted
plastic continuously through a die, which has an opening shaped to produce
a desired finished cross section. Normally it is used for processing
thermoplastic materials, but it can also be used for processing thermosetting
materials. The main application of extrusion is the production of continuous
lengths of film, sheeting, pipe, filaments, wire jacketing, and other useful
forms and cross sections. After the plastic melt has been extruded through
the die, the extruded material is hardened by cooling, usually by air or
l o water.
Extruded thermosetting materials are used increasingly in wire and
cable coverings. The main object here is the production of shapes, parts,
and tolerances not obtainable in compression or transfer molding. Pultrusion
is a special, increasingly used techni~ue for pulling resin soaked fibers
through an orifice, as it offers significant strength improvements. Any
thermoset, granular molding compound can be extruded and almost any type
of filler may be added to the compound. In fiber-filled compounds, the
length of fiber is limited only by the cross-sectional thickness of the
extruded piece.
A metered volume of molding compound is fed into the die feed
zone, where it is slightly warmed. As the ram forces the compound through
the die, the compound is heated gradually until it becomes semi-fluid.
Before leaving the die, the extruded part is cured by controlling the time it
takes to travel through a zone of increasing temperature. The cured material
exits from the die at telllpeldtures of 300 to 350~F and at variable rates.
Thennosetting Plastics
Plastic materials included in the thermosetting plastic category are
alkyds, diallyl phthalates, epoxies, melamines, phenolics, polyesters,
silicones, and ureas. In general, unfilled thermosetting plastics tend to be
harder, more brittle, and not as tough as thermoplastics. Thus, it is common
practice to add fillers to thermosetting materials. A wide variety of fillers
can be used for varying product properties. For molded products, usually
compression or transfer molding, mineral or cellulose fillers are often used
as lower-cost, general-purpose fillers, and glass fiber fillers are often used
for optimum strength or dimensional stability. It should be added that filler
CA 022660~4 1999-03-11
W O 98111159 PCTrUS97/16439
form and fil]er surface treatment can also be major variables. Thus it is
important to consider fillers along with the thermosetting material, especially
for molded products. Other product forms may be filled or unfilled,
depending on requirements.
AlkYds
Alkyds are available in granular, rope, and putty form, some suitable
for molding at relatively low pressures, and at temperatures in the range of
300 to 400~F. They are formulated from polyester-type resins. Other
possible monomers, aside from styrene, are diallyl phthalate and methyl
methacrylate. Alkyd compounds are chemically similar to the polyester
compounds but make use of higher-viscosity, or dry, monomers. Alkyd
compounds often contain glass-fiber filler but may, for example, include
clay, calcium carbonate, or alumina.
These unsaturated resins are produced through the reaction of an
organic alcohol with an organic acid. The selection of suitable
polyfunctional alcohols and acids permits selection of a large variation of
repeating units. Formulating can provide resins that demonstrate a wide
range of characteristics involving flexibility, heat resistance, chemical
resistance, and electrical properties.
Diullyl Phthalates (Allyls)
Diallyl phth~lat~, or allyls, are among the best of the thermosetting
plastics with respect to high insulation resistance and low electrical losses,
which are maintained up to 400~F or higher, and in the presence of high
humidity environments. Also, diallyl phthalate resins are easily molded and
fabricated.
There are several chemical variations of diallyl phthalate resins, but
the two most commonly used are diallyl phthalate (DAP) and diallyl
isophthalate (DAIP). The primary application difference is that DAIP will
withstand somewhat higher temperatures than will DAP.
DAPs are extremely stable, having very low after-shrinkage, on the
order of 0.1 percent. The ultimate in electrical properties is obtained by the
use of the synthetic-fiber fillers. However, these materials are expensive,
have high mold shrinkage, and have a strong, flexible flash that is extremely
difficult to remove from the parts.
CA 022660~4 1999-03-11
WO 98/11159 PCTIUS97/16439
Epoxles
Epoxy resins are characterized by the epoxide group (oxirane rings).
The most widely used resins are diglycidyl ethers of bisphenol A~ These are
made by reacting epichlorohydrin with bisphenol A in the presence of an
alkaline catalyst. By controlling operating conditions and varying the ratio of
epichlorohydrin to bisphenol A, products of different molecular weights can
be made.
Another class of epoxy resins is the novolacs, particularly the epoxy
cresols and the epoxy phenol novolacs. These are produced by reacting a
novolac resin, usually formed by the reaction of o-cresol or phenol and
formaldehyde with epichlorohydrin. These highly functional materials are
particularly recommended for transfer-molding powders, electrical
laminates, and parts where superior thermal properties, high resistance to
solvents and chemicals, and high reactivity with hardeners are needed.
Another group of epoxy resins, the cycloaliphatics, is particularly
important when superior arc-track and weathering resistance are necessary
requirements. A distinguishing feature of cycloaliphatic resins is the
location of the epoxy group(s) on a ring structure rather than on, the
aliphatic chain. Cycloaliphatics can be produced by the peracetic epoxidation
of cyclic olefins and by the condensation of an acid such as
tetrahydrophthalic anhydride with epichlorohydrin, followed by
dehydrohalogenation.
Epoxy resins must be cured with cross-linking agents (hardeners) or
catalysts to develop desirable properties. The epoxy and hydroxyl groups
are the reaction sites through which cross-linking occurs. Useful agents
include amines, anhydrides, aldehyde condensation products, and Lewis
acid catalysts. Careful selection of the proper curing agent is required to
achieve a balance of application properties and initial handling
characteristics.
Aliphatic amine curing agents produce a resin-curing agent mixture
which has a relatively short working life, but which cures at room
temperature or at low baking temperatures in relatively short time. Resins
cured with aliphatic amines usually develop the highest exothermic
temperatures during the curing reaction; thus the amount of material which
can be cured at one time is limited because of possible cracking, crazing, or
.
CA 022660~4 1999-03-11
WO 98/11159 PCT/US97/16439
even charring of the resin system if too large a mass is mixed and cured.
Also, physical and electrical properties of epoxy resins cured with aliphatic
amines tend to degrade as the operating temperature increases. Epoxies
cured with aliphatic amines find their greatest usefulness where small
masses can be used, where room-temperature curing is desirable, and where
the operating temperature required is below l 00~C.
Epoxies cured with aromatic amines have a considerably longer
working life than do those cured with aliphatic amines, but they require
curing at 100~C or higher. Resins cured with aromatic amines can operate at
l O a temperature considerably above the temperature necessary for those cured
with aliphatic amines. However, aromatic amines are not so easy to work
with as aliphatic amines, because of the solid nature of the curing agents and
that some (such as metaphenylene diamine) sublime when heated, causing
stains and residue deposition.
Catalytic curing agents also have longer working lives than the
aliphatic amine materials, and like the aromatic amines, catalytic curing
agents normally require curing of the epoxy system at 100~C or above.
Resins cured with these systems have good high-temperature properties as
compared with epoxies cured with aliphatic amines. With some of the
catalytic curing agents, the exothermic reaction becomes high as the mass of
the resin mixture increases.
Acid anhydride curing agents are particularly important for epoxy
resins, especially the liquid anhydrides. The high-temperature properties of
resin systems cured with these materials are better than those of resin
systems cured with aromatic amines. Some anhydride-cured epoxy-resin
systems retain most electrical properties to 150~C and higher, and are not
affected physically, even after prolonged heat aging at 200~C. In addition,
the liquid anhydrides are extremely easy to work with in that they blend
easily with the resins and reduce the viscosity of the resin system. Also, the
working life of the liquid acid anhydride systems is comparable with that of
mixtures of aliphatic amine and resin, and odors are slight. Amine
promoters such as benzyl dimethylamine (BDMA) or DMP-30 are used to
promote the curing of mixtures of acid anhydride and epoxy resin.
Epoxies are among the most versatile and most widely used plastics
in the electronics field. This is primarily because of the wide variety of
formulations possible, and the ease with which these formulations can be
.
CA 022660~4 1999-03-11
WO 98/11159 PCT/US97/16439
made and utilized with minimal equipment requirements. Formulations
range from flexible to rigid in the cured state, and from thin liquids to thick
pastes and molding powders in the uncured state. Conversion from uncured
to cured state is made by use of hardeners or heat, or both. The largest
application of epoxies is in embedding applications (potting, casting,
encapsulating, and impregnating) in molded parts, and in laminated
constructions such as metal-clad laminates for printed circuits and unclad
laminates for various types of insulating and terminal boards. Molded parts
have excellent dimensional stability.
Melamines and Ureas (Aminos)
As compared with alkyds, dial]yl phthalates, and epoxies, which are
polymers created by addition reactions and hence have no reaction
byproducts, melamines and ureas (also commonly referred to as aminos) are
polymers which are formed by condensation reactions and do give off by-
products. Another example of this type of reaction is the polymerization
reaction, which produces phenolics. Melamines and ureas are a reaction
product of formaldehyde with amino compounds containing NH2 groups.
Hence they are often also referred to a melamine formaldehydes and urea
formaldehydes.
Amino resins have found applications in the fields of industrial and
decorative laminating, adhesives, protective coatings, textile treatment,
paper manufacture, and molding compounds. Their clarity permits products
to be fabricated in virtually any color. Finished products having an amino-
resin surface exhibit excellent resistance to moisture, greases, oils, and
solvents; are tasteless and odorless; are self-extinguishing; offer excellent
electrical properties; and resist scratching and marring. The melamine resins
offer better chemical, heat, and moisture resistance than do the ureas.
Amino molding compounds can be fabricated by economical
molding methods. They are hard, rigid, and abrasion-resistant, and they
have high resistance to deformation under load. These materials can be
exposed to subzero temperatures without embrittlement. Under tropical
conditions, the melamines do not support fungus growth.
Amino materials are self-extinguishing and have excellent electrical
insulation characteristics. They are unaffected by common organic solvents,
greases and oils, and weak acids and alkalies. Melamines are superior to
CA 022660~4 1999-03-ll
WO 98/11159 PCT/US97/16439
ureas in resistance to acids, alkalies, heat, and boiling water, and are
preferred for applications involving cycling between wet and dry conditions
or rough handling. Aminos do not impart taste or odor to foods.
Addition of alpha cellulose filler, the most commonly used filler for
aminos, produces an unlimited range of light-stable colors and high degrees
of translucency. Colors are obtained without sacrifice of basic material
properties. Shrinkage characteristics with cellulose filler are a major
problem.
Melamines and ureas provide excellent heat insulation; temperatures
up to the destruction point will not cause parts to lose their shape. Amino
resins exhibit relatively high mold shrinkage, and also shrink on aging.
Cracks develop in urea moldings subjected to severe cycling between dry
and wet conditions. Prolonged exposure to high temperature affects the
color of both urea and melamine products.
A loss of certain strength characteristics also occurs when amino
moldings are subjected to prolonged e]evated temperatures. Some electrical
characteristics are also adversely affected; the arc resistance of some
industrial types, however, remains unaffected after exposure at 500~F.
Ureas are unsuitable for outdoor exposure. Melamines experience
little degradation in electrical or physical properties after outdoor exposure,
but color changes may occur.
P1~enolics
Like melamines and ureas, phenolic resin precursors are formed by a
condensation reaction. Phenolics are among the oldest, best-known general-
purpose molding materials. They are also among the lowest in cost and the
easiest to mold. An extremely large number of phenolic materials are
available, based on the many resin and filler combinations, and they can be
classified in many ways. One common way of classifying them is by type of
application or grade. In addition to molding materials, phenolics are used to
bond friction materials for automotive brake linings, clutch parts, and
transmission bands. They serve as binders for wood-particle board used in
building panels and core material for furniture, as the water-resistant
adhesive for exterior-grade plywood, and as the bonding agent for
converting both organic and inorganic fibers into acoustical- and thermal
insulation pads, batts, or cushioning for home, industrial, and automotive
CA 022660~4 1999-03-11
WO 98/11159 PCT/US97/16439
applications. They are used to impregnate paper for eJectrical or decorative
laminates and as special additives to tackify, plasticize, reinforce, or harden
a variety of elastomers.
Although it is possible to obtain various molding grades of phenolics
for various applications, as discussed, phenolics, generally speaking, are
not equivalent to diallyl phthalates and epoxies in resistance to humidity and
retention of electrical properties in extreme environments. Phenolics are,
however, quite adequate for a large percentage of electrical applications.
Grades have been developed which yield considerable improvements in
humid environments and at higher temperatures. The glass-filled, heat-
resistant grades are outstanding in thermal stability up to 400~F and higher,
with some being useful up to 500~F. Shrinkage in heat aging varies over a
fairly wide range, depending on the filler used.
l 5 Polybutadienes
Polybutadiene polymers that vary in 1,2 microstructure from 60 to
90 percent offer potential as moldings, laminating resins, coatings, and cast
liquid and formed-sheet products. These materials, being essentially pure
hydrocarbon, have outstanding electrical and thermal stability properties.
