U.S. patent application number 17/309560 was filed with the patent office on 2021-10-28 for polyesters comprising 2,2,4,4-tetraalkyl-1,3-cyclobutanediol.
This patent application is currently assigned to Eastman Chemical (China) Co., Ltd.. The applicant listed for this patent is Eastman Chemical (China) Co., Ltd.. Invention is credited to Christopher Harlan Burk, Nick Allen Collins, Emmett Dudley Crawford, Liu Deng, Sarah Exley Goetz, Thauming Kuo, Wentao Li, John Thorton Maddox, Rui Xie.
Application Number | 20210332184 17/309560 |
Document ID | / |
Family ID | 1000005750388 |
Filed Date | 2021-10-28 |
United States Patent
Application |
20210332184 |
Kind Code |
A1 |
Li; Wentao ; et al. |
October 28, 2021 |
POLYESTERS COMPRISING 2,2,4,4-TETRAALKYL-1,3-CYCLOBUTANEDIOL
Abstract
Adhesive compositions comprise a polyester polyol that includes
residues of at least one 2,2,4,4-tetraalkylcyclobutan e-1,3-diol,
including, for example, 2,2,4,4-tetramethylcyclobutane-1,3-diol
(TMCD). Adhesive compositions as described herein exhibit enhanced
properties as compared to conventional adhesive compositions, and
may be suitable for a wide variety of end use applications,
including, flexible packaging, woodworking, automotive uses, and
electronics.
Inventors: |
Li; Wentao; (Kingsport,
TN) ; Crawford; Emmett Dudley; (Kingsport, TN)
; Xie; Rui; (Pearland, TX) ; Burk; Christopher
Harlan; (Gray, TN) ; Collins; Nick Allen;
(Fall Branch, TN) ; Deng; Liu; (Kingsport, TN)
; Goetz; Sarah Exley; (Kingsport, TN) ; Kuo;
Thauming; (Kingsport, TN) ; Maddox; John Thorton;
(Jonesborough, TN) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
Eastman Chemical (China) Co., Ltd. |
Pudong New District |
|
CN |
|
|
Assignee: |
Eastman Chemical (China) Co.,
Ltd.
Pudong New District
CN
|
Family ID: |
1000005750388 |
Appl. No.: |
17/309560 |
Filed: |
December 6, 2019 |
PCT Filed: |
December 6, 2019 |
PCT NO: |
PCT/CN2019/123674 |
371 Date: |
June 4, 2021 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
|
|
62776179 |
Dec 6, 2018 |
|
|
|
Current U.S.
Class: |
1/1 |
Current CPC
Class: |
C08G 63/672 20130101;
C08G 63/181 20130101; C09J 175/06 20130101; C08G 63/199 20130101;
C08G 2170/00 20130101 |
International
Class: |
C08G 63/199 20060101
C08G063/199; C08G 63/181 20060101 C08G063/181; C08G 63/672 20060101
C08G063/672; C09J 175/06 20060101 C09J175/06 |
Claims
1. A polyester polyol suitable for use in adhesive compositions,
said polyester polyol comprising: (a) an acid component comprising
residues of at least one dicarboxyl monomer; and (b) a diol
component comprising residues of (i) a
2,2,4,4-tetraalkyl-1,3-cyclobutanediol (TACD); and (ii) at least
one diol or polyol other than said TACD, wherein said polyester
polyol has a hydroxyl functionality of less than 2.1 and a glass
transition temperature (Tg) in the range of from about -30.degree.
C. to less than 55.degree. C.
2. The polyester polyol of claim 1, wherein said at least one diol
(b)(ii) is selected from the group consisting of
2,2-dimethyl-1,3-propanediol (neopentyl glycol),
1,2-cyclohexanedimethanol, 1,3-cyclohexanedimethanol,
1,4-cyclohexaned im ethanol, 2,2,4-trim ethyl-1, 3-pentaned iol,
hydroxypivalyl hydroxypivalate, 2-methyl-1,3-propanediol,
2-butyl-2-ethyl-1,3-propanediol, 1,4-butanediol, 1,3-propanediol,
1,2-propanediol, ethylene glycol, diethylene glycol, pentanediol,
dodecandiol, and 1,6-hexanediol.
3. The polyester polyol of claim 1, wherein said dicarboxyl monomer
is selected from the group consisting of isophthalic acid or esters
thereof, terephthalic acid or esters thereof, phthalic acid or
esters thereof, phthalic anhydride, 1,4-cyclohexane-dicarboxylic
acid, 1,3-cyclohexanedicarboxylic acid, hexahydrophthalic
anhydride, tetrahydrophthalic anhydride, dodecanedioic acid,
sebacic acid, azelaic acid, maleic acid or anhydride, fumaric acid,
succinic anhydride, succinic acid, adipic acid, dimer acid,
hydrogenated dimer acid, 2,6-naphthalenedicarboxylic acid, glutaric
acid, and itaconic acid.
4. The polyester polyol of claim 1, wherein said at least one diol
(b)(ii) is selected from the group consisting of diethylene glycol,
1,4-cyclohexanedimethanol, neopentyl glycol, and combinations
thereof, and/or wherein said dicarboxyl monomer is selected from
the group consisting of 1,4-cyclohexanedicarboxylic acid, adipic
acid, isophthalic acid, hexahydrophthalic anhydride, and
combinations thereof.
5. The polyester polyol of claim 1, wherein said diol component
comprises up to about 20 mole percent of residues of said at least
one polyol (b) (ii), based on the total moles of said diol
component.
6. The polyester polyol of claim 1, wherein said acid component
comprises residues of at least two dicarboxyl monomers and wherein
each of the dicarboxyl monomers are present in an amount of at
least about 5 mole percent, based on the total residues of said
acid component.
7. The polyester polyol of claim 1, wherein said TACD comprises
2,2,4,4-tetramethyl-1,3-cyclobutanediol (TMCD).
8. The polyester polyol of claim 1, wherein said polyester polyol
has a glass transition temperature (Tg) of from about -25.degree.
C. to about 20.degree. C. and a hydroxyl number of not more than
150 mg KOH/g.
9. The polyester polyol of claim 1, wherein said polyester polyol
has a number average molecular weight of about 500 to about 10,000
g/mole.
