U.S. patent application number 16/956040 was filed with the patent office on 2021-04-22 for binders and associated products.
The applicant listed for this patent is KNAUF INSULATION, INC., KNAUF INSULATION SPRL. Invention is credited to Carl HAMPSON, Gareth JONES.
Application Number | 20210115164 16/956040 |
Document ID | / |
Family ID | 1000005359397 |
Filed Date | 2021-04-22 |
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United States Patent
Application |
20210115164 |
Kind Code |
A1 |
HAMPSON; Carl ; et
al. |
April 22, 2021 |
BINDERS AND ASSOCIATED PRODUCTS
Abstract
The present invention relates to a water-soluble binder
composition comprising at least one carbohydrate component and at
least one carbon dioxide reaction product comprising at least the
reaction product(s) of carbon dioxide with at least one
nitrogen-containing compound. It further relates to a method of its
manufacture, its use, a method of manufacturing a collection of
matter bound by said polymeric binder, as well as a binder solution
or dispersion comprising said binder composition.
Inventors: |
HAMPSON; Carl; (St. Helens -
Merseyside, GB) ; JONES; Gareth; (Prescot-Merseyside,
GB) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
KNAUF INSULATION SPRL
KNAUF INSULATION, INC. |
Vise
Shelbyville |
IN |
BE
US |
|
|
Family ID: |
1000005359397 |
Appl. No.: |
16/956040 |
Filed: |
December 18, 2018 |
PCT Filed: |
December 18, 2018 |
PCT NO: |
PCT/EP2018/085579 |
371 Date: |
June 19, 2020 |
Current U.S.
Class: |
1/1 |
Current CPC
Class: |
C08B 37/0006 20130101;
C08K 3/20 20130101; B01F 3/04106 20130101; C08B 37/006
20130101 |
International
Class: |
C08B 37/00 20060101
C08B037/00; C08K 3/20 20060101 C08K003/20; B01F 3/04 20060101
B01F003/04 |
Foreign Application Data
Date |
Code |
Application Number |
Dec 19, 2017 |
GB |
1721228.3 |
Claims
1. A water-soluble, curable, thermosetting binder composition,
comprising: at least one carbohydrate component and at least one
carbon dioxide reaction product comprising at least the reaction
product(s) of carbon dioxide with at least one nitrogen-containing
compound.
2. The binder composition according to claim 1, in which the
viscosity of an aqueous solution containing 70 wt.-% of said binder
composition does not increase by more than 500 cP when left to
stand at 20.degree. C. for 12 hours.
3. The binder composition according to claim 1, wherein said binder
composition is capable of reacting with a crosslinker to yield one
or more melanoidins as a water-insoluble composition, under
relevant curing conditions.
4. The binder composition according to claim 1, wherein the ratio
of total carbonyl groups in the carbohydrate component(s) to total
reactive nitrogen-containing groups in the nitrogen-containing
component(s) is 5:1 to 1:5.
5. The binder composition according to claim 1, wherein the at
least one carbohydrate component is selected from the group
consisting of monosaccharides, disaccharides, polysaccharides or a
reaction product thereof.
6. The binder composition according to claim 1, wherein the at
least one carbohydrate component is selected from the group
consisting of reducing sugars, ribose, arabinose, xylose, lyxose,
glucose (dextrose), mannose, galactose, allose, altrose, talose,
gulose, idose, fructose, psicose, sorbose, dihydroxyacetone,
sucrose and tagatose, as well as mixtures thereof.
7. The binder composition according to claim 1, wherein the at
least one nitrogen-containing component is NH.sub.3, an inorganic
amine or an organic amine comprising at least one primary amine
group, as well as salts thereof.
8. The binder composition according to claim 7, wherein the at
least one nitrogen-containing component is a primary polyamine
having the formula H.sub.2N--Q--NH.sub.2, wherein Q is a C6 alkyl
or cyclohexyl, cyclopentyl or cyclobutyl, or benzyl, each of which
being optionally substituted with amino, aminoalkyl, hydroxyl,
halo, or thiol, wherein alkyl is selected from the group consisting
of C.sub.2-C.sub.24 alkyl, C.sub.2-C.sub.9 alkyl, and
C.sub.3-C.sub.7 alkyl.
9. The binder composition according to claim 1, wherein the weight
ratio between the carbohydrate component and the carbon dioxide
reaction product with nitrogen-containing component is 0.5:1 to
30:1.
10. A method of manufacturing a binder composition comprising the
steps of: (i) providing at least one carbohydrate component, (ii)
providing at least one nitrogen-containing component, (iii)
providing carbon dioxide, (iv) mixing in a solvent the carbohydrate
component(s) and the nitrogen-containing component(s), and
optionally cooling at room temperature, and (v) bubbling carbon
dioxide into the mixture obtained in step (iv); or (i') providing
at least one carbohydrate component, (ii') providing at least one
nitrogen-containing component, (iii') providing carbon dioxide,
(iv') reacting the carbon dioxide with the nitrogen-containing
component, and (v') mixing in a solvent the carbohydrate
component(s) and the reaction product of (iv').
11. The method according to claim 10, wherein 0.5 to 50 w %
CO.sub.2 based on the total weight of the binder composition, is
bubbled into the reaction mixture.
12. (canceled)
13. A water-soluble binder composition obtainable by the method
according to claim 10.
14. (canceled)
15. A method of manufacturing a collection of matter bound by a
polymeric binder comprising the steps: (i) providing a collection
of matter, (ii) providing a binder composition according to claim
1, or a binder composition obtained by the method according to
claim 10, in a solvent to obtain a solution or dispersion, (iii)
applying the solution or dispersion obtained in step (ii) to the
collection of matter, and (iv) applying energy to the collection of
matter containing said solution or dispersion to cure the binder
composition.
16. The method according to claim 15, wherein in step (ii) a
crosslinker is added to the binder composition according to claim
1, or the binder composition obtained by the method according to
claim 10, or the solution or dispersion thereof. U.S.
Nationalization of PCT/EP2018/085579 P0461/US HAMPSON, Carl and
JONES, Gareth
17. The method of manufacturing a collection of matter according to
claim 15 or 16, wherein prior to the step of applying the solution
or dispersion obtained in step (ii) to the collection of matter,
the collection of matter is substantially free of binder.
18. A binder solution or dispersion comprising in a solvent the
binder composition according to any one of claims 1 to 9 and a
crosslinker.
Description
[0001] The present invention relates to a water-soluble binder
composition, a method of its manufacture, a use of said binder
composition, a method of manufacturing a collection of matter bound
by a polymeric binder, and a binder solution or dispersion
comprising said binder composition.