Polybutadienes are cured by peroxide catalysts, which produce
carbon-to carbon bonds at the double bonds in the vinyl groups. The final
product is 100 percent hydrocarbon except where the starting polymer is the
--OH or--COOH terminated variety. The nature of the resultant product
may be more readily understood if the structure is regarded as polyethylene
with a cross-link at every other carbon in the main chain.
Use of the high-temperature peroxides maximizes the opportunity
for thermoplastic-like processing, because even the higher-molecular-weight
forms become quite fluid at temperatures well below the cure temperature.
Compounds can be injection-molded in an in-line machine with a
thermoplastic screw.
Polyesters (Thermosetting)
Unsaturated, thermosetting polyesters are produced by addition
polymerization reactions. Polyester resins can be formulated to have a range
of physical properties from brittle and hard to tough and resistant to soft and
flexible. Viscosities at room temperature may range from 50 to more than
.
CA 022660~4 1999-03-11
WO g8/11159 PCT/US97/16439
14
25,000 cP. Polyesters can be used to fabricate a myriad of products by
many techniques, including but not limited to, open-mold casting, hand lay-
up, spray-up, vacuum-bag molding, matched-metal-die molding, filament
winding, pultrusion, encapsulation, centrifugal casting, and injection
molding.
By the a~propliate choice of ingredient~, particularly to form the
linear polyester resin, special properties can be imparted. Fire retardance
can be achieved through the use of one or more of the following: chlorendic
anhydride, aluminum trihydrite, tetrabromophthalic anhydride,
tetrachlorophthalic anhydride, dibromoneopentyl glycol, and chlorostyrene.
Chemical resistance is obtained by using neopentyl glycol, isophthalic acid,
hydrogenated bisphenol A, and trimethyl pentanediol. Weathering
resistance can be enhanced by the use of neopentyl glycol and methyl
methacrylate. Appropriate thermoplastic polymers can be added to reduce or
eliminate shrinkage during curing and thereby minimize one of the
disadvantages historically inherent in polyester systems.
Thermosetting polyesters are widely used for moldings, l~min~tP.d or
reinforced structures, surface gel coatings, liquid castings, furniture
products, fiberglass parts, and structures such as boats, including but not
limited to sailboats, motor boats, and fishing boats; other motor vehicles
such as automobiles, trains, motorcycles, trucks, and airplanes; gliders,
sleds, and bathroom and kitchen components. Cast products include
furniture, bowling balls, simulated marble, gaskets for vitrified-clay sewer
pipe, pistol grips, pearlescent shirt buttons, and implosion barriers for
television tubes.
By lay-up and spray-up techniques large- and short-run items are
fabricated. Examples include boats of all kinds, such as pleasure sailboats
and powered yachts, commercial fishing boats and shrimp trawlers, small
military vessels, dune buggies, all-terrain vehicles, custom auto bodies,
truck cabs, horse trailers, motor homes, housing modules, concrete forms,
and playground equipment.
Molding is also performed with premix compounds, which are
dough-like materials generally prepared by the molder shortly before they
are to be molded by combining the premix constituents in a sigma-blade
mixer or similar equipment. Premix, using conventional polyester resins, is
used to mold au[omotive-heater housings and air-conditioner components.
CA 022660~4 1999-03-11
WO 98/11159 PCTIUS97/16439
Low-shrinkage resin systems permit the fabrication of exterior automotive
components such as fender extensions, lamp housings, hood scoops, and
trim rails.
Wet molding of glass mats or preforms is used to fabricate such
items as snack-table tops, food trays, tote boxes, and stac~able chairs.
Corrugated and flat paneling for room dividers, roofing and siding,
awnings, skylights, fences, and the like is a very important outlet for
polyesters.
Pultrusion techniques are used to make fishing-rod stock and
profiles from which slatted benches and ladders can be fabricated. Chemical
storage tanks are made by filament winding.
Silicones
Silicones are a family of unique synthetic polymers, which are partly
organic and partly inorganic. They have a quartzlike polymer structure,
being made up of alternating silicon and oxygen atoms rather than the
carbon-to-carbon backbone, which is a characteristic of the organic
polymers. Silicones have outstanding thermal stability.
Typically, the silicon atoms will have one or more organic side
groups attached to them, generally phenyl (C6Hs--), methyl (CH3--), or
vinyl (CH2=CH--) units. Other alkyd aryl, and reactive organic groups on
the silicon atom are also possible. These groups impart characteristics such
as solvent resistance, lubricity and compatibility, and reactivity with organic
chemicals and polymers.
Silicone polymers may be filled or unfilled, depending on properties
desired and application. They can be cured by several mech~ni.~m~, either at
room temperature [by room-te-l-peldlule vulcanization (RTV)] or at elevated
temperatures. Their final form may be fluid, gel, elastomeric, or rigid.
Some of the properties which distinguish silicone polymers from
their organic counterparts are (1) relatively uniform properties over a wide
temperature range, (2) low surface tension, (3) high degree of slip or
lubricity, (4) excellent release properties, (5) extreme water repellency, (6)
excellent electrical properties over a wide range of temperatures and
fre~uencies, (7) inertness and compatibility, both physiologically and in
electronic applications, (8) chemical inertness, and (9) weather resistance.
CA 022660S4 1999-03-11
Wo 98/11159 PCT/US97/16439
16
Flexible two-part, solvent-free silicone resins are available in filled
and unfilled forms. Their viscosities range from 3000 cP to viscous
thixotropic fluids of greater than 50,000 cP. The polymer base for these
resins is primarily dimethylpolysiloxane. Some vinyl and hydrogen groups
attached to silicon are also present as part of the polymer.
These products are cured at room or slightly elevated temperatures
During cure there is little if any exotherm, and there are no by-products from
the cure. The flexible resins have Shore A hardness values of 0 to 60 and
Bashore resiliencies of 0 to 80. Flexibility can be retained from -55~C or
lower to 250~C or higher.
Flexible resins find extensive use in electrical and electronic
applications where stable dielectric properties and resistance to harsh
environments are important. They are also used in many industries to make
rubber molds and patterns.
Rigid silicone resins exist as solvent solutions or as solvent-free
solids. The most significant uses of these resins are as paint intermediates to
upgrade thermal and weathering characteristics of organic coatings, as
electrical varnishes, glass tape, and circuit-board coatings.
Glass cloth, asbestos, and mica l~minates are prepared with silicone
resins for a variety of electrical applications. Laminated parts can be molded
under high or low pressures, vacuum-bag-molded, or filament-wound
Thermosetting molding compounds made with silicone resins as the
binder are finding wide application in the electronic industry as encapsulants
for semiconductor devices. Inertness toward devices, stable electrical and
thermal properties, and self-extinguishing characteristics are important
reasons for their use.
Similar molding compounds, containing refractory fillerst can be
molded on conventional thermoset equipment. Molded parts are then fired to
yield a ceramic article. High-impact, long-glass-fiber-filled molding
compounds are also available for use in high-temperature structural
applications.
In general, silicone resins and composites made with silicone resins
exhibit outstanding long-term thermal stabilities at temperatures approaching
300~C, and excellent moisture resistance and electrical properties.
All of the conventional plastics shrink and/or crack to some degree
when molded into large objects. To avoid these problems, elaborate curing
CA 022660~4 1999-03-11
WO 98/11159 PCT/US97/16439
17
schemes often have to be implemented which, in some cases, takes time and
specialized equipment. What is needed is an additive or additives that will
inhibit cracking and shrinkage and a3low the rapid casting of large objects
from a variety of prior art resins. What is also needed are additives that will
strengthen objects made from conventional and gel coat resins without
significantly increasing their weight.
SUMMARY OF THE INVENTION
The present invention comprises novel resin polymer additives
l 0 which can be used to cast large objects in a short time with substantially no
shrinkage or cracking, and without the use of specialized equipment or
special curing environments such as heating. The additives of the present
invention can be used in a wide variety of conventional resins and also with
gel coat resins.
The present invention comprises additives that impart non-shrinking
properties and non-cracking properties to a wide variety of conventional
resins. The additives can be added to resins and by adjusting the
concentration of certain components of the additives, the rate of curing can
be controlled without accompanying side effects such as shrinkage or
cracking.
One of the non-shrinking formulations is a mixture comprising
aldehyde, glycol, perchlorate and metal chlorides. In one preferred
embodiment, this non-shrinking formulation is a mixture comprising
formaldehyde, glycol, copper perchlorate and copper chloride.
A second, non-shrinking formulation is an admixture comprising
peroxide, methacrylates or acrylate monomers, and N-methylpyrrolidinone.
In one preferred embodiment, this second, non-shrinking formulation is an
admixture comprising benzoyl peroxide, methyl methacrylate and N-
methylpyrrolidinone.
The present invention further comprises a non-cracking formulation
containing N-butyl mercaptan and halogenated derivatives, such as tetraethyl
bromine, or various chain extenders.
The present invention further comprises another additive comprising
a formulation which is a hardener solution that may be added to
conventional resins and to gel coat resins to increase the strength of the
objects made from these resins. The hardener solution is made by
CA 022660~4 1999-03-11
WO 98/11159 PCT/US97/16439
18
dissolving dibenzoyl peroxide to saturation in about 50 ml of
methylmethacrylate on a cold water bath. An equal volume of styrene is
added and mixed. Other monomers containing styrene, and other strong
peroxides may be used in the practice of this invention. Optionally,
butanethiol (0.25%), preferably l-butanethiol, may be added to the mix.
Other methacrylate monomers and acrylate monomers such as those in Table
1 may also be used in the practice of this invention.
The present invention further comprises another forrnulation which
may be used to increase the strength of conventional resins and gel coat
resins through the addition of different amounts of a solution of
carboxymethylcellulose (CMC) solution made by first saturating CMC
powder in methanol followed by the addition of water and other ingredients.
By increasing the amount of CMC solution added lo conventional resins and
gel coat resins, the strength of the object made form these resins increases
1~ without significant increases in the weight of the object.
The various formulations can be used in combination or singly
depending upon the resin and filler to which the formulations are to be
added. Preferably, all three formulations are added to the resin before
casting the large object.
The present invention also comprises a filler in the forrn of binders
and polar polymer gels that are treated with a polar solvent.
The present invention also optionally comprises a method of
pretreating glass fiber before it is incorporated into a polymer resin to add
strength to the resin. The pretreated fiber glass comprises conventional
fiberglass that has been treated with a surfactant or dispersant formulation
such as dodecyl benzene sulfonic acid or any other ionic surfactant. The
dodecyl benzene sulfonic acid is dissolved in water and then the voiume is
increased with ethylene glycol at a ratio of approximately 10% to 9Q%
ethylene glycol to approximately 10% to 90% of the aqueous solution of
dodecyl benzene sulfonic acid.
Accordingly, it is an object of the present invention to provide
additives to conventional resins which impart the desirable characteristics of
non-shrinlcage and non-cracking when casting the resin, with the addition of
treated fillers as described above.
CA 022660~4 1999-03-11
WO 98/lllS9 PCT/US97/16439
19
It is another object of the present invention to provide novel
additives and resin compositions that can rapidly be cast into objects
including large objects without shrinking or cracking.
It is another object of the present invention to provide novel
additives that may be used to increase the strength of objects made from
conventional resins and gel coat resins without significantly increasing the
weight of the objects.
It is yet another object of the present invention to provide a novel
method of pouring or casting large objects from polymer resins.
It is yet another object of the present invention to provide a novel
method of manufacturing large objects from polymer resins that are fire-
resistant.
Another object of the present invention is to provide methods and
compositions that can be used in the construction industry.
It is another object of the present invention to provide a method and
composition for casting cultured marble.
Another object of the present invention is to provide additives for
use in casting cultured marble which impart the desirable characteristics of
non-shrinkage and non-cracking when casting the marble, and significantly
accelerate the process of casting the marble.
Another object of the present invention is to provide methods and
materials for rapidly casting objects that are hard. exhibit high resistance to
breakage, and are flexible.
These and other objects, features and advantages of the present
invention will become apparent after a review of the following detailed
description of the disclosed embodiments.
DETAlLED DESCRIPTION OF THE PREFERRED EMBODIMENTS
The present invention comprises a polymer resin that can be rapidly
cast with substantially no shrinkage or cracking. The polymer resin of the
present invention can be cast into a variety of objects, including large
objects, without special curing conditions. The polymer resin is especially
useful in casting large building elements such as blocks, pavers, shingles,
roofs, floors, siding, stairs, bricks, pilings, bridges, sea retaining walls,
piers, docks, foundations, beams, walls, including structural walls and
sound walls, and the like. The present invention may also be used to cast
CA 022660~4 1999-03-11
WO 98/11159 PCT/US97/16439
modular units such as apartments, houses, portable homes, jail cells,
rooms, basements, storage sheds, classrooms, portable schools, portable
offices, and hazardous materials and hazardous chemicals storage cabinets
and buildings. The present invention may also be used to cast toys,
playgrounds, swing sets, jungle gyms, and other items used by children
The methods and compositions of the present invention may be used
to make objects used in the construction industry. For example,
foundations, pilings, walls, floors, tiles, wall tiles, floor tiles, paneling,
sinks, kitchen counter tops, cabinets, laboratory counter and bench tops,
table tops, basins, pedestal wash basins, bidets, toilets, urinals, showers,
shower stalls, tubs, bathtubs, Jacuzzis, hot tubs, whirlpools, vanity tops,
wall surrounds, decorator mirror frames, soap dishes, and towel bars may
all be made as well as other hard surfaces. Plumbing materials including,
but not limited to, pipes, sewer pipes, manholes, manhole covers, storage
tanks, couplings, joints, fixtures, knobs, showerheads, faucets, drains,
water pipes, water mains, and fountains may all be manufactured with the
present invention. Houses may be constructed rapidly and at reduced cost
in geographic areas deficient in traditional building materials such as timber.
