U.S. patent application number 14/729738 was filed with the patent office on 2015-09-24 for ultra-low petroleum plastics.
This patent application is currently assigned to AMERICAN THERMAL HOLDINGS COMPANY. The applicant listed for this patent is American Thermal Holdings Company. Invention is credited to Richard J. Barone, Felix A. Dimanshteyn.
Application Number | 20150267040 14/729738 |
Document ID | / |
Family ID | 37590504 |
Filed Date | 2015-09-24 |
United States Patent
Application |
20150267040 |
Kind Code |
A1 |
Dimanshteyn; Felix A. ; et
al. |
September 24, 2015 |
Ultra-Low Petroleum Plastics
Abstract
Plastic-like compositions having ultra-low contents of petroleum
derived materials are provided. The materials comprise up to about
80% by weight of an inorganic salt having an average particle size
between about 0.001 and about 300 .mu.m and a plastic binder. The
compositions have a low propensity to ignite or smoke in the
presence of heat or flame.
Inventors: |
Dimanshteyn; Felix A.; (West
Hartford, CT) ; Barone; Richard J.; (Wilton,
CT) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
American Thermal Holdings Company |
Richmond Hill |
GA |
US |
|
|
Assignee: |
AMERICAN THERMAL HOLDINGS
COMPANY
Richmond Hill
GA
|
Family ID: |
37590504 |
Appl. No.: |
14/729738 |
Filed: |
June 3, 2015 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
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13411114 |
Mar 2, 2012 |
9080037 |
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14729738 |
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11174321 |
Jul 1, 2005 |
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13411114 |
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Current U.S.
Class: |
523/400 ;
524/141; 524/423 |
Current CPC
Class: |
C08K 3/30 20130101; C08K
3/016 20180101; C08L 75/04 20130101; C08K 5/521 20130101; C08L
75/06 20130101; C08K 2003/3054 20130101; C08K 3/32 20130101 |
International
Class: |
C08K 5/521 20060101
C08K005/521; C08K 3/30 20060101 C08K003/30 |
Claims
1. A composition comprising: (a) about 10 to about 80% by weight of
a thermoplastic polymer and (b) about 20 to about 80% by weight of
an inorganic salt having an average particle size between about
0.001 and about 300 .mu.m, wherein the composition has a reduced
propensity to ignite or smoke in the presence of heat or flame as
compared to the thermoplastic polymer alone, and wherein the
composition meets the U.S. Government standard for flammability
resistance FAR 25.853(b) and/or passes the ASTM E-84 test with a
Class A rating.
2-6. (canceled)
7. The composition of claim 1 wherein the thermoplastic polymer
comprises polyethylene.
8. The composition of claim 1 wherein the thermoplastic polymer
comprises polypropylene.
9. The composition of claim 1 wherein the thermoplastic polymer
comprises a polyvinyl polymer.
10-12. (canceled)
13. The composition of claim 1 wherein the inorganic salt comprises
an ammonium salt.
14. The composition of claim 1 wherein the inorganic salt comprises
a salt of sulfuric acid or phosphoric acid.
15. The composition of claim 13 wherein the inorganic salt
comprises an ammonium salt of sulfuric acid or phosphoric acid.
16. The composition of claim 15 wherein the inorganic salt
comprises ammonium sulfate.
17. The composition of claim 1 wherein the inorganic salt has an
average particle size between about 0.01 and about 100 .mu.m.
18-23. (canceled)
24. The composition of claim 1 further comprising one or more
additives selected from the group consisting of plasticizers,
stabilizers, fillers, blending resins, pigments, and impact
modifiers.
25. The composition of claim 24 wherein the one or more additives
are present in an amount between about 0.05% and about 35% by
weight of the composition.
26. A composition comprising: (a) about 10 to about 80% by weight
of a thermosetting polymer selected from the group consisting of
polyesters, epoxy resins, polyester resins, and combinations
thereof; (b) about 20 to about 80% by weight of an inorganic salt
selected from the group consisting of ammonium salts of sulfuric
and phosphoric acid; the inorganic salt having an average particle
size between about 0.1 and about 100 .mu.m; and (c) one or more
additives selected from the group consisting of plasticizers,
stabilizers, fillers, blending resins, pigments, and impact
modifiers; wherein the composition has a reduced propensity to
ignite or smoke in the presence of heat or flame as compared to the
thermosetting polymer alone, and wherein the composition meets the
U.S. Government standard for flammability resistance FAR 25.853(b)
and/or passes the ASTM E-84 test with a Class A rating.
27-42. (canceled)
43. The composition of claim 26 wherein the one or more additives
comprises a plasticizer.
44. The composition of claim 43 wherein the plasticizer is present
in an amount between about 0.05% and about 35% by weight of the
composition.
45-46. (canceled)
47. A composition comprising a plurality of inorganic salt
particles having an average particle size between about 0.001 and
about 300 .mu.m held in a homogenous physical unit by a plastic
polymeric binder, wherein the composition meets the U.S. Government
standard for flammability resistance FAR 25.853(b) and/or passes
the ASTM E-84 test with a Class A rating.
48. The composition of claim 47 wherein the plastic polymer
comprises a thermoplastic polymer.