[0002] Generally, binders are useful in fabricating articles
because they are capable of consolidating and/or imparting
structural integrity to non- or loosely-assembled matter. For
example, binders enable two or more surfaces to become united. In
particular, binders may be used to produce products comprising
consolidated fibers. Thermosetting binders may be characterized by
being transformed into insoluble and infusible materials by means
of heat, catalytic action or heat in combination with catalytic
action. Examples of a thermosetting binder include a variety of
phenol-aldehyde, ureaaldehyde, melamine-aldehyde, polymeric
methylene diphenyl diisocyanate (p-MDI), and other
condensation-polymerization materials like furane and polyurethane
resins. Binder compositions containing phenol-aldehyde,
resorcinol-aldehyde, phenol/aldehyde/urea,
phenol/melamine/aldehyde, and the like are widely used for the
bonding of fibers, textiles, plastics, rubbers, and many other
materials.
[0003] The mineral wool and wood board industries have historically
used a phenol formaldehyde based binder, generally extended with
urea. Phenol formaldehyde type binders provide suitable properties
to the final products; however, desires for greater sustainability
and environmental considerations have motivated the development of
alternative binders that preferably neither make use of or generate
formaldehyde nor generate substantial quantities of harmful
byproducts during curing. They have been collectively referred to
as formaldehyde-free binders. One such alternative binder is a
carbohydrate based binder. Such carbohydrate based binders may be
derived from reacting a carbohydrate and an acid, for example, U.S.
Published Application No. 2007/0027283 and Published PCT
Application WO2009/019235. Carbohydrate based binders may also be
derived from reacting a carbohydrate with a polyamine, more
specifically a polyamine having at least one primary amine group,
in order to form polymeric carbohydrate polyamine binders. These
are effective substitutes for phenol formaldehyde binders, since
they possess similar or superior binding characteristics and are
highly compatible to the established processes.
[0004] Carbohydrate-based binder compositions are made of
relatively inexpensive precursors and are derived mainly from
renewable resources. However, these binders may also require
reaction conditions for curing that are substantially different
from those conditions under which the traditional phenol
formaldehyde binder system is cured.
[0005] Typically, the carbohydrate polyamine binders are prepared
as a solution, such as an aqueous solution, and are subsequently
applied onto the loosely assembled matter to be bound. The thus
wetted loosely assembled matter is then, for example, heat treated,
or pressed and/or compressed and then heat treated, to cure the
carbohydrate polyamine binder. Nonetheless, the rather high
concentration of solids in the carbohydrate polyamine binder
solution is connected to a variety of disadvantages, such as quick
gelling or solidification of the binder solution, as well as
recrystallization of the carbohydrate component. For all
concentrations of solids in the binder solution, the storage and/or
transport of the said binder solution (comprising carbohydrate and
polyamine) may, for certain combinations of binder components and
under certain conditions, lead to undesirable gelling, which in
turn leads to blockage of spray nozzles that are used to spray the
binder onto a loose collection of matter prior to curing.
[0006] Accordingly, the technical problem underlying the present
invention is to provide improved binder compositions, particularly
carbohydrate based binders which are compatible with the
established processes, are environmentally acceptable and overcome
the aforementioned problems.
[0007] In order to solve the above technical problem, as a first
aspect, the present invention provides a water-soluble binder
composition, comprising (i) at least one carbohydrate component,
and (ii) at least one carbon dioxide reaction product comprising at
least the reaction product(s) of carbon dioxide with at least one
nitrogen-containing compound.
[0008] Without being bound by theory, it has been found that when
bubbling carbon dioxide in a solution comprising at least one
carbohydrate component and at least one nitrogen-containing
component, carbamate compounds are formed which prevent or at least
significantly delay further reaction of the nitrogen-containing
component with other components of the composition, such as further
polymerization or cross-linking. Undesirable viscosity increase of
the binder composition during storage and/or shipping under
non-optimal conditions is prevented or at least substantially
reduced. The binder composition may thus easily be sprayed onto the
loose assembly of matter and then heat treated for curing. The
curing temperatures are sufficiently high to separate the dioxide
bound to some of the components of the composition and thus allow
the curing reaction between the carbohydrate and nitrogen
containing component of the composition again. The stability of the
binder composition is thus increased over extended periods of time
while still substantially maintaining the curing properties and
bond strength of the binder composition.
[0009] The total amount of the at least one carbohydrate component
and the at least one nitrogen-containing component in the starting
material to prepare the binder composition may be at least 5 wt.-%,
based on the solids content or on the total dry weight of the
binder composition. For example, the total amount of the at least
one carbohydrate component and the at least one nitrogen-containing
component may be at least 10 wt.-%, 12 wt.-%, 15 wt.-%, 20 wt.-%,
25 wt.-%, 30 wt.-%, 35 wt.-%, or 40 wt.-% up to 50 wt-%., 55 wt-%.,
60 wt-%., 65 wt-%., 70 wt-%. or 75 wt-%.
[0010] Carbon dioxide is advantageously injected in an amount such
as to reach approx. stoichiometric reaction with the
nitrogen-containing component.
[0011] Term "water-soluble" as used herein is not specifically
restricted and includes all grades of water-solubility of the
binder composition as defined above. In particular, the term
"water-soluble" includes water-solubility at 20.degree. C. of 100
g/l or more, 150 g/l or more, 200 g/I or more, or 250 g/l or more.
For example, the term "water-soluble" may include a
water-solubility of the binder composition as defined above of 300
g/I or more, 400 g/I or more, 500 g/I or more or 600 g/l or more
(at 20.degree. C.). Also virtual infinite water-solubility may be
regarded to be within the scope of the present invention.
[0012] The viscosity of said aqueous binder solution should
preferably not increase by more than 500 cP when left to stand at
20.degree. C. for 12 hours, 24 hours, 48 hours, 72 hours or 96
hours. According to a further preferred embodiment, the viscosity
of said aqueous solution should not increase by more than 500 cP
within a week, 10 days, 12 days or two weeks. Longer periods, such
as three or four weeks, or even two, three or more months, where
the viscosity will not increase by more than 500 cP are even more
preferable.
[0013] According to a further embodiment, the amount by which the
viscosity increases within the first 12 hours when leaving an 70
wt.-% aqueous solution of the binder composition to stand at
20.degree. C. should preferably not exceed 450 cP, or 400 cP or
even 350 cP. Preferred increases in viscosity include increases of
300 cP or less, 280 cP or less, 250 cP or less and 200 cP or
less.
[0014] According to the present invention, the above-defined time
periods and increases in viscosity are not limited to the examples
mentioned above and may be freely combined. For example,
preferably, the above-mentioned 70 wt.-% aqueous solution of the
binder composition does not increase in viscosity by more than 300
cP within the first 48 hours after its preparation, or more than
400 cP within two weeks after its preparation. Generally, if the
viscosity of a respective aqueous solution becomes too high, e.g.
caused by gelling, the composition may become unusable.
