Note: Descriptions are shown in the official language in which they were submitted.
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BINDER COMPOSITIONS AND METHODS FOR MAKING AND USING SAME
BACKGROUND
Field
[00011 Embodiments described herein generally relate to binder compositions
and methods
for making and using same. More particularly, such embodiments relate to
binder
compositions for making composite products.
Description of the Related Art
[00021 Composite products, e.g., fiberglass and wood products, require certain
properties
such as tear strength, cure time, internal bond strength, and the like. For
example, an
important process variable encountered when making commercial and industrial
fiberglass
insulation products is cure time. Curing composite products can be
accomplished, at least in
part, by heating a mixture of particles, e.g., fiberglass and/or wood
particles, and the binder
composition. The speed at which the manufacturing equipment used to produce
commercial
and industrial fiberglass insulation operates makes it desirable and often
necessary to reduce
the time required to cure the binder composition to as short a time as
possible.
[0003] When the binder composition cures, there is a variable temperature
profile with the
surfaces of the product reaching a greater temperature than a center or core
region of the
product. As such, the time required to cure a composite product depends, at
least in part, on
the temperature required to sufficiently cure the binder at the center of the
product.
Accordingly, binder compositions that cure at a reduced temperature, e.g., 195
C as
compared to 205 C, can be more readily used in the production of composite
products such
as commercial and industrial fiberglass insulation because the core of the
product does not
need to be heated to as high of a temperature. By not having to heat the core
of the product
to as high of a temperature, the time required to cure the binder can be
reduced.
[0004] There is a need, therefore, for improved binder compositions having
reduced cure
temperatures for making composite products.
SUMMARY
100051 Binder compositions and methods for making and using same are provided.
The
binder composition can include at least one polyamidoamine prepolymer and at
least one
copolymer. The copolymer can include one or more vinyl aromatic derived units,
and one or
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more unsaturated carboxylic acids, one or more unsaturated carboxylic
anhydrides, or a
combination thereof. The copolymer can be modified by reaction with one or
more base
compounds.
[00061 A method for making a composite product can include contacting a
plurality of
substrates with a binder composition. The binder composition can include at
least one
polyamidoamine prepolymer and at least one copolymer. The copolymer can
include one or
more vinyl aromatic derived units, and one or more unsaturated carboxylic
acids, one or more
unsaturated carboxylic anhydrides, or a combination thereof. The copolymer can
be modified
by reaction with one or more base compounds. The method can also include at
least partially
curing the binder composition to produce a composite product.
[00071 A composite product can include a plurality of substrates and a binder
composition.
The binder composition, prior to curing, can include at least one
polyamidoamine prepolymer
and at least one copolymer. The copolymer can include one or more vinyl
aromatic derived
units, and one or more unsaturated carboxylic acids, one or more unsaturated
carboxylic
anhydrides, or a combination thereof The copolymer can be modified by reaction
with one
or more base compounds.
DETAILED DESCRIPTION
[0008) The binder composition can include at least one polyamidoamine
prepolymer and at
least one copolymer. The copolymer can include one or more vinyl aromatic
derived units.
The copolymer can also include one or more unsaturated carboxylic acids, one
or more
unsaturated carboxylic anhydrides, or a combination thereof. The
copolymer, the
polyamidoamine prepolymer, and/or the binder composition can also include one
or more
base compounds. The copolymer can also be modified by reaction with one or
more base
compounds.
[00091 It has been surprisingly and unexpectedly discovered that combining the
at least one
polyamidoamine prepolymer with the at least one copolymer can provide a binder
composition that can be used to produce fiberglass based composite products
and/or
lignocellulose based composite products at a reduced cure temperature while
maintaining
equivalent or improved physical properties, such as dry tensile strength
and/or hot-wet tensile
strength as compared to a comparative composite product made with a
comparative binder
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composition, where the comparative binder composition contains the same
copolymer, but
does not contain the polyamidoamine prepolymer.
[0010] The binder composition containing the copolymer and the polyamidoamine
prepolymer can be used to produce a fiberglass product, e.g., a mat or
insulation, in which the
binder composition at the center or core of the product reaches a temperature
ranging from
about 150 C to about 199 C. For example, the binder compositions discussed and
described
herein can be used to produce a fiberglass based composite product and/or a
lignocellulose
based composite product in which the binder composition at the center or core
of the product
reaches a temperature ranging from a low of about 150 C, about 155 C, about
160 C, about
165 C, or about 170 C to a high of about 180 C, about 185 C, about 190 C,
about 195 C, or
about 199 C.
[00111 As such, the cure temperature required to produce a fiberglass based
composite
product and/or a lignocellulose based composite product containing the binder
compositions
discussed and described herein can be about 1 C, about 2 C, about 5 C, about 7
C, about
C, about 15 C, about 18 C, about 20 C, about 23 C, about 25 C, about 28 C,
about 30 C,
about 33 C, about 35 C, about 38 C, about 40 C, about 43 C, about 45 C, about
47 C, or
about 50 C less than a cure temperature required to produce a comparative
fiberglass based
composite product and/or lignocellulose based composite product made with the
comparative
binder composition that does not contain the polyamidoamine prepolymer, while
maintaining
equivalent or improved physical properties as compared to the comparative
fiberglass
product. In one example, the center or core of the composite product, during
curing thereof,
can be heated to a temperature ranging from a low of about 150 C, about 155 C,
about 160 C,
or about 165 C to a high of about 180 C, about 185 C, about 190 C, about 195
C, or about
199 C for a time ranging from a low of about 1 second, about 5 seconds, about
10 seconds,
about 15 seconds or about 20 seconds to a high of about 30 seconds, about 45
seconds, about
60 seconds, about 90 seconds, about 120 seconds, about 150 seconds, or about
180 seconds to
produce the composite product.
[0012] The production of fiberglass based composite products at reduced cure
temperatures
can significantly reduce the overall time required to sufficiently cure the
binder composition
to produce the finished composite fiberglass product. Additionally, the
reduced cure
temperature corresponds to a reduction in the overall time required to cure
the binder
composition, which allows for the production of a wider range of composite
fiberglass
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products. By reducing the temperature required to sufficiently cure the binder
composition
containing the polyamidoamine prepolymer and the copolymer, the time required
to
sufficiently cure the binder composition to produce a composite product having
equivalent or
improved physical properties as compared to comparative fiberglass product can
be reduced
by about 1%, about 5%, about 7%, about 10%, about 13%, about 15%, about 18%,
about
20%, about 23%, or about 25%. Since the cure temperature of the binder
compositions
discussed and described herein can be reduced, such binder compositions can be
used to
produce commercial and industrial insulation products as well as other
products that require
reduced cure times while still maintaining acceptable physical product
properties.
100131 The weight ratio of the copolymer to the polyamidoamine prepolymer can
widely
vaiy. For example, the binder composition can include about 1 wt% to about 99
wt% of the
at least one copolymer and conversely about 99 wt% to about 1 wt% of the at
least one
polyamidoamine prepolymer, based on the combined weight of the at least one
copolymer
and the at least one polyamidoamine prepolymers. In another example, the
amount of the
copolymer in the binder composition can range from a low of about 5 wt%, about
10 wt%,
about 15 wt%, about 20 wt%, about 25 wt% about 30 wt%, about 35 wt%, about 40
wt%, or
about 45 wt% to a high of about 60 wt%, about 65 wt%, about 70 wt%, about 75
wt%, about
80 wt%, about 85 wt%, about 90 wt%, or about 95 wt%, based on the combined
weight of the
copolymer and the polyamidoamine prepolymer. In another example, the amount of
the
polyamidoamine prepolymer can range from a low of about 5 wt%, about 10 wt%,
about 15
wt%, about 20 wt%, about 25 wt% about 30 wt%, about 35 wt%, about 40 wt%, or
about 45
wt% to a high of about 60 wt%, about 65 wt%, about 70 wt%, about 75 wt%, about
80 wt%,
about 85 wt%, about 90 wt%, or about 95 wt%, based on the combined weight of
the
copolymer and the polyamidoamine prepolymer. In another example, the copolymer
can
include from about 20 wt% to about 50 wt% of the polyamidoamine prepolymers,
or about 25
wt% to about 45 wt% of the polyamidoamine prepolymer, or about 30 wt% to about
40 wt%
of the polyamidoamine prepolymer, based on the combined weight of the
copolymer and the
polyamidoaminc prepolymer.
[0014] The binder composition that includes the at least one polyamidoamine
prepolymer
and the at least one copolymer can be prepared by mixing, blending, or
otherwise combining
the polyamidoamine prepolymer with the copolymer. The blending or mixing
procedure can
be carried out at ambient temperature or at a temperature greater than ambient
temperature,
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for example a temperature ranging from a low of about 20 C, about 30 C, or
abut 40 C to a
high of about 90 C, about 100 C, about 110 C, or about 125 C. The blending or
mixing
procedure can also be carried out under a vacuum, at atmospheric pressure, or
at a pressure
greater than atmospheric pressure, e.g., 350 kPa. In one example, the
polyamidoamine
prepolymer and the copolymer can be mixed with one another at atmospheric
pressure and at
a temperature ranging from about 30 C to about 100 C. The binder composition
can be used
immediately or stored for a period of time and may be diluted with water to a
concentration
suitable for the desired method of application. If stored for a period of
time, the binder
composition can be continuously or periodically agitated or stirred.
[0015] The polyamidoamine prepolymer can be produced by reacting one or more
polyamide-amine groups and one or more diacids. The one or more polyamide-
amine groups
can be derived from one or more polyalkylene polyamines.
Accordingly, the
polyamidoamine prepolymer can be produced by reacting one or more polyalkylcne
polyamines with one or more diacids. The polyallcylenc polyamines can include,
but are not
limited to, polyethylene polyamines, polypropylene polyamines, polybutylene
polyamines,
and the like. Illustrative polyethylene polyamines can include, but are not
limited to,
diethylene triaminc, triethylene tetramine, tetraethylene pentamine,
bishexamethylcnc
triaminc, bis-2-hydroxyethylethylene diamine, pentaethylene hexamine,
hexacthylene
heptamine, or any combination thereof. Illustrative polypropylene polyamines
can include,
but are not limited to, methyl bis(3-aminopropy1)-amine, dipropylene triamine,
or any
combination thereof.
[0016] The diacid can be or include one or more saturated aliphatic dibasic
carboxylic acids,
one or more aromatic diacids, one or more cyclo-aliphatic diacids, or any
combination
thereof. Suitable saturated aliphatic dibasic carboxylic acid can include from
about 2 to
about 12 carbon atoms, from about 3 to about 10 carbon atoms, or from about 4
to about 8
carbon atoms. Illustrative saturated aliphatic dibasic carboxylic acids can
include, but are not
limited to, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic
acid, subcric acid,
azelaic acid, sebacic acid, or any combination thereof. Illustrative aromatic
diacids can
include, but arc not limited to, phthalic acid, isophthalic acid, terephthalic
acid, or any
combination thereof. Illustrative cyclo-aliphatic diacids can include, but are
not limited to,
cyclobutanedicarboxylic acid, cyclopentanedicarboxylic acid,
cyclohexancdicarboxylic acid,
isomers thereof, or any combination thereof.
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[0017] The polyamidoamine prepolymer can be produced by reacting the diacid
and the
polyalkylene polyamine under conditions sufficient to substantially react the
primary amine
groups of the polyalkylene polyamines with the diacid, but insufficient to
cause reaction of
the secondary amine groups of the polyalkylene polyamine with the diacid to a
substantial
extent. As used herein, the phrase "substantially react the primary amine
groups of the
polyalkylene polyamines with the diacid" means that at least 90% of the
primary amine
groups of the polyalkylene polyamine are reacted with the diacid. As used
herein, the phrase
"insufficient to cause reaction of the secondary amine groups of the
polyalkylene polyamine
with the diacid to a substantial extent" means that less than 10% of the
secondary amine
groups of the polyalkylene polyamine are reacted with the diacid.
[0018] A mixture of the diacid and the polyalkylene polyamine can be reacted
at a
temperature ranging from a low of about 70 C, about 80 C, about 90 C, about
100 C, about
110 C, about 125 C, about 145 C, or about 160 C to a high of about 180 C,
about 200 C,
about 220 C, about 250 C, or about 250 C. For example, the diacid and the
polyalkylene
polyamine can be reacted at a temperature of about 140 C to about 240 C, about
150 C to
about 220 C, or about 160 C to about 200 C. The mixture of the diacid and the
polyalkylene
polyamine can be reacted at a pressure ranging from a vacuum, e.g., about 50
kPa,
atmospheric pressure, to pressures greater than atmospheric pressure, e.g.,
about 500 kPa.
When the pressure is below atmospheric pressure the temperature of the mixture
can be
toward the lower end, e.g., from about 75 C to about 150 C.
[0019] The molar ratio of the polyalkylene polyamine to diacid can range from
a low of
about 0.8:1, about 0.85:1, about 0.9:1, or about 0.95:1 to a high of about
1.2:1, about 1.25:1,
about 1.3:1, about 1.35:1, or about 1.4:1. For example, the mole ratio of the
polyalkylene
polyamine to diacid can range from about 0.8:1 to about 1.4:1, about 0.8:1 to
about 1.3:1, or
about 0.9:1 to about 1.2:1. The time of reaction can depend, at least in part,
on the
temperature and pressure at which the mixture is reacted. The time of reaction
can range
from a low of about 0.5 hours, about 0.75 hours, about 1 hour, or about 1.5
hours to a high of
about 2 hours, about 4 hours, about 6 hours, or about 8 hours. The
polycondensation reaction
of the polyalkylene polyamine and diacid can produce water as a byproduct. At
least a
portion of the water produced during the reaction can be removed using any
desired method,
e.g., distillation. For example, about 1%, about 3%, about 5%, about 10%,
about 15%, about
20%, about 25%, or more of the water produced during the reaction can be
removed. At the
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end of the polycondensation reaction and after removal of the water produced
during the
reaction, the resulting product can be at least partially dissolved in water.
For example, at the
end of the polycondensation reaction and after removal of the water produced
during the
reaction, water can be added to the resulting product to provide a
polyamidoamine
prepolymer at a concentration ranging from a low of about 1%, about 5%, about
10%, about
20%, about 25%, about 30%, about 35%, or about 40% to a high of about 45%,
about 50%,
about 55%, about 60%, about 65%, about 70%, or about 75% by weight total
polymer solids.
In another example, at the end of the polycondensation reaction and after
removal of the
water produced during the reaction, the resulting product can be dissolved in
water to provide
a polyamidoamine prepolymer at a concentration of about 40% to about 60%,
about 40% to
about 55%, about 45% to about 55%, or about 45% to about 50% by weight total
polymer
solids.
100201 The polyamidoaminc prepolymer can have a weight average molecular
weight
("MW') (in Daltons) ranging from a low of about 700, about 750, about 800,
about 900, about
1,000, about 1,300, about 1,500, about 2,000, about 3,000, about 5,000, about
7,000, about
10,000, about 20,000, about 25,000, or about 30,000 to a high of about 70,000,
about 80,000,
about 90,000, or about 100,000. For example, the weight average molecular
weight of the
polyamidoamine prepolymer can range from about 20,000 to about 75,000, about
25,000 to
about 65,000, about 30,000 to about 55,000, or about 35,000 to about 45,000.
In another
example, the weight average molecular weight of the polyamidoamine prepolymer
can range
from about 700 to about 5,000, about 1,000 to about 10,000, about 750 to about
55,000, about
1,000 to about 25,000, or about 700 to about 70,000. The Mw can be measured
using gel
permeation chromatography ("GPC"), also known as size exclusion chromatography
(SEC).
This technique utilizes an instrument containing columns packed with porous
beads, an
elution solvent, and detector in order to separate polymer molecules of
different sizes, and is
well known to those skilled in the art.
[0021] As noted above, the copolymer can include one or more vinyl aromatic
derived units.
Also, as noted above, the copolymer can also include one or more unsaturated
carboxylic
acids, one or more unsaturated carboxylic anhydrides, or a combination
thereof. Illustrative
unsaturated carboxylic acids can include, but are not limited to, maleic acid,
aconitic acid,
itaconic acid, acrylic acid, methacrylic acid, crotonic acid, isocrotonic
acid, citraconic acid,
fumaric acid, polymers thereof, or any combination thereof. Illustrative
unsaturated
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carboxylic anhydrides can include, but are not limited to, maleic anhydride,
aconitic
anhydride, itaconic anhydride, acrylic anhydride, methacrylic anhydride,
crotonic anhydride,
isocrotonic anhydride, citraconic anhydride, polymers thereof, or any
combination thereof.
[0022] The vinyl aromatic derived units can include, but are not limited to,
styrene, alpha-
methylstyrene, vinyl toluene, or any combination thereof. For example, the
vinyl aromatic
derived units can be derived from styrene and/or derivatives thereof. In
another example, the
vinyl aromatic derived units can be derived from styrene. in another example,
the vinyl
aromatic derived units can be derived from styrene and at least one of alpha-
methylstyrene
and vinyl toluene.