Apartment units may be cast rapidly in modular form and assembled quickly
into buildings.
Drainage systems, culverts, driveways, curbs, walkways,
sidewalks, and many other objects typically made from concrete may be
made with the methods and compositions of the present invention.
Components of bridges and other reinforced structures may be constructed
from the present invention due to the strength of these novel materials.
Railroad ties, poles for streetlights, poles for traffic lights, poles for street
signs, telephone poles, poles and structural elements for transmission
systems, electrical manholes, high voltage lines, communication towers,
docks, decks, piers, sea retaining walls, breakwaters, jetties, and other
objects made from timber, concrete and/or steel may be made more
economically and rapidly with the methods and materials of the present
invention .
In addition to forming many of the objects listed above, it is to be
understood that the present invention may be used to place a protective
coating around or on the surface of many of these objects. For example, in
one embodiment of the present invention, existing shipping pilings may be
CA 022660~4 1999-03-11
WO 98/11159 PCT/US97/16439
encapsulated or coated with the composition of the present invention to
increase strength and longevity, and to decrease the need for routine
maintenance such as painting. By encapsulating or coating the surfaces of
structural elements of objects, structural integrity may be preserved for a
longer period of time before replacement is necessary. For example, in
another embodiment of the present invention, steel and/or concrete
components of bridges may be coated with the compositions of the present
invention in order to retard corrosion from sources such as environmental
pollutants and salt water, thereby extending the useful life of the bridge.
l 0 Since the compositions of the present invention are corrosion resistant and
may be colored consistently throughout, coating an object such as a bridge
would decrease or eliminate the need for expensive, laborious and lengthy
routine maintenance and painting. Other objects that may receive coatings of
the present invention include, but are not limited to, siding, shingles, slate,
tile, sound walls, sea walls, docks, jetties, breakwaters, tunnels, ship hulls,
poles including telephone poles and light poles, transmission towers for
communication and power lines, as well as other objects mentioned
elsewhere in the present application.
A wide variety of cooking and kitchen objects may be made with the
compositions and methods of the present invention including cookware,
plates, utensils, glasses, and baking devices.
The present inventions include novel compositions comprising
conventional resins, including, but not limited to, epoxies, polyesters,
polyurethanes, flexible silicones, rigid silicones, polybutadienes,
polysulfides, depolymerized rubber and allylic resins. Polyesters that can
be used in the present invention include, but are not limited to, alpha methyl
styrene, methyl methacrylate, vinyl toluene, diallyl phthalate, trallyl
cyanurate, divinyl benzene, and chlorostyrene.
Initiators for curing the resins include, but are not limited to,
peroxides such as benzoyl peroxide, methyl ethyl ketone peroxide (also
called 2-butanone peroxide), hydrogen peroxide, and dibenzoyl peroxide.
Other initiators that may be used in the present invention include azo
compounds. Polyaniline in N-methylpyrrolidinone may also be used as an
initiator in some formulations.
3~ Catalysts, including but not limited to, cobalt II acetate, cobalt II
naphthanate, methylene II acetate, chromium II acetate, copper II acetate,
CA 022660~4 1999-03-11
WO 98/11159 PCT/US97/16439
calcium oxide, N,N-dimethylaniline, and 3,5-dimethylaniline, can
optionally be used in the present invention. Diethylamines, triethylamines
and other amine-containing catalysts may also be used in the present
invention. Catalysts are dissolved in any suitable solvent before, including
but not limited to solvents such as styrene, water, or alcohol. The catalysts
that can be used in the present invention are well known to those of ordinary
skill in the art. (See Handbook of Plastics, Elastomers and Composites,
Harper, C.A., editor, McGraw-Hill, 1992 which is incorporated by
reference).
Fillers can be used with the present invention in the form of
powders, fibers, flakes, and liquids, for example, tar. Fillers are used to
modify viscosity, increase pot life, reduce exotherm, modify density,
improve heat resistance, modify thermal conductivity (usually to increase
thermal conductivity), increase strength, improve machineability, increase
hardness and wear resistance, modify electrical properties, increase chemical
and solvent resistance, modify friction characteristics, improve thermal
shock resistance, improve adhesion, and impart color.
Generally the fillers should be low in cost, reproducible in
composition, particle size, and shape, easy to disperse in the compound,
and low in density, and they should not increase the viscosity of the mixture
excessively. The filler should stay in suspension or be able to be
resuspended with a minimum of stirring. Fillers that can be used in the
present invention include, but are not limited to, silica, calcium carbonate,
clays, aluminum hydroxide, titanium dioxide, calcium silicate, aluminum
trihydride, glass spheres, hollow spheres, fibers including glass, asbestos,
Dacron, cotton, nylon, metal powders and particles, powders, sand, soil,
fly ash, pigments, carpet and fragments thereof, saw dust, and stone.
The present invention also incorporates reactant fillers. This is a
filler that uniformly is distributed in the resin. The reactant fillers must be
pretreated with a hydroxyl group (e.g., an alcohol such as ethyl alcohol), or
diluted polar solvents or polar polymers such as carboxymethylcellulose
(CMC), or a functional carbonyl group (e.g., an organic acid such as acetic
acid) additive with slightly acidic pH and the non-cracking additive (see
Example 3). It is important to note that the pretreatment of fillers with a
hydroxyl group, with diluted polar polymers, or with a carboxyl group as
described above is essential to the practice of the present invention. The
CA 022660~4 1999-03-11
WO 98/11159 PCT/US97/16439
fillers should further be treated with the dispersant formulation described in
Example 5. In one embodiment, the dispersant formulation comprises an
ionic surfactant, such as dodecylbenzene sulfonic acid, mixed with p-
to]uene sulfonic acid monohydrate in a about l to I ratio. This mixture is
then added to ethylene glycol at a ratio of approximately 2 parts ethylene
glycol to l part of the p-toluene sulfonic acid mixture. The treated filler is
then added to the resin in a conventional manner.
The present invention includes additives that can be added to
conventional resins and fillers that impart desired effects of non-shrinkage
l 0 and non-cracking of the cured objects.
One of the additives that is a non-shrinking formulation is a mixture
comprising aldehyde, glycol, perchlorate and metal chlorides. The
aldehydes that may be used in this formulation include, but are not limited
to, formaldehyde, paraformaldehyde, and glutaraldehyde. The glycols that
may be used in this formulation include, but are not limited to, propylene
glycol and ethylene glycol. The perchlorates that may be used in this
formulation include, but are not limited to, copper perchlorate. The metal
chlorides that may be used in this formulation include, but are not limited to,
copper II chloride, mercuric chloride, magnesium chloride, manganese
chloride, nickel chloride, ferric chloride, ferrous chloride, silver chloride,
gold chloride, zinc chloride, cadmium chloride, and aluminum chloride. In
one preferred embodiment, this non-shrinking formulation is a mixture
comprising formaldehyde, glycol, copper perchlorate and copper chloride.
In this embodiment, this first non-shrinking additive that inhibits shrinking
of the resin during curing comprises formaldehyde (approximately 100
parts), glycol (approximately 100 parts), copper perchlorate (approximately
10 parts), and copper chloride (approximately 20 parts). Depending upon
the resin that is being treated, the composition can vary.
Another additive is a second, non-shrinking formulation which is an
admixture comprising peroxide, methacrylates or acrylate monomers, and
N-methylpyrrolidinone (NMP). The peroxides that may be used in this
formulation include, but are not limited to, benzoyl peroxide, hydrogen
peroxide, dibenzoyl peroxide and methyl ethyl ketone peroxide. Azo
compounds may be used instead of peroxide compounds. The
methacrylates and acrylate monomers that may be used in this formulation
include, but are not limited to, those listed in Table l. In one preferred
CA 02266054 1999-03-11
WO 98111159 PCT/US97/16439
24
embodiment, this second, non-shrinking formulation that inhibits shrinking
of the resin during curing comprises an admixture of benzoyl peroxide,
methyl methacrylate and N-methylpyrrolidinone. In this embodiment,
benzoyl peroxide, methyl methacrylate and NMP are present in a ratio of
S approximately 100:50:20.
CA 022660~4 1999-03-11
WO 98/11159 PCT/US97/16439
TABLE I
Monomer nD of
polymer
methyl methacrylate 1.49
etl1yl methacrylate .~83
n-propyl methacrylate '84
n-butyl methacrylate '83
n-hexyl methacrylate 1.48 ~
isopropyl methacrylate - .473
isobutyl methacrylate 477
tert-butyl methacrylate 463
cyclohexyl methacrylate 507
benzyl methacrylate .568
phenyl me-hacrylate 1 57
I -phenylet-yl methacrylate 1 549
2-phenylet lyl methacrylate 1.559
furfuryl methacrylate 1.538
methyl acrylate 1.4725
ethyl acrylate 1.4685
n-butyl acrylate 1.4634
benzyl acrylate 1.5584
2-chloroethyl acrylate 1.52
vinyl acetate 1.47
vinyl benzoate 1.578
vinyl phenylacetate 1.567
vinyl chloroacetate 1.512
acrylonitrile 1.52
a-methylacrylonitrile 1.52
methyl- a -chloroacrylate I .5172
atropic acid, methyl ester 1.560
o-chlorostyrene 1.6098
p-fluorostyrene .566
o, p-difluorostyrene - .475
pentabromophenylacrvlate .7
pentachlorophenyl me:hacrylate 1.63
pentabromophenylmetlacrylate 1.71
chlorophenylacrylate 1.5
benzylmethacrylate .56
2,4,6 tribromophenylacrylate .6
a, cl), dichloropropyl-dimethylsiloxane : .42
p-isopropyl styrene 1.554
2,2,2-trifluoroethy acrylate 1.37
2,2,2-trifluoroethy methacrylate 1.39
tribromoneopentylmethacrylate 1.6
The present invention further comprises a third additive that is a non-
cracking additive is a formulation containin~ N-butyl mercaptan and
CA 022660~4 1999-03-11
Wo 98/11159 PCT/US97/16439
26
halogenated derivatives, such as tetra ethyl bromine, or various chain
extenders. In one embodiment, N-butyl mercaptan and tetraethyl bromine
are mixed together at a ratio of approximately l 00 parts N-butyl mercaptan
to l part tetraethyl bromine by weight. Other chain extenders may also be
substituted in this formulation to impart non-cracking properties. This
additive should be combined with the other additives disclosed above in the
practice of the present invention.
The various formulations can be used in combination or singly
depending upon the resin and filler to which the formulations are to be
added. In general terms, the present invention provides a method of making
objects comprising treating fillers with polar solvents or polar polymers and
dispersant formulation, mixing the treated fillers with resin, adding ethylene
glycol and styrene, adding in any order the three additives A, B, and C,
described in Examples 1, 2, and 3, adding catalyst and dimethylaniline, and
l S adding initiator.
Typically, these three additives are added at a concentration of
between about 0.1 to 4% by weight with a desired concentration of between
approximately 0.5% to 2% by weight. It is to be understood that the
additives can be used separately or together in the final resin preparation
depending upon the desired properties that need to be imparted to the formed
object.
The present invention also provides a method for strengthening
objects made from resin, and an additive composition which is a hardener
solution that may be added to conventional resins and gel coat resins to
increase the strength of the objects made from these resins. The hardener
solution is made by dissolving dibenzoyl peroxide to saturation in about 50
ml of methylmethacrylate on a cold water bath. An equal volume of styrene
is added and mixed. Optionally, butanethiol (0.25%), preferably 1-
butanethiol~ may be added to the mix. A range of butanethiol that may be
used in the present invention is from about 0.02% to 0.25%. Other
monomers containing styrene, and other strong peroxides may be used in
the practice of this invention. Other methacrylate monomers and acrylate
monomers, such as those in Table I, may also be used in the practice of this
invention.
Another method of the present invention that may be used to
increase the strength of conventional resins and gel coat resins is the
CA 022660~4 1999-03-11
WO 98/11159 PCT/U$97/16439
27
addition of different amounts of a solution of carboxymethylcellulose
(CMC) solution made by first saturating CMC powder in methanol or
ethanol followed by the addition of water and other ingredients. Heat may
optionally be used to accelerate CMC entering solution. By increasing the
amount of CMC solution added to conventional resins and gel coat resins,
the strength of objects made from these resins increases without significant
increases in their weight. Desirable concentration ranges of CMC in
aqueous solution are from about 0.1% to 5.0~, with a more preferred
concentration range of from 0.25% to 5.0% and a most desired
concentration range of from 0.5% to 1%.