10. The polyester polyol of claim 1, wherein said polyester polyol
has an inherent viscosity of about 0.05 to about 0.40 dL/g.
11. The polyester polyol of claim 1, wherein said acid component
comprises about 30 to about 60 mole percent of residues of adipic
acid and about 40 to about 70 mole percent of residues of
isophthalic acid, based on the total moles of said acid component,
wherein said diol component comprises about 20 to about 80 mole
percent of residues of diethylene glycol and about 20 to about 80
mole percent of residues of 2,2,4,4-tetramethyl-1,3-cyclobutanediol
(TMCD), based on the total moles of said diol component, wherein
said polyester polyol has a hydroxyl number in the range of from
about 15 to about 120 mg KOH/g, and a glass transition temperature
of from about -25.degree. C. to about 20.degree. C.
12. The polyester polyol of claim 1, wherein said acid component
comprises about 5 to about 100 mole percent of residues of a
dicarboxyl monomer selected from the group consisting of
1,4-cyclohexanedicarboxylic acid, adipic acid, isophthalic acid,
and hexahydrophthalic acid, based on the total moles of said acid
component, and wherein said diol component comprises about 5 to
about 95 mole percent of residues of said at least one diol is
selected from the group consisting of 1,4-cyclohexanedimethanol,
neopentyl glycol, and combinations thereof, based on the total
moles of said diol component, wherein said polyester polyol has a
hydroxyl number of about 15 to about 50 mg KOH/g and a glass
transition temperature of from about 20 to less than 55.degree.
C.
13. A polyester polyol suitable for use in adhesive compositions,
said polyester polyol comprising: (a) an acid component comprising
residues of at least two dicarboxyl monomers, wherein each of said
dicarboxyl monomers are present in said acid component in an amount
of greater than about 5 mole percent, based on the total moles of
said acid component; and (b) a diol component comprising residues
of a 2,2,4,4-tetraalkyl-1,3-cyclobutanediol (TACD); wherein said
polyester polyol has a hydroxyl functionality of less than 2.1 and
at least one of the following properties (A) and (B) (A) a glass
transition temperature (Tg) in the range of from about -30 to about
120.degree. C.; and (B) a number average molecular weight (Mn) in
the range of from about 500 to about 10,000 g/mole.
14. The polyester polyol of claim 13, wherein said acid component
comprises at least about 5 mole percent of residues of adipic acid,
isophthalic acid, hexahydrophthalic anhydride,
1,4-cyclohexanedicarboxylic acid, and combinations thereof, based
on the total residues of said acid component.
15. The polyester polyol of claim 13, wherein said acid component
comprises not more than about 95 mole percent of residues of
isophthalic acid.
16. The polyester polyol of claim 13, wherein said diol component
further comprises at least about 5 mole percent of residues of at
least one diol selected from the group consisting of
1,4-cyclohexanedimethanol, neopentyl glycol, and diethylene glycol,
and combinations thereof, based on the total residues of said diol
component.
17. The polyester polyol of claim 13, wherein said diol component
comprises residues of 2,2,4,4-tetramethyl-1,3-butanediol (TMCD) in
an amount of about 15 to about 85 mole percent, based on the total
residues of said diol component, and exhibits both of properties
(A) and (B).
18. The polyester polyol of claim 13, wherein said acid component
comprises at least about 10 mole percent of residues of adipic acid
and at least about 10 mole percent of residues of isophthalic acid
and said diol component comprises at least about 10 mole percent of
residues of diethylene glycol and at least about 10 mole percent of
residues of said TACD.
19. The polyester polyol of claim 13, wherein said polyol has a Tg
of about -25.degree. C. to about 20.degree. C., a hydroxyl number
of about 15 to about 70 mg KOH/g, and a number average molecular
weight of about 1500 to about 9000 g/mole.
20. The polyester polyol of claim 13, wherein said polyol has a Tg
of about 0 to about 70.degree. C., a hydroxyl number of about 15 to
about 60 mg KOH/g, and a number average molecular weight of about
2000 to about 5500 g/mole.
Description
FIELD OF THE INVENTION
[0001] This invention relates to polyurethane adhesives based on
polyesters containing residues of a
2,2,4,4-tetraalkyl-1,3-cyclobutanediol (TACD), and, in particular,
residues of 2,2,4,4-tetramethylcyclobutane-1,3-diol (TMCD).
BACKGROUND
[0002] Polyurethanes are widely used as adhesives and sealants to
bond a variety of substrates. Depending on the applications,
polyurethane adhesives and sealants can be formulated to provide
various desirable properties. However, unmet needs still exist for
various applications. For example, improved weatherability can be
desirable for outdoor applications, for example, in building and
construction, and in exterior applications in automotive and
aircraft uses. Thermal stability is one property desirable for auto
interior applications. Hydrolytic stability and chemical resistance
can be desirable for packaging and electronic applications. Impact
resistance can be desirable for auto windshield mounting. Reduced
viscosity can be desirable for ease of applying hot melt adhesives.
Reduced volatile organic compounds (VOC) can be advantageous for
laminating adhesives. Also, a need in the assembly of parts for
consumer electronics is increasingly influenced by the
miniaturization of electronic devices where new materials are
desirable. In addition, as the global manufacturing industry is
transitioning to the use of more lightweight materials, there is a
greater demand for non-traditional materials. Lightweight
materials, such as composites, aluminum and other metal alloys
cannot be fastened in the same way as traditional metals. The
methods of joining different materials together is transitioning
from mechanical fasteners like screws, bolts and welds to adhesives
and joints.
[0003] Thus, there is a need for polyurethane adhesives/sealants
that have improved properties for certain end-use applications,
such as, for example, adequate cure time, green bond strength,
solvent resistance, chemical resistance, hydrolytic stability,
thermal stability, impact resistance, weatherability, improved
applicability, and reduced volatile organic compounds (VOC).
SUMMARY
[0004] In one aspect, the present invention concerns a polyester
polyol suitable for use in adhesive compositions, the polyester
polyol comprising: (a) an acid component comprising residues of at
least one dicarboxyl monomer; and (b) a diol component comprising
residues of (i) a 2,2,4,4-tetraalkyl-1,3-cyclobutanediol (TACD);
and (ii) at least one diol or polyol other than the TACD, wherein
the polyester polyol has a hydroxyl functionality of less than 2.1
and a glass transition temperature (Tg) in the range of from about
-30.degree. C. to less than 55.degree. C.
