Note: Descriptions are shown in the official language in which they were submitted.
POLYURETHANE ELASTOMER COMPOSITIONS, ARTICLES OF
MANUFACTURE COMPRISING SAME, AND PROCESSES
FIELD
[0001] The present invention relates generally to polyurethane and in
particular, to polyurethane elastomer compositions, articles of manufacture
comprising same, and preparation processes.
RELATED APPLICATIONS
[0002] This application is the Canadian counterpart of U.S. Application
Serial
No. 17,015,808 filed September 9, 2020 (now U.S. Patent No. 10,934,385 issued
and published March 2, 2021).
[0003] In related U.S. Application Serial No. 17//015,669 filed
September 9,
2020 (now U.S. Patent No. 10,934,384 issued and published March 2, 2021),
there
are illustrated biocide containing polyurethane elastomers, foam compositions,
and
processes thereof.
BACKGROUND
[0004] In United States Patent Publication 2012/0258269 Al there is
disclosed
a process for preparing polyester polyols from at least one carboxylic acid
recovered
from natural raw materials, and having at least two acid groups, at least one
polyhydric alcohol, at least one organic phosphite group, and at least one
Lewis acid.
The recited polyol polyester composition according to this publication can be
selected
to prepare various thermoplastic polyurethane products.
100051 United States Patent 9,458,277 discloses a method for the
preparation
of polyurethane elastomers based on polyester diols formed from diacids, such
as
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succinic acid, a carbohydrate, diols such as 1,3-propanediol, and an organic
diisocyanate.
[0006] Also, in United States Patent Publication 2013/0035448 there is
disclosed a method for producing a biomass resource-derived polyurethane by
reacting a dicarboxylic acid and an aliphatic diol to produce a polyester
polyol and
reacting the polyester polyol and a polyisocyanate compound, where the
dicarboxylic
acid contains at least one component derived from biomass resources, a content
of
an organic acid in the dicarboxylic acid is more than 0 ppm and not more than
1,000
ppm relative to the dicarboxylic acid, and a pKa value of the organic acid at
25 C. is
not more than 3.7.
[0007] Athletic shoes, whether for running or engaging in sports
activities, lose
massive amounts of energy due to impact and shock, especially in the midsoles.
A
well cushioned shoe disperses the impact and shock that for a period of time
keeps
the feet comfortable and prevents the feet from hurting. High performance
athletic
shoes have well cushioned midsoles that transfer the impact into forward
motion or
lift-offspring-like effect, as if the impact/shock is being turned into a
return energy.
[0008] Thus, a number of polyurethane elastomers are known, many of
which
possess deficiencies such as insufficient life times, poor hardness,
degradation,
unsuitable and consistent properties like tensile strengths, discoloration,
lack of
continued suitable flexibilities, complex and costly preparation processes,
including
the absence of components, such as phosphites, and the absence of polyesters
like
the disclosed amorphous polyester resins and semi-crystalline polyester resins
in
combination with other components, and excellent and in embodiments, improved
bio-contents.
[0009] There is a need for polyurethane elastomers that can be selected
for
molded flexible parts, footwear insoles or midsoles, and which elastomers
with, for
example, a combination of specific mechanical properties, such as a hardness
of, for
example, from about 20 to about 60 Asker C, from about 15 to about 60 Askar C,
from about 20 to about 50 Asker C, and from about 15 to about 35 Askar C, and
for
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insoles a hardness of, for example, from about 22 Asker C to about 44 Asker C,
and
for midsoles a hardness of from about 40 to about 60 Asker C, and containing,
for
example, an amorphous polyester or a semi-crystalline polyester with excellent
melting points.
[0010] Yet also, there is a need for polyurethane elastomer foams and
processes wherein there are selected surfactants, plasticizers, dyes,
crosslinkers,
chain extenders, plasticizers and blowing, or foaming agents.
[0011] Further, there is a need for polyurethane (PU foams) that have an
excellent density, prolonged Asker C hardness, improved tensile strengths,
acceptable and consistent elongation and tear strength properties, and which
foams
are, for example, selected for shoes and similar footwear that contain insoles
and
m idsoles.
[0012] Another need resides in the generation of polyurethane elastomers
where there is eliminated a number of semi-crystalline polyester polyols that
must be
heated above 50 C prior to permitting the initiation of foaming, and which
polyols
increase preheating time, create a highly viscous liquid difficult to use in
manufacturing methods, and where elevated temperatures increase the reaction
kinetics and cause less control over the reaction thereby adversely affect
product
quality.
[0013] Additionally, there is a need for polyurethane elastomer foams
where
the viscosities of the polyol ester reactant may be decreased with the use of
certain
plasticizers.
[0014] There is a need for footwear like athletic shoes with superior
energy
return, that is the ability of footwear, such as athletic shoes to receive and
release
energy upon impact on striking the ground and resilience, which is the ability
to
spring back into its original shape (elasticity) after being compressed and
measured
by the rebound percentage, and where in embodiments the disclosed polyurethane
foam-based midsoles have, for example, a return energy of from about 50
percent to
about 100 percent, from about 55 to about 75 percent, and from about 55 and
from
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about 70 as measured by VF Corporation with their proprietary equipment,
hydrolytic
stability, excellent resilience of, for example, from about 25 percent to
about 60
percent, from about 30 percent to about 60 percent, from about 25 percent to
about
45 percent, and improved compression sets.
[0015] Yet in embodiments, there is a need for polyurethane elastomer
foams
selected for insoles and midsoles that have excellent mechanical properties,
and
where the insoles have a density (grams/centimeter3) of, for example, from
about 0.2
to about 0.3; a hardness (Asker C) of, for example, from about 15 to about 55;
an
elongation of, for example, from about 150 percent to about 700 percent, from
about
450 percent to about 650 percent; a tensile strength of, for example, equal to
or
greater than about 20 MPa; a tear strength of, for example, equal to or
greater than
about 2 Newtons/millimeters2, a rebound test resilience of, for example, equal
to or
from about 40 to about 50 percent; a compression set, for example, of equal to
or
less than about 6 percent; and a hydrolytic stability of, for example, equal
to or at
least 80 percent; and for midsoles a density in grams/centimeters3 of, for
example,
equal to or less than 0.5; a hardness (Asker C) of, for example, from about 30
to
about 50; an elongation of equal to or greater than about 300 percent; a
tensile
strength in MPa of, for example, equal to or greater than about 10; a tear
strength in
Newtons/millimeters of, for example, equal to or greater than about 3; a
rebound test
resilience of, for example, equal to or greater than about 60; a compression
set of, for
example, less than or equal to about 20 percent; an abrasion of, for example,
less
than or equal to about 300 percent; and a hydrolytic stability of, for
example, equal to
or at least 80 percent.
[0016] Also, therefore there is a need for insoles with a density
(grams/centimeters3) of from about 0.2 to about 0.3; a hardness (Asker C) of
about
15 to about 35; an excellent elongation of from about 450 to about 650
percent; a
tensile strength (MPa) of less than about 20; a tear strength
(Newtons/millimeters) of
less than about 2; a rebound test resilience of from about 40 to about 45
percent; a
compression set of greater than about 6 percent; and a hydrolytic stability of
about 80
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percent and above; and for midsoles, a density (grams/centimeters3) of greater
than
about 0.5; a hardness (Asker C) of from about 30 to about 50; an excellent
elongation, a tensile strength (MPa) of less than about 10; a tear strength
(Newtons/millimeters) of less than about 3; a rebound test resilience of less
than
about 60 percent; a compression set of less than about 20 percent; an
excellent and
improved abrasion or hardness of more than about 300 percent; and a hydrolytic
stability of about 80 percent and above.
[0017] An important need resides in polyurethane elastomer foams with a
bio-
content of, for example, from about 50 to about 90, from about 60 to about 90
percent, from about 60 percent to about 75 percent, from about 50 percent to
about
90 percent, from about 40 percent to about 85 percent, from about 70 percent
to
about 85 percent, and from about 60 percent to about 80 percent.
[0018] These and other needs may be accomplished with the disclosed
polyurethane elastomers and foams thereof of the present disclosure.
SUMMARY
[0019] Disclosed herein are polyurethane elastomer compositions which
can
be generated from the reaction of (a) an organic diisocyanate, (b) a polyester
resin,
(c) a chain extender, (d) a crosslinker, (e) a plasticizer, (f) a surfactant,
(g) an optional
foaming agent, and (h) an optional dye, and which compositions can be selected
for
a number of articles, such as footwear, insoles, middle soles, shoes, boots,
sneakers,
slippers, clothing, insulation, automobile components, furniture components
like
coverings, bedding, seals, molded flexible parts, foams, adhesives, and
medical
devices, and as a replacement for a number of known polyurethane elastomers.
[0020] The polyurethane elastomer compositions can be generated, for
example, from the reaction of (a) an organic diisocyanate, (b) a polyester
resin, (c) a
chain extender comprised of a polyhydric alcohol, (d) a crosslinker, (e) a
plasticizer,
(f) a surfactant, (g) an optional foaming agent, and (h) an optional colorant
such as a
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dye, and wherein said elastomer has a hardness value of from about 15 or 20
Asker
C to about 60 Asker C, a tensile strength of from about 1 MPa to about 10 MPa,
a
tensile strength of from about 1 MPa to about 5 MPa, a resilience of from
about 25
percent to about 60 percent, an elongation at break of from about 150 percent
to 700
percent, and a tear strength of from about 2 Newtons/millimeters2 to about 4
Newtons/millimeters2.
[0021] Also disclosed is an article comprised of a polyurethane
elastomer,
such as in the configuration of a foam generated from the reaction of (a) an
organic
diisocyanate, (b) a polyester resin, (c) a chain extender comprised of a
polyhydric
alcohol, (d) a crosslinker, (e) a plasticizer, (f) a surfactant, (g) a foaming
agent, and
(h) a colorant such as a pigment, a dye, or mixtures thereof, and wherein the
elastomer has a hardness value of, for example, from about 15 Asker C to about
60
Asker C, a tensile strength of from about 1 MPa to about 10 MPa, a resilience
of from
about 30 percent to about 60 percent, an elongation at break of from about 150
percent to 700 percent, and a tear strength of from about 2
Newtons/millimeters2 to
about 4 Newtons/millimeters2.