[0023] In at least one example, the copolymer can be or include a copolymer of
styrene and
maleic anhydride and/or maleic acid ("SMA"). In another example, the copolymer
can be or
include a copolymer of styrene and acrylic acid. In another example, the
copolymer can be or
include styrene and polyacrylic acid. In another example, the copolymer can be
or include a
copolymer of styrene and methacrylic acid. In another example, the copolymer
can be or
include a copolymer of styrene and itaconic acid. In another example, the
copolymer can
include a blend of the one or more unsaturated carboxylic acids, one or more
unsaturated
carboxylic anhydrides, or any combination thereof and one or more vinyl
aromatic derived
units and one or more other polymers. For example, the copolymer can include
the
copolymer of the one or more unsaturated carboxylic acids, one or more
unsaturated
carboxylic anhydrides, or any combination thereof and one or more vinyl
aromatic derived
units and at least one of polyacrylic acid and styrene acrylic acid. In
another example, the
copolymer can be or include a terpolymer of styrene and two or more of maleic
anhydride,
maleic acid, acrylic acid, methacrylic acid, and itaconic acid. As such, the
term "copolymer,"
as used herein, can be or include a terpolymer. Said another way, the term
"copolymer," as
used herein, can be or include polymers derived from two or more monomers.
[0024] In one or more embodiments, the copolymer can include from about 7 mol%
to about
50 mol% of the one or more unsaturated carboxylic acids, one or more
unsaturated carboxylic
anhydrides, or any combination thereof and conversely from about 50 mol% to
about 93
mol% of the one or more vinyl aromatic derived units. In one or more
embodiments, the
copolymer can include from about 20 mol% to about 40 mol% of the one or more
unsaturated
carboxylic acids, one or more unsaturated carboxylic anhydrides, or any
combination thereof
and conversely from about 60 mol% to about 80 mol% of the one or more vinyl
aromatic
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derived units. In one or more embodiments, the one or more unsaturated
carboxylic acids,
one or more unsaturated carboxylic anhydrides, or any combination thereof can
be present in
the copolymer in an amount ranging from a low of about 7 mol%, about 10 mol%,
about 12
mol%, or about 15 mol% to a high of about 30 mol%, about 35 mol%, about 40
mol%, or
about 45 mol%, based on the total weight of the one or more unsaturated
carboxylic acids,
one or more unsaturated carboxylic anhydrides, or any combination thereof and
the one or
more vinyl aromatic derived units. In one or more embodiments, the one or more
vinyl
aromatic derived units can be present in the copolymer in an amount ranging
from a low of
about 50 mol%, about 55 mol%, about 60 mol%, or about 65 mol% to a high of
about 75
mol%, about 80 mol%, about 85 mol%, about 90 mol%, or about 95 mol%, based the
total
weight of the one or more unsaturated carboxylic acids, one or more
unsaturated carboxylic
anhydrides, or any combination thereof and the one or more vinyl aromatic
derived units.
[0025] The molecular weight of the copolymer can vary within wide limits.
Preferably, the
copolymer has a Mw between about 500 and about 200,000. For example, the
copolymer can
have a Mw ranging from a low of about 500, about 750, about 1,000, about
1,500, about
2,000, about 2,500, about 3,000, or about 4,000 to a high of about 50,000,
about 60,000,
about 70,000, about 80,000, about 90,000, about 100,000, about 110,000, about
120,000,
about 130,000 about 140,000, about 150,000, about 160,000, about 170,000,
about 180,000,
or about 190,000. In another example, the copolymer can have a Mw ranging from
about 500
to about 60,000, about 1,000 to about 60,000, about 2,000 to about 10,000,
about 10,000 to
about 80,000, or about 1,500 to about 60,000. In another example, the
copolymer can have a
Mw ranging from about 500 to about 10,000, about 1,000 to about 9,000, about
1,500 to
about 7,000, or about 2,500 to about 6,000. In another example, the copolymer
can have a
Mw ranging from a low of about 500, about 700, about 900, about 1,000, about
1,100, about
1,300, or about 1,500 to a high of about 3,000, about 3,200, about 3,400,
about 3,600, about
3,800, or about 4,000. In another example, the copolymer can have a Mw ranging
from a low
of about 500, about 700, about 900, about 1,000, about 1,100, about 1,300, or
about 1,500 to
a high of about 4,500, about 4,700, about 5,000, about 5,300, about 5,700,
about 6,000, about
6,300, about 6,500, about 6,700, or about 7,000. In another example, the
copolymer can have
a Mw ranging from a low of about 1,000, about 1,500, about 2,000, about 2,500,
or about
3,000 to a high of about 4,000, about 5,000, about 6,000, about 7,000, about
8,000, about
9,000, or about 10,000. In another example, the copolymer can have a Mw of
about 500 to
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about 10,000, about 1,000 to about 7,000, about 2,000 to about 6,000, about
2,000 to about
4,000, about 2,500 to about 3,500, about 3,000 to about 5,000, or about 4,500
to about 5,500.
In another example, the copolymer can have a Mw less than about 30,000, less
than about
25,000, less than about 20,000, less than about 17,000, less than about
15,000, less than about
12,000, less than about 10,000, less than about 9,000, less than about 8,000,
less than about
7,000, less than about 6,000, less than about 5,000, less than about 4,500,
less than about
4,000, or less than about 3,500. The weight average molecular weight (Mw) of
the
copolymer can be measured using GPC.
[0026] In one or more embodiments, the copolymer can include a major amount
(greater than
50 mol%, or greater than about 60 mol%, or greater than about 70 mol%, or
greater than
about 80 mol%, or greater than about 90 mol%, based on the combined amount of
unsaturated carboxylic acids and/or unsaturated carboxylic anhydrides) of
maleic anhydride
and/or maleic acid and a minor amount (less than 50 mol%, or less than about
40 mol%, or
less than about 30 mol%, or less than about 20 mol%, based on the combined
amount of the
unsaturated carboxylic acids and/or unsaturated carboxylic anhydrides) of one
or more other
unsaturated carboxylic acids such as aconitic acid, itaconic acid, acrylic
acid, methacrylic
acid, crotonic acid, isocrotonic acid, citraconic acid, fumaric acid, or any
combination thereof
and/or of one or more other unsaturated carboxylic anhydrides such as maleic
anhydride,
aconitic anhydride, itaconic anhydride, acrylic anhydride, methacrylic
anhydride, crotonic
anhydride, isocrotonic anhydride, citraconic anhydride, polymers thereof, or
any combination
thereof. The copolymer can also contain a minor amount (less than 50 mol%, or
less than
about 40 mol%, or less than about 30 mol%, or less than about 20 mol%, based
on the
amount of the one or more vinyl aromatic derived units) of another hydrophobic
vinyl
monomer. Another "hydrophobic vinyl monomer" is a monomer that typically
produces, as a
homopolymer, a polymer that is water-insoluble or capable of absorbing less
than 10% by
weight water. Suitable hydrophobic vinyl monomers are exemplified by (i) vinyl
esters of
aliphatic acids such as vinyl acetate, vinyl propionate, vinyl butyrate, vinyl
caproate, vinyl 2-
ethylhexanoatc, vinyl laurate, and vinyl stcaratc; (ii) diene monomers such as
butadiene and
isoprene; (iii) vinyl monomers and halogenated vinyl monomers such as
ethylene, propylene,
cyclohexene, vinyl chloride and vinylidene chloride; (iv) acrylates and alkyl
acrylatcs, such
as methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-
butyl acrylate,
isobutyl acrylate, tert-butyl acrylate, n-hexyl acrylate, cyclohexyl acrylate,
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hydroxyethylacrylate, hydroxyethylmethacrylate, and 2-ethylhexyl acrylate; and
(v) nitrile
monomers such as acrylonitrile and methacrylonitrile, and mixtures thereof.
[0027] In one or more embodiments, the copolymer can be SMA. In one or more
embodiments, the copolymer can include at least 10 wt%, at least 20 wt%, at
least 30 wt%, at
least 40 wt%, at least 50 wt%, at least 60 wt%, at least 70 wt%, at least 80
wt%, at least 90
wt%, at least 95 wt%, or about 100 wt% SMA.
[0028] As noted above, the copolymer, the polyamidoamine prepolymer, and/or
the binder
composition can also include one or more base compounds. The copolymer can
also be
modified by reaction with one or more base compounds. Illustrative base
compounds can
include, but are not limited to, one or more amines, one or more amides, one
or more
hydroxides, one or more carbonates, or any combination thereof. Suitable
amines can
include, but are not limited to, ammonia, ammonium hydroxide, alkanolamines,
polyamines,
aromatic amines, and any combination thereof. Illustrative alkanolamines can
include, but
are not limited to, monoethanolamine ("MEA"), diethanolamine ("DEA"),
triethanolamine
("TEA"), or any combination thereof. Preferably, the alkanolamine is a
tertiary alkanolamine
or more preferably triethanolamine ("TEA"). An alkanolamine is defined as a
compound that
has both amino and hydroxyl functional groups as illustrated by
diethanolamine,
triethanolamine, 2-(2-aminoethoxy)ethanol, aminoethyl ethanolamine,
aminobutanol and
other aminoalkanols. Illustrative aromatic amines can include, but are not
limited to, benzyl
amine, aniline, oral toludine, meta toludine, para toludine, n-methyl
aniline, N-N'-dimethyl
aniline, di-and tri-phenyl amines, 1-naphthylamine, 2-naphthylamine, 4-
aminophenol,
aminophenol and 2-aminophenol. Illustrative polyamines can include, but are
not limited to,
diethylenetriamine ("DETA"), triethylenetetramine ("TETA"),
tetraethylenepentamine
("TEPA"). Other
polyamines can include, for example, 1,3-propanediamine, 1,4-
butanediamine, polyamidoamines, and polyethylenimines.
[0029] Other suitable amines can include, but are not limited to, primary
amines ("NH2R1"),
secondary amines ("NHR1R2"), and tertiary amines ("NR1R2R3"), where each R1,
R2, and R3
is independently selected from alkyls, cycloalkyls, heterocycloalkyls, aryls,
heteroaryls, and
substituted aryls. The alkyl can include branched or unbranched alkyls having
from 1 to
about 15 carbon atoms or more preferably from 1 to about 8 carbon atoms.
Illustrative alkyls
can include, but are not limited to, methyl, ethyl, n-propyl, isopropyl, n-
butyl, sec butyl, t-
butyl, n-pentyl, n-hexyl, and ethylhexyl. The cycloalkyls can include from 3
to 7 carbon
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atoms. Illustrative cycloalkyls can include, but -are not limited to,
cyclopentyl, substituted
cyclopentyl, cyclohexyl, and substituted cyclohexyl. The term "aryl" refers to
an aromatic
substituent containing a single aromatic ring or multiple aromatic rings that
are fused
together, linked covalently, or linked to a common group such as a methylene
or ethylene
moiety. More specific aryl groups contain one aromatic ring or two or three
fused or linked
aromatic rings, e.g., phenyl, naphthyl, biphenyl, anthracenyl, phenanthrenyl,
and the like. In
one or more embodiments, aryl substituents can have from 1 to about 20 carbon
atoms. The
term "heteroatom-containing," as in a "heteroatom-containing cycloalkyl
group," refers to a
molecule or molecular fragment in which one or more carbon atoms is replaced
with an atom
other than carbon, e.g., nitrogen, oxygen, sulfur, phosphorus, boron, or
silicon. Similarly, the
term "heteroaryl" refers to an aryl substituent that is heteroatom-containing.
The term
"substituted," as in "substituted aryls," refers to a molecule or molecular
fragment in which at
least one hydrogen atom bound to a carbon atom is replaced with one or more
substituents
that are functional groups such as hydroxyl, alkoxy, allcylthio, phosphino,
amino, halo, silyl,
and the like. Illustrative primary amines can include, but are not limited to,
methylamine and
ethylamine. Illustrative secondary amines can include, but are not limited to,
dimethylamine
and diethylamine.
Illustrative tertiary amines can include, but are not limited to,
trimethylamine and triethylamine. Illustrative amides can include, but are not
limited to,
acetamide, ethanamide, dicyandiamide, and the like, or any combination
thereof.
[0030] Suitable hydroxides can include one or more alkali and/or alkaline
earth metal
hydroxides and/or carbonates. Illustrative hydroxides can include, but are not
limited to,
sodium hydroxide, potassium hydroxide, ammonium hydroxide (e.g., aqueous
ammonia),
lithium hydroxide, cesium hydroxide, barium hydroxide, calcium hydroxide,
magnesium
hydroxide, aluminum hydroxide, or any combination thereof. Illustrative
carbonates can
include, but are not limited to, sodium carbonate, sodium bicarbonate,
potassium carbonate,
and ammonium carbonate.
[0031] The copolymer of the vinyl aromatic derived units and the unsaturated
carboxylic
acids and/or the unsaturated carboxylic anhydrides can be combined with the
one or more
base compounds in any desired amount. For example, the binder composition can
include
about 1 wt% to about 99 wt% of the copolymer and conversely about 99 wt% to
about 1 wt%
of the one or more base compounds, based on the combined weight of the
copolymer and the
one or more base compounds. For example, the amount of the copolymer in the
binder
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composition can range from a low of about 5 wt%, about 10 wt%, about 15 wt%,
about 20
wt%, about 25 wt% about 30 wt%, about 35 wt%, about 40 wt%, or about 45 wt% to
a high
of about 60 wt%, about 65 wt%, about 70 wt%, about 75 wt%, about 80 wt%, about
85 wt%,
about 90 wt%, or about 95 wt%, based on the combined weight of the copolymer
and the one
or more base compounds. In another example, the amount of the one or more base
compounds can range from a low of about 5 wt%, about 10 wt%, about 15 wt%,
about 20
wt%, about 25 wt% about 30 wt%, about 35 wt%, about 40 wt%, or about 45 wt% to
a high
of about 60 wt%, about 65 wt%, about 70 wt%, about 75 wt%, about 80 wt%, about
85 wt%,
about 90 wt%, or about 95 wt%, based on the combined weight of the copolymer
and the one
or more base compounds. In another example, the copolymer can include from
about 5 wt%
to about 45 wt% of the one or more base compounds, or about 10 wt% to about 40
wt% of
the one or more base compounds, or about 25 wt% to about 35 wt% of the one or
more base
compounds, or about 5 wt% to about 15 wt% of the one or more base compounds,
based on
the combined weight of the copolymer and the one or more base compounds.
[0032] If the copolymer of the one or more unsaturated carboxylic acids, one
or more
unsaturated carboxylic anhydrides, or any combination thereof, and one or more
vinyl
aromatic derived units is modified by reaction with two or more base
compounds, the two or
more base compounds can be present in any desired amount or ratio relative to
one another.
For example, if a first and second base compound are present, the first base
compound can be
present in an amount ranging from about 1 wt% to about 99 wt%, based on the
combined
weight of the first and second base compounds. In another example, if the
first and second
base compounds are present, the first base compound can be present in an
amount ranging
from a low of about 2 wt%, about 5 wt%, about 15 wt%, or about 25 wt% to a
high of about
50 wt%, about 60 wt%, about 70 wt%, or about 90 wt%, based on the combined
weight of the
first and second base compounds. In another example, if the first and second
base
compounds are present, the first base compound can be present in an amount
ranging from a
low of about 2 wt%, about 5 wt%, or about 10 wt% to a high of about 15 wt%,
about 25 wt%,
about 35 wt%, or about 50 wt%, based on the combined weight of the first and
second base
compounds. Similarly, if three or more base compounds are present, the three
or more base
compounds can be present in any desired proportion or amount with respect to
one another.
[0033] In at least one example, the copolymer can be modified by reaction with
a mixture of
ammonia and at least one of monoethanolamine, diethanolamine, and
triethanolamine, where
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the ammonia can be present in an amount ranging from about 1 wt% to about 99
wt% and
conversely the at least one of monoethanolamine, diethanolamine, and
triethanolamine can be
present in an amount ranging from about 99 wt% to about 1 wt%, based on the
combined
weight of the ammonia and the at least one of monoethanolaminc,
diethanolamine, and
triethanolamine. In another example, the copolymer can be modified by reaction
with a
mixture of ammonia and two or more of monoethanolamine, diethanolamine, and
triethanolamine. In such a mixture, the ammonia can be present, for example,
in an amount
ranging from about 10 wt% to about 40 wt%, e.g., about 33 wt%, and the two or
more of
monoethanolamine, diethanolamine, and triethanolamine can be present in an
amount ranging
from about 80 wt% to about 60 wt%, e.g., about 67 wt%, based on the combined
weight of
the ammonia and the two or more of monoethanolamine, diethanolamine, and
triethanolamine. In at least one example, if two or more base compounds are
reacted with the
copolymer and the base compounds include monoethanolamine, the
monoethanolamine can
be present in an amount less than about 15 wt%, less than about 10 wt%, less
than about 7
wt%, less than about 5 wt%, less than about 3 wt%, less than about 1 wt%, or
less than about
0.5 wt% monoethanolamine, based on the combined weight of the base compounds.