[0005] In one aspect, the present invention concerns a polyester
polyol suitable for use in adhesive compositions, the polyester
polyol comprising: an acid component comprising residues of at
least two dicarboxyl monomers, wherein each of the dicarboxyl
monomers are present in the acid component in an amount of greater
than about 5 mole percent, based on the total moles of the acid
component; and a diol component comprising residues of a
2,2,4,4-tetraalkyl-1,3-cyclobutanediol (TACD); wherein the
polyester polyol has a hydroxyl functionality of less than 2.1 and
at least one of the following properties (A) and (B): (A) a glass
transition temperature (Tg) in the range of from -30 to 120.degree.
C.; and (B) a number average molecular weight (Mn) in the range of
from 500 to 10,000 g/mole.
[0006] In one aspect, the present invention concerns a method of
making a polyester polyol suitable for use in an adhesive
composition, the method comprising reacting at least two dicarboxyl
monomers with a 2,2,4,4-tetraalkyl-1,3-cyclobutanediol (TACD) to
form a polyester polyol, wherein the polyester polyol has a
hydroxyl functionality of less than 2.1 and at least one of the
following properties (A) and (B): (A) a glass transition
temperature (Tg) in the range of from -30 to 120.degree. C.; and
(B) a number average molecular weight (Mn) in the range of from 500
to 10,000 g/mole, wherein the polyester polyol has an acid
component comprising greater than 5 mole percent of each of
residues of each of the dicarboxyl monomers, based on the total
moles of the acid component.
[0007] In one aspect, the present invention concerns an adhesive
composition comprising a prepolymer having an isocyanate
functionality comprising the reaction product of (i) a polyester
polyol comprising the residues of (A)
2,2,4,4-tetraalkylcyclobutane-1,3-diol in an amount of about 5 to
about 95 mole %, based on the total moles of the diols, (B) at
least one diol other than 2,2,4,4-tetraalkylcyclobutane-1,3-diol in
an amount of about 5 to 95 mole % based on the total moles of the
diols, (A) and (B) equaling 100 mole %, and (C) a dicarboxyl
compound, and (ii) a difunctional isocyanate, and (b) water or a
compound having one or more functional groups selected from
hydroxyl, amino, ketoacetate, and carbamate.
[0008] In one aspect, the present invention concerns a laminated
article comprising: a first layer presenting a first surface; a
second layer presenting a second surface; and an adhesive layer
disposed between and at least partially in contact with at least
one of the first and the second surfaces, wherein the adhesive
layer is formed from an adhesive composition comprising a
polyurethane polymer or prepolymer comprising (i) residues of a
polyester polyol having a diol component having residues of
2,2,4,4-tetraalkyl-1,3-butanediol (TACD); and (ii) residues of at
least one isocyanate.
[0009] In one aspect, the present invention concerns a method of
making an adhesive composition, the method comprising: combining
(a) a polyester polyol comprising a diol component having residues
of 2,2,4,4-tetraalkyl-1,3-butanediol (TACD); and (b) at least one
isocyanate to form an adhesive composition, wherein the adhesive
composition exhibits at least one of the following properties (i)
through (v): (i) an offline bond strength of 100 to 1000 g/in; (ii)
24-hour bond strength of 200 to 3000 g/in; (iii) chemical
resistance of 200 to 1000 g/in after boil in bag with 1:1:1 food
simulant; (iv) thermal resistance of 200 to 800 g/in at 90.degree.
C.; and (v) time to achieve substrate failure of .ltoreq.24
hours.
[0010] In one aspect, the present invention concerns a method for
making a laminated article, the method comprising: providing a
first layer presenting a first surface; applying an adhesive
composition to at least a portion of the first surface; contacting
a second surface of a second layer with at least a portion of the
adhesive composition; and adhering the first layer to the second
layer via an adhesive layer formed by the adhesive composition to
form a laminated article, wherein the adhesive layer comprises a
polyester polyol comprising residues of (i) a polyester polyol
comprising a diol component having residues of
2,2,4,4-tetraalkyl-1,3-butanediol (TACD); and (ii) at least one
isocyanate.
[0011] In another aspect, the present invention concerns a hot melt
adhesive composition, the adhesive composition comprising: an
isocyanate-terminated polyurethane prepolymer comprising residues
of (i) at least one polyester polyol comprising a diol component
having residues of 2,2,4,4-tetraalkyl-1,3-cyclobutanediol (TACD)
and (ii) at least one isocyanate, wherein the adhesive composition
has a solids content of at least 95 percent, based on the total
weight of the composition.
[0012] In one aspect, the present invention concerns a hot melt
adhesive composition, the adhesive composition comprising: a
polyurethane prepolymer comprising residues of (i) at least one
polyester polyol comprising a diol component having residues of
2,2,4,4-tetraalkyl-1,3-cyclobutanediol (TACD) and (ii) at least one
isocyanate, wherein at least one property of the adhesive selected
from the group consisting of green strength, heat resistance, and
hydrolytic stability is at least 5 percent higher than the same
property exhibited by an identical adhesive composition formed with
a polyurethane prepolymer having an identical composition as the
polyurethane prepolymer, but having residues of a comparative
polyester polyol instead of said polyester polyol, wherein said
comparative polyester polyol has an acid component comprising 50
mole % terephthalic acid (TPA) and 50 mole % isophthalic acid (IPA)
and a diol component comprising 52 mole % neopentyl glycol (NPG)
and 48 mole % ethylene glycol with a hydroxyl number of 45 mg
KOH/g, a glass transition temperature of 50.degree. C., and a melt
viscosity of 130.degree. C. at 60 Pas, all other components being
the same.
[0013] In one aspect, the present invention concerns a method of
using an adhesive composition, the method comprising: (a) applying
an adhesive composition to a first surface of a first substrate to
form an adhesive layer, wherein the adhesive composition comprises
a polyurethane prepolymer having residues of (i) a polyester polyol
comprising residues of 2,2,4,4-tetraalkyl-1,3-cyclobutanediol
(TACD) and (ii) at least one isocyanate; (b) contacting at least a
portion of the adhesive layer with a second surface of a second
substrate; and (c) adhering the first substrate and the second
substrate to one another via the adhesive layer thereby forming a
layered article.