49-52. (canceled)
53. The composition of claim 48 wherein the thermoplastic polymer
comprises polyethylene.
54. The composition of claim 48 wherein the thermoplastic polymer
comprises polypropylene.
55. (canceled)
56. The composition of claim 47 wherein the plastic polymer
comprises a thermosetting polymer.
57. The composition of claim 56 wherein the thermosetting polymer
comprises an epoxy resin.
58. The composition of claim 56 wherein the thermosetting polymer
comprises a polyester resin.
59. The composition of claim 47 wherein the inorganic salt
comprises an ammonium salt.
60. The composition of claim 47 wherein the inorganic salt
comprises a salt of sulfuric acid or phosphoric acid.
61. The composition of claim 59 wherein the inorganic salt
comprises an ammonium salt of sulfuric acid or phosphoric acid.
62. The composition of claim 61 wherein the inorganic salt
comprises ammonium sulfate.
63. The composition of claim 47 wherein the inorganic salt has an
average particle size between about 0.01 and about 100 .mu.m.
64-69. (canceled)
Description
FIELD OF INVENTION
[0001] The present invention relates generally to plastic-like
materials having diminished contents of petroleum-derived products.
The invention also relates to fire retardant plastic-like
materials.
BACKGROUND OF THE INVENTION
[0002] Conventional plastic materials comprise synthetic polymers
derived predominately from petroleum. The disadvantages of such
petroleum-derived products are well known and include, for example,
the rapid depletion of the world's petroleum reserves, the
deleterious environmental consequences resulting from the poor
biodegradability of petroleum-derived plastic materials, and the
fluctuating cost of plastic production with the price of oil. Even
conventional "low petroleum" plastics such as polyvinyl chloride
("PVC"), which comprises approximately 43% by weight petroleum
feedstock products, suffer from these disadvantages.
[0003] Accordingly, it has long been desirable to decrease the
petroleum content of plastic products. Unfortunately, satisfactory
alternatives to petroleum-derived plastic materials have not
heretofore been commercially viable. Therefore, there is a need in
the art for plastic or plastic-like materials which have a reduced
petroleum content as compared to conventional plastics.
[0004] It is therefore an object of the present invention to
provide plastic-like materials having a reduced content of
petroleum derivatives.
[0005] It is further an object of the present invention to provide
plastic-like materials having chemical properties, such as fire
retardancy and smoke suppression, superior to conventional
plastics.
[0006] It is also an object of the present invention to provide
materials having a reduced content of petroleum derivatives which
are economically viable or superior alternatives to conventional
plastics.
SUMMARY OF THE INVENTION
[0007] In accordance with the foregoing objectives and others, the
present invention provides plastic-like materials having
interesting physical and mechanical properties, chemical properties
such as fire retardancy and smoke suppression superior to
conventional plastics, and diminished petroleum-derived material
content as compared to conventional plastics.
[0008] It has surprisingly been found that plastic-like materials
comprising between about 20 to about 80% by weight of an inorganic
salt can be obtained which have physical, mechanical, and chemical
properties that are useful for many of the applications in which
conventional plastics are employed. Some properties, such as fire
retardancy, smoke suppression, toxicity of smoke release, and heat
resistance are substantially improved as compared to conventional
plastics. Importantly, the plastic-like materials or the invention
are cheaper to produce than conventional plastics.
[0009] In one aspect of the present invention a plastic-like
composition is provided comprising about 10% to about 80% by weight
of a plastic polymer and about 20% to about 80% by weight of an
inorganic salt in particulate form. In an interesting aspect of the
invention, the weight percentage of inorganic salt is above 50% and
tends toward the upper limit of the given range. The composition
has a reduced propensity to ignite or smoke in the presence of heat
or flame as compared to the thermoplastic polymer which it
comprises. The polymer may be either a thermoplastic polymer or a
thermosetting polymer. In one embodiment the plastic is a
thermosetting plastic such as, for example, an epoxy resin. In
another embodiment, the plastic polymer is a thermoplastic polymer
such as, for example, a polyvinyl, polyacrylate, polyurethane,
polycarbonate, polyester, polyamide, or polyolefin polymer, or any
combination thereof. The inorganic salt according to one embodiment
is a salt of phosphoric acid or sulfuric acid and in particular an
ammonium salt of those acids. In another aspect of the invention,
the inorganic salt is provided having a relatively small particle
size, such as, for example between about 0.001 .mu.m to about 1,000
.mu.m. Within this range, it has been found to be desirable to
provide inorganic salts with particle sizes tending toward the
lower limit.
[0010] These and other aspects of the invention will be better
understood by reference to the following detailed description of
the invention.
DETAILED DESCRIPTION OF THE INVENTION
[0011] Unless expressly defined otherwise herein, all terms are
intended to have their ordinary meaning in the art. As used herein,
the term "plastic-like" refers to a material which comprises less
polymeric material than conventional plastics but is nonetheless
capable of being molded or formed with the application of heat or
pressure in the same manner as a conventional plastic material. The
"plastic-like" materials of the present invention share many of the
physical and mechanical properties of conventional plastics, i.e.,
they may be shaped using any of the conventional techniques useful
for shaping conventional plastics, including for example, injection
molding and rolling. However, the plastic-like compositions of the
invention comprise far less polymeric material than conventional
plastics.