In
another example, the copolymer can be modified by reaction with ammonia, e.g.,
an aqueous
solution of ammonia, where the ammonia can be preset in an amount ranging from
about 5
wt% to about 40 wt%, or about 5 wt% to about 15 wt%, or about 10 wt% to about
30 wt%, or
about 7 wt% to about 20 wt%, based on the combined weight of the copolymer and
the
ammonia. In another example, the copolymer can be modified by reaction with
one or more
amines other than ammonia. In other words, the binder composition containing
the
copolymer can be free from any intentionally added ammonia. In another
example, the
copolymer can be modified by reaction with one or more base compounds other
than an
amine such as one or more hydroxides or carbonates. Said another way, the
copolymer can
be modified by reaction with one or more hydroxides, carbonates, or a
combination thereof,
in the absence of any intentionally added amines.
[0034] The binder composition that includes the copolymer modified by reaction
with the
one or more base compounds can have a pH ranging from a low of about 4, about
4.5, about
5, or about 5.5 to a high of about 7, about 8, about 9, or about 10. For
example, the binder
composition can have a pH of about 5 to about 7, about 5.5 to about 6.5, or
about 5.7 to about
6.3.
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[0035] The binder composition that includes the copolymer modified by reaction
with the
one or more base compounds can have a viscosity ranging from a low of about 50
centipoise
("cP"), about 100 cP, about 200, cP, about 300 cP, about 500 cP, about 750 cP,
about 900 cP,
about 1,100 cP, about 1,300 cP, about 1,500 cP, about 1,700 cP, about 2,000
cP, about 2,250
cP, or about 2,500 cP to a high of about 5,000 cP, about 8,000 cP, about
10,000 cP, about
13,000 cP, about 15,000 cP, about 17,000 cP, or about 20,000 cP. The viscosity
of
copolymers, resins, binder compositions and the like, discussed and described
herein, can be
determined using a Brookfield Viscometer at a temperature of 25 C. For
example, the
Brookfield Viscometer can be equipped with a small sample adapter such a 10 mL
adapter
and the appropriate spindle to maximize torque such as a spindle no. 18.
10036] The copolymer can be reacted with the one or more base compounds at a
temperature
ranging from a low of about 40 C, about 70 C, or about 90 C to a high of about
100 C, about
125 C, or about 150 C. The copolymer can be reacted with the one or more base
compounds
under a pressure ranging from a low of about 50 kPa, about 75 kPa, or about
101 kPa to a
high of about 150 kPa, about 300 kPa, or about 500 kPa. The copolymer can be
reacted with
the one or more base compounds for a time ranging from a low of about 30
minutes, about 45
minutes, or about 1 hour to a high of about 4 hours, about 6 hours, or about
10 hours. In at
least one example, the at least one copolymer can be reacted with the one or
more base
compounds at a temperature ranging from about 85 C to about 115 C, at
atmospheric
pressure, and for a time ranging from about 1 hour to about 7 hours. In at
least one other
example, the at least one copolymer can be reacted with the one or more base
compounds at a
temperature ranging from about 85 C to about 115 C, at a pressure ranging from
a low of
about 101 kPa, about 115 kPa, about 130 kPa, or about 145 kPa to a high of
about 155 kPa,
about 200 kPa, about 300 kPa, or about 400 kPa, and for a time ranging from
about 1 hour to
about 7 hours.
[0037] The copolymer and/or the one or more base compounds can be combined and
reacted
with one another alone or in the presence of a liquid medium. The liquid
medium can be or
include one or more polar aprotic solvents, one or more polar protic solvents,
or any
combination thereof. Illustrative polar aprotic solvents can include, but are
not limited to,
tctrahydrofuran ("THF"), dimethyl sulfoxide ("DMSO"), N-methylpyrrolidone
("NMP"),
dimethyl acetamide, acetone, or any combination thereof. Illustrative polar
protic solvents
can include, but are not limited to, water, methanol, ethanol, propanol,
butanol, or any
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combination thereof. Other liquid mediums can include ketones such as methyl
ethyl ketone.
The water can be fresh water or process water. A suitable process water can
include, for
example, an aqueous solution ("white water") of polyacrylamide ("PAA"), amine
oxide
("AO"), hydroxyethylcellulose ("HEC"), or any combination thereof The liquid
medium, if
present, can be added before, during, and/or after the copolymer is reacted
with the one or
more base compounds. For example, the copolymer can be reacted with an aqueous
base
compound, e.g., ammonia and/or sodium hydroxide, and after reaction additional
liquid
medium which can be the same or different, e.g., ammonia or methanol, can then
be added to
the binder composition.
[0038] The amount of the liquid medium combined with the copolymer and the one
or more
base compounds and/or the binder composition, e.g., copolymer modified by
reaction with
the one or more base compounds, can be sufficient to produce a binder
composition having a
solids concentration ranging from about 0.1 wt% to about 75 wt%, based on a
total weight of
the binder composition. As used herein, the solids content of the binder
composition the
copolymer, and the like, as understood by those skilled in the art, can be
measured by
determining the weight loss upon heating a small sample, e.g., 1-5 grams of
the binder
composition, to a suitable temperature, e.g., 125 C, and a time sufficient to
remove the liquid.
By measuring the weight of the sample before and after heating, the percent
solids in the
sample can be directly calculated or otherwise estimated. For example, the
amount of liquid
medium combined with the copolymer and the one or more base compounds and/or
the
copolymer modified by reaction with the one or more base compounds can be
sufficient to
produce a binder composition having a solids concentration ranging from a low
of about 1
wt%, about 5 wt%, about 10 wt% or about 15 wt% or about 20 wt% to a high of
about 30
wt%, about 40 wt%, about 50 wt%, about 60 wt%, about 70 wt%, or about 75 wt%,
based on
the total weight of the binder composition. In at least one example, a
sufficient amount of
water, e.g. fresh water or process water, can be combined with the copolymer
and the one or
more base compounds to provide a binder composition having a solids
concentration ranging
from about 1 wt% about 65 wt%, about 5 wt% to about 40 wt%, about 10 wt% to
about 30
wt%, about 15 wt% to about 45 wt%, about 20 wt% to about 60 wt%, about 45 wt%
to about
55 wt%, or about 40 wt% to about 60 wt%, based on the total weight of the
binder
composition.
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[0039] The copolymer can be reacted with the one or more base compounds in any
device,
system, apparatus, or combination of devices, systems, and/or apparatus. For
example,
copolymer and the base compound can be mixed, blended, or other wise combined
with one
another in a reactor vessel or container and allowed to at least partially
react to produce the
copolymer modified by reaction with the base compounds. The reactor vessel or
container
can include, but is not limited to, mechanical mixing devices such as mixing
blades, ejectors,
sonic mixers, or combinations thereof. One or more heating jackets, heating
coils, internal
heating elements, cooling jacks, cooling coils, internal cooling elements, or
the like, can be
used to adjust or otherwise control the temperature of the reaction mixture.
The reactor
vessel can be an open vessel or an enclosed vessel.
[0040] The copolymer can further include one or more polyols to increase the
crosslink
density of the cured copolymer. As used herein, the terms "curing," "cured,"
and similar
terms are intended to embrace the structural and/or morphological change that
occurs in the
binder composition as it is cured to cause covalent chemical reaction
(crosslinking), ionic
interaction or clustering, improved adhesion to the substrate, phase
transformation or
inversion, and/or hydrogen bonding. As used herein, the term "partially cured"
and similar
terms are intended to refer to a binder composition that has undergone some
covalent
chemical reaction (crosslinking), ionic interaction or clustering, improved
adhesion to the
substrate, phase transformation or inversion, and/or hydrogen bonding, but is
capable of
undergoing additional covalent chemical reaction (crosslinking), ionic
interaction or
clustering, improved adhesion to the substrate, phase transformation or
inversion, and/or
hydrogen bonding.
[0041] As used herein, the term "polyol" refers to compounds that contain two
or more
hydroxyl functional groups. Suitable polyols can include, but are not limited
to, ethylene
glycol, polyglycerol, diethylene glycol, triethylene glycol, polyethylene
oxide (hydroxy
terminated), glycerol, pentaerythritol, trimethylol propane, diethanolamine,
triethanolamine,
ethyl diethanolamine, methyl diethanolamine, sorbitol, monosaccharides, such
as glucose and
fructose, disaccharides, such as sucrose, and higher polysaccharides such as
starch and
reduced and/or modified starches, dextrin, maltodextrin, polyvinyl alcohols,
hydroxyethylcellulose, resorcinol, catcchol, pyrogallol, glycollated urcas,
and 1,4-
cyclohexane diol, lignin, or any combination thereof.
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[0042] The one or more polyols can be combined with the copolymer and/or the
copolymer
reacted with the one or more base compounds to produce a binder composition
containing
from about 1 wt% to about 50 wt% polyols, based on the combined weight of the
polyols and
the copolymer and/or the copolymer reacted with the one or more base
compounds. For
example the one or more polyols can be combined with the copolymer modified by
reaction
with the one or more base compounds to produce a binder composition having a
concentration of the one or more polyols ranging from a low of about 1 wt%,
about 5 wt%,
about 10 wt%, or about 15 wt% to a high of about 30 wt%, about 40 wt%, or
about 45 wt%,
based on the combined weight of the copolymer modified by reaction with the
one or more
base compounds and the one or more polyols. In another example, the binder
composition
can be free from any intentionally added polyol(s).
[0043] In one or more embodiments above or elsewhere herein, the binder
composition can
further include one or more other copolymers or "second" copolymers. As such,
the terms
"copolymer" and "first copolymer" are used interchangeably to refer to the
copolymer that
can include the one or more vinyl aromatic derived units and the one or more
unsaturated
carboxylic acids, the one or more unsaturated carboxylic anhydrides, or a
combination of the
one or more unsaturated carboxylic acids and one or more unsaturated
carboxylic anhydrides.
[0044] The second copolymer can be or include one or more aldehyde based
copolymers.
Illustrative aldehyde based copolymers can include, but are not limited to,
one or more
amino-aldehyde copolymers, phenol-aldehyde copolymers, dihydroxybenzene or
"resorcinol"-aldehyde copolymers, or any combination thereof. The amino
component of the
amino-aldehyde copolymers can be or include, but is not limited to, urea,
melamine, or a
combination thereof. The second copolymer can also be or include one or more
acrylic acid
based copolymers. As such, the second copolymer can be or include, but is not
limited to,
one or more aldehyde based copolymers, one or more acrylic acid based
copolymers, or any
combination thereof.
[0045] The aldehyde compounds, if present in the second copolymer, can
include, but are not
limited to, unsubstituted aldehyde compounds and/or substituted aldehyde
compounds. For
example, suitable aldehyde compounds can be represented by the formula RCHO,
wherein R
is hydrogen or a hydrocarbon radical. Illustrative hydrocarbon radicals can
include from 1 to
about 8 carbon atoms. In another example, suitable aldehyde compounds can also
include the
so-called masked aldehydes or aldehyde equivalents, such as acetals or
hemiacetals.
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Illustrative aldehyde compounds can include, but are not limited to,
formaldehyde,
paraformaldehyde, acetaldehyde, propionaldehyde, butyraldehyde,
furfuraldehydc,
benzaldehyde, or any combination thereof. One or more other aldehydes, such as
glyoxal can
be used in place of or in combination with formaldehyde and/or other
aldehydes. In at least
one example, the aldehyde compound can include formaldehyde, UFC, or a
combination
thereof.
[0046] Aldehyde compounds for making suitable urea-aldehyde, phenol-aldehyde,
melamine-aldehyde, and resorcinol-aldehyde copolymers can be used in many
forms such as
solid, liquid, and/or gas. Considering formaldehyde in particular, the
formaldehyde can be or
include paraform (solid, polymerized formaldehyde), formalin solutions
(aqueous solutions
of formaldehyde, sometimes with methanol, in 37 percent, 44 percent, or 50
percent
formaldehyde concentrations), Urea-Formaldehyde Concentrate ("UFC"), and/or
formaldehyde gas in lieu of or in addition to other forms of formaldehyde can
also be used.
In another example, the aldehyde can be or include a pre-reacted urea-
formaldehyde mixture
having a urea to formaldehyde weight ratio of about 1:2 to about 1:3.
[0047] Suitable urea-formaldehyde polymers that can be used as the second
copolymer can
be prepared from urea and formaldehyde monomers or from urea-formaldehyde
prccondensates in manners well known to those skilled in the art. Similarly,
melamine-
formaldehyde, phenol-formaldehyde, and resorcinol-formaldehyde polymers can be
prepared
from melamine, phenol, and resorcinol monomers, respectively, and formaldehyde
monomers
or from melamine-formaldehyde, phenol-formaldehyde, and resorcinol-
formaldehyde
precondensates. Urea, phenol, melamine, resorcinol, and formaldehyde reactants
arc
commercially available in many forms and any form that can react with the
other reactants
and does not introduce extraneous moieties deleterious to the desired reaction
and reaction
product can be used in the preparation of the second copolymer. One
particularly useful class
of urea-formaldehyde polymers can be as discussed and described in U.S. Patent
No.
5,362,842.
[0048] Similar to formaldehyde, urea, phenol, resorcinol, and melamine are
available in
many forms. For example, with regard to urea, solid urea, such as prill and
urea solutions,
typically aqueous solutions, are commonly available. Further, urea may be
combined with
another moiety, most typically formaldehyde and urea-formaldehyde adducts,
often in
aqueous solution. Any form of urea or urea in combination with formaldehyde
can be used to
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make a urea-formaldehyde polymer. Both urea prill and combined urea-
formaldehyde
products are preferred, such as UFC. These types of products can be as
discussed and
described in U.S. Patent Nos. 5,362,842 and 5,389,716, for example.
[0049] Many suitable urea-formaldehyde polymers are commercially available.
Urea-
formaldehyde polymers such as the types sold by Georgia-Pacific Chemicals LLC.
(e.g.,
GP -2928 and Ge-2980) for glass fiber mat applications, those sold by Hexion
Specialty
Chemicals, and by Arclin Company can also be used. Suitable phenol-
formaldehyde resins
and melamine-formaldehyde resins can include those sold by Georgia Pacific
Resins, Inc.
(e.g., GP`11)-2894 and GP -4878, respectively). These polymers are prepared in
accordance
with well known methods and contain reactive methylol groups which upon curing
form
methylene or ether linkages. Such
methylol-containing adducts may include N,N'-
dimethylol, dihydroxymethylolethylene;
N,Ntis(methoxymethyl), N,N'-
dimethylolpropylene; 5,5-dimethyl-N,N'dimethylolethylene; N,N'-
dimethylolethylene; and
the like.
[0050] Urea-formaldehyde polymers can include from about 45% to about 70%, and
preferably, from about 55% to about 65% solids, generally have a viscosity of
about 50 cP to
about 600 cP, preferably about 150 to about 400 cP, normally exhibit a pH of
about 7 to
about 9, preferably about 7.5 to about 8.5, and often have a free formaldehyde
level of not
more than about 3.0%, and a water dilutability of about 1:1 to about 100:1,
preferably about
5:1 and above.
[00511 Melamine, if present in the second copolymer, can also be provided in
many forms.
For example, solid melamine, such as prill and/or melamine solutions can be
used. Although
melamine is specifically referred to, the melamine can be totally or partially
replaced with
other aminotriazine compounds. Other suitable aminotriazine compounds can
include, but
arc not limited to, substituted melamines, cycloaliphatic guanamines, or
combinations
thereof. Substituted melamines include the alkyl melamines and aryl melamines
that can be
mono-, di-, or tri-substituted. In the alkyl substituted melamines, each alkyl
group can
contain 1-6 carbon atoms and, preferably 1-4 carbon atoms. Illustrative
examples of the
alkyl-substituted melamines can include, but are not limited to, monomethyl
melamine,
dimethyl melamine, trimethyl melamine, monoethyl melamine, and 1-methy1-3-
propy1-5-
butyl melamine. In the aryl-substituted melamines, each aryl group can contain
1-2 phenyl
radicals and, preferably, one phenyl radical. Illustrative examples of aryl-
substituted
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melamines can include, but are not limited to, monophenyl melamine and
diphenyl
melamine. Any of the cycloaliphatic guanamines can also be used. Suitable
cycloaliphatic
guanamines can include those having 15 or less carbon atoms. Illustrative
cycloaliphatic
guanamines can include, but are not limited to, tetrahydrobenzoguanamine,
hexahydrobenzoguanamine, 3 -methyl-tetrahydrob enzoguan amine, 3-
methylhexahydrobenzoguanamine, 3,4-dimethy1-1,2,5,6-tetrahydrobenzoguanamine,
and 3,4-
dimethylhexahydrobenzoguanamine and mixtures thereof. Mixtures of
aminotriazine
compounds can include, for example, melamine and an alkyl-substituted
melamine, such as
dimethyl melamine, or melamine and a cycloaliphatic guanamine, such as
tetrahydrobenzoguanamine.