DETAILED DESCRIPTION
[0014] The present invention may be understood more readily by
reference to the following detailed description of certain
embodiments of the invention and the working examples.
[0015] Adhesive compositions described herein may exhibit unique
and desirable properties such as, for example, improved cure time,
green bond strength, solvent resistance, chemical resistance,
hydrolytic stability, thermal stability, impact resistance,
weatherability, improved applicability, and reduced VOC, as
compared to conventional adhesive compositions. Such compositions
may include polyester polyols comprising residues of at least one
2,2,4,4-tetraalkyl-1,3-cyclobutandiol (TACD), which may itself have
unexpected properties capable of imparting enhanced functionality
or performance to the adhesive composition. Such adhesive
compositions as described herein may be of several types and may be
suitable for a wide array of end uses, such as, for example,
flexible packaging, automotive, building and construction, wood
working, assembly of electronic components, and potting for
electronics.
[0016] Polyester polyols include an acid component and a diol
component. In some embodiments, the diol component may comprise
residues of 2,2,4,4-tetraalkylcyclobutane-1,3-diol (TACD). TACD is
a diol and can be represented by the general structure:
##STR00001##
wherein R.sub.1, R.sub.2, R.sub.3, and R.sub.4 each independently
represent an alkyl radical, for example, a lower alkyl radical
having 1 to 8 carbon atoms, or 1 to 6 carbon atoms, or 1 to 5
carbon atoms, or 1 to 4 carbon atoms, or 1 to 3 carbon atoms, or 1
to 2 carbon atoms, or 1 carbon atom. The alkyl radicals may be
linear, branched, or a combination of linear and branched alkyl
radicals. Examples of TACDs include
2,2,4,4-tetramethylcyclobutane-1,3-diol (TMCD),
2,2,4,4-tetraethylcyclobutane-1,3-diol,
2,2,4,4-tetra-n-propylcyclobutane-1,3-diol,
2,2,4,4-tetra-n-butylcyclobutane-1,3-diol,
2,2,4,4-tetra-n-pentylcyclobutane-1,3-diol,
2,2,4,4-tetra-n-hexylcyclobutane-1,3-diol,
2,2,4,4-tetra-n-heptylcyclobutane-1,3-diol,
2,2,4,4-tetra-n-octylcyclobutane-1,3-diol,
2,2-dimethyl-4,4-diethylcyclobutane-1,3-diol,
2-ethyl-2,4,4-trimethylcyclobutane-1,3-diol,
2,4-dimethyl-2,4-diethyl-cyclobutane-1,3-diol,
2,4-dimethyl-2,4-di-n-propylcyclobutane-1,3-diol,
2,4-n-dibutyl-2,4-diethylcyclobutane-1,3-diol,
2,4-dimethyl-2,4-diisobutylcyclobutane-1,3-diol, and
2,4-diethyl-2,4-diisoamylcyclobutane-1,3-diol. In some embodiments,
TACD may comprise or be TMCD.
[0017] The TACD residues may be present in the diol component of
the polyester polyol in an amount of at least 2 mole %, 3 mole %, 5
mole %, 10 mole %, 15 mole %, 20 mole %, 25 mole %, 30 mole %, 35
mole %, 40 mole %, 45 mole %, 50 mole %, 55 mole %, 60 mole %, 65
mole %, 70 mole %, 75 mole %, 80 mole %, 85 mole %, 90 mole %, or
95 mole % based on the total residues of the diol component.
Additionally, or in the alternative, the diol component of the
polyester polyol may comprise not more than 99 mole %, 97 mole %,
95 mole %, 90 mole %, 85 mole %, 80 mole %, 75 mole %, 70 mole %,
65 mole %, 60 mole %, 55 mole %, 50 mole %, 45 mole %, 40 mole %,
35 mole %, 30 mole %, 25 mole %, 20 mole %, 15 mole %, or 10 mole %
of TACD residues, based on the total moles of the diol
component.
[0018] In one embodiment, the diol component of the polyester
polyol may comprise TACD residues in an amount of about 5 to about
95 mole % or an amount of about 15 to about 60 mole %, based on the
total moles of the diols and the polyol equaling 100 mole % (based
on the total moles of the diol component).
[0019] In some embodiments, TACD residues can be present in the
diol component of the polyester polyol in one of the following
amounts: 5 to 95 mole %; 5 to 90 mole %; 5 to 85 mole %; 5 to 80
mole %; 5 to 75 mole %; 5 to 70 mole %; 5 to 65 mole %; 5 to 60
mole %; 5 to 55 mole %; 5 to 50 mole %; 5 to 45 mole %; 5 to 40
mole %; 5 to 35 mole %; 5 to 30 mole %; 5 to 25 mole %; 5 to 20
mole %; 5 to 15 mole %; 10 to 95 mole %; 10 to 90 mole %; 10 to 85
mole %; 10 to 80 mole %; 10 to 75 mole %; 10 to 70 mole %; 10 to 65
mole %; 10 to 60 mole %; 10 to 55 mole %; 10 to 50 mole %; 10 to 45
mole %; 10 to 40 mole %; 10 to 35 mole %; 10 to 30 mole %; 10 to 25
mole %; 10 to 20 mole %; 15 to 95 mole %; 15 to 90 mole %; 15 to 85
mole %; 15 to 80 mole %; 15 to 75 mole %; 15 to 70 mole %; 15 to 65
mole %; 15 to 60 mole %; 15 to 55 mole %; 15 to 50 mole %; 15 to 45
mole %; 15 to 40 mole %; 15 to 35 mole %; 15 to 30 mole %; 15 to 25
mole %; 20 to 95 mole %; 20 to 90 mole %; 20 to 85 mole %; 20 to 80
mole %; 20 to 75 mole %; 20 to 70 mole %; 20 to 65 mole %; 20 to 60
mole %; 20 to 55 mole %; 20 to 50 mole %; 20 to 45 mole %; 20 to 40
mole %; 20 to 35 mole %; 20 to 30 mole %, based on the total moles
of the diol component.