[0012] The term "particulate form" is mean to expansively include
any form of solid ammonium sulfate including but not limited to,
crystalline particles, microcrystalline particles, micronized
particles, nanoparticles, amorphous particles, and the like. The
term "thermoplastic" is meant to have its ordinary meaning in the
art and generally refers to plastics which are capable of
repeatedly softening when heated and hardening when cooled. The
term "thermosetting" is also meant to have its ordinary meaning in
the art and generally refers to plastics which cannot be re-melted
after being formed.
[0013] In the broadest embodiment of the invention, the
plastic-like composition comprises about 10% to about 80% by weight
of a plastic polymer and about 20% to about 80% by weight of an
inorganic salt in particulate form. The composition has a reduced
propensity to ignite or smoke in the presence of heat or flame as
compared to the plastic polymer, alone. In certain embodiments, the
composition is non-flammable when subjected to flame testing, such
as U.S. Government standard for flammability resistance FAR
25.853(b).
[0014] An essential component of the composition is a plastic
polymer. The plastic polymeric component of the present invention
may be any plastic (i.e., a thermoplastic or a thermosetting). In
one embodiment, the plastic is a thermoplastic polymer. With due
regard to the typical commercial thermoplastic polymers, particular
mention may be made, without intending to limit the invention, to
acrylics, such as polymethyl methacrylate (PMMA), acryl-nitrite
butadiene styrene (ABS), high density polyethylene (HDPE), low
density polyethylene (LDPE), polycarbonates, polyesters, including
polybutylene terephthalate (PBT) and polyethylene terephthalate
(PET), polyamides, such as nylon, polyolefins, including but not
limited to polyethylene and polypropylene, polyorganosiloxane
rubber, polytetrafluoroethylene (PTFE), polystyrene (PS), silicone
polymers and copolymers, styrene-acrylonitrile (SAN), vinyl
plastics, including but not limited to vinyl acetate, polyvinyl
chloride (PVC), chlorinated polyvinyl chloride (CPVC), and polymers
and copolymers of vinyl alcohol (VOH), polyurethanes, and
polyvinylidene chloride (PVDC). Cellulosics, polyamideimide (PAI),
polyarylate (PAR), polyetherimide (PEI), poly(phenylene sulfide)
(PPS), polysulfone, polyethersulfone (PES), polyurea,
polyetherketone (PEK), and polyetheretherketone (PEEK) are also
contemplated to be useful in the practice of the invention.
[0015] Particularly interesting thermoplastic polymers are those
formed by polymerization of vinyl monomers, including, but not
limited to olefinic monomers such as, for example, ethylene,
propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene,
1-nonene, 1-decene, and 4-methyl-1-pentene, wherein the alkyl
substituents may be either linear or branched or may be cycloalkyl
constituents. Vinyl aromatic monomers such as styrene and other
aryl or hetero-aryl substituted vinyl monomers are also suitable.
Exemplary styrenic monomers include styrene, .alpha.-methylstyrene,
p-tertiary butylstyrene, p-methylstyrene, o-methylstyrene,
m-methylstyrene, 2,4-dimethylstyrene, ethylstyrene,
.alpha.-methyl-p-methyl styrene, bromostyrene, and the like.
[0016] Specific examples of homopolymers and copolymers of olefinic
monomers are disclosed in U.S. Pat. No. 6,890,991 to Fujimoto et
al, the disclosure of which is hereby incorporated by reference,
and include low density polyethylene, ultra-low-density
polyethylene, ultra-super-low density polyethylene, linear low
density polyethylene, high density polyethylene, ultrahigh
molecular weight polyethylene, polypropylene, ethylene-propylene
copolymer, polymethylpentene, polybutene, and the like.
[0017] The vinyl monomers may also be vinyl halides. Desirable
halogen substituents are chlorine, bromine, fluorine or
combinations thereof. A preferred halogen is chlorine as in the
case of the vinyl chloride monomer. In that regard, polyvinyl
chloride ("PVC") is a particularly notable plastic for use in the
present invention. Other halogenated monomers include without
limitation vinylidene chloride, tetrafluoroethylene,
chlorotrifluoroethylene, and hexafluoropropylene.
[0018] It will be understood that the term "vinyl plastic" includes
homopolymers and copolymers of vinyl monomers. The term "PVC" is
meant to include homopolymers of vinyl chloride as well as
copolymers of vinyl chloride containing up to about 20% by weight
of other monovinylidene compounds copolymerizable therewith,
including but not limited to vinyl esters, such as vinyl acetate,
vinylidene chloride, and alkyl esters of unsaturated mono- or
dicarboxylic acids such as acrylic acid, methacrylic acid, maleic
acid and fumaric acid, including vinyl acetate, acrylate esters,
and methacrylate esters, and olefins such as ethylene and
propylene, and the like.
[0019] Other suitable monomers for use in the thermoplastic
polymers of the invention include, but are not limited to, those
disclosed in U.S. Pat. No. 6,875,832 to White et al., the
disclosure of which is hereby incorporated by reference, namely
allylic monomers, (meth)acrylic acid, (meth)acrylates,
(meth)acrylamide, N- and N,N-disubstituted (meth)acrylamides, vinyl
esters of carboxylic acids and mixtures thereof.