Polyaniline is also be used to increase the strength of
conventional resins and gel coat resins. Desirable concentration ranges of
polyaniline in aqueous solution are from about 0.1% to 5.0%, with a more
preferred concentration range of from 0.25% to 5.0% and a most desired
concentration range of from 0.5% to 1%. Po]yaniline is sometimes
combined with the CMC in solution in a range of polyaniline to CMC from
about 10% to 90%.
The present invention also includes cultured marble products.
According to the present invention, cultured marble products can be made
without the prior art requirements of carefully controlling the curing process
to avoid shrinkage and cracking of the final poured product. The cultured
marble products made with the present invention may be used in a variety of
applications described above. Some preferred applications of the present
invention are the production of tiles, paneling, sinks, counter tops, basins,
sinks, pedestal wash basins, bidets, table tops, toilets, toilet holders,
urinals, showers, tubs, bathtubs, Jacuzzis, hot tubs, whirlpools, couplings,
joints, fixtures, soap dishes, towel bars, toilet paper dispensers, knobs,
showerheads, faucets, drains, fountains, siding, and surface application to
bricks or stone.
The present invention also includes methods and compositions for
rapidly making strong but flexible objects. Strong and flexible objects have
many uses in a variety of industries. For examp]e, in the transportation
industry, bumpers made with one embodiment of the present invention
would increase protection to motor vehicles such as automobiles, trucks,
and buses. Strong and flexible objects would also be useful as bumpers on
the sides of boats, such as sailboats, as bumpers for loading docks for
,
CA 022660~4 1999-03-ll
Wo 98/11159 PCT/US97/16439
28
trucks and train cars, as crash guards on the highway, as bumpers on
loading docks for boats, ships, trucks, and trains, as protective strips on the
sides of motor vehicles, as mud flaps for motor vehicles, as a material for
use in the construction of dashboards, as a building material in a geographic
area prone to earthquakes, or as a building material in areas subject to
vibrational stress such as near subways, railroads and highways and near
bridges, and as a material for use in construction of playgrounds and
recreational facilities, including surfaces of playgrounds, monkey bars,
jungle gyms, and swing sets.
In one embodiment of the present invention, flexible ob~ects
with high tensile strength may be made by forming a strong, fibrous and
flexible resin in the following manner. In this method, a low molecular
weight polyaniline is employed. To produce the low molecular weight
polyaniline used in the present invention, a prepolymer solution was
prepared by mixing about 21 ml of distilled purified aniline with about 300
ml of l M HCI. The prepolymer solution was then placed in a three necked
flask and purged with nitrogen and cooled to approximately 5~ C. In a
separate container, about 12 gm ammonium persulfate was dissolved in
approximately 200 ml of l M HCl. The container was purged with pure
nitrogen. The ammonium persulfate solution was cooled to about 5~ C and
then added to the 3 necked flask. The mixture was cooled to approximately
0~ C and stirred for about 20 minutes. The temperature of the solution was
then raised to 8~ to 10~ C for about 15 minutes. Next, the solution was
cooled to approximately 0~ C and stirred for about 45 minutes. The
polyaniline precipitate was then washed several times by filtration with
distilled water. The polyaniline precipitate was treated with I M potassium
hydroxide for about 24 hours after which it was filtered, washed again for 6
to 12 hours in distilled H2O, heated, and dried in a vacuum oven for about
24 hours at 50~ C. The dried polyaniline was ground into a powder. The
mixture was optionally extracted with a soxhlet extraction with acetonitrile
for 3 hours until the extract was no longer colored. This extraction
produced a polyaniline powder. The polyaniline was dried in an oven at 50~
C for about 6 to 7 hours and then ground to a powder. It was then treated
with I M KOH for about 24 hours after which it was filtered, washed again
for 6 to 12 hours in distilled H2O and dried in a vacuum oven for about 24
hours at approximately 50~ C. The polyaniline precipitate was then
CA 022660~4 1999-03-11
WO 98/11159 PCT/US97/16439
29
dissolved in a N-methylpyrrolidinone (NMP) to saturation. Different
amounts of polyaniline may be added to NMP to achieve a final percentage
of from 0.1% by weight of the total mixture to a saturated solution. It is to
be understood that pyrrolidone and pyrrolidinone are synonymous as used
throughout the present application. Objects made with strong, fibrous and
flexible resin may be used in numerous applications requiring superior
strength, including but not limited to sheathing for cables, wires, power
lines, transmission lines, communication cables, and fiber optic cable.
A resin mix can be made with the following method. To about 30
ml of polyester resin added approximately 4-8 ml of styrene, 0.5 to l ml
N,N-dimethylaniline, 0.5 to I ml of cobalt II naphthanate as catalyst, 0.2 to
0.8 ml of the saturated solution of polyaniline in N-methylpyrrolidinone as
described above, and about 0.1 to 0.4 ml of the initiator methyl ethyl ketone
peroxide. The resulting resin displays a fibrous matrix and was strong and
1 5 flexible.
Other hard resin mixes can be made with the following method
ranges of reagents: vinylester resin 400 - 450 gm; N,N-dimethylaniline 0.25
- 2 gm; catalyst cobalt II naphthanate 0.25 - 2 gm; Solution 4A (Example
16) 3 -4 gm; Solution 4B (Example 16) 0.8 - 3 gm; Solution SC (Example
16) 3 - 4 gm; calcium oxide 2 - 3 gm. Examples of some of these ranges are
presented in Table 5.
It is to be understood that other catalysts, as described in the present
application, may be used instead of cobalt II naphthanate in the method
described above. Both diethylamine and triethylamine may also be used as
catalysts, as well as other amine-containing catalysts. In addition, other
resins described in the present application may be used instead of polyester
resin, including but not limited to vinyl esters, epoxy resins, and modar
resin.
In another embodiment of the present invention for making strong
flexible materials with fibrous resin, the solution of polyaniline in N-
methylpyrrolidinone as described in the preceding embodiment was used
and methyl ethyl ketone peroxide was not added to the mixture. The
polyaniline in N-methylpyrrolidinone acted as a slower initiator than the
methyl ethyl ketone peroxide. In this embodiment, the addition of methyl
ethyl ketone peroxide, from about 0.1% to 2% by weight, is optional and it
CA 022660~4 1999-03-ll
WO 98/11159 PCT/US97/16439
may be added to accelerate the reaction. The resulting resin displayed a
fibrous matrix and was strong and flexible.
The present invention also includes blends of resins and fiberglass
which exhibit high tensile strength comparable to fiberglass and do not
require the laborious and expensive multiple applications of fiberglass layers
with lengthy curing times. The pretreated fiber glass comprises
conventional fiberglass that has been treated with a surfactant or dispersant
formulation such as dodecyl benzene sulfonic acid or any other ionic
surfactant. The dodecyl benzene sulfonic acid is dissolved in water and then
l 0 the volume is increased with ethylene glycol at a ratio of approximately 10%
to 90% ethylene glycol to approximately 10% to 90% of the aqueous
solution of dodecyl benzene sulfonic acid. In general, glass fiber is
pretreated before it is incorporated into a polymer resin to add strength to theresin. After wetting the fiberglass with the surfactant, about 5 gm of
l 5 pretreated fiberglass and about 400 ml of surfactant are mixed in a high
speed blender until single fibers are apparent. This embodiment of the
present invention produces objects that are strong, lightweight and useful in
applications employing fiberglass including but not limited to the
manufacture of motor vehicles, especially the shell or body of the motor
vehicle, including fenders, panels, hoods, trunks and roofs. In another
specific embodiment, the present invention may be used to produce hulls
and decks of boats and ships, or to coat the surfaces of existing hulls and
decks for protection, maintenance and repair. Boats, including but not
limited to sailboats, cat~m~rans, speedboats, power boats, fishing boats,
cabin cruisers, houseboats, and rowboats may all be made with the present
invention.
It is to be understood that the objects made through the practice of
the present invention possess special properties such as fire retardance,
chemical resistance, weather resistance, biological resistance, including
resistance to microbes, resistance to environmental contaminants and
pollution, corrosive resistance, resistance to ultraviolet radiation, heat
resistance, resistance to cracking and breakage, and electrical properties.
These properties can be enhanced by altering the addition of specific
chemicals disclosed herein.
This invention is further illustrated by the following examples,
which are not to be construed in any way as imposing limitations upon the
CA 022660~4 1999-03-11
WO 98/11159 PCT/US97/16439
scope thereof. On the contrary, it is to be clearly understood that resort may
be had to various other embodiments, modifications, and equivalents thereof
which, after reading the description herein, may suggest themselves to those
skilled in the art without departing from the spirit of the present invention.
S For example, it is to be understood that the amounts of reagents used in the
following Examples are approximate and that those skilled in the art might
vary these amounts and ratios by as much as 30% without departing from
the spirit of the present invention.
Example 1
Non-shrinking Additive (A)
A first non-shrinking additive (A) is a formulation that can be used
with conventional resins to inhibit shrinking of the resin as it cures is
described in this example. The formulation comprises the following:
Additive A (Non-shrinking formulation)
Forrnaldehyde 100 ml
Glycol- 100 ml
Copper perchlorate 10 mg
Copper chloride 20 mg
The copper chloride and copper perchlorate were dissolved into
formaldehyde and glycol.
Example 2
Non-shrinking Additive (B)
A second non-shrinking additive (B) is a formulation that can be
used with conventional resins to inhibit shrinking of the resin as it cures is
described in this example. The formulation comprises the following:~0
CA 022660~4 1999-03-ll
WO 98/11159 PCT/US97/16439
Additive B (Non-shrinking formulation)
Benzoyl peroxide 118 mg
Methyl methacrylate 50 ml
N-methylpyrrolidinone 20 ml
s
The benzoyl peroxide was dissolved into the methyl methacrylate and N-
methylpyrrolidinone.
Example 3
Non-Crac~ing Additive
A third additive is a non-cracking formulation that can be used with
conventional resins to inhibit shrinking of the resin as it cures is described in
this example. The formulation comprises the following:
Additive C (Non-cracking formulation)
N butyl mercaptan 100 mg
Tetraethyl bromine I mg
Example 4
To a polyester resin was added equal amounts of any filler
pretreated with a polar solvent or mixed in dilute polar polymer, such as
slightly acidic water, alcohol, or about 10% carboxymethylcellulose in
slightly acidic water. Next approximately 0.2% of additive A, about 1.8%
of non-shrinking additive B, 1-2% of N,N-dimethylaniline, and
approximately 2% of the non-cracking additive C were added. Next, the
initiator, such as a benzoyl peroxide, and a catalyst, such as cobalt II
acetate, were added at concentrations of about 2% each to polymerize the
resin. The resin polymerized with no detectable shrinkage or cracking. All
percentages in this example are expressed as vol % unless otherwise
indicated.
Example 5
Dispersant Formulatioll
A dispersant formulation for pretreating fillers was prepared as
follows: about 60 grams of dodecylbenzene sulfonic acid (sodium salt) was
dissolved completely in approximately 60 ml of aqueous 0.1 M p-toluene
CA 022660~4 1999-03-ll
WO 98/11159 PCT/US97/16439
sulfonic acid monohydrate. Then, about 2580 ml of ethylene glycol and
about 1200 ml of 0.1M p-toluene sulfonic acid solution were added. The
resulting solution was then thoroughly mixed. Fillers were either added
directly to the formulation or were pretreated with an organic alcohol, such
as ethyl alcohol or an organic carboxylic acid, such as acetic acid
(approximately 0.01 - 0.1 M) at a slightly acidic pH. The fillers to be added
to the resin were immersed in the dispersant formulation for a period of
about 0.5 to 2 hours. The fillers were then added to the resin mixture.
~Pmrle 6
Cultured Marble
This Example describes the production of cultured marble using
the additives of the present invention and a filler that is not a polar polymer.The production of cultured marble is in two parts. The conventional resin
makes up the body of the cultured marble object. The gel coat provides a
smooth surface for the cultured marble object. The surface and the mix are
capable of being colored.
The basic resin in this Example was about 300 ml of diethyl
fumarate trans-2-butene 1,4 diol gel. It is to be understood that any resin or
polyester resin may be used in the practice of the method disclosed in this
Example. The filler was prepared as follows: about 732.5 gm of CaCOl
and approximately 504 gm of TiO2 were mixed and then treated with about
10 - 20% by weight of ethyl alcohol or slightly acidic water for
approximately I hour. Other fillers than CaCO3 and TiO2, including but not
limited to powders, sand, soil, and fly ash may be used in this invention.