[0015] According to a further embodiment, the above-defined binder
composition is capable of allowing the reaction between the
carbohydrate component and the nitrogen-containing component after
degassing the carbon dioxide. It is then also capable of allowing
the reaction of the components with a crosslinker, to obtain a
polymeric binder. For example, this polymeric binder may contain
high molecular weight melanoidins as Maillard reaction products
which are essentially water-insoluble.
[0016] For example, the one or more melanoidins as defined above
may contain the following generic structural motifs:
##STR00001##
[0017] wherein n is an integer of at least 1.
[0018] Herein, the term "crosslinker" is not particularly
restricted and includes any chemical or physical means to crosslink
the binder composition to yield a polymeric binder suitable for
binding loosely assembled matter, such as mineral fibers. According
to a specific embodiment of the present invention, the crosslinker
may be the same nitrogen-containing component which has been
reacted with the carbohydrate component, or may be a different
nitrogen-containing component.
[0019] For example, a binder composition of the invention may be
prepared by mixing a carbohydrate component with
hexamethylenediamine (NMDA) and adding CO.sub.2. Subsequently,
further hexamethylenediamine may be added to the binder composition
to achieve the high grade of polymerization required in the
respective polymerized application. A further example includes the
case where the invention binder composition is prepared by mixing a
carbohydrate component with an aqueous solution of ammonia and
adding CO.sub.2, and for the final curing additional
hexamethylenediamine is added.
[0020] However, the crosslinker is not limited to the
nitrogen-containing components defined herein and includes, as an
example, Lewis acids, isocyanates, blocked isocyanates, epoxides,
blocked epoxides, carbonyl-containing compounds (aldehydes,
ketones, i.e. glyoxal) and organic carbonates. Specific examples of
the crosslinker include citric acid, polycarboxylic acids and
anhydrides (e.g. succinic acid, maleic anhydride, tetra- and
hexa-hydrophthalic anhydrides, styrene-maleic-anhydride
copolymers), solutions of polycarboxylic acid and anhydride
derivatives (e.g. ammonium salts thereof).
[0021] According to a further embodiment of the above-defined
binder composition, the ratio of the total carbonyl groups in the
carbohydrate component to total reactive nitrogen-containing groups
in the nitrogen-containing component is 5:1 to 1:5. For example,
the ratio of carbonyl groups to reactive nitrogen-containing groups
may be 5:1 to 1:4.5, 5:1 to 1:4, 5:1 to 1:3.5, 5:1 to 1:3, 5:1 to
1:2.5, 5:1 to 1:2, 5:1 to 1:1.8, 5:1 to 1:1.5, 5:1 to 1:1.2, 5:1 to
1:1, 5:1 to 1:0.8 and 5:1 to 1:0.5. Further examples include ratios
such as 4:1 to 1:5, 3.5:1 to 1:5, 3:1 to 1:5, 2.5:1 to 1:5, 2:1 to
1:5, 1.5:1 to 1:5, 1:1 to 1:5, 0.8:1 to 1:5 and 0.5:1 to 1:5.
According to the present invention, the upper and lower borders of
the above-mentioned ratios may be freely combined.
[0022] Herein, the term "reactive nitrogen-containing group" is not
particularly restricted and includes any nitrogen-containing groups
in the nitrogen-containing component which are capable of reacting
with the carbohydrate component under relevant curing conditions.
Specifically, examples of such reactive nitrogen-containing groups
include primary, secondary, tertiary and quaternary amine groups,
amide groups, imine and imide groups, as well as cyanate and
isocyanate groups.
[0023] Herein, the term "carbohydrate component" is not
specifically restricted and generally includes any carbohydrate
compound which is capable of reacting with a nitrogen-containing
component, under relevant curing conditions.
[0024] According to one embodiment of the above-defined binder, the
at least one carbohydrate component is selected from the group
consisting of monosaccharides, disaccharides, polysaccharides or a
reaction product thereof.
[0025] Preferably, the carbohydrate component is or comprises a
reducing sugar and/or a component which yields a reducing sugar in
situ. As used herein, the term "reducing sugar" indicates one or
more sugars that contain aldehyde or keto-groups, or that can
isomerize, i.e., tautomerize, to contain aldehyde or keto-groups,
which groups may be oxidized with, for example, Cu-ions to afford
carboxylic acids. According to the present invention, any such
carbohydrate component may be optionally substituted, such as with
hydroxy, halo, alkyl, alkoxy, and the like. In any such
carbohydrate component, one or more chiral centers may be present,
and both possible optical isomers at each chiral center are
included in the invention described herein. Further, it is also to
be understood that various mixtures, including racemic mixtures, or
other diastereomeric mixtures of the various optical isomers of any
such carbohydrate component, as well as various geometric isomers
thereof, may be used in one or more embodiments described
herein.
[0026] Non-reducing sugars, for instance sucrose, may be used as
the or part of the carbohydrate component, especially when capable
and/or subjected to in-situ conversion to a reducing sugar.
Further, it is also understood that a monosaccharide, a
disaccharide, or a polysaccharide may be partially reacted with a
precursor to form a carbohydrate reaction product. To the extent
that the carbohydrate reaction product is derived from a
monosaccharide, a disaccharide, or a polysaccharide, and maintains
similar reactivity with the nitrogen-containing component to form
reaction products similar to those of a monosaccharide, a
disaccharide, or a polysaccharide with a nitrogen-containing
component, the carbohydrate reaction product is within the scope of
term carbohydrate component.
[0027] Preferably, any carbohydrate component should be
sufficiently nonvolatile to maximize its ability to remain
available for reaction with the nitrogen-containing component. The
carbohydrate component may be a monosaccharide in its aldose or
ketose form, including a triose, a tetrose, a pentose, a hexose, or
a heptose; or a polysaccharide; or combinations thereof. For
example, when a triose serves as the carbohydrate component, or is
used in combination with other reducing sugars and/or a
polysaccharide, an aldotriose sugar or a ketotriose sugar may be
utilized, such as glyceraldehyde and dihydroxyacetone,
respectively. When a tetrose serves as the carbohydrate component,
or is used in combination with other reducing sugars and/or a
polysaccharide, aldotetrose sugars, such as erythrose and threose;
and ketotetrose sugars, such as erythrulose, may be utilized. When
a pentose serves as the carbohydrate component, or is used in
combination with other reducing sugars and/or a polysaccharide,
aldopentose sugars, such as ribose, arabinose, xylose, and lyxose;
and ketopentose sugars, such as ribulose, arabulose, xylulose, and
lyxulose, may be utilized. When a hexose serves as the carbohydrate
component, or is used in combination with other reducing sugars
and/or a polysaccharide, aldohexose sugars, such as glucose (i.e.,
dextrose), mannose, galactose, allose, altrose, talose, gulose, and
idose; and ketohexose sugars, such as fructose, psicose, sorbose
and tagatose, may be utilized. When a heptose serves as the
carbohydrate component, or is used in combination with other
reducing sugars and/or a polysaccharide, a ketoheptose sugar such
as sedoheptulose may be utilized. Other stereoisomers of such
carbohydrate components not known to occur naturally are also
contemplated to be useful in preparing the binder compositions as
described herein. In one embodiment, the carbohydrate component is
high fructose corn syrup (HFCS).