[0020] In some embodiments, TACD residues can be present in the
diol component of the polyester polyol in one of the following
amounts: 25 to 95 mole %; 25 to 90 mole %; 25 to 85 mole %; 25 to
80 mole %; 25 to 75 mole %; 25 to 70 mole %; 25 to 65 mole %; 25 to
60 mole %; 25 to 55 mole %; 25 to 50 mole %; 25 to 45 mole %; 25 to
40 mole %; 25 to 35 mole %; 30 to 95 mole %; 30 to 90 mole %; 30 to
85 mole %; 30 to 80 mole %; 30 to 75 mole %; 30 to 70 mole %; 30 to
65 mole %; 30 to 60 mole %; 30 to 55 mole %; 30 to 50 mole %; 30 to
45 mole %; 30 to 40 mole %; 35 to 95 mole %; 35 to 90 mole %; 35 to
85 mole %; 35 to 80 mole %; 35 to 75 mole %; 35 to 70 mole %; 35 to
65 mole %; 35 to 60 mole %; 35 to 55 mole %; 35 to 50 mole %; 35 to
45 mole %, based on the total moles of the diol component.
[0021] In some embodiments, TACD residues can be present in one of
the following amounts: 40 to 95 mole %; 40 to 90 mole %; 40 to 85
mole %; 40 to 80 mole %; 40 to 75 mole %; 40 to 70 mole %; 40 to 65
mole %; 40 to 60 mole %; 40 to 55 mole %; 40 to 50 mole %; 45 to 95
mole %; 45 to 90 mole %; 45 to 85 mole %; 45 to 80 mole %; 45 to 75
mole %; 45 to 70 mole %; 45 to 65 mole %; 45 to 60 mole %; 45 to 55
mole %; 50 to 95 mole %; 50 to 90 mole %; 50 to 85 mole %; 50 to 80
mole %; 50 to 75 mole %; 50 to 70 mole %; 50 to 65 mole %; 50 to 60
mole %, based on the total moles of the diol component.
[0022] In some embodiments, the diol component of the polyester
polyol can comprise residues of at least one diol other than the
TACD diol. Such diols comprise two hydroxyl groups per molecule,
and can be branched or linear, saturated or unsaturated, aliphatic
or cycloaliphatic C.sub.2-C.sub.20 compounds. The hydroxyl groups
on these diols may be primary, secondary, and/or tertiary and, in
some embodiments, may be primary diols.
[0023] Examples of diols other than TACD suitable for inclusion in
the polyester polyol include 2,2-dimethyl-1,3-propanediol
(neopentyl glycol), 1,2-cyclohexanedimethanol,
1,3-cyclohexanedimethanol, 1,4-cyclohexanedimethanol,
2,2,4-trimethyl-1,3-pentanediol, hydroxypivalyl hydroxypivalate,
2-methyl-1,3-propanediol, 2-butyl-2-ethyl-1,3-propanediol,
2-ethyl-2-isobutyl-1,3-propanediol, 1,3-butanediol, 1,4-butanediol,
1,5-pentanediol, 1,6-hexanediol,
2,2,4,4-tetramethyl-1,6-hexanediol, 1,10-decanediol,
1,4-benzenedimethanol, ethylene glycol, 1-3-propylene glycol,
1-4-propylene glycol, diethylene glycol, dipropylene glycol,
triethylene glycol, tetraethylene glycol, polyethylene glycol,
pentanediol, dodecandiol, and 2,2-bis(hydroxymethyl)propionic acid
(dimethylolpropionic acid).
[0024] In some embodiments, the diol other than TACD may be
selected from 2,2-dimethyl-1,3-propanediol (neopentyl glycol),
1,2-cyclohexanedimethanol, 1,3-cyclohexanedimethanol,
1,4-cyclohexanedimethanol, 2,2,4-trimethyl-1,3-pentanediol,
hydroxypivalyl hydroxypivalate, 2-methyl-1,3-propanediol,
2-butyl-2-ethyl-1,3-propanediol, 1,4-butanediol, 1,3-propanediol,
1,2-propanediol, ethylene glycol, diethylene glycol, and
1,6-hexanediol or mixtures thereof. The diol other than TACD may
also be selected from the group consisting of diethylene glycol,
1,4-butanediol, 1,6-hexanediol, pentanediol, dodecandiol, and
combinations thereof. Alternatively, or in addition, the diol other
than TACD may be selected from the group consisting of diethylene
glycol, 1,4-cyclohexanedimethanol, neopentyl glycol, and
combinations thereof.
[0025] In some embodiments, the diol component of the polyester
polyol can comprise residues of a diol other than TACD in an amount
of at least about 3 mole %, at least about 5 mole %, at least about
10 mole %, at least about 15 mole %, at least about 20 mole %, at
least about 25 mole %, at least about 30 mole %, at least about 35
mole %, at least about 40 mole %, at least about 45 mole %, at
least about 50 mole %, at least about 55 mole %, at least about 60
mole %, at least about 65 mole %, at least about 70 mole %, or at
least about 75 mole % and/or not more than about 95 mole %, not
more than about 90 mole %, not more than about 85 mole %, not more
than about 80 mole %, not more than about 75 mole %, not more than
about 70 mole %, not more than about 65 mole %, not more than about
60 mole %, not more than about 55 mole %, not more than about 50
mole %, not more than about 45 mole %, or not more than about 40
mole %, based on the total moles of the diol component.
[0026] In some embodiments, residues of a diol other than TACD can
be present in the diol component of the polyester polyol in one of
the following amounts: 40 to 95 mole %; 40 to 90 mole %; 40 to 85
mole %; 40 to 80 mole %; 40 to 75 mole %; 40 to 70 mole %; 40 to 65
mole %; 40 to 60 mole %; 40 to 55 mole %; 40 to 50 mole %; 45 to 95
mole %; 45 to 90 mole %; 45 to 85 mole %; 45 to 80 mole %; 45 to 75
mole %; 45 to 70 mole %; 45 to 65 mole %; 45 to 60 mole %; 45 to 55
mole %; 50 to 95 mole %; 50 to 90 mole %; 50 to 85 mole %; 50 to 80
mole %; 50 to 75 mole %; 50 to 70 mole %; 50 to 65 mole %; 50 to 60
mole %; 55 to 95 mole %; 55 to 90 mole %; 55 to 85 mole %; 55 to 80
mole %; 55 to 75 mole %; 55 to 70 mole %; 55 to 65 mole %; 60 to 95
mole %; 60 to 90 mole %; 60 to 85 mole %; 60 to 80 mole %; 60 to 75
mole %; 60 to 70 mole %; 65 to 95 mole %; 65 to 90 mole %; 65 to 85
mole %; 65 to 80 mole %; 65 to 75 mole %; 70 to 95 mole %; 70 to 90
mole %; 70 to 85 mole %; 70 to 80 mole %; 75 to 95 mole %; 75 to 90
mole %; 75 to 85 mole %; 80 to 95 mole %; 80 to 90 mole %, based on
the total moles of the diol component.