The dispersant formulation from Example 5 was then added to the filler
preparation at a concentration of about 1.5% by weight. The resin (diethyl
fumarate trans-2-butene 1,4 diol gel) was then mixed with the filler in
dispersant formulation. Additive A from Example 1, additive B from
Example 2 and the non-shrinking additive C from Example 3 were then
added in any order to a final concentration of about 1% by weight of each.
To this mixture was added about 70 ml of ethylene glycol, 70 ml of styrene,
12 ml of cobalt II acetate and 14 ml of N,N-dimethylaniline. This
formulation was thoroughly mixed. To polymerize the conventional resin,
approximately 10 ml of a 30% solution of benzoyl peroxide was added.
This formulation is designated the "basic resin".
CA 022660s4 1999-03-ll
WO 98/11159 PCT/US97/16439
34
The gel coat resin was prepared as follows: A first formulation
was prepared by mixing about 1008 gm of TiO~ or CaCO3 with about 60 ml
of 4% diluted dodecyl benzene in water. Approximately 60 ml of the
conventional resin without benzoyl peroxide was added along with about
6.5 ml of cobalt II acetate. The first formulation was then thoroughly
mixed.
A second gel coat preparation comprises approximately 300 ml
of gel coat resin (gel coat resin from Occidental Chemicals) mixed with
about l05 gm of TiO2. The first preparation and the second gel coat
l 0 preparation were mixed in a ratio of approximately 2 to 1. Just before use,
an initiator such as 10% to 30% methyl ethyl ketone peroxide or l0% to
30% benzoyl peroxide was added at a final concentration of about 2% by
volume.
The gel coat preparation was coated on the surface of a form.
The basic resin formulation was then poured into the form and allowed to
cure. The resin cured to hardness within approximately 5 minutes and was
completely cured within about 1 hour. The resulting object could be
removed from the mold after approximately l0 minutes.
F,l~mrle 7
Rapid Casting Method for Gel Coat Preparations and Conventional Resin
Forml,clations
This example describes a method for rapid casting that may be
employed with both the gel coat preparations, including cultured marble,
and conventional resin formulations. The method involves two steps which
may be practiced at room temperature and involves the use of a polar
polymer as the filler. The method produces a smooth surface. In addition,
the resins from Example 6 may be used in the practice of the method
disclosed in this Example.
Step 1: First the carboxymethylcellulose (CMC) gel was formed
by saturating about Sg of CMC powder with methanol. Next the CMC was
slowly added to approximately 800 ml of water while mixing to make the
CMC solution. Alternatively, CMC has been saturated with ethanol instead
of methanol and mixed with water in a similar manner.
Step 2: To each 40 ml of any gel coat or resin formulation, were
added between approximately 3 ml and 6 ml of the CMC solution.
CA 022660~4 1999-03-11
WO 98/11159 PCT/US97116439
Optionally, approximately 10% to 20% of ethylene glycol and/or styrene
were added to this mixture. The amount of CMC solution is based on the
desired strength, appearance, and cost of the final product. Next, about 1-
2% (vol%) of N.N-dimethylaniline was added together with any known
catalyst while mixing. Catalysts which may be employed at this step
include, but are not limited to methylene II acetate, chromium II acetate,
copper II acetate and cobalt II naphthanate. Catalysts were added at
approximately 10% (vol %) in solvents such as alcohol, styrene, water, or
any suitable solvent for the specific catalyst.
The reaction was initiated by adding about I - 2% (vol %) of
peroxides and mixing into the other ingredients. The peroxides which have
been used include, but are not limited to methyl ethyl ketone peroxide,
hydrogen peroxide, and dibenzoyl peroxide at initial concentrations of about
10% to 30%. Other initiators that have been used include other peroxide
initiators and azo initiators. The curing rate and heat generated vary
depending on the amount of C~C gel and peroxides employed. Addition of
more gel produced less heat and increased curing time while addition of
more gel resulted in generation of higher amounts of heat and reduced
curing times.
The method of this example produced a clear gel coat in contrast
to many methods taught in the art. In addition, this method was amenable to
pouring the gel coat into a mold, and painting or spraying the gel coat onto a
surface. Additional examples of this method are provided in Table 8.
Sample l l in Table 8 produced excellent results.
Example 8
Method of Strengthening Objects Made from Resin Through Addition of a
Hardener Solution
This example describes a hardener solution that can be used to
make an inexpensive, clear and strong resin. In addition, inexpensive and
strong gel coat resins may be produced by the method of this example.
Both conventional resins and gel coat resins may be made stronger using the
hardener solution of the present example.
Step 1: Formulation for a Hardener Solution in a Cold Bath: A
hardener solution was made by dissolving benzoyl peroxide to saturation in
CA 022660~4 1999-03-11
WO 98/11159 PCT/US97/16439
36
about 50 m~ of methylmethacrylate in a beaker maintained in an ice bath. An
equal volume of styrene was added and mixed.
Step 2: Formation of Conventional Resins and Gel Coat Resins
of Increased Strengt~: In order to make an inexpensive clear gel coat,
between about 1 ml and 5 ml of the CMC solution of Step 1 of Example 7
were slowly mixed with approximately 50 ml of polyester resin. It is to be
understood that any CMC or polar polymer or any polymer that will swell in
water may be used in the practice of the present invention. Next, about 50
ml of the gel coat resin of Example 7 was added and slowly mixed.
Between about 0.1 ml and 1.0 ml of N,N dimethylaniline was added
(preferred volume of 0.25 ml). About 0.l ml to 2.0 ml of a cross linker
(poly(ethyleneglycol-400)dimethacrylate) was added. It is to be understood
that any ethyleneglycol cross linker may be employed or other cross linkers
such as divinyl monomers. Next, about 0.1 ml to 1.5 ml of the catalyst,
cobalt II naphthanate, was added. A preferred volume of cobalt II
naphthanate was approximately 0.25 ml. Catalysts which may be employed
at this step include, but are not limited to methylene II acetate, chromium II
acetate, copper II acetate and cobalt II acetate. Catalysts were added at about
10% (vol %) in solvents such as alcohol, styrene, water, or any suitable
solvent for the specific catalyst.
The hardener solution (about 0.5 ml) was then added. The
reaction was initiated by adding from about 0.25 ml to 2.0 ml of the initiator
methyl ethyl ketone peroxide. A preferred volume of methyl ethyl ketone
peroxide was approximately 0.35 ml. Other initiators which have been used
are peroxides including, but are not limited to, methyl ethyl ketone peroxide,
hydrogen peroxide, and dibenzoyl peroxide at concentrations of about 10%
to 30~o. Other peroxide initiators and azo initiators may also be used.
Example 9
Method of Strengthening Objects Cast from CoMventional and Gel Coat
Resins by Varying the Amount of CMC Solution
The following example demonstrates a method for increasing the
structural strength of objects cast from resins. This method may be used to
increase the strength of ob3ects cast from conventional resins and gel coat
resins. As shown in this Example, as the amount of CMC solution of
Example 7 was increased in the presence of the proper amounts of catalysts,
CA 022660~4 1999-03-11
WO 98/lllS9 PCT/US97tl6439
hardeners and initiators, the strength of the res~lting object increased while
the weight decreased.
To about 100 ml of conventional resin was added between
approximately 2 ml and 25 ml of the CMC solution of Example 7. Next,
S about 300 ml of gel coat was added and to this mixture were added
approximately I ml of dimethylaniline, 2 ml of the cross linker of Example 8
(poly(ethyleneglycol-400)dimethacrylate), 1 ml of catalyst (cobalt II
naphthanate), 2 ml of the hardener solution of ~xample 8, and 0.5 ml of the
initiator methyl ethyl ketone peroxide. The initiator methyl ethyl ketone
peroxide, or other initiators that may be used in the present invention are
added last, however there is no special order for adding the other ingredients
described in this Example. It is to be understood that any ethyleneglycol
cross linker may be employed or cross linkers such as divinyl monomers.
In addition, the other initiators and catalysts listed in Example 8 have been
used in the present invention. In this Example, about 2 ml, S ml or 10 ml of
the CMC solution of Example 7 was used and the resulting object tested.
These objects were tested to measure the compression strength and
flexibility using a device with an upper test limit of 3000 pounds per square
inch (psi). The objects made with 2 ml, S ml or 10 ml of the CMC solution
displayed strength of 2500 psi, 2900 psi, and more than 3000 psi,
respectively. The resin would not break in this machine.
Comparative tests of DuPont CORIAN(~) materials of comparable
thickness at twice the weight of the object of the present Example made with
about 10 ml of the CMC solution showed that the CORIAN(~) samples broke
at 2100 psi while the object of the present Example did not break.
Therefore, this object had a strength greater than the upper test limit of the
test machine (greater than 3000psi).
Example 10
Hard Su~ace Material
To approximately 300 ml of a conventional resin, such as polyester
resin, was added about 40 ml of styrene, 20 ml of methylmethacrylate and 5
ml of a dispersant formulation. The dispersant formulation was comprised
of about 20 gm dodecylbenzene sulfonic acid (sodium salt) mixed in about
10 ml of aqueous 0.1 M p-toluene sulfonic acid monohydrate, which was
then mixed with about 20 ml of ethylene glycol, 10 ml of
CA 022660~4 1999-03-11
WO 98/11159 PCT/U~97tl6439
38
methylmethacrylate and 10 ml of styrene. The resulting solution was then
thoroughly mixed and approximately 70 ml of the CMC solution of Example
7 (step l) was added. It is to be understood that any CMC or polar
polymer or any polymer that will swell in water may be used in the practice
of the present invention.
Next, about 300 ml of gel coat resin purchased from Neste Co.
(Atlanta, GA) was added to this solution, followed by addition of
approximately 5% fiberglass (vol%) which was about 35 ml of compacted
fiberglass. The compacted fiberglass was first soaked in about 90%
ethylene glycol and about 10% of the dispersant formulation described
above, mixed briefly in a blender, and pressure was applied until most of
the fluid was removed. Next approximately 4 ml of N,N-dimethylaniline
was added followed by about 8 ml of a cross linker solution, for example a
cross linker solution of poly(ethyleneglycol-400)dimethacrylate or
pentaerythritol tetraacrylate, and about 4 ml of catalyst (cobalt II
naphthanate). These three chemicals were added in any order. Next, 8 ml
of the hardener solution of Example 8, Step l, was added followed by
addition of between 3 to 7 ml of a 30% solution of the initiator methyl ethyl
ketone peroxide in styrene. Other initiators, including peroxide initiators,
have been used at solution strengths of approximately 10%-30% in the
appropriate solvents. Catalysts which could be employed at this step
include, but are not limited to methylene II acetate, chromium II acetate,
copper II acetate and cobalt II acetate. Catalysts were added at about 10%
(vol %) in solvents such as alcohol, styrene, water, or any suitable solvent
for the specific catalyst.
The reaction was initiated by adding from about 3 ml to 7 ml of a
30% solution of the initiator methyl ethyl ketone peroxide. A preferred
volume of initiator methyl ethyl ketone peroxide was S ml. Other initiators
which have been used were peroxides including, but not limited to, methyl
ethyl ketone peroxide, hydrogen peroxide, and dibenzoyl peroxide at
concentrations of 10% to 30% in applopliate solvents. Other peroxide
initiators and azo initiators may also be used. The initiator methyl ethyl
ketone peroxide, or other initiators that may be used in the present invention
were added last. It is to be understood that any ethyleneglycol cross linker
may be employed, or cross linkers such as divinyl monomers. In addition,
the other initiators and catalysts listed in Example 8 could be used in the
CA 022660~4 1999-03-11
WO 98/11159 PCTIUS97/16439
39
present invention. After all reagents were inc]uded, the mixture was poured
into a mold and placed on a vibrating table to facilitate remova] of air
bubbles.
The object made with the method of the present example was tested
to measure the compression strength and flexibility using a device with an
upper limit of 3000 pounds per square inch (psi). Comparative tests of
DuPont CORIAN~) materials of comparable thickness at twice the weight of
the object of the present Example showed that the CORIAN(~) samples broke
at 2100psi while the object of the present Example broke at 2200psi.
In the formation of another object using the method of the present
example, a volume of about 500 ml of resin and about 100 ml of gel coat
were used together with the same volumes of other reagents as reported
above. The resulting object was very hard but compression tests were not
performed. In addition, different volumes of about 30, 40, 50, and 90 ml
of the CMC solution were used together with the different reagent volumes
described above. In general, as the amount of CMC in the mixture
increased, the flexibility of the formed object increased.
Example 11
~ard Sur~ace Material
To approximately 300 ml of a conventional resin, such as polyester
resin, were added about 40 ml of styrene, 30 ml of methylmethacrylate, and
8 ml of the dispersant formulation of Example 10. The dispersant
formulation was comprised of about 20 gm dodecylbenzene sulfonic acid
(sodium salt) mixed in approximately l0 ml of aqueous 0.1 M p-toluene
sulfonic acid monohydrate, which was then mixed with about 20 ml of
ethylene g]ycol, 10 ml of methylmethacrylate and 10 ml of styrene. The
resulting solution was then thoroughly mixed and about 70 ml of the CMC
solution of Example 7 (step 1) was added. It is to be understood that any
CMC or polar polymer or any polymer that will swell in water may be used
in the practice of the present invention.