[0052] The phenol component, if present in the second copolymer, can include a
variety of
substituted phenolic compounds, unsubstituted phenolic compounds, or any
combination of
substituted and/or unsubstituted phenolic compounds. For example, the phenol
component
can be phenol itself (i.e., mono-hydroxy benzene). Examples of substituted
phenols can
include, but are not limited to, alkyl-substituted phenols such as the cresols
and xylenols;
cycloalkyl-substituted phenols such as cyclohexyl phenol; alkenyl-substituted
phenols; aryl-
substituted phenols such as p-phenyl phenol; alkoxy-substituted phenols such
as 3,5-
dimethyoxyphenol; aryloxy phenols such as p-phenoxy phenol; and halogen-
substituted
phenols such as p-chlorophenol. Dihydric
phenols such as catechol, resorcinol,
hydroquinone, bisphenol A and bisphenol F also can also be used. In
particular, the phenol
component can be selected from the group consisting of phenol; alkyl-
substituted phenols
such as the cresols and xylenols; cycloalkyl-substituted phenols such as
cyclohexyl phenol;
alkenyl-substituted phenols; aryl-substituted phenols such as p-phenyl phenol;
alkoxy-
substituted phenols such as 3,5-dimethyoxyphenol; aryloxy phenols such as p-
phenoxy
phenol; halogen-substituted phenols such as p-ehlorophenol; catechol,
hydroquinone,
bisphenol A and bisphenol F. Preferably, about 95 wt% or more of the phenol
component
comprises phenol (monohydroxybenzene).
[0053] The resorcinol component, if present in the second copolymer, can be
provided in a
variety of forms. For example, the resorcinol component can be provided as a
white/off-
white solid or flake and/or the resorcinol component can be heated and
supplied as a liquid.
Any form of the resorcinol can be used with any form of the aldehyde component
to make the
resorcinol-aldehyde copolymer. The resorcinol component can be resorcinol
itself (i.e.,
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Benzene-1,3-diol). Suitable resorcinol compounds can also be described as
substituted
phenols. The solids component of a liquid resorcinol-formaldehyde copolymer
can range
from about 45 wt% to about 75 wt%. Liquid resorcinol-formaldehyde copolymers
can have a
Brookfield viscosity at 25 C that varies widely, e.g., from about 200 cP to
about 20,000 cP.
Liquid resorcinol copolymers typically have a dark amber color.
[0054] Illustrative acrylic acid based copolymers can include, but are not
limited to,
copolymers of acrylic acid and one or more unsaturated carboxylic acid
monomers,
copolymers of acrylic acid and one or more hydroxyl containing unsaturated
monomers,
copolymers of acrylic acid and one or more vinyl derived units, or any
combination thereof.
Suitable unsaturated carboxylic acid monomers can include, but are not limited
to, aconitic
acid, itaconic acid, maleic acid, methacrylic acid, an adduct (ester) of
citric acid and maleic
acid, crotonic acid, isocrotonic acid, citraconic acid, fumaric acid, or any
combination
thereof Other suitable unsaturated carboxylic acid monomers can include
compounds that
are capable of presenting carboxylic moieties during the subsequent curing
reaction such as
maleic anhydride. Suitable hydroxyl containing unsaturated monomers can
include, but are
not limited to, ally' lactate, hydroxyethyl acrylate and hydroxyethyl
methacrylate (hereinafter
identified together as hydroxyethyl (meth)acrylate), hydroxypropyl
(meth)acrylate, and
hydroxyalkyl allyl eithers such as 2-allyloxy ethanol, and the like. The
unsaturated hydroxyl
monomer can also include compounds that are capable of presenting hydroxyl
moieties
during the subsequent curing reaction such as vinyl acetate (vinyl alcohol),
glycidyl
(meth)acrylate, allyl glycidyl ether, and allyl glycidol. Suitable vinyl
derived units can
include, but arc not limited to, styrene, alpha methyl styrene, methyl
acrylate,
methyl(meth)acrylate, ethyl acrylate, methyl ethyl acrylate, butyl acrylate,
or any
combination thereof
[0055] Illustrative second copolymers can include, but are not limited to,
urea-formaldehyde
("UF"), phenol-formaldehyde ("PF"), melamine-formaldehyde ("MF"), resorcinol-
formaldehyde ("RF"), styrene-acrylic acid; acrylic acid maleic acid copolymer,
or any
combination thereof Combinations of amino-aldehyde copolymers can include, for
example,
melamine-urea-formaldehyde ("MUF"), phenol-urea-formaldehyde ("PUF"), phenol-
melamine-formaldehyde ("PMF"), phenol-resorcinol-formaldehyde ("PRF"), and the
like. As
such, the term "second copolymer," as used herein, can be or include polymers
derived from
two or more monomers. In another example, the second copolymer can include a
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combination of an amino-aldehyde copolymer and/or a phenol-aldehyde copolymer
and a
polyacrylic acid, for example, urea-formaldehyde-polyacrylic acid, melamine-
formaldehyde-
polyacrylic acid, phenol-formaldehyde-polyacrylic acid, and the like.
[0056] In one or more embodiments, the second copolymer can be present in the
binder
composition in an amount ranging from about 1 wt% to about 99 wt%, based on
the total
weight of the first copolymer and the second copolymer. For example, the
second copolymer
can be present in an amount ranging from a low of about 5 wt%, about 15 wt%,
about 25
wt%, or about 35 wt% to a high of about 65 wt%, about 75 wt%, about 85 wt%, or
about 95
wt%, based on the total weight of the first copolymer and the second
copolymer. When two
or more polymers are combined to provide the second copolymer, the two or more
polymers
can be present in any amount. For example, a second copolymer containing
phenol-
formaldehyde and urea-formaldehyde can include from about 1 wt% to about 99
wt% of the
phenol-formaldehyde and from about 1 wt% to about 99 wt% of the urea-
formaldehyde,
based on the total weight of the second copolymer.
[0057] The solids of the second copolymer can range from 1 wt% to about 80
wt%. For
example, the second copolymer can have a solids concentration ranging from a
low of about
1 wt%, about 5 wt%, about 10 wt% or about 15 wt% to a high of about 30 wt%,
about 40
wt%, about 50 wt%, about 60 wt%, about 70 wt%, or about 75 wt%.
[0058] The second copolymer and the first copolymer reacted with the one or
more base
compounds can be combined with one another to produce another binder
composition. Such
binder composition can include about 0.1 wt% to about 99.9 wt% of the first
copolymer and
conversely about 99.9 wt% to about 0.1 wt% of the second copolymer. For
example, the first
copolymer can be present in an amount ranging from a low of about 1 wt%, about
5 wt%,
about 10 wt%, about 15 wt%, about 20 wt%, about 25 wt% about 30 wt%, about 35
wt%,
about 40 wt%, or about 45 wt% to a high of about 60 wt%, about 65 wt%, about
70 wt%,
about 75 wt%, about 80 wt%, about 85 wt%, about 90 wt%, about 95 wt%, or about
99 wt%,
based on the combined weight of the first and second copolymer. In another
example, the
second copolymer can be present in the binder composition in an amount ranging
from a low
of about 1 wt%, about 5 wt%, about 10 wt%, about 15 wt%, about 20 wt%, about
25 wt%
about 30 wt%, about 35 wt%, about 40 wt%, or about 45 wt% to a high of about
60 wt%,
about 65 wt%, about 70 wt%, about 75 wt%, about 80 wt%, about 85 wt%, about 90
wt%,
about 95 wt%, or about 99 wt%, based on the combined weight of the first and
second
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copolymer. In another example, the binder composition can include about 1 wt%
to about 99
wt%, or about 1 wt% to about 15 wt%, or about 15 wt% to about 35 wt%, or about
35 wt% to
about 65 wt%, or about 65 wt% about 95 wt%, or about 85 wt% to about 99 wt%,
or about
45 wt% to about 55 wt% of the first copolymer, based on the combined weight of
the first
and second copolymers. In another example, the binder composition can include
about 5
wt% first copolymer and about 95 wt% second copolymer, or about 10 wt% first
copolymer
and about 90 wt% second copolymer, or about 20 wt% first copolymer and about
80 wt%
second copolymer, or about 25 wt% first copolymer and about 75 wt% second
copolymer, or
about 30 wt% first copolymer and about 70 wt% second copolymer, or about 40
wt% first
copolymer and about 60 wt% second copolymer, or about 50 wt% first copolymer
and about
50 wt% second copolymer, or about 60 wt% first copolymer and about 40 wt%
second
copolymer, or about 70 wt% first copolymer and about 30 wt% second copolymer,
or about
75 wt% first copolymer and about 25 wt% second copolymer, or about 80 wt%
first
copolymer and about 20 wt% second copolymer, or about 90 wt% first copolymer
and about
wt% second copolymer, or about 95 wt% first copolymer and about 5 wt% second
copolymer, based on the combined weight of the first and second copolymers.
[0059] The binder composition that includes the first and second copolymers
can have a pH
ranging from a low of about 4, about 4.5, about 5, or about 5.5 to a high of
about 7, about 8,
about 9, or about 10. For example, the binder composition that includes the
first and second
copolymers can have a pH of about 5 to about 7, about 5.5 to about 6.5, or
about 5.7 to about
6.3. The binder composition that includes the first and second copolymers can
have a
viscosity ranging from a low of about 50 cP, about 100 cP, about 200, cP,
about 300 cP,
about 500 cP, about 750 cP, about 900 cP, about 1,100 cP, about 1,300 cP,
about 1,500 cP,
about 1,700 cP, about 2,000 cP, about 2,250 cP, or about 2,500 cP to a high of
about 5,000
cP, about 8,000 cP, about 10,000 cP, about 13,000 cP, about 15,000 cP, about
17,000 cP, or
about 20,000 cP.
100601 The binder composition that includes the first copolymer modified by
reaction with
the one or more base compounds and the second copolymer can be mixed or
combined with a
liquid medium. The liquid medium can be as discussed and described above. The
binder
composition that includes the first and second copolymers can have a solids
concentration
ranging from about 0.1 wt% to about 75 wt%, based on the total weight of the
binder
composition. For example, the amount of liquid medium combined with the first
copolymer
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and the second copolymer can be sufficient to produce a binder composition
having a solids
concentration ranging from a low of about 1 wt%, about 5 wt%, about 10 wt% or
about 15
wt% or about 20 wt% to a high of about 30 wt%, about 40 wt%, about 50 wt%,
about 60
wt%, about 70 wt%, or about 75 wt%, based on a total weight of the binder
composition. In
at least one example, a sufficient amount of water, e.g. fresh water or
process water, can be
combined with the first copolymer and second copolymer to provide a binder
composition
having a solids concentration ranging from about 1 wt% about 65 wt%, about 5
wt% to about
40 wt%, about 10 wt /0 to about 30 wt%, about 15 wt% to about 45 wt%, about 20
wt% to
about 60 wt%, about 45 wt% to about 55 wt%, or about 40 wt% to about 60 wt%,
based on
the total weight of the binder composition.
[0061] in one or more embodiments above or elsewhere herein, the binder
composition can
include one or more carbohydrates, one or more polyols, or any combination
thereof.
Suitable polyols can be as discussed and described above. As used therein, the
term
"carbohydrate"' refers to compounds haying the formula Cm(H20),; that is,
compounds that
include carbon, hydrogen and oxygen, with a hydrogen to oxygen (H:0) atom
ratio of 2:1.
Structurally, the term "carbohydrate" refers to polyhydroxy aldehydes and
polyhydroxy
ketones. The one or more carbohydrates can include one or more
monosaccharides,
disaccharides, oligosaccharides, polysaccharides, or any combinations thereof.
In one or
more embodiments, the one or more carbohydrates can include one or more aldose
sugars. In
one or more embodiments, the monosaccharide can be or include D-Glucose
(dextrose
monohydrate), L-Glucose, or a combination thereof. Other carbohydrate aldose
sugars can
include, but are not limited to, glyceraldehyde, erythrose, threose, ribose,
deoxyribose,
arabinose, xylose, lyxose, allose, altrose, gulose, mannose, idose, galactose,
talose, and any
combination thereof. The carbohydrate can also be or include one or more
reduced or
modified starches such as dextrin, maltodextrin, and oxidized maltodextrins.
[0062] The one or more carbohydrates and/or polyols can be present in an
amount ranging
from a low of about 1 wt%, about 3 wt%, or about 5 wt% to a high of about 70
wt%, about 80
wt%, or about 90 wt%, based on the total weight of the binder composition. In
one or more
embodiment, the binder composition can include from about 5 wt% to about 50
wt%
carbohydrates and/or polyols, based on the total weight of the binder
composition. In one or
more embodiments, the binder composition can include from about 7.5 wt% to
about 15 wt%
carbohydrates and/or polyols, based on the total weight of the binder
composition. In one or
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more embodiments, the binder composition can include from about 5 wt% to about
30 wt%
carbohydrates and/or polyols, based on the total weight of the binder
composition.
[0063] When the one or more carbohydrates and/or polyols, the second
copolymer, and the
first copolymer are present in the binder composition, the combined amount of
the
carbohydrates and/or polyols and second copolymer can range from a low of
about 1 wt%,
about 5 wt%, or about 10 wt% to a high of about 80 wt%, about 90 wt%, or about
99 wt%,
based on the weight of the binder composition. For example, the binder
composition can
include from about 10 wt% to about 90 wt% of the first copolymer and from
about 10 wt% to
about 90 wt% combined carbohydrates and/or polyols and the second copolymer.
The
amount of the carbohydrates and/or polyols can range from about 1 wt% to about
99 wt% and
the amount of the second copolymer can range from about I wt% to about 99 wt%,
based on
the combined weight of the carbohydrates and/or polyols and the second
copolymer. In at
least one specific embodiment, the binder composition can include from about
10 wt% to
about 29 wt% of the first copolymer; about 1 wt% to about 98 wt% carbohydrates
and/or
polyols; and about 1 wt% to about 98 wt% second copolymer, based on the
combined weight
of the first copolymer, the carbohydrates and/or polyols, and the second
copolymer. In
another example, the binder composition can include from about 0.1 wt% to
about 99.9 wt%
of the first copolymer, from about 0.1 wt% to about 99.9 wt% of the second
copolymer, and
from about 1 wt% to about 60 wt% of the carbohydrates and/or polyols, based on
the
combined weight of the first copolymer, the second copolymer, and the
carbohydrates and/or
polyols. In another example, the binder composition can include from about 70
wt% to about
90 wt% of the first copolymer, from about 10 wt% to about 30 wt% of the second
copolymer,
and from about 1 wt% to about 50 wt% of the carbohydrates and/or polyols,
based on the
combined weight of the first copolymer, the second copolymer, and the
carbohydrates and/or
polyols. In another example, the binder composition can include from about 10
wt% to about
30 wt% of the first copolymer, from about 70 wt% to about 90 wt% of the second
copolymer,
and from about 1 wt% to about 50 wt% of the carbohydrates and/or polyols,
based on the
combined weight of the first copolymer, the second copolymer, and the
carbohydrates and/or
polyols. In another example, the binder composition can include from about 40
wt% to about
60 wt% of the first copolymer, from about 40 wt% to about 60 wt% of the second
copolymer,
and from about 1 wt% to about 50 wt% of the carbohydrates and/or polyols,
based on the
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combined weight of the first copolymer, the second copolymer, and the
carbohydrates and/or
polyols.
[0064] In at least one specific embodiment, the binder composition can include
a copolymer
of maleic anhydride and one or more vinyl aromatic derived units, and one or
more amines.
Such binder composition can include about 99.5 mol% to about 99.99 mol%
copolymer and
about 0.01 mol% to about 0.5 mol% amine(s), based on the combined weight of
the
copolymer and amine(s). For example, the amine(s) can be present in an amount
ranging
from a low of about 0.01 mol%, about 0.1 mol%, or about 0.2 mol% to a high of
about 0.3
mol%, about 0.35 mol%, or about 0.4 mol%, based on the combined weight of the
copolymer
and amine(s). In one or more embodiments, the binder composition can include
less than
about 15 wt%, less than about 10 wt%, less than about 7 wt%, less than about 5
wt%, less
than about 3 wt%, less than about 1 wt%, or less than about 0.5 wt%
monoethanolamine,
based on the combined weight of the amines in the binder composition. For
example, the
binder composition can include about 14 wt% monoethanolamine and about 86 wt%
triethanolamine or other amine(s), based on the total weight of the amines in
the binder
composition.
[0065] In at least one specific embodiment, the binder composition can include
the first
copolymer, e.g., a copolymer of maleic anhydride and one or more vinyl
aromatic derived
units and one or more amines, and the second copolymer. Such binder
composition can
include about 1 wt% to about 99 wt% of the first copolymer, about 0.05 wt% to
about 0.5
wt% of the amine(s), and about 1 wt% to about 99 wt% of the second copolymer,
based on
the combined weight of the first copolymer, amine(s), and second copolymer.
For example,
the first copolymer can be present in an amount ranging from a low of about 10
wt%, about
20 wt%, about 30 wt%, or about 40 wt% to a high of about 60 wt%, about 70 wt%,
about 80
wt%, or about 90 wt%, based on the combined weight of the first copolymer,
amine(s), and
second copolymer. The one or more amines can be present in an amount ranging
from a low
of about 0.1 wt%, about 0.15 wt%, or about 0.2 wt% to a high of about 0.3 wt%,
about 0.35
wt%, or about 0.4 wt%, based on the combined weight of the first copolymer,
amine(s), and
second copolymer. The second copolymer can be present in an amount ranging
from a low
of about 10 wt%, about 20 wt%, about 30 wt%, or about 40 wt% to a high of
about 60 wt%,
about 70 wt%, about 80 wt%, or about 90 wt%, based on the combined weight of
the first
copolymer, amine(s), and second copolymer.