[0027] In some embodiments, the diol component of the polyester
polyol may comprise the following residues: TACD residues in the
amount of 15 to 60 mole % and the residues of at least one diol
other than TACD can be present in the amount of 40 to 85%; TACD
residues can be present in the amount of 20 to 60 mole % and the
residues of at least one diol other than TACD can be present in the
amount of 40 to 80%; TACD residues can be present in the amount of
25 to 60 mole % and the residues of at least one diol other than
TACD can be present in the amount of 40 to 75%; TACD residues can
be present in the amount of 30 to 60 mole % and the residues of at
least one diol other than TACD can be present in the amount of 40
to 70%, based on the total moles of the diol component.
[0028] In some embodiments, the diol component of the polyester
polyol may include one of the following compositions: (1) TACD
residues can be present in the amount of 15 to 55 mole % and the
residues of at least one diol other than TACD can be present in the
amount of 45 to 85%; or (2) TACD residues can be present in the
amount of 20 to 55 mole % and the residues of at least one diol
other than TACD can be present in the amount of 45 to 80%; or (3)
TACD residues can be present in the amount of 25 to 55 mole % and
the residues of at least one diol other than TACD can be present in
the amount of 45 to 75%; or (4) TACD residues can be present in the
amount of 30 to 55 mole % and the residues of at least one diol
other than TACD can be present in the amount of 45 to 70%; or (5)
TACD residues can be present in the amount of 35 to 55 mole % and
the residues of at least one diol other than TACD can be present in
the amount of 45 to 65%; or (6) TACD residues can be present in the
amount of 40 to 55 mole % and the residues of at least one diol
other than TACD can be present in the amount of 45 to 60%, based on
the total moles of the diol component.
[0029] In some embodiments, the diol component of the polyester
polyol may include one of the following compositions: (7) TACD
residues can be present in the amount of 15 to 50 mole % and the
residues of at least one diol other than TACD can be present in the
amount of 50 to 85 mole %; or (8) TACD residues can be present in
the amount of 20 to 50 mole % and the residues of at least one diol
other than TACD can be present in the amount of 50 to 80 mole %; or
(9) TACD residues can be present in the amount of 25 to 50 mole %
and the residues of at least one diol other than TACD can be
present in the amount of 50 to 75 mole %; or (10) TACD residues can
be present in the amount of 30 to 50 mole % and the residues of at
least one diol other than TACD can be present in the amount of 50
to 70 mole %; or (11) TACD residues can be present in the amount of
35 to 50 mole % and the residues of at least one diol other than
TACD can be present in the amount of 50 to 65 mole %; or (12) TACD
residues can be present in the amount of 40 to 50 mole % and the
residues of at least one diol other than TACD can be present in the
amount of 50 to 60 mole %, based on the total moles of the diol
component.
[0030] In some embodiments, the diol component of the polyester
polyol may include one of the following compositions: (13) TACD
residues can be present in the amount of 15 to 45 mole % and the
residues of at least one diol other than TACD can be present in the
amount of 55 to 85 mole %; or (14) TACD residues can be present in
the amount 20 to 45 mole % and the residues of at least one diol
other than TACD can be present in the amount of 55 to 80 mole %; or
(15) TACD residues can be present in the amount of 25 to 45 mole %
and the residues of at least one diol other than TACD can be
present in the amount of 55 to 75 mole %; or (16) TACD residues can
be present in the amount of 30 to 45 mole % and the residues of at
least one diol other than TACD can be present in the amount of 55
to 70 mole %; or (17) TACD residues can be present in the amount of
35 to 45 mole % and the residues of at least one diol other than
TACD can be present in the amount of 55 to 65% mole; or (18) TACD
residues can be present in the amount of 40 to 45 mole % and the
residues of at least one diol other than TACD can be present in the
amount of 55 to 60 mole %, based on the total moles of the diol
component.
[0031] In some embodiments, the diol component of the polyester
polyol may include one of the following compositions: (19) TACD
residues can be present in the amount of 15 to 40 mole % and the
residues of at least one diol other than TACD can be present in the
amount of 60 to 85 mole %; or (20) TACD residues can be present in
the amount of 20 to 40 mole % and the residues of at least one diol
other than TACD can be present in the amount of 60 to 80 mole %; or
(21) TACD residues can be present in the amount of 25 to 40 mole %
and the residues of at least one diol other than TACD can be
present in the amount of 60 to 75% mole; or (22) TACD residues can
be present in the amount of 30 to 40 mole % and the residues of at
least one diol other than TACD can be present in the amount of 60
to 70 mole %; or (23) TACD residues can be present in the amount of
35 to 40 mole % and the residues of at least one diol other than
TACD can be present in the amount of 60 to 65 mole %, based on the
total moles of the diol component.
[0032] In some embodiments, the diol component of the polyester
polyol may include one of the following compositions: (24) TACD
residues can be present in the amount of 15 to 35 mole % and the
residues of at least one diol other than TACD can be present in the
amount of 65 to 85 mole %; or (25) TACD residues can be present in
the amount of 20 to 35 mole % and the residues of at least one diol
other than TACD can be present in the amount of 65 to 80 mole %; or
(26) TACD residues can be present in the amount of 25 to 35 mole %
and the residues of at least one diol other than TACD can be
present in the amount of 65 to 75 mole %; or (27) TACD residues can
be present in the amount of 30 to 35 mole % and the residues of at
least one diol other than TACD can be present in the amount of 65
to 70 mole %, based on the total moles of the diol component.