[0020] The thermoplastic polymer of the invention may be a
thermoplastic acrylic polymer or copolymer such as describe in, for
example, U.S. Pat. No. 4,473,679 to Falk et al and U.S. Pat. No.
4,452,941 to Kishida et al., the disclosures of which are hereby
incorporated by reference. Special mention may be made of the
acrylate monomers disclosed in U.S. Pat. No. 6,875,832 which
include, without limitation, C.sub.1-C.sub.20 alkyl (meth)acrylates
(including linear or branched alkyls and cycloalkyls) which
include, but are not limited to, methyl (meth)acrylate, ethyl
(meth)acrylate, propyl (meth)acrylate, isopropyl (meth)acrylate,
n-butyl (meth)acrylate, iso-butyl (meth)acrylate, tert-butyl
(meth)acrylate, 2-ethylhexyl (meth)acrylate, lauryl (meth)acrylate,
isobornyl (meth)acrylate, cyclohexyl (meth)acrylate,
3,3,5-trimethylcyclohexyl (meth)acrylate and isocane
(meth)acrylate; oxirane functional (meth)acrylates which include,
but are not limited to, glycidyl (meth)acrylate,
3,4-epoxycyclohexylmethyl(meth)acrylate, and
2-(3,4-epoxycyclohexyl) ethyl(meth)acrylate; hydroxy alkyl
(meth)acrylates having from 2 to 4 carbon atoms in the alkyl group
which include, but are not limited to, hydroxyethyl (meth)acrylate,
hydroxypropyl (meth)acrylate and hydroxybutyl (meth)acrylate. The
residues may each independently be residues of monomers having more
than one (meth)acryloyl group, such as (meth)acrylic anhydride,
diethyleneglycol bis(meth)acrylate, 4,4'-isopropylidenediphenol
bis(meth)acrylate (bisphenol A di(meth)acrylate), alkoxylated
4,4'-isopropylidenediphenol bis(meth)acrylate, trimethylolpropane
tris(meth)acrylate and alkoxylated trimethylolpropane
tris(meth)acrylate.
[0021] The thermoplastic polymers may also contain maleimide
monomers such as maleimide, N-methyl maleimide, N-iso-propyl
maleimide, N-butyl maleimide, N-hexyl maleimide, N-octyl maleimide,
N-dodecyl maleimide, N-cyclohexyl maleimide, N-phenyl maleimide,
N-2-methyl maleimide, N-2,3-dimethyl phenyl maleimide,
N-2,4-dimethyl phenyl maleimide, N-2,3-diethyl phenyl maleimide,
N-2,4-diethyl phenyl maleimide, N-2,3-dibutyl phenyl maleimide,
N-2,4-dibutyl phenyl maleimide, N-2,6-dimethyl phenyl maleimide,
N-2,3-dichlorophenyl maleimide, N-2,4-dichlorophenyl maleimide,
N-2,3-dibromophenyl maleimide or N-2,4-dibromophenyl maleimide, and
the like as disclosed in U.S. Pat. No. 6,855,769 to Su, the
disclosure of which is hereby incorporated by reference.
[0022] The thermoplastic polymers may comprise a polyester resin as
described in, for example, U.S. Pat. No. 6,890,991 to Fujimoto et
al, the disclosure of which is hereby incorporated by reference.
Such polyester resins are obtained by the polycondensation reaction
of one or more dicarboxylic acids such as, for example,
terephthalic acid, isophthalic acid, naphthalenedicarboxylic acid,
4,4'-diphenyldicarboxylic acid, diphenyletherdicarboxylic acid,
.alpha., .beta.-bis (4-carboxyphenoxy)ethane, adipic acid, sebacic
acid, azelaic acid, decanedicarboxylic acid, dodecanedicarboxylic
acid, cyclohexanedicarboxylic acid and dimer acid, or ester-forming
derivarives thereof, and one or more glycols such as, for example,
ethylene glycol, propylene glycol, butanediol, pentanediol,
neopentyl glycol, hexanediol, octanediol, decanediol, cyclohexane
dimethanol, hydroquinone, bisphenol A,
2,2-bis(4'-hydroxyethoxyphenyl)propane, xylene glycol, polyethylene
ether glycol, polytetrafluoroethylene ether glycol, and aliphatic
polyester oligomer having a hydroxyl group at both terminals. The
polyester resin may be either a homopolyester or a copolyester.
Other exemplary thermoplastic polyesters are disclosed in, for
example, U.S. Pat. No. 6,809,151 to Lacroix et al., the disclosure
of which is hereby incorporated by reference. Particularly
interesting polyesters are polybutylene terephthalate (PBT) and
polyethylene terephthalate (PET).
[0023] Suitable thermoplastic polyurethanes materials include those
disclosed in U.S. Pat. No. 6,881,856 to Tanaka et al., the
disclosure of which is hereby incorporated by reference. As
disclosed in that patent, theremoplastic polyurethanes are obtained
by reaction of polyethercarbonate diols with a diisocyanate and a
chain extender, such as a polyol or polyamine compound, by a
polyurethane-producing reaction. The exemplary polyethercarbonate
diols, diisocyanates, and chain extenders disclosed in U.S. Pat.