Next, about 300 ml of gel coat resin purchased from Neste Co.
(Atlanta, GA) was added to this solution, followed by addition of
approximately 5% fiberglass (vol%) which is about 35 ml of compacted
fiberglass. The compacted fiberglass was first soaked in about 90%
ethylene glycol and 10% dispersant formulation, mixed briefly in a blender,
CA 022660S4 1999-03-11
WO g8/11159 PCT/US97/16439
and pressure was applied until most of the fluid was removed. Next
approximately 4 ml of N,N-dimethylaniline was added followed by about 8
ml of a cross linker solution of either poly(ethyleneglycol-
400)dimethacrylate, or pentaerythritol tetraacrylate and 4 ml of catalyst
(cobalt II naphthanate). These three chemicals could be added in any order.
Next, about 8 ml of the hardener solution of Example 8, Step 1, was added
followed by about 5 ml of the initiator methyl ethyl ketone peroxide.
Catalysts which could be employed at this step include, but are not limited to
methylene II acetate, chromium II acetate, copper II acetate and cobalt II
acetate. Catalysts were added at 10% (vol %) in solvents such as alcohol,
styrene, water, or any suitable solvent for the specific catalyst.
The reaction was initiated by adding from about 3 ml to 7 ml of the
initiator methyl ethyl ketone peroxide. A preferred volume of initiator
methyl ethyl ketone peroxide was about 5 ml. Other initiators which were
IS used were peroxides including, but not limited to, methyl ethyl ketone
peroxide, hydrogen peroxide, and dibenzoyl peroxide at concentrations of
about 10% to 30% in appluL)Iiate solvents. Other peroxide initiators and azo
initiators may also be used. The initiator methyl ethyl ketone peroxide, or
other initiators that were used in the present invention were added last. It is
to be understood that any ethyleneglycol cross linker may be employed or
cross linkers such as divinyl monomers. In addition, the other initiators and
catalysts listed in Example 8 may be used in the present invention. After all
reagents were included, the mixture was poured into a mold and placed on a
vibrating table to facilitate removal of air bubbles.
The object made with the method of the present example was tested
to measure the compression strength and flexibility using a device with an
upper limit of 3000 psi. Co,-,par~live tests of DuPont CORIAN6~) materials
of comparable thickness at twice the weight of the object of the present
Example showed that the CORIAN(~) samples broke at 2100 psi while the
object of the present Example broke at 2400 psi.
In the formation of another object using the method of the present
example, a volume of about 500 ml of resin and about 100 ml of gel coat
were used together with the same volumes of other reagents as reported
above. The resulting object was very hard but compression tests were not
performed.
CA 022660~4 1999-03-11
WO 98/11159 PCT/US97/16439
Fx~mp1e 12
~ard Surf~ce Material
To about 300 ml of a conventional resin, such as polyester resin,
were added approximately 30 ml of styrene, about 40 ml of
polymethylmethacrylate (20% wt/vol), and approximately 15 ml of a
dispersant formulation. The dispersant formulation was comprised of about
20 gm dodecylbenzene sulfonic acid (sodium salt) mixed in approximately
10 ml of aqueous 0.1 M p-toluene sulfonic acid monohydrate, which was
then mixed with about 20 ml of ethylene glycol, 10 ml of
methylmethacrylate and 10 ml of styrene. The resulting solution was then
thoroughly mixed and approximately 70 ml of the CMC solution of Example
7 (step 1 ) was added. It is to be understood that any CMC or polar polymer
or any polymer that will swell in water could be used in the practice of the
present invention.
Next, about 300 ml of gel coat resin purchased from Neste Co.
(Atlanta, GA) was added to this solution, fo]lowed by addition of
approximately 5% fiberglass (vol%) which is about 35 ml of compacted
fiberglass. The compacted fiberglass was first soaked in about 90%
ethylene glycol and about 10% dispersant formulation, mixed briefly in a
blender, and pressure was applied until most of the fluid was removed.
Next approximately 5 ml of N,N-dimethylaniline was added followed by
about 9 ml of a cross linker solution of either poly(ethyleneglycol-
400)dimethacrylate or pentaerythritol tetraacrylate and 5 ml of catalyst
(cobalt II naphthanate). These three chemicals were added in any order.
Next, about 9 ml of the hardener solution of Example 8, Step 1, was added
followed by 6 ml of the initiator methyl ethyl ketone peroxide. Catalysts
which may be employed at this step include, but are not limited to methylene
II acetate, chromium II acetate, copper II acetate and cobalt II acetate.
Catalysts were added at 10% (vol %) in solvents such as alcohol, styrene,
water, or any suitable solvent for the specific catalyst.
The reaction was initiated by adding from about 4 ml to 8 ml of the
initiator methyl ethyl ketone peroxide. A preferred volume of initiator
methyl ethyl ketone peroxide was 6 ml. Other initiators which have been
used were peroxides including methyl ethyl ketone peroxide, hydrogen
peroxide, and dibenzoyl peroxide at concentrations of 10% to 30% in
appropriate solvents. Other peroxide initiators and azo initiators may also be
CA 022660~4 1999-03-ll
WO 98/11159 PCT/US97/16439
42
used. The initiator methyl ethyl ketone peroxide, or other initiators used in
the present invention were added last. It is to be understood that any
ethyleneglycol cross linker may be employed or cross linkers such as
divinyl monomers. In addition, the other initiators and catalysts listed in
Example 8 may be used in the present invention. After all reagents are
included, the mixture was poured into a mold and placed on a vibrating table
to facilitate removal of air bubbles.
The object made with the method of the present example was tested
to measure the compression strength and flexibility using a device with an
upper limit of 3000 psi. Comparative tests of DuPont CORIAN(~ materials
of comparable thickness at twice the weight of the object of the present
Example made showed that the CORIAN(~) samples broke at 2100 pSi while
the object of the present Example did not break, and therefore had a strength
greater than the upper test limit of the test machine (greater than 3000 pSi).
l S In the formation of another object using the method of the presentexample, a volume of about 500 ml of resin, and about 100 ml of gel coat
were used together with the same volumes of other reagents as reported
above. The resulting object was very hard but compression tests were not
performed.
Example 13
Flexible Hard Materials
This example presents three methods of making a flexible hard
material.
Mixture A: Mixture A was prepared by mixing the following
reagents: between about 470 to 530 gm of calcium carbonate; about 65 ml of
a solution comprised of approximately 80% by volume of water, 18% ethyl
alcohol and 2% acetone; about 350 ml of gel coat resin or po}yester resin;
and approximately 10 ml of polyacrylic acid solution. The polyacrylic acid
solution was made by wetting I gm of polyacrylic acid with ethanol
followed by addition of about 50 ml of water.
Mixture B: Mixture B was prepared by mixing the following
reagents: between about 470 to 530 gm of calcium carbonate; about 65 ml of
a solution comprised of approximately 80% by volume of water, 18% ethyl
alcohol and 2% acetone; about 350 ml of gel coat resin and approximately
30 ml of polyacrylic acid.
CA 022660~4 1999-03-11
WO 98/11159 PCT/US97/16439
43
Method 1: To about 350 ml of mixture A were added sequentially
about 200 ml of epoxy resin, approximately l0 ml of the dispersant of
Example 12, and about 100 ml of ethylene glycol. Next, about 100 ml of
styrene and about 100 ml of polymethylmethacrylate were added in any
order. Approximately 4 ml of N,N-dimethyJanilhle, about l l ml of a cross
linker solution of poly(ethyleneglycol-400)dimethacrylate, and 4 ml of
catalyst (cobalt II naphthanate) were added. Next approximately 11 ml of
the hardener solution of Example 8 (Step 1), and about 5 to 9 ml of the
initiator methyl ethyl ketone peroxide were added. A preferred volume of
l 0 methyl ethyl ketone peroxide was 7 ml. Other initiators which may be used
are peroxides including, but not limited to, methyl ethyl ketone peroxide,
hydrogen peroxide, and dibenzoyl peroxide at concentrations of 10% to
30~o in appropriate solvents. Other peroxide initiators and azo initiators
may also be used. The initiator solution was always added last and was
l S preceded by the hardener solution.
Method 2: To about 350 ml of mixture A were added approximately
350 ml of epoxy resin, about l00 ml of ethylene glycol, approximately 100
ml of styrene, about 100 ml of methylmethacrylate, about 20 ml of the
dispersant of Example 12, approximately 5 ml of N,N-dimethylaniline,
about 11 ml of cross linker solution of Example 8 (poly(ethyleneglycol-
400)dimethacrylate), approximately 5 ml of catalyst (cobalt II naphthanate),
approximately 11 ml of the hardener solution of Example 8 (Step 1), and
about 6 to l 0 ml of the initiator methyl ethyl ketone peroxide. A preferred
volume of methyl ethyl ketone peroxide was 8 ml. It is to be understood
that other initiators as described in Method I may be used. The object
resulting from practice of this method was extremely flexible and did not
break at a pressure of 3000 psi.
Method 3: To approximately 350 ml of mixture B were added about
350 ml of epoxy resin, approximately 100 ml of ethylene glycol,
approximately 100 ml of styrene about 100 ml of polymethylmethacrylate
about 20 ml of the dispersant of Example 12, approximately 5 ml of
dimethylaniline, approximately 11 ml of the cross linker solution of
Example 8 (poly(ethyleneglycol-400)dimethacrylate), about 5 ml of catalyst
(cobalt II naphthanate), approximately 11 ml of the hardener solution of
Example 8 (Step I ), and about 6 to 10 ml of the initiator methyl ethyl ketone
peroxide. A preferred volume of methyl ethyl ketone peroxide was 8 ml. It
CA 022660~4 1999-03-ll
WO 98/11159 PCTIUS97/16439
44
is to be understood that other initiators as described in Method l may be
used.
It should be understood that other initiators, cross-linkers, catalysts
and resins described in preceding example 12 may be used in the practice of
the invention disclosed in this example.
Example 14
Flexible Materials with ~igh Tensile Strength
Preparati(7M of Low Molecular Weight Polyarlilinc~ used to make the Flexible
Materials with High Tensile Strength
To produce the low molecular weight polyaniline used in the
present invention, a prepolymer solution was prepared by mixing about 21
ml of distilled purified aniline with about 300 ml of l M HCI. The
prepolymer solution was then placed in a three necked flask and purged with
nitrogen and cooled to about 5~ C. In a separate container, approximately 12
gm ammonium persulfate was dissolved in about 200 ml of I M HCl. The
container was purged with pure nitrogen. The ammonium persulfate
solution was cooled to about 5~ C and then added to the 3 necked flask. The
mixture was cooled to about 0~ C and stirred for approximately 20 minutes.
The temperature of the solution was then raised to a temperature between
approximately 8~ to 10~ C for 15 minutes. Next, the solution was cooled to
about 0~ C and stirred for 45 minutes. The polyaniline precipitate was then
washed several times by filtration with distilled water. The polyaniline
precipitate was treated with I M potassium hydroxide for 24 hours after
which it was filtered, washed again for 6 to 12 hours in distilled H2O,
heated, and dried in a vacuum oven for about 24 hours at 50~ C. The dried
polyaniline was ground into a powder. The mixture was optionally
extracted with a soxhlet extraction with acetonitrile for 3 hours until the
extract was no longer colored. This extraction produced a polyaniline
powder. The polyaniline was dried in an oven at about 50~ C for 6 to 7
hours and then ground to a powder. It was then treated with 1 M KOH for
approximately 24 hours after which it was filtered, washed again for 6 to 12
hours in distilled H2O and dried in a vacuum oven for 24 hours at 50~ C.
The polyaniline precipitate was then dissolved in a N-methylpyrrolidinone
(NMP) to saturation. Different amounts of polyaniline may be added to
NMP to achieve a final percentage of from approximately 0.1% by weight
CA 022660~4 l999-03-ll
WO 98/11159 PCT/US97/16439
of the total mixture to a saturated solution. It is to be understood that
pyrrolidone and pyrrolidone are synonymous as used throughout the present
application.
A resin mix was made with the following method. To about 30 ml
S of polyester resin were added in sequence approximately 6 ml of styrene,
0.75 ml N,N-dimethylaniline, 0.75 ml of cobalt Il naphthanate as catalyst,
0.5 ml of the saturated solution of polyaniline in N-methylpyrrolidinone as
described above, and about 0.25 ml of the initiator methyl ethyl ketone
peroxide.
l 0 The resulting resin displayed a fibrous matrix and was strong and
flexible.
Example 15
Flexible Materials with High Tensile Strength
In another embodiment of the present invention, the solution of
polyaniline in N-methylpyrrolidinone as described in the preceding example
14, was used and methyl ethyl ketone peroxide was not added to the
mixture. The polyaniline in N-methylpyrrolidinone acted as a slower
initiator than the methyl ethyl ketone peroxide.
The resulting resin displayed a fibrous matrix and was strong and
flexible.