[0033] In some embodiments, the diol component of the polyester
polyol may include one of the following compositions: (28) TACD
residues can be present in the amount of 15 to 30 mole % and the
residues of at least one diol other than TACD can be present in the
amount of 70 to 85 mole %; or (29) TACD residues can be present in
the amount of 20 to 30 mole % and the residues of at least one diol
other than TACD can be present in the amount of 70 to 80 mole %; or
(30) TACD residues can be present in the amount of 25 to 30 mole %
and the residues of at least one diol other than TACD can be
present in the amount of 70 to 75 mole %, based on the total moles
of the diol component.
[0034] In some embodiments, the diol component of the polyester
polyol may include one of the following compositions: (31) TACD
residues can be present in the amount of 15 to 25 mole % and the
residues of at least one diol other than TACD can be present in the
amount of 75 to 85 mole %; or (32) TACD residues can be present in
the amount of 20 to 25 mole % and the residues of at least one diol
other than TACD can be present in the amount of 75 to 80 mole %,
based on the total moles of the diol component.
[0035] According to some embodiments, the diol component of the
polyester polyol may comprise not more than 25 mole % of one or
more certain types of diols. For example, in some embodiments, the
diol component of the polyester polyol may comprise not more than
20 mole %, not more than about 15 mole %, not more than about 10
mole %, not more than about 8 mole %, not more than about 5 mole %,
not more than about 3 mole %, not more than about 2 mole %, not
more than about 1 mole %, or not more than about 0.5 mole % of
aromatic diols, based on the total moles of the diol component. In
some embodiments, the diol component of the polyester polyol may
comprise not more than 20 mole %, not more than about 15 mole %,
not more than about 10 mole %, not more than about 8 mole %, not
more than about 5 mole %, not more than about 3 mole %, not more
than about 2 mole %, not more than about 1 mole %, or not more than
about 0.5 mole % of ethylene glycol, based on the total moles of
the diol component.
[0036] In some embodiments, the diol component of the polyester
polyol may further comprise residues of at least one polyol. As
used herein, the term "polyol" refers to a monomeric compound
having at least three hydroxyl groups.
[0037] When present, the polyol used to form the polyester polyol
described herein can be branched or linear, saturated or
unsaturated, aliphatic or cycloaliphatic C.sub.2-C.sub.20
compounds. The hydroxyl groups can be primary, secondary, and/or
tertiary, and, in one embodiment, at least two of the hydroxyl
groups may be primary. In one embodiment, the polyols may be
hydrocarbons and may not contain atoms other than hydrogen, carbon
and oxygen. Examples of suitable polyols may include, but are not
limited to, 1,1,1-trimethylolpropane (TMP),
1,1,1-trimethylolethane, glycerin, pentaerythritol, erythritol,
threitol, dipentaerythritol, sorbitol, mixtures thereof, and the
like. In one embodiment, the polyol can comprise TMP.
[0038] In some embodiments, the polyester polyol can include a diol
component in which a polyol may be present in an amount of 0 to
about 60 mole %, about 0 to about 50 mole %, about 0 to about 40
mole %, about 0 to about 30 mole %, about 0 to about 20 mole %, or
about 0 to about 15 mole %, based on the total moles of the diol
component. In certain embodiments, the polyol may be present in one
of the following amounts: 5 to 60 mole %; 5 to 55 mole %; 5 to 50
mole %; 5 to 45 mole %; 5 to 40 mole %; 5 to 35 mole %; 5 to 30
mole %; 5 to 25 mole %; 5 to 20 mole %; 5 to 15 mole %; 10 to 60
mole %; 10 to 55 mole %; 10 to 50 mole %; 10 to 45 mole %; 10 to 40
mole %; 10 to 35 mole %; 10 to 30 mole %; 10 to 25 mole %; 10 to 20
mole %; 15 to 60 mole %; 15 to 55 mole %; 15 to 50 mole %; 15 to 45
mole %; 15 to 40 mole %; 15 to 35 mole %; 15 to 30 mole %; 15 to 25
mole %; 20 to 60 mole %; 20 to 55 mole %; 20 to 50 mole %; 20 to 45
mole %; 20 to 40 mole %; 20 to 35 mole %; 20 to 30 mole %; 25 to 60
mole %; 25 to 55 mole %; 25 to 50 mole %; 25 to 45 mole %; 25 to 40
mole %; 25 to 35 mole %; 30 to 60 mole %; 30 to 55 mole %; 30 to 50
mole %; 30 to 45 mole %; 30 to 40 mole %; 35 to 60 mole %; 35 to 55
mole %; 35 to 50 mole %; 35 to 45 mole; 40 to 60 mole %; 40 to 55
mole %; 40 to 50 mole %; 45 to 60 mole %; 45 to 55 mole %; or 50 to
60 mole %. In one embodiment, the polyol may be present in the
amount of 0 to 60 mole %, while, in another embodiment, the
polyester polyol may include a diol component in which the in the
amount of 5 to 30 mole %, based on the total moles of the diol
component.
[0039] The polyester polyols described herein also include an acid
component comprising residues of at least one dicarboxyl monomer.
Dicarboxyl monomers may comprises one or more dicarboxylic acids,
derivatives of dicarboxylic acids, or combinations thereof. A
dicarboxylic acid may include two carboxylic acid groups,
derivatives thereof, or combinations thereof, capable of forming an
ester linkage with a hydroxyl component. Examples of derivatives
include, but are not limited to, dimethyl ester or other dialkyl
esters of a dicarboxylic acid, a diacid chloride or other diacid
halide, or a diacid anhydride. Specific types of dicarboxylic acids
can include, for example, aliphatic dicarboxylic acids, alicyclic
dicarboxylic acids, aromatic dicarboxylic acids, derivatives of
each, or mixtures of two or more of these acids.