No. 6,881,856 are hereby incorporated by reference.
[0024] The thermoplastic polymers of the invention may also
comprise thermoplastic polyamides (nylons) such as those disclosed
in U.S. Pat. No. 6,870,005 to Lieberman et al., the disclosure of
which is hereby incorporated by reference. These thermoplastic
polyamides may be prepared by polymerization of, for example, one
or more epsilon lactams such as caprolactam, pyrrolidone,
lauryllactam and aminoundecanoic lactam, or amino acid, or by
condensation of dibasic acids and diamines. Exemplary polyamides
include polycaprolactam (nylon 6), polylauryllactam (nylon 12),
polyhexamethylenedipamide (nylon 6,6), polyhexamethyleneazelamide
(nylon 6,9), polyhexamethylenesebacamide (nylon 6,10),
polyhexamethyleneisophthalamide (nylon 6,10), the condensation
product of 11-aminoundecanoic acid (nylon 11),
polytetramethyleneadipamide (nylon 4,6),
polyhexamethyleneazelaamide (nylon 6,9),
polyhexamethylenesebacamide (nylon 6,10),
polyhexamethylenedodecanediamide (nylon 6,12), and
polydodecanemethylenedodecanamide (nylon 12,12). Other suitable
nylon resins are disclosed in, for example, U.S. Pat. No.
6,861,470, the disclosure of which is hereby incorporated by
reference.
[0025] Thermoplastic polycarbonate plastics are also well known in
the art and include, for example, those described in U.S. Pat. No.
5,756,641 to Kuhling et al., the disclosure of which is hereby
incorporated by reference. Such polycarbonates are formed by
transesterification of aromatic diphenols with carboxylic acid
diaryl esters. Exemplary diphenols include, without limitation,
4,4'-dihydroxydiphenyl, 4,4'-dihydroxydiphenyl sulphide,
2,2-bis-(4-hydroxyphenyl)-propane,
2,2-bis-(3,5-dimethyl-4-hydroxyphenyl)-propane,
2,2-bis-(3,5-dichloro-4-hydroxyphenyl)-propane,
2,2-bis-(3,5-dibromo-4-hydroxyphenyl)-propane,
1,1-bis-(4-hydroxyphenyl)-cyclohexane, and
1,1-bis-(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane. Exemplary
carboxylic acid diesters include without limitation
di-C.sub.6-C.sub.20-aryl esters, such as the diesters of phenol or
of alkyl-substituted phenols. Special mention may be made of
diphenyl carbonate or dicresyl carbonate.
[0026] Particularly interesting polymers according to the invention
comprise polyvinyls, polyacrylates, polyurethanes, polycarbonates,
polyesters, polyamides, polyolefins, and combinations thereof.
Polyvinyl and polyolefin polymers are especially interesting
polymers according to the invention.
[0027] The foregoing monomers and polymers are provided by way of
example only and are not intended to limit the scope of the
invention. The skilled artisan will recognize that any of the
numerous thermoplastic polymers known in the art are contemplated
to be within the scope of the present invention.
[0028] Alternatively, the plastic component may be a thermosetting
plastic such as, without limitation, epoxy resin, polyester resin,
natural rubbers such as latex, melamine plastics such as
Formica.RTM., phenolics such as Bakelite, urea-formaldehyde, and
the like.
[0029] The compositions of the present invention also include as an
essential component an inorganic salt. While it is contemplated
that a wide variety of inorganic salts will be useful in the
practice of the invention, it is advantageous to employ a fire
extinguishing inorganic salt. Particular mention may be made of
inorganic salts of phosphoric acid, metaphosphoric acid,
orthophosphoric acid, pyrophosphoric acid, polyphophoric acid,
sulfuric acid, and hydrochloric acid. Ammonium salts are especially
useful. Accordingly, particularly interesting inorganic salts
include but are not limited to ammonium phosphates, such as
(NH.sub.4)H.sub.2PO.sub.4 (mono-ammonium phosphate or ammonium
phosphate) and (NH.sub.4).sub.2HPO.sub.4 (di-ammonium phosphate),
and ammonium sulfates, including (NH.sub.4).sub.2SO.sub.4 (ammonium
sulfate or di-ammonium sulfate) and (NH.sub.4)HSO.sub.4 (ammonium
hydrogen sulfate or ammonium bisulfate), and (NH.sub.4).sub.2Cl. In
one interesting embodiment, the inorganic salt comprises ammonium
sulfates, especially (NH.sub.4).sub.2SO.sub.4. Combinations of any
of the foregoing inorganic salts are also contemplated to be
useful.
[0030] The inorganic salt is in particulate form. While it is
contemplated that any size inorganic salt particulate material will
be useful in the practice of the invention, preferred materials
will have average particle diameters of below about 1 mm.
Accordingly, in one embodiment of the invention, the inorganic salt
particulate material has an average particle size of about 0.001
.mu.m to about 1,000 .mu.m. In another embodiment, the inorganic
salt particulate material has an average particle size of about
0.01 .mu.m to about 300 .mu.m. In particularly interesting
embodiments, the particle size of the inorganic salt is between
about 0.1 to about 30 .mu.m, 1 and about 10 .mu.m, and about 5 to
about 8 .mu.m. Further, the invention embraces embodiments within
the range of 0.001 .mu.m to about 1,000 .mu.m wherein the lower and
upper limits are increased or decreased by intervals of 5 .mu.m,
each such sub-range being an embodiment of the invention.