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[0066] In at least one specific embodiment, the binder composition can include
the first
copolymer, e.g., a copolymer of maleic anhydride and one or more vinyl
aromatic derived
units and one or more amines, and one or more carbohydrates and/or polyols.
Such binder
composition can include about 1 wt% to about 99 wt% of the first copolymer,
about 0.05
wt% to about 0.5 wt% of the amine(s), and about 1 wt% to about 99 wt% of the
carbohydrates and/or polyols, based on the combined weight of the first
copolymer, amine(s),
and carbohydrates and/or polyols. For example, the first copolymer can be
present in an
amount ranging from a low of about 10 wt%, about 20 wt%, about 30 wt%, or
about 40 wt%
to a high of about 60 wt%, about 70 wt%, about 80 wt%, or about 90 wt%, based
on the
combined weight of the first copolymer, amine(s), and carbohydrates and/or
polyols. The
one or more amines can be present in an amount ranging from a low of about 0.1
wt%, about
0.15 wt%, or about 0.2 wt% to a high of about 0.3 wt%, about 0.35 wt%, or
about 0.4 wt%,
based on the combined weight of the first copolymer, amine(s), and
carbohydrates and/or
polyols. The carbohydrate(s) can be present in an amount ranging from a low of
about 10
wt%, about 20 wt%, about 30 wt%, or about 40 wt% to a high of about 60 wt%,
about 70
wt%, about 80 wt%, or about 90 wt%, based on the combined weight of the first
copolymer,
amine(s), and carbohydrates and/or polyols. The polyols can be present in an
amount ranging
from a low of about 10 wt%, about 20 wt%, about 30 wt%, or about 40 wt% to a
high of
about 60 wt%, about 70 wt%, about 80 wt%, or about 90 wt%, based on the
combined weight
of the first copolymer, amine(s), and carbohydrate(s) and/or polyol(s).
[0067] In at least one specific embodiment, the binder composition can include
the first
copolymer, e.g., a copolymer of maleic anhydride and one or more vinyl
aromatic derived
units and one or more amines, and one or more carbohydrates and/or polyols,
and the second
copolymer. Such binder composition can include about 1 wt% to about 98 wt% of
the first
copolymer, about 0.05 wt% to about 0.5 wt% of the amine(s), about 1 wt% to
about 98 wt%
of the carbohydrate(s) and/or polyol(s), and about 1 wt% to about 98 wt% of
the second
copolymer, based on the combined weight of the first copolymer, amine(s),
carbohydrate(s)
and/or polyol(s), and second copolymer. For example, the first copolymer can
be present in
an amount ranging from a low of about 10 wt%, about 20 wt%, or about 30 wt%,
or about 40
wt% to a high of about 60 wt%, about 70 wt%, about 80 wt%, or about 90 wt%,
based on the
combined weight of the first copolymer, amine(s), carbohydrate(s) and/or
polyol(s), and
second copolymer. The one or more amines can be present in an amount ranging
from a low
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of about 0.1 wt%, about 0.15 wt%, or about 0.2 wt% to a high of about 0.3 wt%,
about 0.35
wt%, or about 0.4 wt%, based on the combined weight of the first copolymer,
amine(s),
carbohydrate(s) and/or polyol(s), and second copolymer. The one or more
carbohydrates can
be present in an amount ranging from a low of about 10 wt%, about 20 wt%,
about 30 wt%,
or about 40 wt% to a high of about 60 wt%, about 70 wt%, about 80 wt%, or
about 90 wt%,
based on the combined weight of the first copolymer, amine(s), carbohydrate(s)
and/or
polyol(s), and second copolymer. The one or more polyols can be present in an
amount
ranging from a low of about 10 wt%, about 20 wt%, about 30 wt%, or about 40
wt% to a high
of about 60 wt%, about 70 wt%, about 80 wt%, or about 90 wt%, based on the
combined
weight of the first copolymer, amine(s), carbohydrate(s) and/or polyol(s), and
second
copolymer. The second copolymer can be present in an amount ranging from a low
of about
wt%, about 20 wt%, about 30 wt%, or about 40 wt% to a high of about 60 wt%,
about 70
wt%, about 80 wt%, or about 90 wt%, based on the combined weight of the first
copolymer,
amine(s), carbohydrate(s) and/or polyol(s), and second copolymer.
[0068] In at least one specific embodiment, the binder composition can include
one or more
carbohydrates and/or polyols and the second copolymer. Such binder composition
can
include about 1 wt% to about 99 wt% of the one or more carbohydrates and/or
polyols and
from about 1 wt% to about 99 wt% of the second copolymer, based on the
combined weight
of the carbohydrates and/or polyols and the second copolymers. For example,
the one or
more carbohydrates can be present in an amount ranging from a low of about 3
wt%, about 5
wt%, or about 10 wt% to a high of about 25 wt%, about 35 wt%, or about 45 wt%,
based on
the combined weight of the carbohydrates and/or polyols and the second
copolymer. In
another example, the one or more polyols can be present in an amount ranging
from a low of
about 3 wt%, about 5 wt%, or about 10 wt% to a high of about 25 wt%, about 35
wt%, or
about 45 wt%, based on the combined weight of the carbohydrates and/or polyols
and the
second copolymer. The second copolymer can be present in an amount ranging
from a low
of about 55 wt%, about 65 wt%, or about 75 wt% to a high of about 90 wt%,
about 95 wt%,
or about 97 wt%, based on the combined weight of the carbohydrates and/or
polyols and the
second copolymer.
[0069] In at least one specific embodiment, the binder composition can be a no-
added
formaldehyde binder composition. As used herein, the term "no-added
formaldehyde" refers
to a binder composition that does not include intentionally added
formaldehyde. In order to
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minimize the formaldehyde content of the composition additives that do not
contain
formaldehyde and/or do not generate formaldehyde during drying and/or curing
can be used.
The term "no-added formaldehyde" can also refer to a binder composition
formulated with no
added formaldehyde as part of the resin cross linking structure that meets the
performance
standard defined in Section 93120.3 of the California Air Resources Board
("CARB") Air
Toxic Control Measure ("ATCM"). Illustrative no-added formaldehyde binder
compositions
can include, but are not limited to, binders made from soy, polyvinyl acetate,
or methylene
diisocyanate.
[0070] The binder composition can be applied as a dilute aqueous solution to a
plurality of
fibers and at least partially cured to produce a fiber product, e.g., a
fiberglass mat. The binder
composition can be applied as a dilute aqueous solution to a plurality of
fibers and cured, e.g.,
fully cured, to produce a fiber product, e.g., a fiberglass mat. In at least
one embodiment, the
aqueous solution can have a pH ranging from about 3 to about 12. For example,
the pH can
range from a low of about 4, 5, 6, or 7 to a high of about 8, 9, 10, or 11. In
another example,
the aqueous solution can have a pH of about 5 or more, about 6 or more, about
7 or more, or
about 8 or more. The pH of the aqueous solution can be adjusted by adding any
suitable base
or alkaline compound, e.g., one or more organic bases, inorganic bases, or any
combination
thereof. Suitable bases or alkaline compounds can include, but are not limited
to, hydroxides,
carbonates, ammonia, amines, amides, or any combination thereof. Illustrative
hydroxides,
carbonates, and amines can include those discussed and described above or
elsewhere herein.
[0071] Fiberglass products may be used by themselves or incorporated into a
variety of
products. For example, fiberglass products can be used as or incorporated into
insulation
batts or rolls, composite flooring, asphalt roofing shingles, siding, gypsum
wall board, roving,
microglass-based substrate for printed circuit boards, battery separators,
filter stock, tape
stock, carpet backing, commercial and industrial insulation, and as
reinforcement scrim in
cementitious and non-cementitious coatings for masonry.
[0072] In one or more embodiments above or elsewhere herein, the binder
composition can
be cured or crosslinked via an esterification reaction between pendant
carboxyl groups of the
first copolymers (e.g., SMA copolymer) and when optional polyol(s) is added
both pendant
hydroxyl groups of the first copolymers (e.g., SMA copolymer) and hydroxyl
groups of the
polyol(s). Additional crosslinking may occur with any additional polyol that
may optionally
be added to the composition. A thermal process or heat can also be used to
cure the binder
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composition. For example, an oven or other heating device can be used to cure
the binder
composition.
[0073] As used herein, the terms "fiber," "fibrous," "fiberglass," "fiber
glass," "glass fibers,"
and the like arc used interchangeably and refer to materials that have an
elongated
morphology exhibiting an aspect ratio (length to thickness) of greater than
100, generally
greater than 500, and often greater than 1000. Indeed, an aspect ratio of over
10,000 is
possible. Suitable fibers can be glass fibers, natural fibers, synthetic
fibers, mineral fibers,
ceramic fibers, metal fibers, carbon fibers, or any combination thereof.
Illustrative glass
fibers can include, but are not limited to, A-type glass fibers, C-type glass
fibers, E-type glass
fibers, S-type glass fibers, ECR-type glass fibers, wool glass fibers, and any
combination
thereof. The term "natural fibers," as used herein refers to plant fibers
extracted from any
part of a plant, including, but not limited to, the stem, seeds, leaves,
roots, or phloem.
Illustrative natural fibers can include, but are not limited to, cotton, jute,
bamboo, ramic,
bagasse, hemp, coir, linen, kenaf, sisal, flax, henequen, and any combination
thereof.
Illustrative synthetic fibers can include, but arc not limited to, synthetic
polymers, such as
polyester, polyamide, aramid, and any combination thereof. In at least one
specific
embodiment, the fibers can be glass fibers that are wet use chopped strand
glass fibers
("WUCS"). Wet use chopped strand glass fibers can be formed by conventional
processes
known in the art. The WUCS can have a moisture content ranging from a low of
about 5%,
about 8%, or about 10% to a high of about 20%, about 25%, or about 30%.
[0074] Prior to using the fibers to make a fiberglass product, the fibers can
be allowed to age
for a period of time. For example, the fibers can be aged for a period of a
few hours to
several weeks before being used to make a fiberglass product. For fiberglass
mat products
the fibers can typically be aged for about 3 to about 30 days. Ageing the
fibers includes
simply storing the fibers at room temperature for the desired amount of time
prior to being
used in making a fiberglass product.
[0075] In one or more embodiments, a method for binding loosely associated,
non-woven
mat or blanket of fibers can include, but is not limited to (1) contacting the
fibers with the
binder composition and (2) heating the curable binder composition to an
elevated
temperature, which temperature is sufficient to at least partially cure the
binder composition.
Preferably, the binder composition is cured at a temperature ranging from
about 75 C to
about 300 C, usually at a temperature between about 100 C and up to a
temperature of about
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250 C. The binder composition can be cured at an elevated temperature for a
time ranging
from about 1 second to about 15 minutes. The particular curing time can
depend, at least in
part, on the type of oven or other heating device design and/or production or
line speed.
[0076] In preparing the binder composition, the first copolymer, e.g., maleic
anhydride and
one or more vinyl aromatic derived units, can be initially modified by
reaction with one or
more amines, for example an alkanolamine. The modification can be accomplished
by
mixing the first copolymer, which usually is supplied in flake or powder form,
with the
amine(s). The amine-modified copolymer can then be diluted with water.
Usually, the
modification is accomplished by mixing the first copolymer with an aqueous
solution of the
amine(s). Alternatively, initial mixing of the first copolymer and amine(s)
can be in the
absence of water (neat) with subsequent addition of water and optionally
additional amine(s).
[0077] The amine(s) can be provided in an amount relative to the first
copolymer, sufficient
to provide at least 0.05 moles of amine moiety per mole of the one or more
unsaturated
carboxylic acids and/or the one or more unsaturated carboxylic anhydrides in
the first
copolymer. For example, the amine(s) can be present in an amount, relative to
the first
copolymer, to provide at least 0.1, or 0.3, or 0.5, or 0.7, or 0.9, or 1.1, or
1.3, or 1.5, or 1.7, or
1.9 moles of amine moiety per mole of the one or more unsaturated carboxylic
acids and/or
the one or more unsaturated carboxylic anhydrides in the first copolymer. In
one or more
embodiments, the amount of amine moieties can be less than about 2 moles of
amine moieties
for each mole of the one or more unsaturated carboxylic acids and/or the one
or more
unsaturated carboxylic anhydrides in the first copolymer or less than about 1
mole of amine
moieties for each mole of the one or more unsaturated carboxylic acids and/or
one or more
unsaturated carboxylic anhydrides. In one or more embodiments, the amine(s)
can be present
in an amount relative to the first copolymer, sufficient to provide between
about 0.05 mole to
about 0.4 mole of amine moiety per mole of the one or more unsaturated
carboxylic acids
and/or one or more unsaturated carboxylic anhydrides in the copolymer.
[0078] While an aqueous-based reaction between the first copolymer and the
amine(s) can
occur at an ambient temperature, usually to minimize the duration of this
procedure it can be
preferred to conduct the reaction at a temperature in the range of about 40 C
to about 125 C
or higher. In order to minimize the amount of water that accompanies the
binder composition
during shipment and storage, it can be preferable to use a concentrated
solution of the
amine(s) for modifying the first copolymer. In any event, the solution of the
amine(s) used
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for preparing the binder composition will usually contain between about 10 and
about 99.9
weight % of the amine(s).
[00791 Initially on mixing the first copolymer with the amine(s) a reaction
between the one or
more unsaturated carboxylic acids and/or the one or more unsaturated
carboxylic anhydrides
of the first copolymer and the amine group of alkanolamincs and/or monoethanol
amines, for
example, results is the formation of a hydroxyl terminated amide group and a
free carboxyl
group. Some of these adjacent groups may also react to form a hydroxyl-
terminated imide
group. Formation of the imide is favored under normal heating conditions in
the range from
about 70 C to about 200 C. Imide formation may be advantageous as it provides
a
copolymer with additional hydrophobicity that may further augment the wet
tensile strength
properties of fiber products cured with the binder composition.
[0080] The binder composition can have a pH of about 5 or more, about 7 or
more, and still
about 9 or more. In order to increase the pH of the binder composition one or
more bases or
"base compounds" can be added. A preferred base compound for this purpose can
be or
include ammonia. Other suitable base compounds can include amines, e.g.,
primary,
secondary, and tertiary amines and polyamines, sodium hydroxide ("NaOH"),
potassium
hydroxide ("KOH"), and other basic compounds. Furthermore, the addition of,
for example,
a secondary alkanolaminc, a tertiary alkanolamine, and mixtures thereof can
also serve as a
source of polyols for participating in cross-linking reactions that cause the
binder
composition to cure. The addition of, for example, one or more polyamines can
also increase
the cross-linking reactions.
Illustrative polyamines can include diethylenetriamine
("DETA"), triethylenetetramine ("TETA"), tetraethylenepentamine ("TEPA"), and
any
combination thereof.
[0081] The amount of polyol in the composition, whether or not supplied in
whole or in part
by an alkanolamine, should preferably provide a mole ratio of --COON
contributed by the
first copolymer (and any other optional polyacid in the composition) to --OH
contributed
both by the first copolymer and by any additional polyol component (i.e., the -
-COOH:--OH
ratio of the composition) in the range of about 10:1 to about 1:10, most often
in the range of
about 5:1 to about 1:5 and most usually in the range of about 2:1 to about
1:2. This mole
ratio can be determined by calculating the ratio of the number of moles of the
modified
copolymer multiplied by its average --COOH functionality (plus any other
polyacid
component) to the sum of the number of moles of the modified copolymer
multiplied by its
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average --OH functionality and the number of moles of the polyol component(s)
multiplied
by its (their) average functionality. Preferably, the mole ratio of --COOH to -
-OH in the
composition is in the range of about 2:1 to about 1:2 and more preferably in
the range of
about 1.5:1 to about 1:1.5.
10082] In one or more embodiments, other additives for augmenting the cross-
linking of the
binder composition can be introduced thereto. For example, urea and polyamino
compounds,
both synthetic and natural (e.g., protein sources such as soy) can be
introduced to the binder
composition for augmenting the cross-linking.
[0083] As noted above, in the making of non-woven fiber products, such as
fiberglass mat,
the binder composition can be formulated into a dilute aqueous solution and
then applied,
such as by a curtain coating, spraying, or dipping, onto fibers, such as glass
fibers. The
aqueous solution can be fresh water, process water, or a combination thereof.
Binder
compositions containing somewhere between about 1 wt% and about 50 wt% solids
are
typically used for making fiber products, including glass fiber products. For
example, the
aqueous binder composition can have a solids concentration ranging from a low
of about 10
wt%, about 13 wt%, about 15 wt%, or about 18 wt% to a high of about 22 wt%,
about 26
wt%, about 30 wt%, or about 33 wt%.
[00841 The amount of binder composition applied to the fiberglass product,
e.g., a fiberglass
mat product, can vary considerably. Loadings typically can range from about 3
wt% to about
45 wt%, about 10 wt% to about 40 wt%, or from about 15 wt% to about 30 wt%, of
nonvolatile binder composition based on the dry weight of the bonded
fiberglass product.