[0028] As mentioned above, the carbohydrate component may be
polysaccharide. For example, the carbohydrate component may be
polysaccharide with a low degree of polymerization and includes
e.g. molasses, starch, cellulose hydrolysates, or mixtures thereof.
According to a specific example, the carbohydrate component is a
starch hydrolysate, a maltodextrin, or a mixture thereof. While
carbohydrates of higher degrees of polymerization may not be
preferable, they may none the less be useful within the scope of
the present invention by in-situ depolymerization.
[0029] Furthermore, according to the present invention, the
carbohydrate component may be used in combination with a
non-carbohydrate polyhydroxy reactant. Examples of non-carbohydrate
polyhydroxy reactants which can be used in combination with the
carbohydrate component include, but are not limited to,
trimethylolpropane, glycerol, pentaerythritol, polyvinyl alcohol,
partially hydrolyzed polyvinyl acetate, fully hydrolyzed polyvinyl
acetate, and mixtures thereof. For example, the non-carbohydrate
polyhydroxy reactant is sufficiently nonvolatile to maximize its
ability to remain available for reaction with a monomeric or
polymeric polyamine. Moreover, according to the present invention,
the hydrophobicity of the non-carbohydrate polyhydroxy reactant may
be a factor in determining the physical properties of a binder
prepared as described herein. Other co-reacting compounds, for
example, like carbonyl-containing compounds--aldehydes, ketones,
carboxylic acids and anhydrides, may be used.
[0030] In a preferred embodiment of the above-defined binder
composition, the at least one carbohydrate component is selected
from the group consisting of ribose, arabinose, xylose, lyxose,
glucose (dextrose), mannose, galactose, allose, altrose, talose,
gulose, idose, fructose, psicose, sorbose, dihydroxyacetone,
sucrose and tagatose, as well as mixtures thereof.
[0031] Further, herein the expression "nitrogen-containing
component" is not particularly limited and includes any chemical
compound, or mixture of compounds, which contain at least one
nitrogen atom and which is capable of reacting with the at least
one carbohydrate component under curing conditions.
[0032] According to one embodiment, in the binder composition as
defined above, the at least one nitrogen-containing component is
NH.sub.3, an inorganic amine or an organic amine comprising at
least one primary amine group, as well as salts thereof. For
example, as the nitrogen-containing component NH.sub.3 may be used
as such (e.g. in form of an aqueous solution), as well as any type
of inorganic and organic ammonium salts, as long as these salts are
capable of reacting with the carbohydrate component defined above.
Specific examples of inorganic ammonium salts include ammonium
sulfate (AmSO.sub.4), ammonium phosphate, ammonium chloride, and
ammonium nitrate.
[0033] According to the present invention, the nitrogen-containing
component may be a polyamine. Herein, the term "polyamine" includes
any organic compound having two or more amine groups, which may
independently be substituted. As used herein, a "primary polyamine"
is an organic compound having two or more primary amine groups
(--NH.sub.2). Within the scope of the term primary polyamine are
those compounds which can be modified in situ or isomerize to
generate a compound having two or more primary amine groups
(--NH.sub.2).
[0034] For example, the polyamine may be a primary polyamine.
According to one embodiment of the present invention, the primary
polyamine may be a molecule having the formula
H.sub.2N--Q--NH.sub.2, wherein Q is an alkyl, cycloalkyl,
heteroalkyl, or cycloheteroalkyl, each of which may be optionally
substituted. For example, Q may be an alkyl group selected from a
group consisting of C.sub.2-C.sub.4, an alkyl selected from a group
consisting of C.sub.2-C.sub.9, an alkyl selected from a group
consisting of C.sub.3-C.sub.7. According to a preferred embodiment,
Q is a C.sub.6 alkyl. According to another embodiment, Q may be a
cyclohexyl, cyclopentyl or cyclobutyl, or a benzyl group.
[0035] According to another embodiment of the present invention,
the primary polyamine may comprise a triprimary triamine having
spacer groups between each of three primary amines. As used herein,
a triprimary triamine is an organic compound having three and only
three amines, each of which amine is a primary amine (--NH.sub.2).
Accordingly, in concert with the instant embodiment of the present
invention, the triprimary triamine(s) may be selected from
triprimary triamine(s) having spacer groups between each of the
three primary amines which spacer groups consist of carbon chains;
triprimary triamine(s) having spacer groups between each of the
three primary amines wherein each spacer group has a spacer length
which is less than or equal to 12 polyvalent atoms; and triprimary
triamine(s) having a total number of polyvalent atoms which is less
than or equal to 23. Accordingly, a triprimary triamine having
spacer groups between each of the three primary amines which spacer
groups consist of carbon chains means that the spacer groups
consists only of carbon atoms bonded to hydrogen atoms or to other
carbon atoms.
[0036] Illustratively, triprimary triamine(s) may be selected from
the group consisting of triaminodecanes, triaminononanes, notably
4-(aminomethyl)-1,8-octanediamine, triaminooctanes,
triaminoheptanes, notably 1,4,7-triaminoheptane, triaminohexanes,
notably 1,3,6-triaminohexane, triaminopentanes, and including
isomers and combination thereof.
[0037] As used herein, the term "alkyl" includes a chain of carbon
atoms, which may optionally be branched. As used herein, the terms
"alkenyl" and "alkynyl" independently include a chain of carbon
atoms, which may optionally be branched, and include at least one
double bond or triple bond, respectively. It is to be understood
that alkynyl may also include one or more double bonds. It is to be
further understood that alkyl is advantageously of limited length,
including C.sub.1-C.sub.24, C.sub.1-C.sub.12, C.sub.1-C.sub.8,
C.sub.1-C.sub.6, and C.sub.1-C.sub.4. It is to be further
understood that alkenyl and/or alkynyl may each be advantageously
of limited length, including C.sub.2-C.sub.24, C.sub.2-C.sub.12,
C.sub.2-C.sub.8, C.sub.2-C.sub.6, and C.sub.2-C.sub.4. In
particular, shorter alkyl, alkenyl, and/or alkynyl groups may add
less hydrophilicity to the compound and accordingly will have
different reactivity towards the carbohydrate component and
solubility in a binder solution.