[0022] Moreover, disclosed is a process for the preparation of a
polyurethane
elastomer composition comprising mixing, and then reacting (a) an organic
diisocyanate, (b) a polyester resin derived from an organic diacid and an
organic diol,
(c) a chain extender comprised of a polyhydric alcohol, (d) a crosslinker, (e)
a
plasticizer, (f) a surfactant, (g) a foaming agent, (h) a dye, and (i) a
catalyst, and
wherein the elastomer has a hardness of from about 20 Asker C to about 60
Asker C,
a tear strength of from about 2 to about 4 Newtons/millimeters2, a resilience
of from
about 25 percent to about 45 percent, and a compression set of from about 3
percent
to about 6 percent.
[0023] Yet additionally, there is disclosed a polyurethane elastomer
foam
composition prepared by the reaction of an organic diisocyanate, an amorphous
polyester resin or a semi-crystalline polyester resin with a melting point of
less than
about 70 C, a chain extender comprised of a polyhydric alcohol, a crosslinker,
a
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plasticizer, a dye, a surfactant, and a foaming agent, and wherein the
elastomer has
a hardness of from about 15 Asker C to about 60 Asker C, and/or from about 20
to
about 60 Asker C, a tensile strength of from about 1 to about 10 MPa, and an
elongation at break of from about 150 percent to about 700 percent, and which
elastomers can be, for example, selected for shoe articles comprised of an
insole and
a midsole.
[0024] Further, in embodiments there is disclosed a polyurethane
elastomer
foam composition and processes thereof, and more specifically, a polyurethane
elastomer foam composition that can be selected for footwear, such as shoe
articles
comprised of an insole, a midsole, or both the insole and midsole and the
other uses
disclosed herein. More specifically, there is disclosed a polyurethane
elastomer
derived from (a) an organic diisocyanate, (b) an amorphous polyester or semi-
crystalline polyester resin derived from an organic diacid and organic diol
polyester
polyol, (c) a chain extender comprised of a polyhydric alcohol, (d) a
crosslinker, (e) a
plasticizer, (f) a surfactant, (h) a foaming component, such as water, and
wherein the
elastomer has a hardness of from about 30 to about 60 Asker C, a tensile
strength of
from about 1 to about 5 MPa, and an elongation at break of from about 250
percent
to about 625 percent.
[0025] Furthermore, there are disclosed amorphous polyester polyols
with
melting points of less than about 5 C to less than about 25 C, and more
specifically,
an amorphous polyester resin with no or zero melting point and a glass
transition
temperature of less than about -10 C, like from about -2 C to about -8 C.
Also, other
properties for the amorphous polyester include weight average molecular
weights as
determined, for example, by known techniques like Gel Permeation
Chromatography
(GPC) of from about 700 Daltons to 4,000 Daltons, hydroxyl values of from
about 35
to about 65, and acid numbers of less than about 5 milligrams/grams of KOH,
and
more specifically, from about 0.5 to about 1 milligram/gram of KOH. These
polyols
can be subsequently used to prepare polyurethane foams for the footwear
industry
and the automobile industry.
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Date Recue/Date Received 2021-11-17
[0026] There are also disclosed polyurethane elastomers and polyurethane
foam compositions comprised of from about 40 to about 55 percent by weight of
a
polyol polyester, from about 1 to about 3 percent by weight of a chain
extender, from
about 1 to about 7 percent by weight of a crosslinker, from about 8 to about
15
percent by weight of a plasticizer, from about 0.2 to about 0.5 percent by
weight of a
surfactant, from about 0.5 percent by weight to about 3 percent by weight of a
chain
extender, from about 0.1 percent by weight to about 0.5 percent by weight of a
catalyst, from about 0.1 percent by weight to about 3 percent by weight of
foaming
agent, from about 0.5 percent by weight to about 5 percent by weight of
colorant of,
for example, a dye, a pigment, or mixtures thereof, and with from about 10
percent by
weight to about 25 percent by weight of an organic diisocyanate where all the
percents by weight disclosed are equal to 100 weight percent.
[0027] Moreover, there are disclosed processes for the preparation of a
polyurethane elastomer foam comprised of contacting a homogenized mixture of
from about 40 to about 60 parts of a polyester polyol, from about 8 percent by
weight
to about 20 percent by weight of a plasticizer, from about 0.5 to about 0.5
percent by
weight of surfactant, from about 0.5 to about 2 parts of chain extender, from
about
0.1 to about 0.6 part of a catalyst, from about 0.1 part to about 5 parts of a
foaming
agent of water, from about 0.1 to about 5 parts of crosslinker, from about 0.3
to about
parts of dye, with from about 9 parts to about 15 parts of diisocyanate.
[0028] In addition, the following disclosures are provided:
[0029] The disclosed polyurethane elastomer compositions can be prepared
from (i) a first mixture comprised of an amorphous or semi-crystalline
polyester polyol
resin, plasticizer, surfactant, chain extender, crosslinker, catalyst,
optional foaming
agent like water, and a dye, and contacting this mixture with a diisocyanate.
Polyurethane foams are generated by the reaction between, for example, the
polyester polyol, and isocyanate as the main reactive ingredients, chain
extender,
crosslinker and water, and wherein the plasticizer, surfactant, water and dye
are
additives, or mostly non-reactant components to render the elastomer into a
foam.
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[0030] In one production process embodiment, the polyurethane
elastomers
can be prepared using a multistage process comprising soft-segment pre-
extensions,
where A) one or more substantially linear polyester diols with functionality
of from
about 1.8 to about 2.2 are reacted with a portion, such as one part of an
organic
diisocyanate or a plurality of organic diisocyanatos in a molar NCO:OH ratio
of from
1.1:1 to 3.5:1, and from about 1.3:1 to about 2.5:1 to provide a relatively
high-
molecular-weight isocyanate-terminated prepolymer ("NCO prepolymer"); B) the
prepolymer obtained in stage A) is blended with a portion 2 of the organic
diisocyanate or of the plurality of organic diisocyanatos, where the entirety
of portion
1 and portion 2 corresponds to the entire amount of diisocyanatos used; C) the
mixture obtained in stage B) is reacted with one or more diol chain extenders
with, for
example, weight average molecular weights of from about 60 to about 350, where
the
molar NCO:OH ratio resulting from the components used in A), B), and C) is at,
for
example, from about 0.9:1 to about 1.1:1, and where the substantially linear
polyester
diols in stage A) are comprised of succinic acid and 1,3-propanediol, and have
an
optional average molar mass of from about 750 to about 3,500 grams/mol.
[0031] In embodiments, the disclosed polyurethane elastomers, which in
embodiments are biodegradable, can be derived from the reaction of a polyester
polyol of from about 45 to about 55 percent by weight, a chain extender of
from about
0.1 to about 2 percent by weight, a crosslinker of from about 1 to about 5
percent by
weight, a foaming agent of from about 0.1 to about 2 percent by weight, and a
diisocyanate of from about 40 to about 50 percent by weight, and wherein the
total
thereof is 100 percent by weight. Polyurethane foams are generated by the
reaction
between, for example, the polyester polyol, and isocyanate as the main
reactive
ingredients, chain extender, crosslinker, and wherein the plasticizer,
surfactant, water
and colorant like a dye may be considered as being non-reactive.
[0032] Accordingly, in one aspect there is provided a polyurethane
elastomer
composition comprising (a) an organic diisocyanate, (b) a polyester resin, (c)
a chain
extender, (d) a crosslinker, (e) a plasticizer, (f) a surfactant, (g) an
optional foaming
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agent, and (h) an optional colorant, wherein the polyurethane elastomer has a
hardness value of from about 15 Asker C to about 60 Asker C, a tensile
strength of
from about 1 MPa to about 10 MPa, a resilience of from about 25 percent to
about 60
percent, an elongation at break of from about 150 percent to 700 percent, and
a tear
strength of from about 2 Newtons/millimeters2 to about 4 Newtons/millimeters2.
[0033] The bio-content of the polyurethane elastomer may be from about 50
percent to about 90 percent, and further comprising a catalyst.
[0034] The polyurethane elastomer may be in the configuration of a foam,
and
wherein the foaming agent is present, and the bio-content of the polyurethane
elastomer foam may be from about 70 percent to about 85 percent.
[0035] The polyester may be selected from the group comprising an amorphous
polyester resin and a semi-crystalline polyester resin, and wherein the
melting point
of said semi-crystalline resin may be from about 15 degrees Centigrade to
about 49
degrees Centigrade.
[0036] The polyester may be generated from reaction of organic diacid and
an
organic diol, wherein said organic diacid may be selected from the group
comprising
succinic acid, adipic acid, sebacic acid, 1,12-dodecanedioic acid, a dimer
diacid, and
polymerized fatty acids, and said organic diol may be selected from the group
comprising 1,5-pentane-diol, ethylene glycol, diethylene glycol, 1,3-
propanediol, 1,2-
propanediol, dipropylene glycol, 1,4-butanediol, 3-methyl-1,5-pentanediol, 1,6-
hexanediol, 1,9-nonanediol, and a dimer diol.
[0037] The polyurethane elastomer may optionally be in the configuration of
a
foam, wherein the foaming agent may be present, and wherein said organic
diisocyanate may be selected from the group comprising diphenylmethane 4,4'-
diisocyanate, isophorone diisocyanate, dicyclohexylmethane 4,4-diisocyanate,
hexamethylene 1,6-diisocyanate, naphthalene 1,5-diisocyanate, and mixtures
thereof.
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[0038]
The organic diisocyanate may be methylenediphenyl diisocyanate and said
polyester may be a semi-crystalline polyester selected from the group
comprising
poly(1,3-propylene-succinate), and
copoly(1,3-propylene-succinate)-copoly(1,2-
propylene-succinate).
[0039]
The plasticizer may be selected from the group comprising tributyl-citrate,
an ester, triethyl-citrate, trimethyl-citrate, an adipate, alkyl aryl
phthalates, and alkyl
benzyls.
[0040]
The surfactant may be selected from the group comprising a polyether-
silicone oil, a silicone surfactant of sodium dodecylbenzene sulfonate, sodium
dodecylnaphthalene sulfate, dialkyl benzenealkyl, adipic acid, polyvinyl
alcohol,
polyacrylic acid, methalose, methyl cellulose, and ethyl cellulose.
[0041]
The chain extender may be selected from the group comprising polyhydric
alcohols, alkylene diols and alkylene glycols, and may further include a
catalyst.
[0042] The crosslinker may be selected from the group comprising
diethanolamine, glycerol, trimethylol propane, pentaerythritol, 1,2,4-
butanetriol,
thioglycolic acid, 2,6-dihydroxybenzoic acid, melamine, and mixtures thereof.