For inorganic fibrous mats, the amount of binder composition applied to a
fiberglass product
can normally be confirmed by measuring the percent loss on ignition ("LOP') of
the fiber mat
product.
[0085] The aqueous solution of the modified copolymer can be blended with
other additives
or ingredients commonly used in binder compositions for preparing fiber
products and diluted
with additional water to a desired concentration which is readily applied onto
the fibers, such
as by a curtain coater. Illustrative additives can include, but are not
limited to, dispersants,
biocides, viscosity modifiers, pH adjusters, coupling agents, surfactants,
lubricants,
defoamers, and the like. For example, the binder composition can be added to
an aqueous
solution ("white water") of polyacrylamide ("PAA"), amine oxide ("AO"),
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hydroxyethylcellulose ("HEC"), or any combination thereof. In another example,
a coupling
agent (e.g., a silane coupling agent, such as an organo silicon oil) can also
be added to the
solution.
[0086] The binder composition may be prepared by combining the aqueous
solution of the
copolymer and the additives in a relatively easy mixing procedure. The mixing
procedure
can be carried out at ambient temperature or at a temperature greater than
ambient
temperature, for example about 50 C. The binder composition can be used
immediately or
stored for a period of time and may be diluted with water to a concentration
suitable for the
desired method of application, such as by a curtain coater onto the glass
fibers.
[0087] Fiberglass mats can be manufactured in a wet-laid or dry-laid process.
In a wet-laid
process, chopped bundles of fibers, having suitable length and diameter, can
be introduced to
an aqueous dispersant medium to produce an aqueous fiber slurry, known in the
art as "white
water." The white water can typically contain about 0.5 wt% fibers. The fibers
can have a
diameter ranging from a low of about 0.5 1.1m, about 5 gm, about 10 gm, or
about 20 gm to a
high of about 30 gm, about 35 gm, about 40 gm, about 45 gm, or about 50 gm,
for example.
The fibers can have a length ranging from a low of about 5 mm, about 10 mm,
about 15 mm,
or about 25 mm to a high of about 50 mm, about 70 mm, about 100 mm, or about
130 mm,
for example. The fibers can be sized or unsized and wet or dry, as long as the
fibers can be
suitably dispersed within the aqueous fiber slurry.
[0088] The dispersing agent(s) can be present in an amount ranging from about
10 ppm to
about 8,000 ppm, about 100 ppm to about 5,000 ppm, or from about 200 ppm to
about 1,000
ppm. The introduction of one or more viscosity modifiers can reduce settling
time of the
fibers and can improve the dispersion of the fibers in the aqueous solution.
The amount of
viscosity modifier used can be effective to provide the viscosity needed to
suspend the fibers
in the white water as needed to form the wet laid fiber product. The optional
viscosity
modifier(s) can be introduced in an amount ranging from a low of about 1 cP,
about 1.5 cP,
or about 2 cP to a high of about 8 cP, about 12 cP, or about 15 cP (Brookfield
Viscometer
measured at 25 C). For example, optional viscosity modifier(s) can be
introduced in an
amount ranging from about 1 cP to about 12 cP, about 2 cP to about 10 cP, or
about 2 cP to
about 6 cP. In one or more embodiments, the fiber slurry can include from
about 0.03 wt% to
about 25 wt% solids. The fiber slurry can be agitated to produce a uniform
dispersion of
fibers having a suitable consistency.
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[0089] The fiber slurry, diluted or undiluted, can be introduced to a mat-
forming machine
that can include a mat forming screen, e.g., a wire screen or sheet of fabric,
which can form a
fiber product and can allow excess water to drain therefrom, thereby forming a
wet or damp
fiber mat. The fibers can be collected on the screen in the form of a wet
fiber mat and excess
water is removed by gravity and/or by vacuum assist. The removal of excess
water via
vacuum assist can include one or a series of vacuums.
[0090] As discussed above, a curable binder composition can be formulated as a
liquid and
applied onto the dewatered wet fiber mat. Application of the binder
composition can be
accomplished by any conventional means, such as by soaking the mat in an
excess of binder
solution or suspension, a falling film or curtain coater, dipping, or the
like. The binder
composition can include, for example, from about 5 wt% to about 45 wt% solids.
Excess
binder composition can be removed, for example under vacuum.
100911 The aqueous binder composition, after it is applied to the fibers, can
be at least
partially cured. For example, the fiberglass product can be heated to effect
final drying and
curing. The duration and temperature of heating can affect the rate of
processability and
handleability, degree of curing and property development of the treated
substrate. As
discussed and described above, the binder composition and fiber mixture can be
heated
sufficiently to cause the center or core of the composite product to reach a
temperature
ranging from a low of about 150 C, about 155 C, about 160 C, or about 165 C to
a high of
about 180 C, about 185 C, about 190 C, about 19.5 C, or about 199 C for a time
ranging from
a low of about 1 second, about 5 seconds, about 10 seconds, about 15 seconds
or about 20
seconds to a high of about 30 seconds, about 45 seconds, about 60 seconds,
about 90 seconds,
about 120 seconds, about 150 seconds, or about 180 seconds to produce the
composite
product.
[0092] On heating, at least a portion of any water present in the binder
composition can
evaporate, and the composition can undergo curing. These processes can take
place in
succession or simultaneously. As used herein, the terms "curing," "cured," and
similar terms
are intended to refer to the structural and/or morphological change that
occurs in the binder
composition as it is cured to cause covalent chemical reaction (crosslinking),
ionic interaction
or clustering, improved adhesion to the substrate, phase transformation or
inversion, and/or
hydrogen bonding. As used herein, the phrases "at least partially cure," "at
least partially
cured," and similar terms are intended to refer to a binder composition that
has undergone at
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least some covalent chemical reaction (crosslinking), ionic interaction or
clustering, improved
adhesion to the substrate, phase transformation or inversion, and/or hydrogen
bonding, but
may also be capable of undergoing additional covalent chemical reaction
(crosslinking), ionic
interaction or clustering, improved adhesion to the substrate, phase
transformation or
inversion, and/or hydrogen bonding.
[0093] Alternatively or in addition to heating the fiberglass product
catalytic curing can be
used to cure the fiberglass product. Catalytic curing of the fiberglass
product can include the
addition of an acid catalyst. Illustrative acid catalysts can include, but are
not limited to,
ammonium chloride or p-toluenesulfonic acid.
[0094] In one or more embodiments, the drying and curing of the binder
composition can be
conducted in two or more distinct steps. For example, the composition may be
first heated at
a temperature and for a time sufficient to substantially dry but not to
substantially cure the
binder composition and then heated for a second time at a higher temperature
and/or for a
longer period of time to effect curing (cross-linking to a thermoset
structure). Such a
preliminary procedure, referred to as "B-staging," may be used to provide a
binder-treated
product, for example, in roll form, which may at a later stage be fully cured,
with or without
forming or molding into a particular configuration, concurrent with the curing
process. This
makes it possible, for example, to use fiberglass products which can be molded
and cured
elsewhere.
[0095] The fiber mat product can be formed as a relatively thin product of
about 0.25 mm to
a relatively thick product of about 25.4 mm. Other fiberglass products can
have substantially
greater thickness. For example fiberglass insulation can have a thickness
ranging from a low
of about 5 cm, about 10 cm, about 15 cm, or about 20 cm to a high of about 30
cm, about 35
cm, about 40 cm, about 45 cm, or about 50 cm. Depending on formation
conditions, the
density of the product can also be varied from a relatively fluffy low density
product to a
higher density of about 0.096 g/cm3 to about 0.16 g/cm3 (about 6 to about 10
pounds per
cubic foot) or higher. In one or more embodiments, the fiber mat product can
have a basis
weight ranging from a low of about 0.1 pound, about 0.5 pounds, or about 0.8
pounds to a
high of about 3 pounds, about 4 pounds, or about 5 pounds per 100 square feet.
For example,
the fiber mat product can have a basis weight from about 0.6 pounds per 100
square feet to
about 2.8 pounds per 100 square feet, about 1 pound per 100 square feet to
about 2.5 pounds
per 100 square feet, or about 1.5 pounds per 100 square feet to about 2.2
pounds per 100
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square feet. In at least one specific embodiment, the fiber mat product can
have a basis
weight of about 1.2 pounds per 100 square feet, about 1.8 pounds per 100
square feet, or
about 2.4 pounds per 100 square feet.
[0096] The fibers can represent the principal material of the non-woven fiber
products, such
as a fiberglass mat product. For example, 60 wt% to about 90 wt% or about 60
wt% to about
99 wt% of the fiberglass product, based on the combined amount of binder and
fibers can be
composed of the fibers. The binder composition can be applied in an amount
such that the
cured binder constitutes from about 1 wt% to about 40 wt% of the finished
fiberglass product.
For example, the binder composition can be applied in an amount such that the
cured binder
constitutes a low from about 1 wt%, about 5 wt%, or about 10 wt% to a high of
about 15
wt%, about 20 wt%, or about 25wt% of the finished fiberglass product.
[0097] The fiberglass mat product can have a thickness ranging from a low of
about 0.25 mm
(10 mils), about 0.63 mm (25 mils), about 0.76 mm (30 mils), about 1.3 mm (50
mils), or
about 1.9 mm (75 mils) to a high of about 6.4 mm (250 mils), about 12.7 mm
(500 mils),
about 19 mm (750 mils), or about 25.4 mm (1,000 mils). For example, the
fiberglass mat
product can have a thickness of about 0.5 mm (20 mils), about 1 mm (39 mils)
about, or
about 2 mm (79 mils). in another example, the fiberglass mat product can have
a thickness
from about 0.5 mm (20 mils) to about 1.3 mm (50 mils), about 0.6 mm (25 mils)
to about 1.1
mm (45 mils), or about 0.8 mm (30 mils) to about 1 mm (40 mils).
[0098] In one or more embodiments, fiberglass mats containing one or more of
the binder
compositions disclosed herein can have an average dry tensile strength of at
least 50 lbs/3
inch; at least 75 lbs/3 inch, at least 100 lbs/3 inch, at least 110 lbs/3
inch, at least 115 lbs/3
inch, at least 120 lbs/3 inch, at least 125 lbs/3 inch, at least 130 lbs/3
inch, at least 135 lbs/3
inch, at least 140 lbs/3 inch, at least 145 lbs/3 inch, at least 150 lbs/3
inch, at least 155 lbs/3
inch, at least 160 lbs/3 inch, at least 165, lbs/3 inch, at least 170 lbs/3
inch, at least 175 lbs/3
inch, at least 180 lbs/3 inch, at least 185 lbs/3 inch, at least 190 lbs/3
inch, at least 195, or at
least 200 lbs/3 inch. For example, fiberglass mats containing one or more of
the binder
compositions disclosed herein can have an average dry tensile strength from
about 100 lbs/3
inch to about 135 lbs/3 inch, or from about 115 lbs/3 inch to about 145 lbs/3
inch, or from
about 120 lbs/3 inch to about 150. The average dry tensile strength of the
fiberglass mats can
be determined using a Thwing-Albert Tensile Tester. The average dry tensile
strength of the
fiberglass mats can be determined according to the Technical Association of
the Pulp and
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Paper Industry (TAPPI) test method - tensile strength and elongation at break
for fiber glass
mats, test method T 1009, using a 3 inch sample size.
[0099] In one or more embodiments, fiberglass mats containing one or more of
the binder
compositions disclosed herein can have an average Elmendorf tear strength of
about 275
grams force ("0"), about 300 gf, about 325 gf, about 350 gf, about 375 gf,
about 400 gf,
about 425 gf, 450 gf, about 475 gf, about 500 gf, about 525 gf, about 550 gf,
about 575 gf,
about 600 gf, about 625 gf, about 650 gf, about 675 gf, about 700 gf, about
725 gf, about 750
gf, about 775 gf, or about 800 gf. In one or more embodiments, fiberglass mats
containing
one or more of the binder compositions disclosed herein can have an average
tear strength of
at least 485 gf, at least 490 gf, at least 495 gf, at least 500 gf, at least
505 gf, at least 510 gf, at
least 515 gf, at least 520 gf, at least 525 gf, at least 530 gf, at least 535
gf, at least 540 gf, at
least 545 gf, at least 550 gf, at least 555 gf, at least 560 gf, at least 565
gf, at least 570 gf, or
at least 575 gf. In one or more embodiments, fiberglass mats containing one or
more of the
binder compositions disclosed herein can have an average tear strength ranging
from a low of
about 500 gf, about 525 gf, about 550 gf, or about 575 gf to a high of about
590 gf, about 620
gf, about 650 gf, about 700 gf, about 750 gf, about 800 gf, about 850 gf, or
about 900 gf.
[00100] In one or more embodiments, the fiberglass mats can have a basis
weight ("BW")
ranging from a low of about 1.5 lbs/100 ft2, about 1.6 lbs/100 ft2, about 1.7
lbs/100 ft2, or
about 1.8 lbs/100 ft2 to a high of about 2 lbs/100 ft2, about 2.1 lbs/100 ft2,
about 2.2 lbs/100
ft2, or about 2.3 lbs/100 ft2. For example, the fiberglass mats can have a
basis weight of
about 1.65 lbs/100 ft2, about 1.75 lbs/100 ft2, about 1.85 lbs/100 ft2, about
1.95 lbs/100 ft2, or
about 2.1 lbs/100 ft2.
[00101] In one or more embodiments, the fiberglass mats can have a percent of
hot-wet
retention ("% HW") of greater than about 50%, about 55%, about 60%, about 65%,
about
70%, about 75%, about 80%, about 85%, about 80%, or about 95%.
[00102] The binder compositions discussed and described herein can also be
applied to a
plurality of lignocellulose substrates, which can be formed into a desired
shape before or after
application of the binder composition, and the binder composition can be at
least partially
cured to produce a lignocellulose composite product. In another example, the
binder
composition can be applied to a wood or other lignocellulose based veneers
and/or substrates
and the binder composition can be at least partially cured to adhere or
otherwise bond the
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veneer(s) and/or substrate(s) to one another. In another example, a binder
composition can be
applied to a plurality lignocellulose fibers, particles, flakes, strands,
and/or the like, formed
into a mat or board, and then at least partially cured to produce a
lignocellulose composite
mat or board. The plurality of lignocellulose fibers can be randomly oriented.
[00103] The lignocellulose substrates can be contacted with the binder
composition by
spraying, coating, mixing, brushing, falling film or curtain coater, dipping,
soaking, or the
like. The lignocellulose substrates contacted with the binder composition can
be formed into
a desired shape before, during, and/or after at least partial curing of the
binder composition.
Depending on the particular product, the lignocellulose substrates contacted
with the binder
composition can be pressed before, during, and/or after the binder composition
is at least
partially cured. For example, the lignocellulose substrates contacted with the
binder
composition can be consolidated or otherwise formed into a desired shape, if
desired pressed
to a particular density and thickness, and heated to at least partially cure
the binder
composition.
1001041 The pressure applied to the furnish can depend, at least in part, on
the particular
product. For example, the amount of pressure applied in a particleboard
production process
can range from about 1 MPa to about 5 MPa or from about 2 MPa to about 4 MPa.
In
another example, the amount of pressure applied in a MDF production process
can range
from about 2 MPa to about 7 MPa or from about 3 MPa to about 6 MPa. The
temperature the
product can be heated to produce an at least partially cured product can range
from a low of
about 100 C, about 125 C, about 150 C, or about 170 C to a high of about 180
C, about
200 C, about 220 C, or about 250 C. The binder composition at the core or
center of the
product can be heated to a temperature ranging from a low of about 120 C,
about 130 C,
about 140 C, about 150 C, or about 155 C to a high of about 160 C, about 170
C, about
180 C, about 190 C, about 195 C, or about 199 C. The length of time the
pressure can be
applied can range from a low of about 15 second, about 30 seconds, about 1
minute, about 3
minutes, about 5 minutes, or about 7 minutes to a high of about 10 minutes,
about 15
minutes, about 20 minutes, about 30 minutes, about 1 hour, about 2 hours, or
more, which
can depend, at least in part, on the particular product and/or the particular
dimensions, e.g.,
thickness of the product. For example, the length of time the pressure and/or
heat can be
applied to the furnish can range from about 30 seconds to about 10 minutes,
about 30 seconds
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to about 2 minutes, about 1 minute to about 3 minutes, about 1.5 minutes to
about 4 minutes,
or about 45 seconds to about 3.5 minutes.
[00105] The amount of the binder composition applied to the lignocellulose
substrates can
range from a low of about 1 wt%, about 2 wt%, about 3 wt%, about 4 wt%, about
5 wt% or
about 6 wt% to a high of about 10 wt%, about 12 wt%, about 15 wt%, or about 20
wt%,
based on dry a weight of the lignocellulose substrates. For example, a
composite product of
the lignocellulose substrates can contain from about 5 wt% to about 15 wt%,
about 8 wt% to
about 14 wt%, about 10 wt% to about 12 wt%, or about 7 wt% to about 10 wt%
binder
composition, based on a dry weight of the lignocellulose substrates. In
another example, a
composite product of the lignocellulose substrates can contain from about 1
wt% to about 4
wt%, about 1.5 wt% to about 5 wt%, about 2 wt% to about 4 wt%, about 2 wt% to
about 6
wt%, or about 0.5 wt% to about 5.5 wt% binder composition, based on a dry
weight of the
lignocellulose substrates.