[0038] As used herein, the term "cycloalkyl" includes a chain of
carbon atoms, which may optionally be branched, where at least a
portion of the chain is cyclic. Moreover, according to the present
invention it is to be noted that the term "cycloalkylalkyl" is
regarded as a subset of cycloalkyl, and that the term "cycloalkyl"
also includes polycyclic structures. For example, such cycloalkyls
include, but are not limited to, cyclopropyl, cyclopentyl,
cyclohexyl, 2-methylcyclopropyl, cyclopentyleth-2-yl, adamantyl,
and the like. As used herein, the term "cycloalkenyl" includes a
chain of carbon atoms, which may optionally be branched, and
includes at least one double bond, where at least a portion of the
chain is cyclic. According to the present invention, said at least
one double bond may be in the cyclic portion of cycloalkenyl and/or
the noncyclic portion of cycloalkenyl. Moreover, it is to be
understood that cycloalkenylalkyl and cycloalkylalkenyl are each
regarded as subsets of cycloalkenyl. Moreover, according to the
present invention "cycloalkyl" may be polycyclic. Examples of such
cycloalkenyls include, but are not limited to, cyclopentenyl,
cyclohexylethen-2-yl, cycloheptenylpropenyl, and the like.
Furthermore, the chain forming cycloalkyl and/or cycloalkenyl is
advantageously of limited length, including C.sub.3-C.sub.24,
C.sub.3-C.sub.12, C.sub.3-C.sub.8, C.sub.3-C.sub.6, and
C.sub.5-C.sub.6. According to the present invention, shorter alkyl
and/or alkenyl chains forming cycloalkyl and/or cycloalkenyl,
respectively, may add less lipophilicity to the compound and
accordingly will have different behavior.
[0039] As used herein, the term "heteroalkyl" includes a chain of
atoms that includes both carbon and at least one heteroatom, and is
optionally branched. Examples of such heteroatoms include nitrogen,
oxygen, and sulfur. In certain variations, said hetero-atoms also
include phosphorus, and selenium. In one embodiment, a heteroalkyl
is a polyether. As used herein, the term "cycloheteroalkyl"
including heterocyclyl and heterocycle, includes a chain of atoms
that includes both carbon and at least one heteroatom, such as
heteroalkyl, and may optionally be branched, where at least a
portion of the chain is cyclic. Similarly, examples of
cycloheteroalkyl include, but are not limited to, tetrahydrofuryl,
pyrrolidinyl, tetrahydropyranyl, piperidinyl, morpholinyl,
piperazinyl, homopiperazinyl, quinuclidinyl, and the like.
[0040] Herein, the term "optionally substituted" includes the
replacement of hydrogen atoms with other functional groups on the
radical that is optionally substituted. Such other functional
groups illustratively include, but are not limited to, amino,
hydroxyl, halo, thiol, alkyl, haloalkyl, heteroalkyl, aryl,
arylalkyl, arylheteroalkyl, nitro, sulfonic acids and derivatives
thereof, carboxylic acids and derivatives thereof, and the like.
Illustratively, any of amino, hydroxyl, thiol, alkyl, haloalkyl,
heteroalkyl, aryl, arylalkyl, arylheteroalkyl, and/or sulfonic acid
is optionally substituted.
[0041] For example, the primary polyamine may be a diamine,
triamine, tetraamine, or pentamine. According to one embodiment,
the polyamine is a triamine selected from a diethylenetriamine,
1-piperazineethaneamine, or bis(hexamethylene)triamine. In another
embodiment, the polyamine is a tetramine, for example
triethylenetetramine. In another embodiment, the polyamine is a
pentamine, for example tetraethylenepentamine.
[0042] One aspect of the primary polyamine is that it may possess
low steric hindrance. For example, 1,2-diaminoethane,
1,4-diaminobutane, 1,5-diaminopentane, 1,6-diaminohexane,
1,12-diaminododecane, 1,4-diaminocyclohexane, 1,4-diaminobenzene,
diethylenetriamine, triethylenetetramine, tetraethylenepentamine,
1-piperazine-ethaneamine, 2-methyl-pentamethylenediamine,
1,3-pentanediamine, and bis(hexamethylene)triamine, as well as
1,8-diaminooctane have low steric hindrance within the scope of the
present invention. According to a preferred embodiment of the
binder composition as defined above, the nitrogen-containing
component is the primary polyamine 1,6-diaminohexane
(hexamethylenediamine, HMDA). In a further embodiment the
nitrogen-containing component is 1,5-diamino-2-methylpentane
(2-methyl-pentamethylened iamine).
[0043] In another embodiment, the nitrogen-containing component is
the primary polyamine polyether-polyamine. For example, according
to the present invention, said polyether-polyamine is a diamine or
a triamine. In one embodiment, the polyetherpolyamine is a
trifunctional primary amine having an average molecular weight of
440 known as Jeffamine T-403 Polyetheramine (Huntsman Corporation).
EDR-104 and EDR-148 (Huntsman) may also be used.
[0044] In a further embodiment, the nitrogen-containing component
may include a polymeric polyamine. For example, polymeric
polyamines within the scope of the present invention include
chitosan, polylysine, polyethylenimine, poly(N-vinyl-N-methyl
amine), polyaminostyrene and polyvinylamines. In a specific
example, the nitrogen-containing component comprises a polyvinyl
amine. As used herein, the polyvinyl amine can be a homopolymer or
a copolymer.
[0045] The term "solvent" used herein is not particularly
restricted and includes any solvent which may be used to carry out
a reaction between the carbohydrate component and the
nitrogen-containing component. For example, the solvent may be
water, an organic solvent or mixtures thereof. Examples of organic
solvents include alcohols, ethers, esters, ketones, aldehydes,
alkanes and cycloalkanes. Preferably, the solvent consists of or
consists essentially of water.
[0046] A further embodiment of the present invention relates to the
above-defined binder composition, wherein the weight ratio between
the carbohydrate component and the carbon dioxide reaction product
with said nitrogen-containing component is 0.5:1 to 30:1. Examples
of further molar ratios include ratios of 0.7:1 to 25:1, 1:1 to
22:1, 1.5:1 to 20:1, 2:1 to 15:1, 2.5:1 to 10:1 or 3:1 to 8:1.
However, according to the present invention, the molar ratio of
carbohydrate component to nitrogen-containing component is not
limited to said ranges and the above upper and lower borders may be
freely combined.
[0047] Depending on its chemical composition, the binder
composition of the present invention may be used as such, i.e. by
applying it to loosely assembled matter and curing it, for example
through application of heat and/or radiation to arrive at a
polymeric binder. In the course of the curing, the carbon dioxide
bound to components of the binder composition is substantially
eliminated, thus allowing for proper curing and/or cross-linking
reactions.