[0043]
The polyurethane elastomer may be in the configuration of a foam, wherein
said colorant is a dye present in an amount of from about 0.5 percent by
weight to
about 5 percent by weight, and wherein the foaming agent may be present.
[0044] The foaming agent may be present, and said elastomer may possess a
hydrolytic stability of from about 80 percent to about 150 percent, and may
possess a
resilience of from about 35 percent to about 60 percent, and may have a
compression set of from about 3 percent to about 6 percent.
[0045]
The semi-crystalline polyester may be selected from the group consisting
of poly(1,3-propylene-succinate), and copoly(1,3-propylene-succinate)-
copoly(1,2-
propylene-succinate), said plasticizer may be tributyl citrate, said
crosslinker may be
an amine, said chain extender may be a propane diol, said foaming agent may be
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present and may be water or carbon dioxide, and said colorant may be present
and
may be comprised of a dye or a pigment.
[0046] The polyurethane elastomer may be in the configuration of a foam,
and
said colorant may be present in an amount of from about 0.5 percent by weight
to
about 5 percent by weight, and said colorant may be comprised of a dye of
black,
cyan, magenta, yellow, green, red, orange, blue, white, purple or mixtures
thereof;
and wherein said foaming agent may be present and may be comprised of carbon
dioxide or water.
[0047] The polyester may be poly(1,3-propylene-succinate), said plasticizer
may
be tributyl citrate, said surfactant may be a silicone component, and said
organic
diisocyanate may be methylenediphenyl diisocyanate, said chain extender may be
1,3-propanediol, said crosslinker may be diethanolamine, said colorant may be
present, and may be comprised of a dye.
[0048] The polyurethane elastomer may be in the configuration of a foam,
and
said polyester may be poly(1,3-propylene-succinate), said organic diisocyanate
may
be methylenediphenyl diisocyanate, and said colorant may be present and may be
comprised of a component selected from the group comprising a dye and a
pigment,
and said foaming agent may be present.
[0049] In another aspect, there is provided an article of manufacture
comprising a
polyurethane elastomer composition comprising (a) an organic diisocyanate, (b)
a
polyester resin, (c) a chain extender, (d) a crosslinker, (e) a plasticizer,
(f) a
surfactant, (g) an optional foaming agent, (h) an optional colorant, and an
optional
catalyst; and wherein said elastomer has a hardness value of from about 20
Asker C
to about 60 Asker C, a tensile strength of from about 1 MPa to about 10 MPa, a
resilience of from about 25 percent to about 60 percent, an elongation at
break of
from about 150 percent to 700 percent, and a tear strength of from about 2
Newtons/millimeters2 to about 4 Newtons/millimeters2.
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[0050] The elastomer may be selected for footwear of an insole, for a
midsole, or
for both said insole and said midsole, and said Asker C may be from about 15
to
about 40 Asker C, and said tensile strength may be from about 2 MPa to about 3
MPa,
[0051] The colorant may be present and may be comprised of a dye, a pigment,
or mixtures thereof, and said foaming agent is present and is comprised of
water.
[0052] The article may be in the configuration of a foam, wherein the
polyester
may be a semi-crystalline polyester selected from the group consisting of
poly(1,3-
propylene-succinate), and copoly(1,3-propylene-succinate)-copoly(1,2-propylene-
succinate), said plasticizer is tributyl citrate, said crosslinker may be an
amine, said
chain extender may be a propane diol, said foaming agent may be present and
may
be comprised of water or carbon dioxide, and said colorant may be present and
may
be comprised of a dye or a pigment.
[0053] In another aspect, there is provided a process for preparing
polyurethane
elastomers by mixing and then reacting: (a) an organic diisocyanate, (b) a
polyester
resin, (c) a chain extender, (d) a crosslinker, (e) a plasticizer, (f) a
surfactant, (g) a
foaming agent, and (h) an optional colorant, wherein said elastomer has a
hardness
value of from about 15 Asker C to about 60 Asker C, a tensile strength of from
about
1 MPa to about 10 MPa, a resilience of from about 30 percent to about 60
percent,
an elongation at break of from about 150 percent to 700 percent, and a tear
strength
of from about 2 Newtons/millimeters2 to about 4 Newtons/millimeters2.
[0054] The polyurethane elastomer may be a foam selected for an insole, for
a
midsole, or said both insole and midsole, and the foam may optionally have a
density
of from about 0.25 gram/centimeter3 to about 0.55 gram/centimeter3, a bio-
content of
from about 70 to about 90 percent, and a compression set of from about 3
percent to
about 6 percent and an elongation at break of from about 300 percent to 650
percent.
[0055] The polyester may be generated from reaction of organic diacid and
an
organic diol, and said organic diacid may be selected from the group
comprising
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succinic acid, adipic acid, sebacic acid, 1,12-dodecanedioic acid, and a dimer
diacid,
polymerized fatty acids, and mixtures thereof, and said organic diol may be
selected
from the group comprising 1,5-pentanediol ethylene glycol, diethylene glycol,
1,3-
propanediol, 1,2-propanediol, dipropylene glycol, 1,4-butanediol, 3-methyl-1,5-
pentanediol, 1,6-hexanediol, 1,9-nonanediol, and a dimer diol, and optionally
said
organic diol and said organic diacid may be obtained from natural
carbohydrates,
biobased carbohydrates or from the fermentation of carbohydrates.
EMBODIMENTS
[0056] Disclosed are polyurethane elastomer compositions comprising (a)
an
organic diisocyanate, (b) a polyester resin, (c) a chain extender, (d) a
crosslinker, (e)
a plasticizer, (f) a surfactant, (g) an optional foaming agent, and (h) an
optional
colorant; and wherein said elastomer has a hardness value of from about 20
Asker C
to about 60 Asker C, a tensile strength of from about 1 MPa to about 10 MPa,
and a
tensile strength of from about 1 MPa to about 5 MPa, a resilience of from
about 25
percent to about 60 percent, an elongation at break of from about 150 percent
to
about at least 700 percent, and a tear strength of from about 2
Newtons/millimeters2
to about 4 Newtons/millimeters2.
Polyesters
[0057] The disclosed amorphous and semi-crystalline polyester polyol
resins
can be prepared by a polycondensation process by reacting suitable organic
diols
and suitable organic diacids in the presence of polycondensation catalysts.
Generally, a stoichiometric equimolar ratio of organic diol and organic diacid
is
utilized, however, an excess of organic diol can be selected such that the
resulting
polymer displays a hydroxyl number of from about 30 to about 40, an acid
number of
less than about 5 milligrams/gram of KOH, and more specifically, less than
about 3
milligrams/gram of KOH, and with a molecular weight average of from about
1,500 to
about 5,000 Daltons as determined by GPC. In some instances, where the boiling
point of the organic diol is from, for example, about 180 C to about 230 C, an
excess
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Date Recue/Date Received 2021-11-17
amount of diol, such as an alkylene glycol of, for example, ethylene glycol or
propylene glycol of from about 0.2 to 1 mole equivalent, can be utilized and
removed
during the polycondensation process by distillation. The amount of catalyst
utilized
varies, and can be selected in amounts as disclosed herein, and more
specifically, for
example, from about 0.01 percent by weight to about 1 percent by weight, or
from
about 0.1 to about 0.75 percent by weight based on the polyester resin.
[0058] Examples of organic diacids or diesters, which can also be those
obtained through fermentation process, natural sources like chemically derived
from
natural (bio-based) sources, selected for the preparation of the amorphous
polyester
resins and the semi-crystalline polyester resins include fumaric, maleic,
oxalic acid,
succinic acid, fumaric acid, itaconic acid, glutaric acid, adipic acid,
suberic acid,
azelaic acid, sebacic acid, 1,12-dodecanedioic acid, C-18 dimer acids, or
dimerized
fatty acids of dicarboxylic acids prepared by dimerizing unsaturated fatty
acids
obtained from tall oil, usually on clay catalysts; hydrogenated/saturated
dimer acids,
and other known suitable organic diacids, and the like; 1,16-octadecanedioic
acid,
phthalic acid, isophthalic acid, terephthalic acid, naphthalene-2,6-
dicarboxylic acid,
naphathalene-2,7-dicarboxylic acid, cyclohexane dicarboxylic acid, malonic
acid and
mesaconic acid, and diesters or anhydrides thereof, and other suitable known
diacids. The organic diacid is selected in an amount of, for example, from
about, 35
to about 60 percent by weight, and from about 45 to about 50 percent by weight
of
the polyester resin.
[0059] The organic diol reactant selected, which can also be obtained
from
biomasses generated through fermentation process, natural sources, and
chemically
derived from natural sources, includes 1,5-pentanediol, 1,2-propanediol(1,2-
propylene glycol), 1,3-propanediol, 1,4-butanediol, 1,10-decanediol, 1,9-
nonanediol,
dimer diols, which include aliphatic dimer diols with, for example, from about
2 carbon
atoms to about 36 carbon atoms, includes PRIPOL 2033 dimer diols,
commercially
available from Croda International PLc, and other known suitable organic
diols.
-15-
Date Recue/Date Received 2021-11-17
[0060] Aliphatic dial reactant examples with, for example, from about 2
carbon
atoms to about 36 carbon atoms, include 1,2-ethanediol, 1,2-propanediol, 1,3-
propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol,
1,8-
octanediol, 1,9-nonanediol, 1,10-decanediol, 1,12-dodecanediol, 2-ethyl-2-
butyl-1,3-
propanediol, alkylene glycols like ethylene glycol, propylene glycol,
monoethylene
glycol, diethylene glycol, monopropylene glycol, dipropylene glycol,
isosorbide,
mixtures thereof, and the like. The organic diol is selected, for example, in
an
amount of from about 45 percent to about 65 percent, and from about 50 percent
by
weight to about 55 percent by weight of the polyester resin.
[0061] In embodiments of the present disclosure, examples of specific
dimer
diols and dimer diacids enabling enhanced hydrophobic characteristics, and
thus
excellent hydrolytically stable characteristics for the polyesters, include as
dimer
acids PRIPOL 1013, PRIPOL 1017, PRIPOL 1009, and PRIPOL 1012, and as
dimer diols PRIPOL 2033 and PRIPOL 2043.