[0031] The particles size distribution of the inorganic salt
particulate material may be selected by any known method in the
art, including the use of mesh sieves. The particle sizes which
will pass through standard (Tyler or BS-410) mesh sizes are well
known in the art. Inorganic salt particulate materials which have
an average particle size sufficiently small to pass through any of
the standard Tyler mesh sizes are contemplated to be useful in the
practice of the present invention. Accordingly, with regard to the
standard Tyler mesh sizes, the invention embraces embodiments
having particle sizes of less than about 297, 250, 210, 177, 149,
105, 74, 62, 53, 44, 37, 20, 10, and about 5 .mu.m, respectively.
Further control over the distribution of particle size is
obtainable by passing the material through two sieves of different
mesh, as is well known in the art. The skilled artisan will
recognize that various permutations of standard mesh sizes can by
employed to obtain a variety of particle size ranges, each of which
is contemplated to be an embodiment of the invention. Of course, it
is also within the skill in the art to employ non-standard mesh
sizes to obtain any desired particle sizes which are larger,
smaller, or intermediate to those provided by the standard Tyler
mesh sizes.
[0032] Methods for mechanically micronizing particulate matter
(i.e., crushing, grinding, and milling) are well known in the art
as disclosed in, for example, U.S. Pat. No. 6,726,133 to Hahn et al
and U.S. Pat. No. 5,732,894 to Sheahan, the disclosures of which is
hereby incorporated by reference. Non-mechanical methods for
forming micronized and nanoparticulate materials are also well
known in the art, as disclosed in, for example, U.S. Pat. No.
5,874,029 to Subramaniam et al., the disclosure of which is hereby
incorporated by reference. It is within the skill in the art to
provide inorganic salts in particulate form having the particle
sizes disclosed herein.
[0033] For example, U.S. Patent Application Pub. No. 2002/0065198
to Highsmith et al., which is incorporated herein by reference,
discloses a process for ball milling commercially available
ammonium sulfate granules of approximately 1 mm average size to
produce micronized ammonium sulfate particles having the particle
size profile shown in Table I:
TABLE-US-00001 TABLE I Tyler Sieve No. Wt. % Retained 48 Less than
0.1 60 0.3 80 0.4 100 0.3 200 18 230 49 400 19 pan 13
[0034] The compositions of the invention generally comprise the
plastic polymer between about 10% and about 80% by weight and
comprise the inorganic salt between about 20% to 80% by weight,
with the proviso the sum of the weight % of each component not
exceed 100%. In variations of this embodiment, the lower limit of
the weight ranges of inorganic salt may be at least 26%, 27%, 28%,
or at least 29% by weight. The invention also contemplates
sub-ranges within the foregoing ranges wherein the lower and/or
upper limits are increased or decreased, respectively, by intervals
of 5 weight %, each such sub-range being an embodiment of the
invention.
[0035] In one embodiment, the compositions comprise the plastic
polymer between about 10% and about 60% by weight and comprise the
inorganic salt between about 30% to 80% by weight. In another
embodiment, the compositions comprise the plastic polymer between
about 10% and about 50% by weight and the inorganic salt between
about 40% to 80% by weight. In another embodiment, the compositions
comprise the plastic polymer between about 10% and about 40% by
weight and the inorganic salt between about 50% to 80% by weight.
In a further embodiment, the compositions comprise the plastic
polymer between about 10% and about 30% by weight and the inorganic
salt between about 60% to 80% by weight. In an yet another
embodiment, the compositions comprise the plastic polymer between
about 10% and about 20% by weight and the inorganic salt between
about 70% to 80% by weight. The weight ratio of plastic polymer to
inorganic salt is typically in the range of about 1:8 to about 5:1,
including embodiments of 1:7 to about 4:1, 1:5 to about 3:1, 1:3 to
about 2:1, and 1:2 to about 1:1.
[0036] One variant of the plastic-like compositions of the
invention comprises: (a) about 10 to about 80% by weight of a
plastic polymer; and (b) about 10 to about 80% by weight of an
inorganic salt having an average particle size between about 0.001
and about 300 .mu.m; said composition having a reduced propensity
to ignite or smoke in the presence of heat or flame as compared to
said plastic polymer alone; with the proviso that when the weight
of the inorganic salt component is ammonium sulfate comprising 25%
or less by weight of the composition, the plastic-like composition
is substantially non-intumescent.
[0037] It is believed that the compositions of the invention
comprise a plurality of inorganic salt particles, such as ammonium
sulfate in particulate form, having any of the average particle
sizes set forth above, held in a homogenous physical unit by a
plastic polymeric binder. By "homogenous physical unit" it is meant
that the inorganic salt and the plastic are not readily separable
from one another. Unlike conventional plastics, in which a
polymeric material forms a matrix which constitutes the bulk of the
material, the bulk of the compositions of the invention may be
provided by the inorganic salt. It is believed that in the present
invention, the plastic material serves as a binder to hold the
particulate matrix in place and impart flexibility, ductility, and
the like, to the compositions.
[0038] The compositions of the invention may comprise additives.