[0048] In a further embodiment, the binder composition may be used
by subsequently adding a crosslinker, applying the mixture onto the
loosely assembled matter and curing the mixture, thus forming a
highly crosslinked polymeric binder having similar or even improved
properties over the known carbohydrate-based binders. In this case,
the binder composition of the present application may
advantageously be prepared, stored and/or shipped, and used later
and/or at a different place by adding a cross-linker, to complete
the final binder composition.
[0049] If not stated otherwise, any of the above definitions also
apply to the further aspects and embodiments of the present
invention described below.
[0050] A further aspect of the present invention relates to a
method of manufacturing the binder composition as defined above,
comprising the steps: [0051] (i) providing at least one
carbohydrate component, [0052] (ii) providing at least one
nitrogen-containing component, [0053] (iii) providing carbon
dioxide, [0054] (iv) mixing in a solvent the carbohydrate
component(s) and the nitrogen-containing component(s), and cooling
at room temperature, and [0055] (v) bubbling carbon dioxide into
the mixture obtained in step (iv); or [0056] (i') providing at
least one carbohydrate component, [0057] (ii') providing at least
one nitrogen-containing component, [0058] (iii') providing carbon
dioxide, [0059] (iv') reacting the carbon dioxide with the
nitrogen-containing component, and [0060] (v') mixing in a solvent
the carbohydrate component(s) and the reaction product of
(iv').
[0061] According to the present invention, carbon dioxide may be
bubbled into the mixture at a rate of 0.5 to 50 w % based on the
total weight of the binder composition, or at a rate of 1 to 45 w
%, or at a rate of 1 to 40 w %, or 1 to 35 w %, or 1 to 30 w %, or
1 to 25 w %, or 1 to 20 w %, or 1 to 15 w %, or 1 to 10 w %, or 1
to 5 w %. Alternatively, "soda water" (carbonic acid) may be used
to supply part of the carbon dioxide or may constitute the entire
source of carbon dioxide in the binder composition. In another
variant of the present invention, a preformed carbamate of the at
least one nitrogen-containing component may be utilized.
[0062] In a preferred embodiment, the preparation of the binder
composition is carried out in a solvent, such as water, to directly
yield a binder solution usable for storage, shipping or as a basis
for preparing the final binder composition. For example, the
invention binder composition may be prepared in a concentrated
aqueous solution of the carbohydrate component and
nitrogen-containing component. The thus obtained concentrated
binder solution may then be used, for example, at a later time
and/or a different place, e.g. by dilution and addition of a
crosslinker, as an effective binder for consolidating loosely
assembled matter.
[0063] According to a preferred embodiment of the present
invention, the above steps (i) to (v) or (i') to (v') are carried
out while the carbohydrate component(s) and nitrogen-containing
component(s) are not in contact with a collection of matter which
is to be bound by a polymeric binder.
[0064] According to a further embodiment, the viscosity of the
solution or dispersion during step (iv) of mixing the carbohydrate
component(s) and the nitrogen-containing component(s) does not
increase by more than 300 cP, when determined at 20.degree. C. and
a starting concentration of 70 wt.-% total carbohydrate and
nitrogen-containing components present before said step (iv). For
example, the viscosity does not increase by more than 275 cP, more
than 250 cP, more than 225 cP, more than 200 cP, more than 175 cP,
more than 150 cP, more than 100 cP, more than 75 cP, or more than
50 cP.
[0065] The mixing step (iv) or (v') may be carried out at or
substantially at atmospheric pressure, for example in an open
reaction vessel. Step (v) may preferably be carried out in a closed
reaction vessel, at atmospheric pressure or at a pressure above
atmospheric pressure.
[0066] As mentioned before, a sufficient quantity of carbon dioxide
is bubbled into the solution in order to obtain an approx.
stoichiometric reaction with the nitrogen-containing component.
Practically, 0.5 to 50 w % CO.sub.2, preferably more than 1 w %,
more preferably more than 6 w %, even more preferably more than 7 w
% CO.sub.2, and up to 40 w %, preferably up to 35 w %, more
preferably up to 25 w % CO.sub.2, may be bubbled into the reaction
mixture obtained after mixing step (iv). The addition of carbon
dioxide lowers the pH of the mixture. In one preferred embodiment,
1 to 2 w % CO.sub.2 is bubbled into to the mixture obtained at the
end of step (iv).
[0067] According to another aspect, the present invention relates
to a water-soluble binder composition obtainable by the method as
defined above.
[0068] For example, one embodiment relates to the invention binder
composition as defined above, wherein said binder-composition is
obtainable by mixing in a solvent the at least one carbohydrate
component with the at least one nitrogen-containing component at a
temperature of at least 10.degree. C. for a period of at least 5
minutes and thereafter injecting carbon dioxide into the obtained
product mixture.
[0069] According to another aspect, the present invention relates
to a use of the water-soluble binder composition as defined above
in the manufacture of a product comprising a collection of matter
bound by a polymeric binder.
[0070] Herein, the term "collection of matter" is not particularly
restricted and includes any collection of matter which comprises
fibers selected from the group consisting of mineral fibers
(including slag wool fibers, stone wool fibers, glass fibers),
aramid fibers, ceramic fibers, metal fibers, carbon fibers,
polyimide fibers, polyester fibers, rayon fibers, brake lining
fibers and cellulosic fibers. Further examples of a collection of
matter include: particulates such as coal, sand; cellulosic fibers;
wood shavings, sawdust, wood pulp, ground wood, wood chips, wood
strands, wood layers; other natural fibers such as jute, flax,
hemp, and straw; wood veneers; facings; wood facings, particles,
woven or non-woven materials (e.g. comprising fibers, notably of
the type(s) referred to above).
[0071] A further aspect of the present invention relates to a
method of manufacturing a collection of matter bound by a polymeric
binder comprising the steps: [0072] (i) providing a collection of
matter, [0073] (ii) providing the above-defined binder composition,
or a binder composition obtained by the method as defined above, in
a solvent to obtain a solution or dispersion, [0074] (iii) applying
the solution or dispersion obtained in step (ii) to the collection
of matter, and [0075] (iv) applying energy to the collection of
matter containing said solution or dispersion to degas carbon
dioxide and cure the binder composition.
[0076] The step (iv) of applying energy to the collection of matter
as defined in the above method is not particularly restricted and
includes, for example, heating in an oven at a temperature of
100.degree. C. to 350.degree. C., depending on the type of matter,
the amount of binder and other conditions.
[0077] According to one embodiment of the above method, in step
(ii) a crosslinker is added to the invention binder composition as
defined above or the invention binder composition obtained by the
method as defined above, or the solution or dispersion thereof.
[0078] According to a further embodiment of the above-defined
method of manufacturing a collection of matter, prior to the step
of applying the solution or dispersion obtained in step (ii) to the
collection of matter, the collection of matter is substantially
free of binder.