[0062] Polycondensation catalysts utilized for the preparation of
crystalline and
amorphous polyesters or the bio-based catalysts thereof include tetraalkyl
titanates,
dialkyltin oxide such as dibutyltin oxide, tetraalkyltin such as dibutyltin
dilaurate,
dialkyltin oxide hydroxide such as butyltin oxide hydroxide, aluminum
alkoxides, alkyl
zinc, dialkyl zinc, zinc oxide, stannous oxide, zinc acetate, titanium (iv)
isopropoxide
(Tyzor TE), or mixtures thereof, and other known suitable catalysts; and which
catalysts are selected in amounts of, for example, from about 0.01 percent by
weight
to about 5 percent by weight, from about 0.1 to about 0.8 percent by weight,
and from
about 0.2 to about 0.6 percent by weight, based on the starting diacid or
diester used
to generate the polyester resins, and other suitable known catalysts.
[0063] Examples of semi-crystalline polyesters, amorphous polyesters,
and
mixtures thereof, and in some instances where the semi-crystalline polyesters
can be
converted to an amorphous polyester by altering the amount of the comonomers
of
the amorphous polyester in the reaction mixture, are as illustrated herein,
and other
known suitable polyesters.
-16-
Date Recue/Date Received 2021-11-17
[0064]
Examples of semi-crystalline polyester resins with, for example, a
melting point range of equal to or less than, for example, about 60 C include
those
resins derived from straight chain aliphatic organic diacids, such as succinic
acid,
glutaric acid, adipic acid, suberic acid, azelaic acid, sebacic acid, 1,12-
dodecane
dioic acid, and straight chain aliphatic organic diols, such as 1,2-
ethanediol, 1,3-
propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol,
1,8-
octanediol, 1,9-nonanediol, 1,10-decanediol, and 1,12-dodecanediol, include
poly(1,2-ethylene-succinate), poly(1,2-ethylene-adipate),
poly(1,2-ethylene-
sebacate), poly(1,2-ethylene-decanoate), poly(1,2-ethylene-nonoate), poly(1,2-
ethylene-dodeanoate), poly(1,2-ethylene-azeleoate), poly(1,3-propylene-
succinate),
poly(1,3-propylene-adipate), poly(1,3-propylene-sebacate), poly(1,3-propylene-
decanoate), poly(1,3-propylene-nonoate), poly(1,3-propylene-dodeanoate),
poly(1,3-
propylene-azeleoate), poly(1,4-butylene-succinate),
poly(1,4-butylene-adipate),
poly(1,4-butylene-sebacate), poly(1,4-butylene-
decanoate), poly(1,4-butylene-
nonoate), poly(1,4-butylene-dodeanoate), poly(1,4-butylene-azeleoate),
poly(1,6-
hexylene-succinate), poly(1,6-hexylene-adipate),
poly(1,6-hexylene-sebacate),
poly(1,6-hexylene-decanoate), poly(1,6-hexylene-
nonoate), poly(1,6-hexylene-
dodeanoate), poly(1,6-hexylene-azeleoate), poly(1,8-octylene-succinate),
poly(1,8-
octylene-adipate), poly(1,8-octylene-sebacate),
poly(1,8-octylene-decanoate),
poly(1,8-octylene-nonoate), poly(1,8-octylene-
dodeanoate), poly(1,8-octylene-
azeleoate), poly(1,9-nonylene-succinate), poly(1,9-nonylene-adipate), poly(1,9-
nonylene-sebacate), poly(1,9-nonylene-decanoate), poly(1,9-nonylene-nonoate),
poly(1,9-nonylene-dodeanoate), poly(1,9-nonylene-azeleoate), poly(1,10-
decylene-
succinate), poly(1,10-decylene-adipate), poly(1,10-decylene-sebacate),
poly(1,10-
decylene-decanoate), poly(1,10-decylene-nonoate),
poly(1,10-decylene-
dodeanoate), poly(1,10-decylene-azeleoate, mixtures thereof, other suitable
known
polyesters and the like.
[0065]
The semi-crystalline polyester resins with melting points of less than
from about 70 C, and more specifically, from about 40 C to about 60 C, and
less
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Date Recue/Date Received 2021-11-17
than about 50 C, such as from about 15 C to about 49 C, can be prepared from a
mixture of at least one straight chain aliphatic organic diacid, at least one
straight
chain aliphatic diol, and a branched aliphatic diol, such as 1,2-propanediol,
1,3-
butanediol, 2,3-butanediol, 3,3-dimethyl pentanediol; 1,5-pentanediol,
mixtures
thereof, and the like. The organic diacid of at least one aliphatic straight
chain
organic diacid is selected in an amount of, for example, from about 45 to
about 50
percent by weight of the polyester resin. The straight chain aliphatic diol is
selected
in an amount of, for example, from about 20 to about 40 percent by weight of
the
polyester resin, and the branched aliphatic diol is selected in an amount of,
for
example, from about 20 percent by weight to about 40 percent by weight of the
polyester resin. These polyester resins include copoly(1,3-propylene-
succinate)-
copoly(1,2-proplyene-succinate),
copoly(1,4-butylene-succinate)-copoly(1,2-
proplyene-succinate),
copoly(1,3-propylene-sebacate)-copoly(1,2-proplyene-
sebacate), copoly(1,3-propylene-dodecanoate)-copoly(1,2-proplyene-
dodecanoate),
copoly(1,3-propylene-azeleoate)-copoly(1,2-proplyene-azeleoate), and the like,
and
mixtures thereof.
[0066]
More specifically, the semi-crystalline polyester resins have a melting
point of less than about 50 C, such as from about 10 C to about 49 C, less
than from
about 70 C, and from about 40 C to about 60 C.
[0067]
The semi-crystalline resins with excellent melting points can be
prepared from a mixture of at least one straight chain aliphatic organic
diacid, at least
one straight chain aliphatic diol, and a branched aliphatic diol, such as 1,2-
propanediol, 1,3-butanediol, 2,3-butanediol, 3,3-dimethyl-pentanediol mixture
thereof,
and the like. The organic diacid of at least one aliphatic straight chain
organic diacid
is selected in an amount of, for example, from about 45 to about 50 percent by
weight of the polyester resin. The straight chain aliphatic diol is selected
in an
amount of, for example, from about 20 percent by weight to about 40 percent by
weight of the polyester resin, and the branched aliphatic diol is selected in
an amount
of, for example, from about 20 to about 40 percent by weight of the polyester
resin.
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Date Recue/Date Received 2021-11-17
These polyester resins include copoly(1,3-propylene-succinate)-copoly(1,2-
proplyene-succinate),
copoly(1,4-butylene-succinate)-copoly(1,2-proplyene-
succinate),
copoly(1,3-propylene-sebacate)-copoly(1,2-proplyene-sebacate),
copoly(1,3-propylene-dodecanoate)-copoly(1,2-proplyene-dodecanoate),
copoly(1,3-
propylene-azeleoate)-copoly(1,2-proplyene-azeleoate), and the like, and
mixtures
thereof.
[0068]
Amorphous polyester resin examples selected for the preparation of the
polyurethane elastomers usually do not possess a melting point and can have a
glass transition temperature of, for example, from about -25 C to about 10 C,
and
can be prepared from a mixture of at least one or more straight chain
aliphatic
diacids, branched aliphatic diols with optionally one or more straight chain
aliphatic
diols. The straight chain aliphatic diol is selected in an amount of, for
example, from
about 45 to about 50 percent by weight of the polyester resin, and the
branched
aliphatic diol is selected in an amount of, for example, from about 30 to
about 55
percent by weight of the polyester resin, and the optionally one or more
straight chain
aliphatic diols is selected in an amount of, for example, from about 0 to
about 20
percent by weight of the polyester resin. These amorphous polyester resins
include
copoly(1,2-propylene-succinate)-copoly(1,2-proplyene-sebacate),
copoly(1,2-
propylene-succinate)-copoly(1,2-proplyene-dodecanoate),
copoly(1,2-propylene-
sebacate)-copoly(1,2-proplyene-dodecanoate), copoly(1,2-propylene-dodecanoate)-
copoly(1,2-proplyene-azeloate),
copoly(1,2-propylene-azeleoate)-copoly(1,2-
proplyene-succinate), poly(butylene-succinate),
poly(butylene-2,5-furanate),
poly(butylene-itaconate), poly(propylene-succinate), poly(propylene-2,5-
furanate),
poly(propylene-itaconate), and the like, and mixtures thereof.
[0069]
The amorphous polyester, the semi-crystalline polyester, and mixtures
thereof can be present in the polyurethane elastomer in amounts of, for
example,
percent by weight of from about 1 to about 99, from about 10 to about 85, from
about
18 to about 75, from about 25 to about 65, from about 30 to about 55, and from
about
40 to about 60 percent by weight based on the polyurethane elastomer weight.
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Date Recue/Date Received 2021-11-17
Plasticizers
[0070] The plasticizer is selected, for example, from tributyl-citrate,
CITROFOL available from Jungbunzlauer, Hallstar IM 8830, an ester available
from
Hallstar, triethyl-citrate; trimethyl-citrate, adipates such as EDENOL 650R
available
from Emery Olechemicals, tributyl citrate, alkyl aryl phthalates, alkyl benzyl
phthalates, including butyl benzyl phthalate, alkyl benzyl phthalate, and
wherein the
alkyl group has a carbon chain of from seven to nine carbon atoms, TEXANOLTm,
benzyl phthalate, (2,2,4-trimethyl-1,3-pentanediol-monobutyrate benzyl
phthalate),
alkylphenyl phthalate, symmetrical and unsymmetrical dialkyl phthalates,
including
diisononyl phthalate, diisodecyl phthalate, dioctyl phthalate, di-n-butyl
phthalate,
dioctyl phthalate, dihexyl phthalate, diheptyl phthalate, butyloctyl
phthalate, linear
dialkyl phthalate, wherein the alkyl groups are independently carbon chains
having
from about seven to about eleven carbon atoms, and butyl cyclohexyl phthalate;
phosphate plasticizers, such as tris-(2-chloro-1-methylethyl)phosphate, tris-
(alpha-
chloroethyl)phosphate (TCEP), tris-(2,3-dichloro-1-propyl)phosphate, YOKE-V6
(tetrakis-(2-chloroethyl)dichloroisopentyldiphosphate), and the like;
phosphate ester
plasticizers, such as, for example, 2-ethylhexyl diphenyl phosphate, isodecyl
diphenyl
phosphate, mixed dodecyl and tetradecyl diphenyl phosphate, trioctyl
phosphate,
tributyl phosphate, butylphenyl diphenyl phosphate, and isopropylated
triphenyl
phosphate; and benzoate plasticizers, such as, for example, TEXANOLTm benzoate
(which is 2,2,4-trimethyl-1,3-pentanediol-monobutyrate benzoate), glycol
benzoate,
propylene glycol dibenzoate, dipropylene glycol is dibenzoate, and
tripropylene glycol
dibenzoates, in amounts of, for example, from about 1 percent by weight to
about 30
percent by weight, and from about 1 percent by weight to about 15 percent by
weight
based on the amount of the polyurethane elastomer, and other known suitable
plasticizers.