Example 16
Polyester Preparations and Compositions
The following solutions were used in surf~ctant formulations listed
below and were combined with the polyester preparations and compositions
described in subsequent examples. Percentages indicate volume %.
Solution 1
To 3000 ml of H20 were added acetone and l-butanethiol to achieve final
volume percentages of approximately 0.2% and 0.04% respectively.
Solution 2 - (Final volume percentages are shown)
Methyl ethyl ketone peroxide 99~o
Hydrogen peroxide (30% stock solution) 1%
CA 022660~4 1999-03-ll
WO 98/11159 PCT/US97/16439
46
Solution 3
Dodecylbenzenesulfonic acid (sodium salt)20.0 g
p-toluene sulfonic acid (0.IM) 10.0 g
Hydrochloric acid (0.IM) 1.0 ml
Methylene chloride (10% solution) in methanol 1.0 ml
Ethylene glycol 20.0 ml
Methylmethacrylate 10.0 ml
Styrene 10.0 ml
Hardener solution (Example 8) 1.0 ml
Solution 4
Carboxymethyl cellulose I g
Polyacrylic acid I g
H2O 100 ml
Solution 4(A)
Carboxymethyl cellulose I g
Polyacrylic acid 1 g
Sodium hydroxide (lM) 50 ml
H~O 50 ml
Solution 4(B)
Solution 4A 50 ml
Sodium hydroxide 2 g
Solution 5(A)
Solution A (0.5% aqueous solution of CMC)25 g
Polyacrylic acid o.5 g
Solution 5(B)
Solution A (0.5% aqueous solution of CMC)25 g
KOH 0.25 g
Polyacrylic acid 0.5 g
CA 022660~4 1999-03-11
WO 98/lllS9 PCT/US97116439
47
Solution 5(C)
Solution A (0.5% aqueous solution of CMC) 25 g
NaOH 0.25 g
Polyacrylic acid 0.5 g
Solution A (0.5% solution of CMC)
Water 100 g
CMC- o.5 g
*A range of CMC concentrations from 0.25% to 5% have been successfully
employed in Solution A.
Surfactant A
Component 1 40 ml
Component I was made as follows:
5% polyvinyl alcohol solution (aqueous) 30 ml was added to 70 ml
ethylene glycol
(this solution was heated to about 110~C while stirring, and the
volume was reduced to 70 ml total
To 40 ml of Component I was added
Ethyl alcohol (distilled) 20 gm
Dodecylbenzenesulfonic acid, sodium salt 2.5 g
Surfactant B
Component2 20 g
Component 2 was made as follows:
I ) Ethylene glycol 20 g; plus
2) Dodecylbenzenesulfonic acid, sodium salt 2.5 g
to 20 g of Component 2 was added
Ethyl alcohol (distilled) 5 g
CA 022660~4 l999-03-ll
WO 98/11159 rCT/US97116439
48
Surfactant C
Polyethylene glycol average molecular weight 200 20 g
Dodecylbenzenesulfonic acid 2.5 g
Heat of 70~C to 80~C was applied either while dissolving
S dodecylbenzenesulfonic acid in polyethylene glycol or before the
dodecylbenzenesulfonic acid was added to the polyethylene glycol.
Surfactant D
Polyethylene glycol average molecular weight 400 20 g
Dodecylbenzenesulfonic acid 2.5 g
Heat of 70~C to 80~C was applied either while dissolving
dodecylbenzenesulfonic acid in polyethylene glycol or before the
dodecylbenzenesulfonic acid was added to the polyethylene glycol.
Surfactant E
Polyethylene glycol average molecular weight 600 20 g
Dodecylbenzenesulfonic acid 2.5 g
Heat of 70~C to 80~C was applied either while dissolving
dodecylbenzenesulfonic acid in polyethylene glycol or before the
dodecylbenzenesulfonic acid was added to the polyethylene glycol.
Example 17
Flexible and flame retardant sample
In a container, approximately 250 ml of epoxy resin, about 200 m]
of polyester resin, and 3 ml of Solution 4 from Example 16 were thoroughly
mixed. In a separate container, about 200 ml of fly ash and approximately
20 ml of Solution I from Example 16 were mixed thoroughly to ensure that
the liquid was dispersed evenly through the filler matrix. The contents of
both containers were combined into a single container and mixed
thoroughly. While mixing, about 2 ml each of N,N-dimethylaniline,
polyethylene glycol 400 dimethacrylate, cobalt naphthanate and Solution 2
from Example 16 were added. All constituents were mixed until evenly
distributed. The contents were poured into mold a and ejected when cured.
-
CA 022660~4 1999-03-11
WO 98/11159 PCT/US97/16439
49
Example 18
High flexibility sample
Step I Mixture: About 20 ml each of polyester resin and methyl
methacrylate were combined in a container and mixed thoroughly In a
separate container, about 50 ml of epoxy resin and l ml each of
polyethylene glycol 400 dimethacrylate and solution 2 from Example 16
were added and mixed thoroughly. Approximately l ml each of N,N-
dimethylaniline and cobalt naphth~n~te were added and mixed thoroughly.
Next, about S0 ml of vinylester resin, 5 ml of the step l mixture and
l ml of solution 2 were added. These reagents were mixed thoroughly.
Approximately I ml each of N,N-dimethylaniline, cobalt naphthanate and
Solution 2 were added while mixing and then thoroughly mixed. The
contents were poured into a mold and ejected when cured.
Example 19
Flexible"flame retardant sample
In a container, approximately 50 ml of vinylester resin and 0.5 ml of
Solution 4(B) from Example 16 were combined and mixed thoroughly.
About l ml of 3,5-dimethylaniline, 0.5 ml of polyethylene glycol 400
dimethacrylate, I ml each of cobalt naphthanate and Solution 2 from
Example 16 were added while mixing. The contents were poured into a
mold and ejected when cured.
Example 20
Flexible sample
Step l Mixture: Approximately 20 ml each of polyester resin and
methyl methacrylate were combined in a container and mixed thoroughly.
In a separate container about 50 ml of epoxy resin and about I ml each of
polyethylene glycol 400 dimethacrylate, Solution 4(B) and Solution 2 from
Example 16 were combined and mixed thoroughly. Next, about 1.5 ml
each of N,N-dimethylaniline and cobalt naphthanate were added and mixed
thoroughly .
Next, approximately 50 ml of vinylester resin, 5 ml of the Step I
Mixture and I ml of Solution 2 were added. All ingredients were mixed
thoroughly. About 1.5 ml of each of N,N-dimethylaniline and cobalt
CA 022660=74 1999-03-ll
WO 98/11159 PCT/US97/16439
naphthanate were added and mixed thoroughly. The contents were poured
into a mold and ejected when cured.
Example 21
S Flexible, flame retardant sample with elevatedfillel- content
In a container were combined about 50 gm each of polyester resin,
epoxy resin and 2.5 gm of Solution 4 from Example 16 and mixed
thoroughly. In a separate container, were mixed about 120 gm of calcium
carbonate and 12.7 gm of Solution l. Next, the ingredients of both
l O containers were combined. While mixing, about 20 gm of ethylene glycol
was added while mixing. Next approximately 0.25 ml each of N,N-
dimethylaniline, polyethylene glycol 400 dimethacrylate, cobalt naphthanate
and Solution 2 from Example 16 were added while mixing. All ingredients
were well distributed and then poured into a mold and ejected when cured.
Example 22
Flexible, flame retardant sample with elevatedfiller content
In a container were combined about 50 gm each of polyester resin,
epoxy resin and 2.5 gm of Solution 4. These ingredients were mixed
thoroughly. In a separate container were mixed about 120 gm of calcium
carbonate and 12.7 gm of solution 1 from Example 16. The ingredients of
both containers were combined. Approximately 20 gm of ethylene glycol
was added and mixed thoroughly. Next, about 0.5 ml each of 3,5-
dimethylaniline and 0.25 gm each of polyethylene glycol 400
dimethacrylate, cobalt naphthanate and Solution 2 were added while mixing.
When all ingredients were well distributed, the mixture was poured into a
mold and ejected when cured.
Example 23
Flame retardant sample suitable for ca~le joints
A mixture l was made according to the following formula:
CA 022660~4 1999-03-11
WO 98tlll59 PCT/US97/16439
Component Amount
(gm)
Castor Oil 365
Linseed Oil 17
Dibutyltin dilaurate 0.07
Sylosiv 1 0.8
To prepare the sample for molding, about 56.1 gm of mixture 1 was
mixed with 18.3 gm of calcium carbonate (Ultrafine) and mixed thoroughly.
To this mixture were added about 22.5 gm of 4,4' diphenylmethane
S diisocyanate and 108.5 gm of a filler such as course sand. The mixture
gelled in about 20 minutes.
F,~mple 24
Flame retardant sample suitable for cable joints
To prepare the sample for molding, approximately 55.4 gm of
mixture I were mixed with 18.1 gm of calcium carbonate (Ultrafine) and
thoroughly mixed. To this mixture were added approximately 22.5 gm of
4,4' diphenylmethane diisocyanate, 166.3 gm of a filler such as course sand
and 3.397 gm of surfactant A from Example 16. The results showed
swelling of the gel.
Example 25
Flame retardantsample with 75%f'illersuitableforcable joints
To prepare the sample for molding, approximately 46.7 gm of
mixture I was mixed with 19.3 gm of calcium carbonate (Ultrafine) and
thoroughly mixed. To this mixture were added about 18.7 gm of 4,4'
diphenylmethane diisocyanate, 177.4 gm of a filler such as course sand and
3.397 gm of surfactant A from Example 16. The results showed swelling
of the gel.
CA 022660~4 1999-03-11
WO 98/11159 PCT/US97/16439
52
Example 26
Flame retardant sample suitable for shieldingfiber optical cable joints
A mixture l was made according to the following formula:
Component Amount
(gm)
Castor Oil 34.8
Linseed Oil 1.69
Sylosiv 1.02
Calcium Carbonate 20.71
4,4' diphenylmethane 15.04
diisocyanate
Calcium Oxide 0.8
Benzoperoxide 1.0
Course sand 140.3
The ingredients were added in the order presented and were
thoroughly mixed. The mixture gelled in approximately 20 min. The
results showed swelling of the gel.
Example 27
~lame retardant sample suitable for cable joints
A mixture l was made according to the following formula:
Component Amount
(gm)
Castor Oil 365
T.inse.ed Oil 17
Dibutyltin dilaurate 0.07
Sylosiv l 0.8
To prepare the sample for molding, 55.4 gm of mixture l was mixed
with approximately 18.1 gm of calcium carbonate (Ultrafine). Mix
thoroughly. To the mixture 11 were added about 22.2 gm of 4,4'
diphenylmethane diisocyanate, 166.3 gm of a filler such as course sand and
CA 022660~4 1999-03-11
WO 98/11159 PCT/US97/16439
3.4 gm of a surfactant. The surfactant used in this example was surfactant
A. The mixture gelled in about 20 minutes. The results showed some
swelling of the gel.
Table 2 presents several additional examples of samples made with
the indicated amounts of reagents.
F,~mrle 28
Method of Making Non-flammable, Liquid, Resi-1
Method 1: A non-flammable liquid resin was made by a method
comprising the following steps: about lO0 gm methylmethacrylate, 5 gm
polymethylmethacrylate (molecular weight about 75,000), 0.5 gm cobalt II
naphthanate, 0.2 gm oc-picoline, and 0.3 gm 2,2'-azobisisobutyronitrile
(AIBN) were mixed; the mixture was heated to approximately 50~C until
boiling. Next, about I ml of lM hydrochloric acid was added to stop
polymerization. Next, powdered styrene was added to this mixture and the
mixture was heated to a temperature from about 60~C to 70~C until the
styrene dissolved.
Method 2: A non-fl~mm~ble liquid resin was made by a method
comprising the following steps: about 100 g of styrene, 0.5 gm cobalt II
naphthanate, 0.4 gm o~-picoline, and 0.3 gm 2,2'-azobisisobutyronitrile
(AIBN) were mixed; the mixture was heated to approximately 80~C until
boiling for a period of about 10 minutes. Next, about l ml of IM
hydrochloric acid was added to stop polymerization.
Method 3: A non-flammable liquid resin is made by a method
comprising the following steps: a resin formulation is made by mixing about
98.06 gm of maleic anhydride and about 62.07 gm of ethylene glycol or
propylene glycol while purging with inert gas, such as nitrogen, throughout
the entire reaction, in a vacuum oven; heating the mixture to approximately
l 90~C to 200~C for about 4 hours; then at 21 5~C t'or about 3 hours slowly
cooling the mixture and next adding ethylene chloride. The mixture is then
cooled for 2 hours at about 5~C. The resulting polyester powder was then
dissolved separately in the solvents of Methods I and 2 to produce two non-
flammable ]iquid resin formulations.