[0079] A further aspect of the present invention relates to a
binder solution or dispersion comprising in a solvent the invention
binder composition as defined above and a crosslinker. In the
alternative, the invention relates to the combination, possibly in
different containers, of a binder solution or dispersion comprising
in a solvent the invention binder composition as defined above, and
a cross-linker.
[0080] The invention binder composition solution or dispersion,
particularly in the state applied to the material to be bound, may
comprise:
[0081] at least 5%, 10%, 12%, or 15% solids and/or
[0082] less than 75%, 70%, 65% or 60% (particularly in the case of
wood board applications) or less than 50%, 40% or 20% solids
(particularly in the case of mineral fibre insulation applications)
particularly determined as bake out solids by weight after drying
at 140.degree. C. for 2 hours.
[0083] Binders in accordance with the present invention may be used
as binders e.g. in articles selected from the group consisting of:
thermal insulation materials; mineral wool insulation (including
glass wool insulation and stone wool insulation); woven and
non-woven textile veils; woven and non-woven mineral fiber veils;
wood boards; fiberboards; wood particle boards; chip boards;
orientated strand board; medium density fiberboards; plywood; high
pressure laminates; and sand cores.
[0084] The quantity of binder in the finished product, particularly
in the case of mineral wool insulation, may be:
[0085] Greater than: 1%, 2%, 2.5%, 3%, 3.5% or 4%; and/or
[0086] Less than: 20%, 15%, 10% or 8% measured by dry weight of the
finished product.
[0087] The quantity of binder for mineral wool insulation is
typically measured by loss on ignition (LOI).
[0088] Where the application is for mineral wool insulation, latter
may have one or more of the following characteristics:
[0089] A density greater than 5, 8 or 10 kg/m.sup.3;
[0090] A density less than 200, 180 or 150 km/m.sup.3
[0091] Comprise glass wool fibres and have a density greater than
5, 8 or 10 kg/m.sup.3 and/or less than 80, 60 or 50 kg/m.sup.3;
[0092] Comprise stone wool fibres and have a density greater than
15, 20 or 25 kg/m.sup.3 and/or less than 220, 200 or 180
kg/m.sup.3;
[0093] A thermal conductivity A of less than 0.05 W/mK and/or
greater than 0.02 W/mK
[0094] Comprise less than 99% by weight and/or more than 80% by
weight mineral fibres.
[0095] A thickness of greater than 10 mm, 15 mm or 20 mm and/or
less than 400 mm, 350 mm or 300 mm.
[0096] Where the product is wood board product, it may have one or
more of the following characteristics:
[0097] Dimensions of at least 50cm.times.80 cm, preferably at least
1 m.times.2m
[0098] Thickness of at least 11 mm, 12 mm or 15 mm
[0099] A curing time of less than 25, 15, 12 or 10 minutes
[0100] An internal bond strength measured in accordance with EN319
of at least: 0.4 N/mm.sup.2 or 0.45 N/mm.sup.2 (particularly for
particle board or fibre boards) or measured in accordance with
EN300 of at least 0.28 N/mm.sup.2 (particularly for orientated
strand board)
[0101] A thickness swelling after 24 hours in water at 20.degree.
C. according to EN317 of less than 12%, preferably less than
10%
[0102] A water absorption after 24 hours in water at 20.degree. C.
of less than 40%, preferably less than 30%
[0103] A modulus of elasticity according to EN310 of at least: 1800
N/mm.sup.2 (particularly for particle board or fibre boards) or
2500 N/mm.sup.2 (particularly for orientated strand board) or 3500
N/mm.sup.2 or 4800 N/mm.sup.2
[0104] A bending strength (MOR) of at least: 14 N/m.sup.2
(particularly for particle board or fibre boards) or 18 N/mm.sup.2
(particularly for orientated strand board) or 20 N/mm.sup.2 or 28
N/mm.sup.2
[0105] Wax as an additive, for example in the range 0.1 to 2% by
weight, preferably 0.5 to 1% by weight
[0106] A binder content (weight of dry resin to weight of dry wood
particles) in the range 8 to 18% by weight, preferably 10 to 16% by
weight, more preferably 12 to 14% by weight. Be cured in a press,
particularly between plates or platens having a temperature of
greater than 180.degree. c or 200.degree. C. and/or less than
280.degree. C. or 260.degree. C.
[0107] Various additives can be incorporated into the binder
composition. These additives give the binders of the present
invention additional desirable characteristics. For example, the
binder may include a silicon-containing coupling agent. Many
silicon-containing coupling agents are commercially available from
the Dow-Corning Corporation, Evonik Industries, and Momentive
Performance Materials. Illustratively, the silicon-containing
coupling agent includes compounds such as silylethers and
alkylsilyl ethers, each of which may be optionally substituted,
such as with halogen, alkoxy, amino, and the like. In one
variation, the silicon-containing compound is an amino-substituted
silane, such as, gamma-aminopropyltriethoxy silane (SILQUEST
A-1101; Momentive Performance Materials, Corporate Headquarters: 22
Corporate Woods Boulevard, Albany, N.Y. 12211 USA). In another
variation, the silicon-containing compound is an amino-substituted
silane, for example, aminoethylaminopropyltrimethoxy silane (Dow
Z-6020; Dow Chemical, Midland, Mich.; USA). In another variation,
the silicon-containing compound is
gamma-glycidoxypropyltrimethoxysilane (SILQUEST A-187; Momentive).
In yet another variation, the silicon-containing compound is an
aminofunctional oligomeric siloxane (HYDROSIL 2627, Evonik
Industries, 379 Interpace Pkwy, Parsippany, N.J. 07054).
[0108] The silicon-containing coupling agents are typically present
in the binder in the range from about 0.1 percent to about 1
percent by weight based upon the dissolved binder solids (i.e.,
about 0.05% to about 3% based upon the weight of the solids added
to the aqueous solution). These silicone containing compounds
enhance the ability of the binder to adhere to the matter the
binder is disposed on, such as glass fibers
[0109] Enhancing the binder's ability to adhere to the matter
improves, for example, its ability to produce or promote cohesion
in non- or loosely-assembled substance(s).
[0110] In another illustrative embodiment, a binder of the present
invention may include one or more corrosion inhibitors. These
corrosion inhibitors prevent or inhibit the eating or wearing away
of a substance, such as, metal caused by chemical decomposition
brought about by an acid. When a corrosion inhibitor is included in
a binder of the present invention, the binder's corrosivity is
decreased as compared to the corrosivity of the binder without the
inhibitor present. In one embodiment, these corrosion inhibitors
can be utilized to decrease the corrosivity of the mineral
fiber-containing compositions described herein. Illustratively,
corrosion inhibitors include one or more of the following, a
dedusting oil, or a monoammonium phosphate, sodium metasilicate
pentahydrate, melamine, tin (II) oxalate, and/or methylhydrogen
silicone fluid emulsion. When included in a binder of the present
invention, corrosion inhibitors are typically present in the binder
in the range from about 0.5 percent to about 2 percent by weight
based upon the dissolved binder solids.