Crosslinkers
[0071] The crosslinker is, for example, selected from diethanolamine,
glycerol,
trimethylol propane, pentaerythritol, 1,2,4-butanetriol, thioglycolic acid,
2,6-
-20-
Date Recue/Date Received 2021-11-17
dihydroxybenzoic acid, melamine, diglycolamine, 1,2,6-hexanetriol, glycerol,
1,1,1-
trimethylolethane, 1,1,1-trimethylolpropane (TM P), pentaerythritol,
triisopropanol
amine, triethanol amine, tartaric acid, citric acid, malic acid, trimesic
acid, trimellitic
acid, trimellitic anhydride, pyromellitic acid, and pyromellitic dianhydride;
trim ethylolpropane, trimethylolethane; pentaerythritol, polyethertriols,
tartaric acid,
citric acid, malic acid, trimesic acid, trimellitic acid, trimellitic
anhydride, pyromellitic
acid, and pyromellitic dianhydride;
trim ethylolpropane, trim ethylolethane;
pentaerythritol, polyethertriols, and glycerol, and especially polyols, such
as
trim ethylolpropane, pentaerythritol, and glycerol, and bio-based materials
thereof,
present in amounts of, for example, from about 0.1 percent by weight to about
10
percent by weight, and from about 0.1 percent by weight to about 5 percent by
weight
based on the amount of polyurethane elastomer, and other known suitable known
crossl in kers.
Chain Extenders
[0072]
Chain extender examples include alcohols, such as polyhydric alcohols,
carboxylic acid derivatives having two functional groups can be selected for
the
elastomers and processes disclosed herein. More specifically, chain extender
examples contain, for example, two hydroxyl moieties such as 1,2-ethanediol,
1,2-
propanediol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol,
1,7-
heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,12-
dodecanediol, 2-
ethyl-2-butyl 1,3-propanediol; alkylene glycols like ethylene glycol,
propylene glycol,
monoethylene glycol, diethylene glycol, monopropylene glycol, dipropylene
glycol,
mixtures thereof, other known suitable chain extenders, and the like, present
in
amounts of, for example, from about 0.1 percent by weight to about 10 percent
by
weight, from about 0.1 percent by weight to about 5 percent by weight based on
the
polyurethane elastomer, and other known suitable known chain extenders.
Surfactants
-21-
Date Recue/Date Received 2021-11-17
[0073] The surfactants that can be selected are, for example, polyether-
silicone oil mix (TEGOSTAB B4113) available from Evonik, 8383, silicone
surfactant
DABCO DC 193, and TEGOSTAB B8383 available from Evonik, sodium
dodecylbenzene sulfonate, sodium dodecylnaphthalene sulfate,
dialkylbenzenealkyl,
sulfates and sulfonates, adipic acid, available from Aldrich, NEOGEN RTM,
NEOGEN
SCTM, available from Daiichi Kogyo Seiyaku, polyvinyl alcohol, polyacrylic
acid,
methalose, methyl cellulose, ethyl cellulose, propyl cellulose, hydroxy ethyl
cellulose,
carboxy methyl cellulose, polyoxyethylene cetyl ether, polyoxyethylene lauryl
ether,
polyoxyethylene octyl ether, polyoxyethylene octylphenyl ether,
polyoxyethylene oleyl
ether, polyoxyethylene sorbitan monolaurate, polyoxyethylene stearyl ether,
polyoxyethylene nonylphenyl ether, dialkylphenoxypoly(ethyleneoxy) ethanol,
available from Rhodia as IGEPAL CA-210TM, IGEPAL CA-520TM, IGEPAL CA-720TM,
IGEPAL CO-890TM, IGEPAL CO-720TM, IGEPAL CO-290TM, ANTAROX890Tm, and
ANTAROX897Tm, and other suitable known surfactants in amounts of, for example,
from about 0.1 percent by weight to about 10 percent by weight, and from about
0.1
percent by weight to about 3 percent by weight based on the polyurethane
elastomer
amount.
Catalysts
[0074] Polycondensation catalysts utilized for the preparation of the
crystalline
and amorphous polyesters, include tetraalkyl titanates, dialkyltin oxide such
as
dibutyltin oxide, tetraalkyltin such as dibutyltin dilaurate, dialkyltin oxide
hydroxide
such as butyltin oxide hydroxide, aluminum alkoxides, alkyl zinc, dialkyl
zinc, zinc
oxide, stannous oxide, zinc acetate, titanium (iv) isopropoxide (Tyzor TE),
other
suitable known catalysts or mixtures thereof; and which catalysts are selected
in
amounts of, for example, from about 0.01 percent by weight to about 5 percent
by
weight, from about 0.1 to about 0.8 percent by weight, and from about 0.2 to
about
0.6 percent by weight, and other suitable, percentages, based on the starting
diacid
or diester used to generate the polyester.
-22-
Date Recue/Date Received 2021-11-17
[0075]
Examples of catalysts selected for the preparation of the polyurethane
elastomers, and which catalysts can react with the organic diisocyanates
include, for
example, known tertiary amines, such as triethylamine,
dimethylcyclohexylamine, N-
methylmorpholine, N,N'-dimethylpiperazine,
2-(dimethylam inoethoxy)ethanol,
diazabicyclo[2.2.2]octane, DAPCO 33 LV (33 percent triethylenediamine
dissolved in
67 percent dipropylene glycol), BICAT 8109 (bismuth neodecanoate), Jeffcat-Zf-
54
(bis-(2-dimethylaminoethyl)ether in dipropylene glycol), KOSMOS 75 MEG, and
the
like; organometallic compounds, such as titanic esters, iron compounds, tin
compounds, such as tin diacetate, tin dioctoate, tin dilaurate, the dialkyl
tin salts of
aliphatic carboxylic acids like dibutyltin diacetate and dibutyltin dilaurate,
other
suitable catalysts and the like. The total amount of catalysts selected is
generally
from about 0.1 percent by weight to about 5 percent by weight, and more
specifically,
from about 0.1 to about 1 percent by weight, based on the polyurethane
elastomer.
Colorants
[0076]
Colorant examples that can be selected for the preparation of the
polyurethane elastomer compositions present, for example, in amounts of from
about
0.1 percent by weight to about 5 percent by weight, and from about 0.1 percent
by
weight to about 3 percent by weight based on the amount of the polyurethane
elastomer, include pigments, dyes, mixtures thereof, and the like. Examples of
colorants include dyes and pigments include inorganic pigments, such as carbon
black, whiteners, such as titanium oxide which has weather resistance, and
organic
pigments and dyes, such as phthalocyanine blue, azo dyes, Indigo, Congo Red,
Methyl Orange, Malachile Green, purple dyes, brown dyes, black dyes, Pigment
Blue
15:3 or C.I. Pigment Blue 15:4, phthalocyanine green, quinacridone red,
indanthrene
orange, and isoindolinone yellow, C.I. Pigment Red 254 and C.I. Pigment Red
122,
C.I. Pigment Yellow 151 and C.I. Pigment Yellow 74, Fates Dye and Keen Dye
available from BAO Shen Polyurethane Tech.LTD-China, purple dyes, brown dyes,
and other suitable known colorants, such as known dyes and pigments
illustrated in
the Colour Index (C.I.), and magenta, yellow, and cyan colorants.
-23-
Date Recue/Date Received 2021-11-17
Foaming Agents
[0077]
There is selected as the foaming (or blowing) agent water and other
suitable known blowing agents present in the reaction mixture and in the
flexible
polyurethane foams thereof, and which increases the firmness of the resulting
foams.
A soft, flexible, plasticized water-blown polyurethane foam composition can be
produced from the reaction of a natural polyol and methylene diphenyl
diisocyanate,
(MDI) or an equivalent isocyanate, and by optionally adding a plasticizer.
[0078]
Specific examples of foaming agents include water, compressed gases,
such as CO2, N2, air or low boiling liquids like cyclopentane, pentane,
isobutane and
hydrofluorocarbons, added in amounts of from about 0.5 percent by weight to
about 3
percent by weight of the polyurethane elastomer. Also, for example, CO2 may be
generated in-situ by the decomposition of NaHCO3 or the reaction of water with
isocyanate and other known suitable foaming agents.
Organic Diisocvanates
[0079]
Examples of organic diisocyanates selected for the compositions and
processes illustrated herein include aliphatic diisocyanates, such as
hexamethylene
diisocyanate, cycloaliphatic diisocyanates, such as isophorone diisocyanate,
cyclohexane 1,4-diisocyanate, 1-methylcyclohexane 2,4-diisocyanate, and 1-
methylcyclohexane 2,6-diisocyanate, and the corresponding isomer mixtures,
d icyclohexylm ethane 4,4'-d iisocyanate, dicyclohexylmethane 2,4'-d
iisocyanate,
dicyclohexylmethane 2,2'-diisocyanate, and the corresponding isomer mixtures,
aromatic diisocyanates, such as tolylene 2,4-diisocyanate, mixtures of
tolylene 2,4-
diisocyanate and tolylene 2,6-diisocyanate, diphenylmethane 4,4'-diisocyanate,
diphenylmethane 2,4'-diisocyanate, and diphenylmethane 2,2'-diisocyanate,
mixtures
of diphenylmethane 2,4'-diisocyanate and diphenylmethane 4,4'-diisocyanate,
urethane-modified liquid diphenylmethane 4,4'-diisocyanates or diphenylmethane
2,4'-diisocyanates, 4,4'-diisocyanato-1,2-diphenylethane, and naphthylene 1,5-
diisocyanate.
Especially selected diisocyanates are hexamethylene 1,6-
diisocyanate, cyclohexane 1 ,4-diisocyanate, isophorone
diisocyanate,
-24-
Date Recue/Date Received 2021-11-17
dicyclohexylmethane diisocyanate, diphenylmethane diisocyanates with more than
96 percent by weight content of diphenylmethane 4,4'-diisocyanate,
diphenylmethane
4,4'-diisocyanate, and naphthylene 1,5-diisocyanate, suitable known
diisocyanates,
and mixtures thereof, and the like, and other known suitable organic
diisocyanates.