[00106] The lignocellulose substrates (material that includes both cellulose
and lignin) can
include, but is not limited to, straw, hemp, sisal, cotton stalk, wheat,
bamboo, sabai grass, rice
straw, banana leaves, paper mulben-y (i.e., bast fiber), abaca leaves,
pineapple leaves, esparto
grass leaves, fibers from the genus Hesperaloe in the family Agavaceae jute,
salt water reeds,
palm fronds, flax, ground nut shells, hardwoods, softwoods, recycled
fiberboards such as
high density fiberboard, medium density fiberboard, low density fiberboard,
oriented strand
board, particleboard, animal fibers (e.g., wool, hair), recycled paper
products (e.g.,
newspapers, cardboard, cereal boxes, and magazines), or any combination
thereof. Suitable
woods can include softwoods and/or hardwoods. Illustrative types of wood can
include, but
are not limited to, alder, ash, aspen, basswood, beech, birch, cedar, cherry,
cottonwood,
cypress, elm, fir, gum, hackbeny, hickory, maple, oak, pecan, pine, poplar,
redwood,
sassafras, spruce, sycamore, walnut, and willow.
[00107] The starting material, from which the lignocellulose substrates can be
derived from,
can be reduced to the appropriate size or dimensions by various processes such
as hogging,
grinding, hammer milling, tearing, shredding, and/or flaking. Suitable forms
of the
lignocellulose substrates can include, but are not limited to, chips, flakes,
wafers, fibers,
shavings, sawdust or dust, or the like. The lignocellulose substrates can have
a length
ranging from a low of about 0.05 mm, about 0.1 mm, about 0.2 mm to a high of
about 1 mm,
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about 5 mm, about 10 mm, about 20 mm, about 30 mm, about 40 mm, about 50 mm,
or about
100 mm.
[00108] The starting material, from which the lignocellulose substrates can be
derived from,
can also be formed into the appropriate size or dimensions by skiving,
cutting, slicing,
sawing, or otherwise removing a thin layer or sheet from a source of
lignocellulose material,
e.g., a wood log, to produce a veneer or layer. One or more composite products
can be
produced from two or more veneer. For example, composite products produced
with veneer,
in finished form, can include those products typically referred to as
laminated veneer lumber
("LVL"), laminated veneer boards ("LVB"), and/or plywood. As such,
suitable
lignocellulose substrates can include, but are not limited to, wood chips,
wood fibers, wood
flakes, wood strands, wood wafers, wood shavings, wood particles, wood veneer,
or any
combination thereof.
[00109] Depending, at least in part, on the particular product that can
incorporate the
veneer(s), the veneers can have any suitable shape, e.g., rectangular,
circular, or any other
geometrical shape. Typically the veneers can be rectangular, and can have a
width ranging
from a low of about 1 cm, about 5 cm, about 10 cm, about 15 cm, about 20 cm,
or about 25
cm to a high of about 0.6 m, about 0.9 m, about 1.2 m, about 1.8 m, or about
2.4 m. The
veneers can have a length ranging from a low of about 0.3 m, about 0.6 m,
about 0.9 m, about
1.2 m, or about 1.8 m to a high of about 2.4 m, or about 3 m, about 3.6 m,
about 4.3 m, about
4.9 m, about 5.5 m, about 6.1 m, about 6.7 m, about 7.3 m, or about 7.9 m. For
example, in a
typical veneer product such as plywood, the veneers can have a width of about
1.2 m and a
length of about 2.4 m. The veneers can have a thickness ranging from a low of
about 0.8
mm, about 0.9 mm, about 1 mm, about 1.1 mm or about 1.2 mm to a high of about
3 mm,
about 4 mm, about 5 mm, about 6 mm, about 7 mm, about 8 mm, about 9 mm, or
about 10
mm.
1001101 Illustrative composite wood products or articles produced using the
binder
compositions can include, but are not limited to, particleboard, fiberboard
such as medium
density fiberboard ("MDF") and/or high density fiberboard ("HDF"), plywood
such as
hardwood plywood and/or softwood plywood, oriented strand board ("OSB"),
laminated
veneer lumber ("LVL"), laminated veneer boards ("LVB"), and the like.
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[00111] Wood based or wood containing products, such as particleboard,
fiberboard,
plywood, and oriented strand board, can have a thickness ranging from a low of
about 1.5
mm, about 5 mm, or about 10 mm to a high of about 30 mm, about 50 mm, or about
100 mm.
Wood based or wood containing products can be formed into sheets or boards.
The sheets or
boards can have a length of about 1.2 m, about 1.8 m, about 2.4 m, about 3 m,
or about 3.6 m.
The sheets or boards can have a width of about 0.6 m, about 1.2 m, about 1.8
m, about 2.4 m,
or about 3 m.
[001121 Another lignocellulose. composite product can include panels or other
multi-layered
products. For example, a lignocellulose product can include two, three, four,
five, six, seven,
eight, nine, ten, or more individual lignocellulose layers bonded together.
The binder
composition can be contacted with the lignocellulose substrates of any one or
more of the
individual layers. In one example, the individual lignocellulose layers of a
multi-layer
product can be veneer. In another example, the individual lignocellulose
layers of a multi-
layer product can include a plurality of lignocellulose substrates bonded to
one another to
produce an individual layer. In another example, a multi-layer lignocellulose
product can
include one or more individual layers that include veneer and one or more
layers that include
a plurality of lignocellulose substrates bonded to one another to produce an
individual layer.
Examples
[00113] In order to provide a better understanding of the foregoing
discussion, the following
non-limiting examples are offered. Although the examples may be directed to
specific
embodiments, they are not to be viewed as limiting the invention in any
specific respect. All
parts, proportions, and percentages are by weight unless otherwise indicated.
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Example 1
[00114] Examples 1 and 2 were a 3,000 molecular weight (Mw) SMA solution with
TEA.
Example 1 and 2 polymers were made by adding 200 g of 3,000 Mw SMA, 352 g of
water,
14 g MEA, 80 g of TEA, and 33 g of aqueous ammonia (28%) to a standard sealed
polymer
reactor. The mixture was heated to about 98 C for about 4 to about 6 hours at
which point
the SMA had dissolved and the solutions became clear. The final pH was between
about 8
and 8.5. The Example 3 and 4 polymers were the same SMA-TEA solution as
Examples 1
and 2; however, the SMA-TEA solution was modified with a dextrose solution by
adding 172
g of a 50% dextrose solution to 200 g of the SMA-TEA solution.
[00115] The comparative examples (C5 and C6) are a 10% latex modified urea
formaldehyde
polymer that yields a high tear strength glass mat. The urea formaldehyde
polymer, prior to
modifying with the 10% latex, is referred to herein as the "unmodified UF
polymer." The
10% latex modified urea-formaldehyde polymer was blended, at room temperature,
directly
with the UF polymer for about 30 minutes. A Rohm and Haas model 4297 was used
to blend
the 10% latex modified UF polymer and all other examples having two or more
components
blended or mixed.
TABLE 1
Cure Avg. Dry
Ex. Time, Tensile, BW, Avg.
No. sec. lbs/3 in lbs/100ft2 Tear, gf % LOI DTN % HW
1 70 136.6 1.83 589 19.9 3.75 83.7
2 90 140.7 1.81 511 19.4 4.01 78.8
3 70 100.9 1.84 650 20.4 2.69 95.8
4 90 120.0 1.83 561 19.7 3.33 84.8
C5 50 128.4 1.82 485 19.7 3.58 76.3
C6 70 127.1 1.84 518 20.1 3.44 78.2
[00116] For all inventive examples (1-4, 7, 8, 10-16, 18-19, and 21-24) and
comparative
examples (C5, C6, C9, C17, C20, C25 and C26), a handsheet study was performed
for each
sample. Dilutions were made to approximately 13% solids with PAA white water.
PAA
white water is an aqueous solution of polyacrylamide. The PAA white water also
included
3.75 g/4 L of dispersant. The handsheets were cured at a temperature of 205 C
for various
times. The curing time for Examples 1-4, 7, 8, 10-16, and 18-21 and
comparative examples
C5, C6, C9, C17, and C20 are listed in Tables 1-4. For Examples 21-24 and
comparative
examples C25 and C26, the curing time was 70 seconds.
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[00117] Three handsheets for each example were made. The handsheets were 10.5
in. x 10.5
in. The thickness of the handsheets prior to curing, i.e. while wet, were not
measured. The
thickness of the handsheets after curing was about 35 mils. The glass fibers
for Examples I,
II, and III had an average length of about 1.25 inches. The glass fibers for
Examples IV and
V had an average length of about 0.75 inches. Each set was tested for dry and
wet tensile
strength on a Thwing-Albert tensile tester (0-200 kg load cell) and Elmendorf
tear strength on
a Thwing-Albert Pro Tear (1600g pendulum).
[00118] The Elmendorf tear strength tests and the tear strength values were
determined
according to the following procedure. The test samples were cut to a width of
63 mm (2.48
in.) in the tearing direction and a length of about 75 mm (3 in.). The samples
were long
enough to be held by the full width of each sample clamp. The test samples
were placed in
the clamps of the Thwing-Albert Pro Tear tester while ensuring that the bottom
of each
sample rested squarely on the bottom of the sample clamps. The sample was
aligned with the
front edge of the pendulum clamp. Any excess material was allowed to hang over
the rear of
the stationary clamp. The clamps were then closed. The cutter handle was then
pressed all
the way down to cut a 20 mm (0.79 in) slit in the sample. The "test" key of
the instrument
was then pressed and the pendulum was allowed to make one full swing in the
tearing
direction and the pendulum was stopped on the return swing and gently lowered
until it
rested against the pendulum stop.
[00119] Percent loss of ignition ("% LOT") was determined by weighing samples
after 30
minutes at 650 C. Percent hot-wet retention ("A HW") is the amount of dry
tensile strength
retained after immersing the sample in an 80 C water bath for 10 minutes.
Replications for
each test were made and standard deviations for each example were calculated.
The average
tear strength values shown in Tables 1-5 are the average of 9 measurements,
i.e. the average
of three tests performed on each handsheet. The dry tensile number ("DTN")
values shown in
Tables 1-5 are the average of 6 measurements, i.e. the average of two tests
performed on each
handsheet. The percent loss of ignition ("LOT") and Basis Weight ("BW") shown
in Tables
1-5 are the average of 3 measurements, i.e. the average of one test performed
on each
handsheet.
[00120] Referring to Table 1, Examples 1-4 and comparative examples (C5 and
C6) had a hot-
wet retention rate ("% HW") > 75% under the various cure conditions. Overall,
Examples 3
and 4 had a higher hot-wet retention rate as compared to Examples 1 and 2 and
the
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comparative examples (C5 and C6). As shown in Table 1, the average dry tensile
strength
for Examples 1, 2 and 4 were statistically equal to the comparative examples
(C5 and C6).
The average dry tensile strength for Example 3 was statistically less than the
comparative
examples (C5 and C6).
[00121] Due to the variation in basis weight ("BW"), loss of ignition ("LOP),
and hot-wet
retention ("HW"), the dry tensile number ("DTN") was calculated for each
binder
composition. The DTN was determined from the following equation:
DT dry tensile strength
, =
(LOI* basis weight)
[00122] When DTN was calculated, there was an improvement noted for Examples 1
and 2
over the comparative examples (C5 and C6). Specifically, Examples 1 and 2 had
DTN values
of 3.75 and 4.01, respectively; while the comparative examples (C5 and C6) had
DTN values
of 3.58 and 3.44, respectively.
[00123] Examples 1, 3 and 4, which were cured for 70 seconds, 70 seconds, and
90 seconds,
respectively; each had a higher average tear strength (gf) than the
comparative examples (C5
and C6).
Example II
[00124] Two inventive examples (7 and 8) and one comparative example (C9) are
provided
and summarized below in Table 2. Examples 7 and 8 are two acrylic solutions
combined
with an unmodified UF polymer. Specifically, Example 7 was a polymer
containing a
combination of an unmodified UF polymer and the Example 1 polymer. For Example
7, the
ratio of unmodified UF polymer to the Example 1 polymer was 40 wt% to 60 wt%
(40:60).
Example 8 is a polymer containing a combination of an unmodified UF polymer
and the
Example 3 polymer. For Example 8, the ratio of unmodified UF polymer to the
Example 3
polymer was 40 wt% to 60 wt% (40:60). As discussed above, the unmodified UF
polymer
for both Example 7 and 8 is the same polymer as the Comparative Examples 5 and
6, but
without the 10% latex. The unmodified UF polymer used to make Examples 7 and 8
was
made by standard techniques for making urea-formaldehyde polymers, such as
those
discussed and described in U.S. Patent No. 5,362,842. Comparative Example C9
is the same
10% latex modified UF polymer used for comparative examples C5 and C6.
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TABLE 2
Cure Avg. Dry Avg.
Time, Tensile, BW, Tear, %
Ex. No. sec. lbs/3 in lbs/100ft2 gf LOI DTN % HW
7 70 137.3 1.82 593 20.5 3.69 57.7
8 90 133.8 1.82 716 20.1 3.67 53.0
C9 70 135.9 1.81 470 20.6 3.65 72.8
[00125] All examples had a hot-wet retention rate ("% HW") > 50% under the
various cure
conditions. Overall, Examples 7 and 8 had a lower hot-wet retention rate as
compared to
comparative example (C9).
[00126] The average dry tensile strength and the DTN were statistically equal
for the inventive
Examples 7 and 8 and the comparative example C9. However, the average tear
strength for
both Example 7 and 8 increased from the comparative example (C9) value of 470
to 593 and
716, respectively. Surprisingly and unexpectedly the tensile strength of both
Example 7 and
8 was maintained at 137.3 lbs/3 in and 133.8 lbs/3 in, which are about equal
to the
comparative example (C9) of 135.9 lbs/3 in. The substantial increase in tear
strength while
maintaining the tensile strength is contrary to what is normally observed, as
an increase in
mat tear strength is normally accompanied by a decrease in tensile strength.
Example III
[00127] Seven inventive polymers (Examples 10-16) and one comparative example
(C17) are
provided and summarized below in Table 3. The polymer used in above Examples 3
and 4
was further studied by varying the cure time in order to modify the properties
of the
polymers. These samples correspond to Examples 10-14. Also, the polymer used
in
Examples 3 and 4 was blended with unmodified UF polymer in order to determine
if lower
levels of acrylic in the polymer will improve properties of the samples and
not require the
addition of the latex. Example 15 is a blend of 14% by weight of the Examples
3 and 4
polymer and 86% by weight of the unmodified UF polymer. Example 16 is a blend
of 27%
by weight of the Examples 3 and 4 polymer and 73% by weight of the unmodified
UF
polymer.
TABLE 3
Cure Avg. Dry Avg.
Time, Tensile, BW, Tear,
Ex. No. sec. lbs/3 in lbs/100ft2 gf LOI DTN % HW
35 72.3 1.83 915 20.5 1.94 102.5
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11 50 88.2 1.83 916 19.8 2.44 95.2
12 65 105.5 1.82 764 19.9 2.91 91.5
13 80 107.0 1.82 752 19.4 3.03 87.7
14 95 108.8 1.82 621 18.9 3.16 90.9
15 70 154.3 1.84 580 20.0 4.20 67.8
16 70 155.0 1.83 580 19.7 4.31 62.2
C17 70 134.5 1.83 593 19.3 3.82 74.9
[00128] All the Examples 10-16 and the comparative example (C17) had a hot-wet
retention
rate (% HW) > 60%. Increasing the cure time from 35 seconds to 95 seconds for
Examples
10-14, had very little effect on the hot-wet retention for the inventive
polymer. Examples 15
and 16, which are the two blends, had a lower hot-wet retention than Examples
10-14 and the
comparative example (C17). This result is similar to the Examples 7 and 9,
which were also
polymer blends.
[00129] As the cure time increased from 35 to 95 seconds for Examples 10-14,
the average
dry tensile strength also increased from 72.3 lbs/3 in to 108.8 lbs/3 in.
However, all of the
Examples 10-14 had a lower average dry tensile strength than the comparative
example
(C17). Interestingly, Examples 15 and 16, the blends, had a higher average dry
tensile
strength than the comparative example (C17).
[00130] The average tear strength for Examples 10-14, which ranged from 915 gf
to 621 gf,
were all significantly greater than the comparative example (C17) and Examples
15 and 16.
For examples 10-14, as the cure time increased from 35 seconds to 95 seconds,
the average
tear strength decreased from 915 gf to 621 gf.
Example IV
[00131] Two inventive polymers (Examples 18 and 19) and one comparative
polymer (C20)
are provided and summarized below in Table 4. Examples 18 and 19 evaluate the
effect
dextrose has as a modifier for urea formaldehyde polymers. A 40% solution of
dextrose was
used as a modifier for the unmodified urea-formaldehyde polymer. The dextrose
was added
to the urea-formaldehyde polymer by blending, at room temperature, the 40%
solution of
dextrose for about 30 minutes. Specifically, Examples 18 and 19 were modified
to include
7.7 wt% and 15 wt% dextrose, respectively.