[0111] Binders in accordance with the present invention are
preferable thermosetting binders; they may be formaldehyde free or
substantially formaldehyde free binders. They are preferably
applied in liquid form.
[0112] The accompanying Figures show:
[0113] FIG. 1: the impact of CO.sub.2 injection on the viscosity of
a binder composition of the invention.
[0114] FIG. 2: the effect of CO.sub.2 injection on the browning of
a binder composition of the invention.
[0115] FIG. 3 the addition of CO.sub.2 has no significant effect on
the cure rates of binder compositions.
[0116] FIG. 4 the addition of CO.sub.2 has no significant effect on
the bond strength.
[0117] The present invention will be further illustrated in the
following examples, without limitation thereto.
EXAMPLE 1
Binder Composition of Glucose/Fructose and HMDA (75%/25%) and
Carbon Dioxide
[0118] A carbohydrate component composed of 50 w % glucose and 50 w
% fructose was dissolved in water and mixed with a corresponding
amount of HMDA (hexamethylenediamine) in aqueous solution, under
atmospheric pressure, in order to produce 500 g binder solution
comprising 75%w carbohydrate and 25%w HMDA, and 37.5 solids (pure
glucose required: 70.3125 g, pure fructose required: 70.3125 g,
pure HMDA required: 46.875 g). Whilst under mild agitation, the pH
is constantly monitored for the first 20 minutes. The pH dropped
from 11.82 to 11.4 of its own accord. A first 50 g samples is taken
at that point in time.
[0119] Carbon dioxide was then bubbled into the remaining 450 g
binder solution at a slow rate for approx. 30 min. Further 50 gram
samples were removed and bottled when the binder solution showed a
pH of 11, 10, 9 and 8.5, respectively. An increase in binder
temperature of 3-4.degree. C. was observed during the
experiment.
TABLE-US-00001 CO2 efficiency CO2 used Binder weight % CO2 pH (g)
increase (g) utilized Starting pH 11.58 pH 11 11 9.5 7.19 75.68% pH
10 10 21.89 15.08 68.89% pH 9.5 9.5 31 18.54 59.81%
[0120] All five samples were left in a water bath at 30.degree. C.
and tested over the course of 3 weeks to monitor changes in shelf
life, by way of cure rate, viscosity, browning and bond
strength.
[0121] Viscosity was measured using an LV-Torque Brookfield
Viscosimeter, spindle LV-63 at 60 rpm (for example).
[0122] FIG. 1 clearly shows that for the samples treated with
carbon dioxide the viscosity increases significantly later than for
the sample that has not been treated with carbon dioxide. From
these results, it can be concluded that self-curing leading to
increased viscosity is significantly delayed, in this test by more
than 2 weeks. Shelf-life hence is increased concomitantly.
[0123] Browning was measured by IR absorbance (visible) at 470
nm.
[0124] FIG. 2 clearly shows that browning of 002-treated samples is
significantly slower than non-treated sample.
[0125] Curing of binders: To follow cure rates, drops of binder
were placed on glass fibre filters and cured for various times. The
cured spots were extracted into water and the absorbance of the
leachate measured using a spectrophotometer. Absorbance rose
initially owing to the formation of soluble coloured compounds. The
absorbance then fell due to the cross linking of these soluble
compounds. The cure speed is considered to be the time taken for
the absorbance to fall to the minimum value.
[0126] As shown in FIG. 3, the cure rate of all samples is
essentially unaffected by the carbon dioxide treatment of the
binder samples.
[0127] Bonding strength was measured via a standard glass veil
tensile test method.
[0128] As can be seen in FIG. 4, the bonding strength is not
substantially affected or may even be slightly improved when the
invention binder samples are treated with carbon dioxide.
EXAMPLE 2
Binder Composition of Dextrose and HMDA Carbamate
[0129] Further work has been carried out on a binder composition
based on dextrose and a commercial carbamate of HMDA (Vucofac HMDAC
by Safic Alcan). The HMDA carbamate was dissolved in water until
saturation (approx. 30%wt) before adding the carbohydrate component
(a high fructose corn syrup at a glucose:fructose ratio of 58:42 by
Cargill) 1 to form a 37.5% solids aqueous binder composition
comprising 75 wt % carbohydrate and 25 wt % HMDA carbamate. Shelf
live was tested as per Example 1 in comparison with a standard HMDA
binder composition at 37.5 (:)/0 solids (same carbohydrate
component but HMDA instead of HMDA carbamate, at same ratio).
TABLE-US-00002 Standard HMDA binder HMDA carbamate binder 34 days
229 days
[0130] Clearly, the carbamate derivative of the amine component in
the binder composition significantly improves shelf live of the
composition, meaning self-polymerization being significantly
delayed.
EXAMPLE 3
Binder Composition of HFCS and Tri-Amino Nonane Carbamate
[0131] The carbohydrate component (high fructose corn syrup with a
glucose:fructose ratio of 58:42) was dissolved in water and mixed
with a corresponding amount of 4-(aminomethyl)-1,8-octanediamine
(TAN) in aqueous solution, under atmospheric pressure, to form a
37.5 solids composition comprising 75 wt % carbohydrate and 25 wt %
TAN. Whilst under mild agitation, the pH is constantly monitored
for the first 20 minutes. The pH dropped to 11.59 of its own
accord. A first 50 g samples is taken at that point in time.
[0132] Carbon dioxide was then bubbled through the remaining binder
solution at a slow rate for approx. up to 178 minutes. Further 50
gram samples were removed and bottled when the binder solution
showed a pH of 11, 10, and 9, respectively. No significant increase
in binder temperature was observed during the experiment.
TABLE-US-00003 pH Time (min) Temperature (C. .degree.) CO.sub.2
used 11.59 0 25 0 g 11 65 24 15.03 g 10 98 24 41.40 g 9 178 24
91.97 g
[0133] It has been found that the cure rates were not significantly
affected by the carbamate formation. The completion of cure
occurred between 5 and 6 minutes and the curing curves were very
similar for all pH values. For the test method, refer to Example
1.
[0134] The relevant samples were left in humidity cabinet set at
30.degree. C. and shelf live was monitored over time, in accordance
with the methodology of Example 1.
TABLE-US-00004 Sample 1 sample 2 sample 3 sample 4 pH 11.59 pH 11
pH 10 pH 9 6 days 9 days 23 days 49 days
* * * * *