[0080] In embodiments, there can be selected mixtures of a diisocyanate
and
a polyisocyanate in an amount of up to about 15 percent by weight, based on
the
total diisocyanates present, however, up to about 40 percent by weight of
polyisocyanate can be added, and that provides an improved thermoplastically
processable product. Examples of polyisocyanates include triisocyanates,
biurets
and isocyanurate trimer. For example, triphenylmethane 4,4',4"-triisocyanate
and
polyphenylpolym ethylene polyisocyanates as well as hexam ethylene
diisocyanate
(HDI) biuret trimer, isocyanurate trimer, and isophorone (IPDI) isocyanurate
trimer.
[0081] Generally, for the polyurethane plasticizer foam preparation in
embodiments and the appropriate Examples that follow, the active reactant
components of, for example, the polyester resin, the crosslinker, the chain
extender,
and the foaming agent, and the non-reactive components of, for example, the
bio-
additives disclosed, for example, in the copending application 2020-02 being
filed
concurrently herewith, the disclosure of which is totally incorporated herein
by
reference, colorant, plasticizer, and surfactant, are initially admixed
followed by the
addition of the organic diisocyanate and heating. Further, the disclosed
polyurethane
elastomer foams have excellent bio-contents originating, for example, from the
polyester polyol, the plasticizer, and the chain extender.
[0082] The characteristics and properties of the polyurethane products
can be
measured as illustrated herein, and by known processes and devices. More
specifically, there was selected as a tensile tester, the ADMET eXpert 7601
Tensile
Tester, to measure tensile strength, elongation, tear strength and compression
set,
by preparing a sample of the polyurethane composition foam material
compositions
in dog bone shapes with a die cutter with a standard thickness of about 10
millimeters and a length of about 140 millimeters based on ASTM D412, ASTM
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Date Recue/Date Received 2021-11-17
D3574-17, SATRA TM-2 standards. The sample removed was placed between
clamps and where the tensile tester applies the appropriate force at a
particular
speed (generated by the software) on the test material sample to provide the
characteristics, properties and values of the polyurethane products.
[0083] Density was measured using the equation Density = Mass/Volume,
where mass represents the mass of the material in a mold measured on an
analytical
balance. Volume of the mold was obtained from the dimensions of the mold. For
example, if a mold was producing 10 millimeters, or 1 centimeter polyurethane
foam
plaques with dimensions length equal to 21 centimeters with width equal to
14.8
centimeters, and the thickness equal to 10 millimeters, then the volume was
calculated to be 21 times 14.8 times 1 equals 310.80 centimeters3.
[0084] The hardness was measured on the Asker C scale, and can also be
measured by a durometer.
[0085] The bio-content of the disclosed polyurethane elastomer foams
can be
determined by various methods. In one method, the bio-content can be measured
as
follows and where, for example, the polyester polyol, plasticizer, and chain
extender
can also impart bio-content characteristics to the polyurethane elastomer
foams.
[0086] Add the total weight of the components/ingredients = X grams
[0087] Add the weight of the components ingredients that are bio-based,
the
polyester resin plus the chain extender plus the plasticizer = Y grams
[0088] Total bio-content = (Y/X) x 100 = the bio-content in percent.
[0089] More specifically, for example, when 100 grams of the polyester
resin
are selected and 5 percent by weight of the bio-additive/filler is added, then
based on
the polyester resin, the amount of the bio additive-based filler is 100 x 0.05
= 5
grams.
[0090] Total weight of ingredients including the bio-filler = Z grams
[0091] Weight of the bio-based ingredients, which also includes the bio
additive-filler = W grams
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Date Recue/Date Received 2021-11-17
[0092] New bio-content = (W/Z) x 100 = N7 N represents the new bio-
content
with the biocide additive, or where the bio-content can be derived from the
polyol
polyester, the plasticizer and the chain extender.
[0093] Based on the above disclosed calculation, 1 percent by weight of
the
bio additive-filler will increase the bio-content by 0.1 percent; 2.5 percent
by weight
bio additive-filler will increase the bio-content by 0.3 percent; 5.0 percent
by weight of
the bio additive-filler will increase the bio-content by 0.7 percent; and 10.0
percent of
the bio additive-filler will increase the bio-content by 1.3 percent. Thus,
based on the
bio-content of the ingredients present in the polyurethane foam formulations,
the bio-
content for the polyurethane elastomer foam is, for example, from about 60
percent
to about 90 percent, from about 50 percent to about 90 percent, from about 65
percent to about 85 percent, from about 40 percent to about 85 percent, from
about
70 percent to about 85 percent, and from about 60 percent to about 80 percent.
[0094] Specific embodiments of the present disclosure as illustrated in
the
following Examples are for illustrative purposes and are not limited to the
materials,
conditions, or process parameters set forth in these embodiments. Percent by
weight
is a known quantity and is usually based on the total of the components
present.
Molecular weights were provided by the sources involved, or by GPC, and from
about
to about includes all the values in between and some values that exceed or may
not
exceed the values disclosed. Also, the components of (a) to (h) can be mixed
in
various sequences to obtain the polyurethane elastomers and the polyurethane
foams, both of which can be biodegradable. The viscosities were measured by
the
Brookfield CAP2000 Viscometer.
EXAMPLE 1
[0095] Preparation of the semipolyester resin, poly(1,3-propylene-
succinate),
generated from 1,3-propanediol and succinic acid, and with a resin melting
point of
49.3 C, as determined by DSC.
[0096] To a 300 milliliter three-necked round bottom flask equipped
with a
mechanical stirrer were added 169 grams of succinic acid, 137 grams of 1,3-
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Date Recue/Date Received 2021-11-17
propanediol and 0.1 gram of titanium (iv) isopropoxide (Tyzor TE) catalyst.
The
reaction mixture was kept under constant nitrogen flow of about 5 standard
cubic feet
per minute (scfm) and heated to 140 C over 30 minutes. The mixture obtained
was
then stirred at 200 rpm, and the temperature was increased by 10 C every 15
minutes until the temperature reached 200 C. Samples, about 2 grams each, were
removed every 20 minutes using a glass pipette, and when a viscosity of about
5180
centipoise was obtained, as measured by the Brookfield CAP2000 Viscometer at
80 C and a spindle rate of 100 rpm, there followed discharging the resin
mixture into
a metal pan. The acid value of the obtained resin was 1.09 milligram/gram of
KOH,
measured by dissolving a sample in tetrahydrofuran containing phenolphthalein
indicator, and subsequently titrating with a 0.1 N potassium hydroxide
solution in
ethanol. The melting point of the semipolyester resin, poly(1,3-propylene-
succinate)
product was determined to be 49.3 C using a DuPont 910 Differential Scanning
Calorimetry (DSC) with a heating rate of 20 C/minute on the second scan, and
taking
the peak value of the melting point transition curve.
EXAMPLE 2
[0097] Preparation of the semi-crystalline polyester resin poly(1,3-
propylene-
succinate) with a melting point of 49.1 C as measured by DSC was prepared from
1,3-propanediol and succinic acid.
[0098] To a 300 milliliter three-necked round bottom flask equipped
with a
mechanical stirrer were added 155 grams of succinic acid, 130 grams of 1,3-
propanediol and 0.1 gram of titanium (iv) isopropoxide (Tyzor TE) catalyst.
The
reaction mixture was kept under constant nitrogen flow of about 5 standard
cubic feet
per minute (scfm) and then heated to 140 C over 30 minutes. The mixture
resulting
was then stirred at 200 rpm, and the temperature was increased by 10 C every
15
minutes until the temperature reached 200 C. Samples of the resin, about 2
grams
each, were taken every 20 minutes using a glass pipette, and when a viscosity
of
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Date Recue/Date Received 2021-11-17
about 3750 centipoises was obtained, the resin mixture was discharged into a
metal
pan. The acid value of the obtained polyester was 0.93 milligram/gram of KOH.
EXAMPLE 3
[0099] Preparation of a semi crystalline polyester resin, copoly(1,3-
propylene-
succinate)-copoly(1,2-propylene-succinate), from succinic acid, 1,3-
propanediol, 1,2-
propanediol, and wherein the molar ratio of 1,3-propanediol to 1,2-propanediol
was
7.67.
[00100] To a 300 milliliter three-necked round bottom flask equipped
with a
mechanical stirrer were added 155 grams of succinic acid, 115 grams of 1,3-
propanediol, 15 grams of 1,2-propanediol, and 0.1 gram of titanium (iv)
isopropoxide
(Tyzor TE) catalyst. The reaction mixture was kept under constant nitrogen
flow of
about 5 standard cubic feet per minute (scfm) and heated to 140 C over 30
minutes.
The mixture obtained was then stirred at 200 rpm, and the temperature was
increased by 10 C every 15 minutes until the temperature reached 200 C.
Samples
of the resin, about 2 grams each, were then taken with a glass pipette every
20
minutes and when a viscosity of about 3735 centipoise was obtained, the
resulting
resin mixture was discharged into a metal pan. The acid value of the semi-
crystalline
polyester obtained was 1.88 milligrams/gram of KOH, and the melting point
thereof of
this resin was determined to be 43.9 C as determined by DSC.
EXAMPLE 4
[00101] Preparation of the semi crystalline polyester resin derived from
succinic
acid, 1,12-dodecanedioic acid, 1,3-propanediol, 1,2-propanediol, and wherein
the
molar ratio of 1,3-propanediol to 1,2-propanediol is 3, and the molar ratio of
succinic
acid to 1,12-dodecanedioic acid was 1.
[00102] To a 300 milliliter three-necked round bottom flask equipped
with a
mechanical stirrer were added 77.5 grams of succinic acid, 151.1 grams of 1,12-
dodecanedioic acid, 115 grams of 1,3-propanediol, 15 grams of 1,2-propanediol,
and
0.1 gram of titanium (iv) isopropoxide (Tyzor TE) catalyst. The reaction
mixture was
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Date Recue/Date Received 2021-11-17
kept under constant nitrogen flow of about 5 standard cubic feet per minute
(scfm)
and heated to 140 C over 30 minutes. The mixture obtained was then stirred at
200
rpm, and the temperature was increased by 10 C every 15 minutes until the
temperature reached 200 C. Samples of the resin, about 2 grams for each
sample,
were taken every 20 minutes using a glass pipette, and when a viscosity of
about
4310 centipoises was obtained, the resin mixture was discharged into a metal
pan.