TABLE 4
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Post Cure Avg. Dry BW,
Addition Time, Tensile, lbs/100ft Avg.
Ex. No. Modifier sec. lbs/3 in 2 Tear, gf LOI DTN % HW
18 7.7 wt%
dextrose 70 119.1 1.81 490 19.5 3.37 71.9
19 15 wt%
dextrose 70 117.4 1.80 562 19 3.42 68.3
C20
None 70 114.2 1.81 439 20.1 3.14 89.4
[00132] The dextrose modified polymers (Examples 18 and 19) and the
comparative example
(C20) all had hot-wet retention rates (% HW) > 68%.
[00133] As shown in Table 4, dextrose modified polymers (Examples 18 and 19)
provide a
glass mat with a statistically equal tensile strength as compared to the
comparative polymer
C20. However, the dextrose modified polymers (Examples 18 and 19) show
significant
increases in tear strength. Specifically, the average tear strength for the
dextrose modified
polymers (Examples 18 and 19) increased from the comparative polymer (C20)
value of 439
to 490 and 562, respectively. This result is surprising and unexpected as an
increase in tear is
normally accompanied by a decrease in tensile strength.
Example V
[00134] Four inventive polymers (Examples 21-24) and two comparative polymers
(C25 and
C26) are provided and summarized below in Table 5. Example 21 is a blend of
the
unmodified UF polymer and the inventive polymer of Examples 3 and 4, discussed
above.
Specifically, Example 24 contains 80% by weight unmodified UF polymer and 20%
by
weight of the inventive polymer of Examples 3 and 4. Example 22 is a blend of
the
unmodified UF polymer and the inventive polymer of Examples 1 and 2, discussed
above.
Specifically, Example 22 contains 80% by weight unmodified UF polymer and 20%
by
weight of the inventive polymer of Examples 1 and 2. Example 23 is the
inventive polymer
of Examples 3 and 4 and Example 27 is the inventive polymer of Examples 1 and
2,
discussed above. The comparative example (C25) was a standard urea-
formaldehyde
polymer modified with 10% RH 618 latex posted blended at room temperature for
30
minutes. The comparative example C26 was the same 10% latex modified polymer
of
comparative examples (C5 and C6). All Examples 21-24 and the comparative
examples
(C25 and C26) were cured for 70 seconds at a temperature of 205 C.
TABLE 5
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Post Avg. Dry
Addition Tensile, BW, Avg.
Ex. No. Modifier lbs/3 in lbs/100ft2 Tear, gf % LOI
DTN % HW
21 20 wt% 167.8 2.2 675 21.9 3.47 62
Examples
3 and 4
Polymer
22 20 wt% 177.5 2.18 633 21.5 3.79 52.9
Examples
1 and 2
Polymer
23 None 140.3 2.18 601 20.3 3.17 75.1
24 None 200.8 2.17 625 21 4.41 65.7
C25 None 162.7 2.2 558 21.3 3.47 68.4
C26 None 174.1 2.16 502 21.1 3.82 65.3
[00135] All the Examples 21-24 and the comparative examples (C25 and C26) had
a hot-wet
retention rate (% HW) > 52%. However, Example 22 that contained the 80% by
weight
unmodified UF polymer and 20% by weight of the inventive polymer of Examples 1
and 2
had a noticeably lower hot-wet retention rate compared to the other examples.
Examples 21-
22 all had statistically equal average dry tensile strengths to that of the
comparative examples
(C25 and C26). Surprisingly, Example 24 had the highest average dry tensile
strength of
200.8 lbs/3 in, which was an increase of more than 25 lbs/3 in. over the
comparative
examples (C25 and C26). As mentioned above, a substantial increase in tear
strength while
maintaining tensile strength is contrary to what is normally observed, as an
increase in tear
strength is normally accompanied by a decrease in tensile strength. -
Increasing both the
tensile strength and the tear strength was surprising and unexpected.
Example VI
[00136] One comparative example (C27) and one inventive example (Ex. 28) are
provided
and summarized below in Table 6. Comparative example C27 was prepared by
combining
about 700 grams water and about 519 grams of a SMA having a number-average
molecular
weight (Mn) of about 5,000, and about 180 grams of NH3 within a reactor
vessel. The Mn
was determined via GPC. The reactor vessel was closed, agitation was started,
and the
temperature within the reactor was raised to about 95 C. As the temperature
increased the
pressure within the reactor increased to and was maintained between about 6
psig and about 9
psig. After about 2 hours the reaction of the SMA and NH3 was completed and
the
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temperature was reduced down to room temperature. The SMA copolymer modified
by
reaction with the NH3 had a solids concentration of about 38 wt%, a pH of
about 5.8, and a
viscosity of about 1,250 cP. The SMA copolymer modified by reaction with the
NH3 was
used to prepare the fiberglass mat of comparative example C27.
1001371 For Example 28 a polyamidoaminc prepolymers was prepared in a 2 L
reactor
equipped with a stainless steel stir shaft, heating element, and
reflux/distillation condenser.
About 600 grams of diethylenetriamine (about 5.82 mole) was added to the
reactor and
stirring was started. About 877 grams of solid adipic acid (about 6.00 mole)
was slowly
added over 30 minutes to the reactor. The reaction exothermed from room
temperature to
about 145 C over this time, and reflux was observed. After the adipic acid was
added the
reaction was slowly heated to about 155 C and the condenser was changed to
distillation.
Water was removed from the reactor until the viscosity of a diluted reaction
mixture sample
reached a bubble tube viscosity of about BCC to about D (Gardner Holdt
viscosity) and the
condenser was switched back to reflux and water was added slowly to dilute the
reaction
mixture. To determine the Gardner Holdt viscosity a sample of the reaction
mixture, e.g.,
about 50 g was dissolved in about 100 g of water. The dissolved mixture had a
Refractive
Index that ranged from about 1.3978 to about 1.3984. When the Gardner Holdt
viscosity was
from about 1.3979 to about 1.3984 the condenser was switched back to reflux
and water was
slowly added to produce a polyamidoamine prepolymer that had a viscosity of
about 300 cP
at 45 wt% solids. The viscosity was measured with as measured with a
Brookfield
Viscometer, Model DV-II+, with a number 3 spindle, at 25 C. The weight
average
molecular weight Mw of the polyamidoamine prepolymers was about 40,000
Daltons. The
Mw was determined via GPC.
[00138] The binder composition used to prepare the fiberglass mat of Example
28 was
prepared by mixing about 364 grams of the SMA copolymer modified by reaction
with the
NH3 of comparative example C27 with about 61 grams of the polyamidoamine
prepolymer to
provide a binder composition containing about 65 wt% SMA copolymer modified by
reaction
with the NH3 and about 35 wt% of the polyamidoamine prepolymer.
1001391 The handsheets were prepared by diluting the binder compositions of
C27 and Ex. 28
to approximately 13% solids with PAA white water. The PAA white water also
included
3.75 g/4 L of dispersant. The handsheets were cured at a temperature of about
205 C (C27)
and 185 C (Ex. 28) for about 90 seconds. Three handsheets for each example
were made.
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The handsheets were 10.5 in. x 10.5 in. The thickness of the handsheets prior
to curing, i.e.
while wet, were not measured. The thickness of the handsheets after curing was
about 35
mils. The glass fibers had an average length of about 1.25 inches. Each set
was tested for
dry and wet tensile strength on a Thwing-Albert tensile tester (0-200 kg load
cell) and
Elmendorf tear strength on a Thwing-Albert Pro Tear (1600g pendulum).
TABLE 6
Avg. Dry Avg. H/W
Ex. Cure Time, Cure BW, Tensile, Tensile,
No. sec. Temp., C lbs/100ft2 lbs/3 in lbs/3 in
% LOT HW DTN
C27 90 205 1.86 160 124 21.0 77.4 4.10
28 90 185 1.83 173 111 18.0 64.1 5.25
[00140] Surprisingly and unexpectedly, it was found that the cure temperature
for Ex. 28
could be significantly reduced (185 C as compared to 205 C), while still
maintaining
statistically equivalent dry tensile strength, H/W tensile strength, and % HW
retention. The
physical properties of C27 and Ex. 28 were determined as discussed above with
reference to
Examples I-V.
[00141] Embodiments of the present invention further relate to any one or more
of the
following paragraphs:
[00142] 1. A binder composition, comprising: at least one polyamidoamine
prepolymer; and
at least one copolymer modified by reaction with one or more base compounds,
wherein the
copolymer comprises: one or more vinyl aromatic derived units, and one or more
unsaturated
carboxylic acids, one or more unsaturated carboxylic anhydrides, or a
combination thereof.
[00143] 2. A method for making a composite product, comprising: contacting a
plurality of
substrates with a binder composition, wherein the binder composition
comprises: at least one
polyamidoamine prepolymer; and at least one copolymer modified by reaction
with one or
more base compounds, wherein the copolymer comprises: one or more vinyl
aromatic
derived units, and one or more unsaturated carboxylic acids, one or more
unsaturated
carboxylic anhydrides, or a combination thereof; and at least partially curing
the binder
composition to produce a composite product.
[00144] 3. A composite product, comprising: a plurality of substrates and a
binder
composition, wherein the binder composition, prior to curing, comprises: at
least one
polyamidoamine prepolymer; and at least one copolymer modified by reaction
with one or
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more base compounds, wherein the copolymer comprises: one or more vinyl
aromatic
derived units, and one or more unsaturated carboxylic acids, one or more
unsaturated
carboxylic anhydrides, or a combination thereof
[00145] 4. The binder composition, method, or composite product according to
any one of
paragraphs 1 to 3, wherein the one or more base compounds comprise one or more
amines,
one or more amides, one or more hydroxides, one or more carbonates, or any
combination
thereof.
[00146] 5. The binder composition, method, or composite product according to
any one of
paragraphs 1 to 4, wherein the one or more base compounds comprise ammonia, a
primary
alkanolamine, a secondary alkanolamine, a tertiary alkanolaminc, sodium
hydroxide,
potassium hydroxide, or any combination thereof
[00147] 6. The binder composition, method, or composite product according to
any one of
paragraphs 1 to 5, wherein the one or more base compounds is ammonia.
[00148] 7. The binder composition, method, or composite product according to
any one of
paragraphs 1 to 6, wherein the at least one copolymer comprises from about 7
mol% to about
50 mol% of the one or more unsaturated carboxylic acids, the one or more
unsaturated
carboxylic anhydrides, or the combination thereof, based on a total weight of
the one or more
unsaturated carboxylic acids, the one or more unsaturated carboxylic
anhydrides, or the
combination thereof and the one or more vinyl aromatic derived units
[00149] 8. The binder composition, method, or composite product according to
any one of
paragraphs 1 to 7, wherein the at least one copolymer has a weight average
molecular weight
(Mw) of about 500 to about 200,000.
[00150] 9. The binder composition, method, or composite product according to
any one of
paragraphs 1 to 8, wherein the at least one polyamidoamine prepolymer
comprises a reaction
product of one or more polyalkylene polyamines and one or more diacids.
[00151] 10. The binder composition, method, or composite product according to
paragraph
9, wherein the one or more polyalkylene polyamines comprise one or more
polyethylene
polyamines, one or more polypropylene polyamines, one or more polybutylene
polyamines,
or any combination thereof.
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[00152] 11. The binder composition, method, or composite product according to
paragraph
9, wherein the one or more polyalkylene polyamines comprise diethylene
triamine,
triethylene tetramine, tetraethylene pentamine, bishexamethylene triamine, bis-
2-
hydroxyethylethylene diamine, pentaethylene hexamine, hexaethylene heptamine,
methyl
bis(3-aminopropy1)-amine, dipropylene triamine, or any combination thereof.
[00153] 12. The binder composition, method, or composite product according to
any one of
paragraphs 9 to 11, wherein the one or more diacids comprise malonic acid,
succinic acid,
glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic
acid, phthalic acid,
isophthalic acid, terephthalic acid, cyclohexanedicarboxylic acid, or any
combination thereof.
[00154] 13. The binder composition, method, or composite product according to
any one of
paragraphs 1 to 12, wherein the at least one polyamidoamine prepolymer
comprises a
reaction product of: at least one of diethylenetriamine, methyl bis(3-
aminopropy1)-amine,
triethylene tetramine, and tetraethylene pentamine; and at least one of adipic
acid and glutaric
acid.
[00155] 14. The binder composition, method, or composite product according to
any one of
paragraphs 1 to 13, wherein the at least one polyamidoamine prepolymer has a
weight
average molecular weight (Mw) ranging from about 700 to about 100,000.
[00156] 15. The binder composition, method, or composite product according to
any one of
paragraphs 1 to 14, wherein the at least one polyamidoamine prepolymer has a
weight
average molecular weight (Mw) ranging from about 30,000 to about 50,000.
[00157] 16. The binder composition, method, or composite product according to
any one of
paragraphs 1 to 15, wherein the at least one copolymer is present in an amount
ranging from
about 60 wt% to about 95 wt%, based on a total weight of the copolymer and the
one or more
base compounds.
[00158] 17. The binder composition, method, or composite product according to
any one of
paragraphs 1 to 16, wherein the at least one polyamidoamine prepolymer is
present in an
amount ranging from about 5 wt% to about 50 wt%, based on a total weight of
the at least
one copolymer and the at least one polyamidoamine prepolymer.
[00159] 18 The binder composition, method, or composite product according to
any one of
paragraphs 1 to 17, wherein the at least one polyamidoamine prepolymer is
present in an
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amount ranging from about 25 wt% to about 45 wt%, based on a total weight of
the at least
one copolymer and the at least one polyamidoamine prepolymer.
[00160] 19. The method according to paragraph 2, wherein at least a portion of
the binder
composition is heated to a temperature of about 195 C or less to at least
partially cure the
binder composition and form the composite product.
[00161] 20. The method according to paragraph 2 or 19, wherein at least a
portion of the
binder composition is heated to a temperature of about 185 C or less to at
least partially cure
the binder composition and form the composite product.
[00162] 21. The method or composite product according to any one of paragraphs
2, 3, 19,
or 20, wherein the substrates comprise glass fibers.
[00163] 22. The method or composite product according to any one of paragraphs
2, 3, or 19
to 21, wherein the substrates comprise lignocellulose substrates.
[00164] 23. The method or composite product according to any one of paragraphs
2, 3, or 19
to 22, wherein the composite product is a particleboard, a fiberboard, a
plywood, an oriented
strand board, a fiberglass mat, or a fiberglass insulation.
[00165] 24. The method or composite product according to any one of paragraphs
2, 3, or 19
to 23, wherein the substrates comprise wood fibers, glass fibers, or a
combination thereof.
[00166] 25. The binder composition, method, or composite product according to
anyone of
paragraphs 1 to 24, wherein the at least one copolymer comprises styrene
maleic anhydride.
[00167] 26. The binder composition, method, or composite product according to
anyone of
paragraphs 1 to 25, wherein the at least one copolymer comprises styrene
maleic anhydride,
and wherein the at least one polyamidoamine prepolymer comprises a reaction
product of one
or more polyalkylene polyamines and one or more diacids.
[001681 27. The binder composition, method, or composite product according to
anyone of
paragraphs 1 to 26, wherein the at least one copolymer comprises styrene
maleic anhydride,
wherein the at least one polyamidoamine prepolymer comprises a reaction
product of one or
more polyalkylene polyamines and one or more diacids, wherein the one or more
polyalkylene polyamines comprise one or more polyethylene polyamines, one or
more
polypropylene polyamines, one or more polybutylene polyamines, or any
combination
thereof, and wherein the one or more diacids comprise malonic acid, succinic
acid, glutaric
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acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid,
phthalic acid,
isophthalic acid, terephthalic acid, cyclohexanedicarboxylic acid, or any
combination thereof.
[00169] 28. The binder composition, method, or composite product according to
anyone of
paragraphs 1 to 27, wherein the at least one polyamidoamine prepolymer
comprises a
reaction product of: at least one of diethylenetriamine, methyl bis(3-
aminopropy1)-amine,
triethylene tetramine, and tetraethylene pentamine; and at least one of adipic
acid and glutaric
acid, and wherein the at least one copolymer comprises styrene maleic
anhydride.
[00170] Certain embodiments and features have been described using a set of
numerical
upper limits and a set of numerical lower limits. It should be appreciated
that ranges from
any lower limit to any upper limit arc contemplated unless otherwise
indicated. Certain
lower limits, upper limits and ranges appear in one or more claims below. All
numerical
values are "about" or "approximately" the indicated value, and take into
account experimental
error and variations that would be expected by a person having ordinary skill
in the art.
[00171] Various terms have been defined above. To the extent a term used in a
claim is not
defined above, it should be given the broadest definition persons in the
pertinent art have
given that term as reflected in at least one printed publication or issued
patent. Furthermore,
all patents, test procedures, and other documents cited in this application
are fully
incorporated by reference to the extent such disclosure is not inconsistent
with this
application and for all jurisdictions in which such incorporation is
permitted.
[00172] While the foregoing is directed to embodiments of the present
invention, other and
further embodiments of the invention may be devised without departing from the
basic scope
thereof, and the scope thereof is determined by the claims that follow.
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