When present, additives may comprise between about 0.01% and about
35% by weight of the composition. In one embodiment, the additives
comprises about 20% by weight of the composition.
[0039] The additives include all those well known in the art,
including but not limited to, intumescent additives, plasticizers,
stabilizers, fillers, blending resins, pigments, and additives, as
well known to one skilled in the art. Any plasticizer, stabilizer,
filler, or other additive known in the art may be used in the
present invention. Suitable plasticizer, stabilizer, fillers, and
other additives, include but are not limited to, those disclosed in
U.S. Pat. No. 6,706,820 to Kumaki, et al., U.S. Pat. No. 5,552,484
to Enomoto, and U.S. Pat. No. 4,042,556 to Yoshinaga, the contents
of which are hereby incorporated by reference herein. The plastics
may further comprise U.V. stabilizers, colorants, and impact
modifiers. Additives including, but not limited to, low
flammability oils such as soybean and corn oils, calcium carbonate,
calcium stearate, titanium dioxide, paraffin wax, oxidized PE
lubricant, phthalate plasticizers, heat stabilizers, impact
modifiers, and intumescent additives are particularly notable. The
plasticizer 2-ethyl hexyl diphenyl (Santicizer.RTM. 141, Ferro
Corp.) has been found useful in the practice of the invention.
Thinners for processing may also be desirable in some
applications.
[0040] If desired, blowing agents such as for example, chlorinated
fluorocarbons, HCFCs, butane, isopentane, carbon dioxide, nitrogen,
argon, and the like, may also be used to produce foamed products,
all in accordance with well known practice in the art. Methods for
making foamed plastic are disclosed in, for example, U.S. Pat. Nos.
3,983,296 and 4,120,833 to Purvis, et al., U.S. Pat. No. 4,017,657
to Foley, et al., U.S. Pat. No. 4,042,556 to Yoshinaga, U.S. Pat.
Nos. 5,391,585 and 5,324,461 to Grohman, U.S. Pat. No. 5,686,025 to
Martin, U.S. Pat. Nos. 5,783,613 and 5,786,399 to Beekman et al.,
U.S. Pat. Nos. 6,225,365 and 6,225,365 to Zerafati, et al., and S.
K. Dey et al. "Inert-Gas Extrusion of Rigid PVC Foam" Journal of
Vinyl & Additive Technology, March 1996, Vol. 2, No. 1., the
contents of which are hereby incorporated by reference herein.
[0041] The compositions of the invention may be formed in any
technique conventional for forming thermoplastics or
thermosettings, including, for example, extrusion, injection
molding, blow molding, rotomolding, thermoforming, calandering, and
compression molding. The materials of the invention may be extruded
in the same manner as conventional plastics, as disclosed in, for
example, U.S. Pat. No. 6,350,400 to Piotrowski, U.S. Pat. No.
4,322,170 to Papenmeier; U.S. Pat. No. 3,983,186 to Eilers, et al.,
M. J. Stevens, "Extruder Principals and Operation", Elsevier
Applied Science Publishers, New York, N.Y. (1985), and C.
Rauwendaal, "Polymer Extrusion", Hanser Publishers, New York, N.Y.
(1986), the contents of which are hereby incorporated by reference
herein. The compositions are suitable for injection molding and the
like. The compositions of the invention may also be formed by
rolling under heat as is also well known in the art.
[0042] As evident from the foregoing, the compositions of the
invention contain far less polymeric material derived from
petroleum than conventional plastics. For example, conventional
compounded PVC has the makeup given in Table II.
TABLE-US-00002 TABLE II Weight Percent Material (based on PVC
resin) PVC Resin 100 Impact Modifier 5.0 Heat Stabilizer 0.8 Filler
(CaCO.sub.3) 10 Calcium Stearate 1.4 Processing Aid 0.8 Oxidized PE
Lubricant 0.15 Paraffin Wax 1.2 TiO.sub.2 2.0
[0043] As shown in Table III, conventional compounded PVC comprises
approximately 83% by weight polyvinyl chloride polymer, which
itself comprises 43% by weight petroleum-derived material. Thus,
even polymers such as PVC, which is generally considered to be a
"low-petroleum" content material, contains 0.36 pounds (or 36% by
weight) of polymer derived from petroleum for every pound of
compounded PVC. In contrast, Table III provides three exemplary
low-petroleum content formulations of the invention. In each case,
the compounded PVC resin is mixed with ammonium sulfate and
plasticizer in the ratios given.
TABLE-US-00003 TABLE III Weight % ammonium Compounded of petroleum-
sulfate Plasticizer PVC derived polymeric Sample (wt. %) (wt. %)
(wt. %) component 1 60 19 21 7.6 2 55 19 26 9.4 3 50 19 31 11.2
[0044] Based on the foregoing, the benefits of the present
invention as applied to high petroleum content plastics, such as,
for example, polyethylene and polypropylene, are immediately
apparent. The petroleum based content of such plastics can be
reduced by at least about 30%, 35%, 40%, 45%, 50%, 55%, 60%, 65%,
70%, 75%, or 80%, each being considered an embodiment of the
invention. It is contemplated that even greater reductions in the
petroleum based content of plastic materials are achievable with
the present invention.