The acid value obtained for the resulting semi crystalline polyester was 2.54
milligrams/gram of KOH, and the melting point for this resin was determined to
be
37.8 C as measured by DSC.
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Date Recue/Date Received 2021-11-17
EXAMPLE 5
[00103] Preparation of the polyester resin derived from succinic acid,
sebacic
acid, 1,3-propanediol, 1,2-propanediol, and wherein the molar ratio of 1,3-
propanediol to 1,2-propanediol is 7.67, and the molar ratio of succinic acid
to sebacic
acid is 1.
[00104] To a 300 milliliter three-necked round bottom flask equipped
with a
mechanical stirrer are added 77.5 grams of succinic acid, 132.7 grams of
sebacic
acid (bio-based), 115 grams of 1,3-propanediol, 15 grams of 1,2-propanediol
and 0.1
gram of titanium (iv) isopropoxide (Tyzor TE) catalyst. The reaction mixture
resulting
is kept under constant nitrogen flow of about 5 standard cubic feet per minute
(scfm)
and is heated to 140 C over 30 minutes. The mixture is then stirred at 200
rpm, and
the temperature is increased by 10 C every 15 minutes until a temperature of
200 C
is reached. Samples of the resin, about 2 grams each, are then taken every 20
minutes with a glass pipette, and when a viscosity of about 4300 centipoise is
obtained, the resin mixture is discharged into a metal pan.
EXAMPLE 6
[00105] Preparation of a semi-crystalline polyester resin, derived from
succinic
acid, octadecane-dioc-acid, 1,3-propanediol, 1,2-propanediol, and wherein the
molar
ratio of 1,3-propanediol to 1,2-propanediol is 7.67, and the molar ratio of
succinic
acid to octadecane-dioc-acid is 1.
[00106] To a 500 milliliter three-necked round bottom flask equipped
with a
mechanical stirrer were added 77.5 grams of succinic acid, 206.4 grams of
octadecane-dioc-acid (available as C-18 Dimer Diacid from Elevance), 115 grams
of
1,3-propanediol, 15 grams of 1,2-propanediol, and 0.1 gram of titanium (iv)
isopropoxide (Tyzor TE) catalyst. The reaction mixture resulting was kept
under
constant nitrogen flow of about 5 standard cubic feet per minute (scfm) and
heated to
140 C over 30 minutes. The mixture obtained was then stirred at 200 rpm, and
the
temperature was increased by 10 C every 15 minutes until the temperature
reached
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Date Recue/Date Received 2021-11-17
200 C. Samples of the resin, about 2 grams each, were taken every 20 minutes
using a glass pipette, and when a viscosity of about 4110 centipoises was
obtained,
the resin mixture was discharged into a metal pan. The acid value obtained for
the
resulting semi-crystalline polyester resin was 1.07 milligram/gram of KOH, and
the
melting point of this semi-crystalline polyester resin was determined by DSC
to be
61.6 C.
EXAMPLE 7
[00107] Preparation of an amorphous polyester resin derived from
succinic acid,
octadecane-dioc-acid (dimer acid), 1,3-propanediol, 1,2-propanediol, and
wherein the
molar ratio of 1,3-propanediol to 1,2-propanediol is 1, and the molar ratio of
succinic
acid to the dimer acid is 1.
[00108] To a 500 milliliter three-necked round bottom flask equipped
with a
mechanical stirrer were added 77.5 grams of succinic acid, 206.4 grams of
octadecane-dioc-acid (available as C-18 dimer diacid from Elevance), 60 grams
of
1,3-propanediol, 60 grams of 1,2-propanediol, and 0.1 gram of titanium (iv)
isopropoxide (Tyzor TE) catalyst. The reaction mixture obtained was kept under
constant nitrogen flow of about 5 standard cubic feet per minute (scfm) and
heated to
140 C over 30 minutes. The mixture was then stirred at 200 rpm, and the
temperature was increased by10 C every 15 minutes until the temperature
reached
200 C. Samples of the resin, about 2 grams each, were then taken every 20
minutes
using a glass pipette, and when a viscosity of about 4110 centipoises was
obtained,
the resin mixture was discharged into a metal pan. The acid value obtained for
the
generated amorphous polyester resin was 1.07 milligrams/gram of KOH. There was
no melting point transition indicated by DSC for the obtained amorphous
polyester.
EXAMPLE 8
[00109] Preparation of an amorphous polyester resin, derived from
succinic
acid, dilinoleic diol (DLA-OH), 1,3-propanediol, and 1,2-propanediol.
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Date Recue/Date Received 2021-11-17
[00110]
To a 500 milliliter three-necked round bottom flask equipped with a
mechanical stirrer were added 65.88 grams of succinic acid, 78.05 grams of
dilinoleic
diol (available as C-35 PRIPOL 2033 Dimer Diol) from Croda Industrial
Chemicals),
55.31 grams of 1,3-propanediol, 55.31 grams of 1,2-propanediol and 0.146 gram
of
titanium (iv) isopropoxide (Tyzor TE) catalyst. The reaction mixture was kept
under
constant nitrogen flow of about 5 standard cubic feet per minute (scfm) and
heated to
155 C over 30 minutes. The mixture obtained was then stirred at 200 rpm, and
the
temperature was increased by 10 C every 15 minutes until temperature reached
195 C. Samples of the resin, about 2 grams each, were then taken every 20
minutes
using a glass pipette, and when a viscosity of about 4480 centipoises was
obtained,
the resin mixture was discharged into a metal pan. The polyester polyol was
obtained as a clear transparent viscous liquid that flowed upon cooling to
ambient
temperature.
The acid value obtained for the generated product was 0.5
milligrams/gram of KOH.
EXAMPLE 9
[00111]
Insole materials comprised of a polyurethane foam, free rise bun, in
open air and not in a mold, to test for the formation of the polyurethane
product.
[00112]
In a 200 milliliter glass container is added 35 grams of the molten (at
70 C) semi-crystalline polyester resin obtained in Example 1. To this is then
added
10.5 grams of the plasticizer tributyl citrate (available from Jungbunzlauer
as
CITROF00), 0.19 gram of TEGOSTAB surfactant (available from Evonik), 1.03
gram of the chain extender 1,3-propanediol, 0.37 gram of DABCO LV catalyst
(available from Evonik), 0.32 gram of water, 0.035 gram of diethanolamine
crosslinker, available from Evonik as DEOA, 1.24 gram of FATE dye (available
from
BAO Shen PolyurethaneTech.LTD-China), and the mixture is then maintained at 50
to 55 C for 5 minutes, and then homogenized at 1500 rpm for 4 minutes, after
which
11.9 milliliters of methylenediphenyl diisocyanate (MDI) (available from
Huntsman as
Suprasec 2379) is added with a syringe, and the mixture is further homogenized
for 5
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Date Recue/Date Received 2021-11-17
seconds. The aforementioned mixture is then poured into a cup, and a foam is
formed by the reaction of the polyester polyol mixture with MDI isocyanate and
generated as a free rise bun. The stable bun is formed with a cream time of
about 10
to 12 seconds, a tack free time of about 100 to about 110 seconds, a demold
time of
6 minutes, resulting in a density of 0.15 gram/centimeter3, and where the
hardness is
17, determined using a durometer, and there is no shrinkage or scorching.
After the
free rise, the foam is cut into test materials of regular dimension pieces of
appropriate
length, width and thickness, and the mass is measured by an analytical scale
in
grams. The density of the resulting free rise foam is determined from the
volume
estimated from Lx Wx T (1 centimeter x 1 centimeter x 4 centimeters = 4
centimeters3) following the known standard ASTM D7487-13 methods.
[00113] Density equals Mass/Volume for the insole foam, the density of
the
foam was 0.16 +/- 1 gram/centimeter3.
[00114] As an example, mass equals 0.6432 gram, volume equals 4
centimeters3, hence foam density equals 0.1608.
[00115] The test material is placed on a scale, which scale was tared
and then
a durometer was placed on the test material. A force was applied on the
durometer
until the scale reads a mass of 2400 grams. This method assures
standardization of
the force applied on the test material. The hardness is read on the durometer
digital
scale in Asker C of 17.
EXAMPLE 10
Insole Polyurethane Foams
[00116] An insole foam was first prepared from a footbed. A footbed mold
was
considered a mold with a cavity of certain design replicating an insole or a
midsole of
footwear like a shoe. The cavity has a certain volume where the formulation
mixture
is poured and closed to form the foam product.
[00117] A mold, volume 155 millimeters3, was first conditioned by
preheating it
at 50 C to 55 C for 2 hours to primarily ensure equal distribution of
temperature.
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Date Recue/Date Received 2021-11-17
Then, the footbed mold was opened and an insole fabric was attached to the
upper
part of the mold. A mold release agent EASE RELEASE 2831 TM, available from
Mann Release Technologies, was lightly brushed along the lower part of the
mold
resulting in a shiny waxy consistency. Forty grams of the semi-crystalline
polyester
resin of Example 2 was oven melted in a 200 milliliter glass can at 70 C for 2
hours.
To this were added 12 grams of tributyl citrate (available from Jungbunzlauer
as
CITROF00), 0.22 gram of TEGOSTAB a surfactant (available from Evonik), and
0.37 gram of DABCO LV catalyst (available from Evonik), 0.324 gram of water,
0.1
gram of diethanolamine as a crosslinker component, and 1.42 grams of FATE dye
(available from BAO Shen Polyurethane Tech.LTD-China). The resulting mixture
was then stirred for 4 minutes at 1500 rpm with a homogenizer. While
homogenizing,
16.4 milliliters of MDI diisocyanate (available from Huntsman as SUPRASECTM
2379)
was added using a syringe, and the mixture resulting was further homogenized
for 5
seconds. The mixture formed was then poured into a footbed mold, which was
closed shut and the foam material formed was allowed to cure at a temperature
of
from about 50 C to about 55 C. The demold time was 15 to 20 minutes after
which
the mold was opened, and the foam attached to the fabric was removed and
placed
on a flat surface. The footbed foam density was calculated from the following
equation. Density equals Mass/Volume. The target density was 0.32 hence the
mass of material poured into the mold was about 49.6 grams. Volume of the
footbed
equals 155 centimeters3, mass equals 49.6 grams, density 0.32
gram/centimeter3,
hardness 27, assuming no shrinkage.