CA 022660~4 1999-03-ll
WO 98/11159 PCT/US97/16439
54
Example 29
Method of Making Objec~s With Hig~ S~rength, Low or No Shrinkage, and
Low Flammability
Objects were made by mixing gel coat resin, hard surface resin
(McWhorter Co., Inc.), polar polymer (an aqueous solution of CMC
(0.5%)), polyacrylic acid, methylmethacrylate, N,N-dimethylaniline, cross-
linker (polyethylene glycol 400 dimethacrylate), catalyst (cobalt II
naphthanate), and solution 2 from Example l6, in the amounts and in the
order indicated in Table 3. The best results are indicated by asterisks next to
l 0 the sample number at the top of the corresponding column.
Objects were made by mixing resin (vinyl ester resin), polar polymer
(an aqueous solution of CMC (0.5%)), calcium carbonate, Solution l from
Example 16, ethylene glycol, monomer (styrene), diisocyanate, N,N-
dimethylaniline, catalyst (cobalt II naphthanate). hardener solution (Step l
l 5 from Example 8), solution 2 from Example 16, and cross-linker
(polyethylene glycol 400 dimethacrylate), in the amounts and in the order
indicated in Table 4. The best results are indicated by asterisks next to the
sample number at the top of the corresponding column.
Objects were made by mixing resin (vinyl ester resin), a basic
solution of polar polymer (an aqueous solution of CMC (0.5%)) and
polyacrylic acid, in some cases Solution 4 from Example l 6, in some cases
cross-linker (polyethylene glycol 400 dimethacrylate), N,N-dimethylaniline,
in some cases diisocyanate-methylmethacrylate, catalyst (polyethylene
glycol 400 dimethacrylate), and Solution 2 from Example 16, in the
amounts and in the order indicated in Table 5. Preferred embodiments were
obtained in Samples 2 and 3 shown in Table 5 with the most preferred
embodiment shown as Sample 4 of Table 5.
The objects made with this method demonstrated very low or no
shrinkage. Tests conducted with up to seven applications of the flame of a
propane torch for periods of 30 seconds showed that the objects made with
this method did not burn or smoke.
, ~
CA 022660~4 1999-03-11
WO 98/11159 PCT/US97/16439
Example 30
Method of Making Lightweight, Economical, Non-flammable Objects With
High Filler Content
Lightweight, non-flamm~hle objects with high filler content were
made according to the following methods. These objects are useful in the
construction industry and could be used as roofing tiles, among other
objects. Some of the objects have high epoxy content and exhibit flexibility
while other objects made with low epoxy content were rigid and hard.
These properties were obtained using a finai resin content of about 6.5%.
All the formulations are pourable and castable into a desirable shape.
Method 1: Objects were made by mixing calcium carbonate,
Solution 1 from Example 16, polyester resin, Solution 4 from Example 16,
epoxy resin. ethylene glycol, N,N-dimethylaniline or 3, 5-dimethylaniline,
cross-linker (polyethylene glycol 400 dimethacrylate), catalyst (cobalt II
naphthanate), and initiator (Solution 2 from Example 16) in the amounts and
in the order indicated in Table 6. Preferred embodiments were obtained in
Samples I and 2 shown in Table 6.
Method 2: Objects were made by mixing polyester resin, Solution 4
from Example 16, styrene, Surfactant E from Example 16, filler (sand,
coarse fly ash, or fine fly ash), calcium carbonate, Solution I from
Example 16, N,N-dimethylaniline, catalyst (cobalt II naphthanate), and
initiator (Solution 2 from Example 16) in the amounts and in the order
indicated in Table 7. The preferred embodiment is shown as sample I in
Table 7 which contained about 78% solids and about 6.5% resin.
Example 31
Method of Making Soft, Lightweight, Flexible, Fla~Me-Resistant Objects
To about 21.5 gm of castor oil was added 56.6 gm of polyester
resin. These reagents were thoroughly mixed. Next, about 20.5 gm of
calcium carbonate (AD grade) was added and mixed thoroughly.. About
65.8 gm of 4,4' diphenylmethane diisocyanate, 1.5 gm of dibutyltin
dilaurate, l.5 ml of triethylamine, and 4.2 gm of calcium oxide were added
and mixed well. Next, 1 ml of N,N-dimethylaniline, 1 ml of cross-linker
(polyethylene glycol 400 dimethacrylate), I ml of catalyst (cobalt II
naphthanate), and 1 gm of benzoyl peroxide were added and mixed well.
CA 022660~4 1999-03-ll
WO 98/lllS9 PCT/US97/16439
56
The resulting object was soft, lightweight, flexible, flame-resistant and
exhibited sufficient low density that it floated in water.
Example 32
Method of Making Hard, Lightweight, Flame-Resistant Objects
To about 20.5 gm of castor oil was added 56.6 gm of vinylester
resin. These reagents were thoroughly mixed. Next, about 20.2 gm of
calcium carbonate (AD grade) was added and mixed thoroughly.. About
3.0 gm of benzoyl peroxide mix consisting of 30% benzoyl peroxide in
calcium carbonale was added and mixed thoroughly. Next, 65.5 gm of 4,4'
diphenylmethane diisocyanate, 1.5 ml of dibutyltin dilaurate, 1.5 ml of
triethylamine, and 4.4 gm of calcium oxide were added and mixed well.
Next, I ml of N,N-dimethylaniline, I ml of cross-linker (polyethylene
glycol 400 dimethacrylate), and l ml of catalyst (cobalt II naphthanate),
were added and mixed well. The resulting object was hard, lightweight,
flame-resistant and exhibited sufficient low density that it floated in water.
In a separate experiment, fiberglass was added to reinforce the object made
with this method.
Additional experiments were conducted with the following ranges of
reagents: castor oil (25 - 26 gm); vinylester resin (25 - 55 gm); calcium
carbonate (70 - 90 gm); benzoyl peroxide mix (3 - 3.5 gm); calcium oxide
(3.6 - 4.5 gm); 4,4' diphenylmethane diisocyanate (25.1 - 52.1 gm);
dibutyltin dilaurate (0.25 - 0.75 ml); triethylamine (0.25 - 0.75 ml); N,N-
dimethylaniline (0.25 - 0.75 ml); cobalt II naphthanate (0.25 - 0.75 ml);
polyethylene glycol 400 dimethacrylate (l ml); and Solution 2 from Example
16 (0.25 - 0.75 ml). These experiments all produced hard, lightweight,
flame-resistant objects that exhibited sufficient low density that they floated
in water. The initiators were added at the end of the order of the addition of
reagents, whereas calcium carbonate, benzoyl peroxide mix, and calcium
oxide may be added in any order.
.. .....
CA 02266054 1999-03-11
WO 98/lllS9 PCT/US97/16439
57
'~ ~ o -- -- o o ~
~ ~~ -- 'D Z Al
n o -- -- o ~ o ~
# C~ ~ ~ V Z; V
O ~ o O ~ o ~ ~ C~
'I ~ Z v
o o o o
Z V
o o O ~ o -- V~
~ ~ o ~ ~ Z V
c~l -- O cr~ O O O
1-- ~ ~ ~ V Z V
-- -- o o~ o O ~ o ~
t~ D ~ ~ Z v
O ~ ~ oo ~
o ~ o a~ o ~ o ~ ~o u~~q vv)
C'~
~ ~ ~t o
Oo~ o ~ ~ o O
v~ o - - oo o ~ ~ ~ z v
~>
o~oo - ~ z v- ~
o -- _ 00 ''i O _
~! ~ -- ~~D ~ o
O-- _ O O ~ C
oo -- ~ Z Vt_
o~ V~ ~ o oo ~ C~
Z v
., ~, oa~ o ~o~
~ C~
V~ oo o ~ O O ~ ~ ~ ZV
~ X O'DtO ~ O ~ ~V~~VC 3
~ -- O
a _ O ~ l Z
CA 022660~4 1999-03-ll
WO 98/11159 rCT/US97/16439
TABLE 3
1 2 3 4 s 6 7 8 9**
I Gel Coat 350 3so 3so 350 3so 3so 3so 3so
2 Hard Surface Resin 350 3so 350 3so 350 3so 350 350 350
3 CMC sol. (0.5%) 9 50 50 50 l5 2s 2s 2s
4 Polyacrylic acid 9 lO 10 lO 20 2s 2s 2s
Methylmethacrylate 17.s 20 loo 20 2u 20
6 N~N-dimethylaniline 4.2s 4.2s 1S 7 7 7 7 7 7
7 Polyelhylene glycol 20 20 30 20 20 8 9 9 9
400 dimethacrylate
8 Mix A* 350
9 PMMA (30%) loo loo loo
in MMA
Silica (Colloidal silica in 20 20 30 20 20 30 50 50 50
MEKP)
I l Cobalt Il naphthanate4.2s4.2s Is 7 7 7 7 7 7
12 Solution 2 Is 1S Is 2s 25 25 2s 20 20
*Mix A consisted of the following: 500 ml calcium carbonate, 65 ml CMC solution, 350
ml gel coat, 5 ml polyaniline. ** Indicates best sample. All reagents shown in ml.
PMMA in MMA is polymethylmethacrylate in methylmethacrylate.
CA 02266054 1999-03-ll
WO 98/11159 PCT/US97/16439
59
TABLE 4
2 ~ 4 5 6 7**
Vinyl ester resin 20 60 60 60 60 60 60
2 CMC sol. ~0.5%) 2 1 20 lo
3 CaCO~ lO0 lO0 lO0 lO0100 lO
4 Solution l 20 20 20 1 o
S Elhylene Rlycol 10
6 styrene S
7 Diisocyanate 3 3 3 3
N.N-dimethylaniline 0.5 3 3 3 3 3 3
9 Cobalt 11 naphthanate0.5 3 3 3 3 3 3
l 0 Hardener 0.5 3 3 3 3 3 3
l l Solution 2 0.5 3 3 3 3 3 3
12 Polyethylene glycol-400 3 3 3 3
dimethacrylate
Gel Time (minutes) 4 5-6 4
All reagenls shown in ml. ~* Indicates best sample.
CA 022660S4 1999-03-11
WO 98/11159 PCT/US97/16439
TABLE 5
2 3 4**
Vinyl ester resin4004()0400.01 400
2 Solution of 5
50 ml polyacrylic acid
and CMC and ].04 ~ NaOH
3 Solulion 5C 3 3 3.09
4 Polyethylene glycol 400 2.05
dimethacrylate
5 N.N-dimethylaniline 2 l1.02 l.01
6 Distilled methyl 20
methacrylate
7 Cobalt II naphthanate0.5 0.5 0.71 0.64
8 Solution 2 0.50.65 0.6 0.64
** Indicates best sample. All reagents shown in gm.
CA 02266054 l999-03-ll
WO 98/1l159 PCT/US97/16439
61
TABLE 6
CaCO3 140 140
2 Solution 2 14.2 14.2
3 Polyester resin 35 35
4 Solution 4 2.5 2.5
Epoxy resin 35 35
6 Ethylene~lycol 40 40
7 Styrene
X N~N-dimethylaniline0.25
9 3,5-dimethylaniline 0.25
Polyethylene glycol 4000.25 0.25
dimethacrylate
I l CobaltII n~r~hth~ tc 0.25 0.25
12 Solution 2 0.25 0.25
Gel time (minutes0.5 0.5
All reagents shown in gm.
CA 02266054 1999-03-11
WO 98/11159 PCT/US97/16439
62
TABLE 7
l** 2 ~ 4 5 6
Polyester resin10 lO l() lO lO lO
2 Solution 4 0.6 0~5 0.5 0.5 0.5 0.5
3 Styrene 5 5 5 5
4 Suriactant E 5. l 5.0 7.1 7. l 7.0 7.0
Fly ash (fine) 95l l() llO i20
6 Fly ash (coarse) 120
7 Sand 80.2
X CaCO3 40
9 Solution l 12 9.4 l l 22.1 25 25
N.N-dimethylaniline0.5 0.5 0.5 0.50.75 0.75
l l Cobalt 11 naphthanate 0.5 0.5 0.5 0.5 0 75 0 75
12 0 5 0 5 0 5 0.5 0 750 75
** Indicates best sample. All reagents shown in gm.
CA 02266054 1999-03-11
WO 98/11159 PCTtUS97tl6439
V~ ~ o ~ ~ V'~ _
~ ~ ~ -- o ~ ''!--
o o
o ~ V~
o ~ V~
O o o
~ 5,
O ~'1 ~ o ~
o ~
o o o C,~
t~
~ o ~ o O
o ~ ~ ~ ~ ~ ._
r-- ~ o ~ ~ ~
o ~ V
~ o ~ o ~
00
C~ C'l ~ ~ o
o o ,
o O
~ ~ O
C~l ~ O ~ o ~
o O O O ~ ~ ._
o o ~
E E E E E E E E E E ~
a C E
~ '~ ~ ~ Z; o o o
CA 02266054 1999-03-11
WO 98/11159 PCT/US97116439
64
It should be understood, of course, that the foregoing relates
only to preferred embodiments of the present invention and that numerous
modifications or alterations may be made therein without departing from the
S spirit and the scope of the invention.