[0045] The compositions of the invention have a reduced propensity
to ignite or smoke in the presence of heat or flame as compared to
the plastic binder material alone. This property is believed to
arise from the reduced petroleum content of the materials and the
fact that flame retardant inorganic salts, such as ammonium
sulfate, release inert gases (i.e., N.sub.2) upon decomposition
with heat. Accordingly, in particularly desirable embodiments, the
inorganic salt is a flame retardant inorganic salt. The
compositions of the invention are substantially non-intumescent, in
the absence of added intumescent material. This does not preclude,
however, the addition of minor amounts of intumescent additives
such as intumescent catalysts, carbonifics, and/or blowing agents
to the compositions.
EXAMPLE 1
Preparation of Micronized Ammonium Sulfate
[0046] Approximately 20 pounds of ammonium sulfate and
approximately 15 pounds of glass balls with sizes ranging from 0.5
to 1 inches were placed in a standard cement mixer. The ammonium
sulfate was ground for about four hours. The material was then
passed through a 500 Tyler mesh screen. Substantially all of the
material passed through the screen indicating that the maximum
particle size was about 25 .mu.m. This material was used to make
the materials described in the following examples.
EXAMPLE 2
[0047] Approximately 60 gm of micronized ammonium sulfate from
Example 1 was mixed with approximately 21 gm of a standard
compounded PVC (see Table II) and approximately 19 gm pounds of the
2-ethyl hexyl diphenyl plasticizer Santicizer.RTM. 141 (Ferro
Corp.). The mixture was formed into sheets having a thickness of
about 30 mil with twin rollers operating at 380.degree. F. for
about five minutes, or until homogeneous.
EXAMPLE 3
[0048] Approximately 55 gm pounds of micronized ammonium sulfate
from Example 1 was mixed with approximately 26 gm pounds of a
standard compounded PVC (see Table II) and approximately 19 gm
pounds of the 2-ethyl hexyl diphenyl plasticizer Santicizer.RTM.
141 (Ferro Corp.). The mixture was formed into sheets having a
thickness of about 30 mil with twin rollers operating at
380.degree. F. for about five minutes, or until homogeneous.
[0049] This material was tested for fire retardancy by an
independent laboratory with the Underwriters Laboratories ("UL")
flame test designated UL-94. The material received the highest
UL-94 rating of V-0.
[0050] The material also passed the U.S. Government standard for
flammability resistance FAR 25.853. That test involves subjecting a
panel to edge burning by a flame maintained at 1550.degree. F. for
a period of 60 seconds and requires that the material be
self-extinguishing before 15 seconds and that it be non-dripping.
After subjecting the material to flame for 60 seconds, there was no
flaming or dripping of the material.
EXAMPLE 4
[0051] Approximately 50 gm of micronized ammonium sulfate from
Example 1 was mixed with approximately 31 gm of a standard
compounded PVC (see Table II) and approximately 19 gm pounds of the
2-ethyl hexyl diphenyl plasticizer Santicizer.RTM. 141 (Ferro
Corp.). The mixture was formed into sheets having a thickness of
about 30 mil with twin rollers operating at 380.degree. F. for
about five minutes, or until homogeneous.
EXAMPLE 5
[0052] Approximately 35 gm of micronized ammonium sulfate from
Example 1 was mixed with approximately 46 gm pounds of a standard
compounded PVC (see Table II) and approximately 19 gm pounds of the
2-ethyl hexyl diphenyl plasticizer Santicizer.RTM. 141 (Ferro
Corp.). The mixture was formed into sheets having a thickness of
about 30 mil with twin rollers operating at 380.degree. F. for
about five minutes, or until homogeneous.
[0053] The material also passed the U.S. Government standard for
flammability resistance FAR 25.853(b). That test involves
subjecting a panel to edge burning by a flame maintained at
1550.degree. F. for a period of 12 seconds and requires that the
material be self-extinguishing before 15 seconds and that it be
non-dripping. After subjecting the material to flame for 12
seconds, there was no flaming or dripping of the material.
EXAMPLE 6
[0054] This example provides a material according to the invention
wherein the polymeric binder is a thermosetting polymer. 48 parts
of polyester resin 48 (approximately 4 pounds) was mixed with 52
parts (approximately 4.5 pounds) ammonium sulfate from Example 1 in
one gallon container. The composition was mixed until homogenous,
about 5 minutes, with a drill blade. After mixing, about 900 drops
of a methyl ethyl ketone peroxide (MEKP) hardener was added to set
the material.
[0055] A 24 feet, 30 mil thick coating of this material was
subjected to ASTM E-84 flame spread and smoke evolution testing.
The flame spread index was 15 and smoke index was 45. There was no
evidence of progressive combustion after 30 minutes. Thus, the
material passed ASTM E-84 with a Class A rating.
[0056] It will be understood that the recitation of ranges
contained herein are as a matter of convenience only and the
inventors are in possession of every value intermediate within the
ranges. That is, every intermediate value or sub-range within a
disclosed range should be understood to be inherently
disclosed.
[0057] The invention having been described by the foregoing
description of the preferred embodiments, it will be understood
that the skilled artisan may make modifications and variations of
these embodiments without departing from the spirit or scope of the
invention as set forth in the following claims.
* * * * *