EXAMPLES 11 TO 15
Plaques of Polyurethane Insole Foams
[00118]
The processes of Example 10 were substantially repeated for the
preparation of plaques. Plaques foam materials were formed from a rectangular
mold with cavity of dimensional volume, V equals length times width times
thickness,
designated as LxWx T, where L equals 21.0 centimeters, W equals 14.8
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Date Recue/Date Received 2021-11-17
centimeters, and T equals Y centimeters. In the following Table 1, Y equals 3
millimeters to 40 millimeters (0.3 centimeter to 4 centimeters) and the
appropriate
properties, such as volumes, were then determined, and are reported in Table
1.
TABLE 1
Mold
Tensile Elon- Tear Compres- Resi-
Example Plaque Volume Density Strength gation Strength sion
lience
Number (cm3) g/cm3 MPa (%) N/mm Set (%)
(%)
Example 3 mm 93 0.35 2.57 663 4.55 4.21
41.9
11
Example 6 mm 186 0.30 1.79 639 3.44 2.45
33.2
12
Example 10 mm 311 0.33 1.60 561 2.3 1.87
42.4
13
Example 20 mm 622 0.40 1.45 348 4.92 3.39
39.0
14
Example 40 mm 878 0.737 2.56 2.34 2.34 3.34
40.0
[00119]
The footbed foam density was calculated by the following equation
Density equals Mass/Volume. The calculated density was 0.33 hence the mass of
material poured into the mold was about 102.63 grams. The plaques having
dimensions, length equals 21 centimeters, width equals 15 centimeters,
thickness
equals 10 millimeters, were cut into dog-bone type prototypes for mechanical
testing.
Tensile strength, elongation, and tear strength were measured by a known
tensile
tester. Compression set was measured by a known compression set tester;
resilience was measured by dropping a standard steel ball of known mass from a
predetermined height onto a foam and then measuring how high the ball bounces
back after hitting the test foam. The rebound was the percentage of the height
of
rebound divided by the original height the ball was dropped from.
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Date Recue/Date Received 2021-11-17
EXAMPLE 16
Plaques of PU Foam and Hydrolytic Stability
[00120] 75 Grams of the polyester of Example 3 was melted in a 400
milliliter
glass can at 70 C for 2 hours using an oven. To this was added 22.5 grams of
tributyl citrate (available from Jungbunzlauer as CITROFOL ), 0Ø413 gram of
TEGOSTAB surfactant (available from Evonik), 2.198 grams of 1,3 propanediol,
1.2
grams of DABCO DC catalyst (available from Evonik), 0.75 gram of water, 2.63
grams of FATE dye (available from BAO Shen Polyurethane Tech.LTD-China), and
0.225 gram of diethanol amine. 1.5 Grams of carbodiimide (available from Stahl
as
PICASSIAN XL-725) were then added to the glass can and the mixture resulting
was stirred for 4 minutes at 1500 rpm to homogenize. While stirring with a
SUPRASECTM 2379 available from Huntsman, the organic diisocyanate ISO, 30.19
grams, was injected into the SUPRASECTm2379 via a pre-weighed syringe. After
the
syringe was empty the resulting mixture was stirred for a further 5 seconds,
and then
the obtained mixture was poured into plaque mold with a 10 millimeter
thickness.
The mold conditions were the same as described in Example 11. The plaque was
tested for mechanical properties after cutting it into appropriate dog-bone
shapes
resulting in a density of 0.33 gram/centimeters3, a hardness of 30, a tensile
strength
of 1.4 MPa, an elongation of 369 percent, a tear strength of 2.4
Newtons/millimeters2,
and a resilience of 25 percent.
[00121] The above foam was also tested for hydrolytic stability according
to the
following procedure.
[00122] Plastic bottles were filled with distilled water and the above
prepared
dog-bone shaped foam material was hung using a string ensuring the foam
material
was completely immersed into the water. The product obtained was then placed
in
the oven and kept there for 2 weeks while maintaining the temperature in the
range
of 65 C to 70 C. After the test period, a sample was removed from the water
and
dried in the oven at about 70 C. The ratio of mechanical properties after
hydrolysis
divided by that before hydrolysis should be above about 80 percent for both
tensile
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Date Recue/Date Received 2021-11-17
strength and percent elongation. For the polyurethane plaque of this Example,
the
stability was found to be 85 percent for tensile strength and 125 percent for
elongation.
EXAMPLE 17
Plaques of PU, Polyurethane Elastomers Foams for Insole Testinq
[00123]
The plaque of foam prepared in Example 16, thickness 10 millimeters
(mold volume, 311 centimeters3), was first conditioned by preheating it at 50
C to
55 C for 2 hours to ensure equal distribution of the temperature. The mold was
then
opened, and a mold release agent was lightly brushed along the lower and upper
part of the mold resulting in the development of a shiny waxy consistency.
Sixty (60)
grams of the polyester of Example 1, and 15 grams of the polyester polyol of
Example 8, were melted in a 400 milliliter glass can at 70 C for 2 hours
inside an
oven. To this was added 22.5 grams of tributyl citrate (available from
Jungbunzlauer
as CITROFOL ), 0Ø413 gram of TEGOSTAB surfactant (available from Evonik),
2.198 grams of 1,3-propanediol, 1.2 grams of DABCO LV catalyst (available
from
Evonik), 0.75 gram of water, 2.63 grams of FATE dye (available from BAO Shen
Polyurethane Tech.LTD-China), 0.225 gram of diethanolamine, and 1.5 grams of
carbodiimide (available from Stahl as PICASSIAN XL-725 ). The mixture
resulting
was then stirred for 4 minutes at 1500 rpm using a homogenizer. To the
obtained
product and while homogenizing, 19 millimeters of MDI diisocyanate (available
from
Huntsman as SUPRASECTM 2379) were added using a syringe, and the mixture
obtained was further homogenized for 5 seconds. The mixture resulting was then
poured into a mold, which was then closed shut and allowed to cure at a
temperature
of from about 50 C to 55 C. The demold time was 15 to 20 minutes after which
the
mold was opened, and the foam plaque was removed and placed on a flat surface.
The plaque was cut into appropriate dog-bone shapes for mechanical testing.
The
density and hardness were tested according to the procedures illustrated in
the
preceding Examples resulting in a density: of 0.32 gramicentimeters3, a
hardness of
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Date Recue/Date Received 2021-11-17
30, a tensile strength of 1.2 MPa, an elongation of 420 percent, a tear
strength of 2.2
Newtons/millimeters2, and a resilience of 37 percent.
EXAMPLE 18
Preparation of Midsoles Comprised of Polyurethane Elastomers
[00124] A
plaque mold, thickness 10 millimeters (mold volume, 311
centimeters3), was first conditioned by preheating at about 50 to 55 C for 2
hours to
ensure equal distribution of temperature. The mold was opened, and a mold
release
agent was lightly brushed along the lower and upper part of the mold which
results in
a shiny waxy consistency. Seventy-two (72) grams of polyol PSA 3000 and 8
grams
of polyol PSA 2000 blend (available from Bioamber) was melted in a 400
milliliter
glass can at 70 C for 2 hours in an oven. To this was added, 24 grams of
plasticizer
(available from Jungbunzlauer as CITROF00), 0.44 gram of TEGOSTAB
surfactant (available from Evonik), 4 grams of 1,3-propane diol chain
extender, 0.24
gram of DABCO LV catalyst (available from Evonik), 0.16 gram of water, 4
grams of
polysaccharide (available as NULVOLVE from DuPont) were added to the can, and
the mixture obtained stirred for 4 minutes at 1500 rpm to homogenize. While
stirring,
there was injected the diisocyanate ISO MM103 33.55 milliliters via pre-
weighed
syringe. Once the syringe was empty, the obtained mixture was stirred for a
further 5
seconds to homogenize. The mixture obtained was then poured into mold which
was
closed shut and allowed to cure at the mold temperature. The demold time was
15 to
20 minutes after which the mold was opened, and the foam plaque was removed
and
placed on a flat surface. The plaques resulting were cut into appropriate dog-
bone
shapes for mechanical testing, measured as disclosed herein, with the
following
results. Density 0.433 gram/centimeter3, tensile strength 2.12 MPa, elongation
409
percent, tear strength 3.10 Newtons/millimeters2, and a resilience of 42
percent.
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Date Recue/Date Received 2021-11-17
EXAMPLE 19
Preparation of the Polyurethane Elastomer for Midsoles
[00125] A plaque mold, thickness 10 millimeters (mold volume, 311
centimeters3) was first conditioned by preheating at 50 C to 55 C for 2 hours
to
ensure the equal distribution of the temperature. The mold was then opened and
a
mold release agent was lightly brushed along the lower and upper part of the
mold,
resulting in a shiny waxy consistency. Polyol PSA 3000, 81.45 grams, and 9.05
grams of polyol PSA 2000 blend was melted in a 400 milliliter glass can at 70
C for 2
hours in an oven. The six ingredients of Example 18 except with 27.15 grams of
plasticizer, 0.50 gram of surfactant, 4.53 grams of chain extender, 0.18 gram
of
catalyst, 0.14 gram of water, and 4.53 grams of polysaccharide) were added to
the
can, and the mixture obtained stirred for 4 minutes at 1500 rpm to homogenize.
While stirring, there was then injected ISO MM103, 37.07 millimeters by a pre-
weighed syringe. Once the syringe was empty, the mixture present was stirred
for a
further 5 seconds to homogenize. Then, the mixture was poured into mold which
was closed shut and allowed to cure at the mold temperature. The demold time
was
15 to 20 minutes after which the mold was opened, and the foam plaque was
removed and placed on a flat surface. The plaque was cut into appropriate dog-
bone
shapes for mechanical testing. The density was tested according to the
procedures
as disclosed herein such as mentioned in the preceding Examples with the
following
results. Density 0.433 gram/centimeter3, tensile strength 1.87 MPa, elongation
395
percent, tear strength 2.52 Newtons/millimeters, and a resilience of 42
percent.
[00126] The claims, as originally presented and as they may be amended,
include alternatives, modifications, improvements, equivalents, and
substantial
equivalents of the disclosed embodiments and teachings, including those that
are
presently unforeseen, or unappreciated, and that, for example, may arise from
applicants/patentees and others. Unless specifically recited in a claim,
steps, or
components of claims should not be implied, or imported from the
specification, or
any other claims as to any particular order, number, position, size, shape,
angle,
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Date Recue/Date Received 2021-11-17
color, or material. Percent by weight is a known quantity and is usually based
on the
total of the components present divided by the specific component present.
-41 -
Date Recue/Date Received 2021-11-17