[0040] In some embodiments, the acid component of the polyester
polyol may include residues of at least two dicarboxyl monomers. In
such cases, the residues of each dicarboxyl monomer may be present
in an amount of at least about 3 mole %, at least about 5 mole %,
at least about 10 mole %, at least about 15 mole %, at least about
20 mole %, at least about 25 mole %, at least about 30 mole %, at
least about 35 mole %, at least about 40 mole %, at least about 45
mole %, at least about 50 mole %, at least about 55 mole %, at
least about 60 mole %, at least about 65 mole %, at least about 70
mole %, or at least about 75 mole % and/or not more than about 95
mole %, not more than about 90 mole %, not more than about 85 mole
%, not more than about 80 mole %, not more than about 75 mole %,
not more than about 70 mole %, not more than about 65 mole %, not
more than about 60 mole %, not more than about 55 mole %, not more
than about 50 mole %, not more than about 45 mole %, or not more
than about 40 mole %, not more than about 35 mole %, not more than
about 30 mole %, not more than about 25 mole %, not more than about
20 mole %, or not more than about 15 mole %, based on the total
moles of the acid component.
[0041] In some embodiments, the acid component may consist of, or
consist essentially of, residues of a single type of dicarboxyl
monomer. In such embodiments, the acid component may comprise at
least about 90 mole %, at least about 92 mole %, at least about 95
mole %, at least about 97 mole %, at least about 99 mole %, or 100
mole % of residues of a certain dicarboxyl monomer. Thus, the acid
component may comprise not more than about 10 mole %, not more than
about 8 mole %, not more than about 5 mole %, not more than about 3
mole %, or not more than about 1 mole %, or 0 mole % of residues
other than residues of a specified dicarboxyl monomer, based on the
total residues of the acid component.
[0042] In some embodiments, one or both of the dicarboxyl monomers
may be present in an amount of 5 to 60 mole %; 5 to 55 mole %; 5 to
50 mole %; 5 to 45 mole %; 5 to 40 mole %; 5 to 35 mole %; 5 to 30
mole %; 5 to 25 mole %; 5 to 20 mole %; 5 to 15 mole %; 10 to 60
mole %; 10 to 55 mole %; 10 to 50 mole %; 10 to 45 mole %; 10 to 40
mole %; 10 to 35 mole %; 10 to 30 mole %; 10 to 25 mole %; 10 to 20
mole %; 15 to 60 mole %; 15 to 55 mole %; 15 to 50 mole %; 15 to 45
mole %; 15 to 40 mole %; 15 to 35 mole %; 15 to 30 mole %; 15 to 25
mole %; 20 to 60 mole %; 20 to 55 mole %; 20 to 50 mole %; 20 to 45
mole %; 20 to 40 mole %; 20 to 35 mole %; 20 to 30 mole %; 25 to 60
mole %; 25 to 55 mole %; 25 to 50 mole %; 25 to 45 mole %; 25 to 40
mole %; 25 to 35 mole %; 30 to 60 mole %; 30 to 55 mole %; 30 to 50
mole %; 30 to 45 mole %; 30 to 40 mole %; 35 to 60 mole %; 35 to 55
mole %; 35 to 50 mole %; 35 to 45 mole; 40 to 60 mole %; 40 to 55
mole %; 40 to 50 mole %; 45 to 60 mole %; 45 to 55 mole %; or 50 to
60 mole %, while the other dicarboxyl monomer may be present in an
amount of 40 to 95 mole %; 40 to 90 mole %; 40 to 85 mole %; 40 to
80 mole %; 40 to 75 mole %; 40 to 70 mole %; 40 to 65 mole %; 40 to
60 mole %; 40 to 55 mole %; 40 to 50 mole %; 45 to 95 mole %; 45 to
90 mole %; 45 to 85 mole %; 45 to 80 mole %; 45 to 75 mole %; 45 to
70 mole %; 45 to 65 mole %; 45 to 60 mole %; 45 to 55 mole %; 50 to
95 mole %; 50 to 90 mole %; 50 to 85 mole %; 50 to 80 mole %; 50 to
75 mole %; 50 to 70 mole %; 50 to 65 mole %; 50 to 60 mole %; 55 to
95 mole %; 55 to 90 mole %; 55 to 85 mole %; 55 to 80 mole %; 55 to
75 mole %; 55 to 70 mole %; 55 to 65 mole %; 60 to 95 mole %; 60 to
90 mole %; 60 to 85 mole %; 60 to 80 mole %; 60 to 75 mole %; 60 to
70 mole %; 65 to 95 mole %; 65 to 90 mole %; 65 to 85 mole %; 65 to
80 mole %; 65 to 75 mole %; 70 to 95 mole %; 70 to 90 mole %; 70 to
85 mole %; 70 to 80 mole %; 75 to 95 mole %; 75 to 90 mole %; 75 to
85 mole %; 80 to 95 mole %; 80 to 90 mole %, based on the total
moles of the acid component.
[0043] Examples of dicarboxyl monomers used to form polyester
polyols of the present invention can include, but are not limited
to, isophthalic acid (or dimethyl isophthalate or esters thereof),
terephthalic acid (or dimethyl terephthalate or esters thereof),
phthalic acid or esters thereof, phthalic anhydride,
1,4-cyclohexane-dicarboxylic acid, 1,3-cyclohexanedicarboxylic
acid, hexahydrophthalic anhydride, tetrahydrophthalic anhydride,
tetrachlorophthalic anhydride, dodecanedioic acid, sebacic acid,
azelaic acid, maleic acid or anhydride, fumaric acid, succinic
anhydride, succinic acid, adipic acid, dimer acid, hydrogenated
dimer acid, 2,6-naphthalenedicarboxylic acid, glutaric acid,
itaconic acid, and their derivatives, diglycolic acid;
2,5-norbornanedicarboxylic acid; 1,4-naphthalenedicarboxylic acid;
2,5-naphthalenedicarboxylic acid; diphenic acid; 4,4'-oxydibenzoic
acid; 4,4'-sulfonyidibenzoic acid, and mixtures thereof. In some
embodiments, the dicarboxyl monomer may be selected from the group
consisting of 1,4-cyclohexanedicarboxylic acid, adipic acid,
isophthalic acid, hexahydrophthalic anhydride, and combinations
thereof.
[0044] In some embodiments, the acid component of the polyester
polyol may comprise residues of adipic acid. When present, the acid
component may comprise adipic acid residues in an amount of at
least about 5 mole %, at least about 10 mole %, at least about 15
mole %, at least about 20 mole %, at least about 25 mole %, at
least about 30 mole %, at least about 35 mole %, at least about 40
mole %, at least about 45 mole %, or at least about 50 mole %
and/or not more than about 95 mole %, not more than about 90 mole
%, not more than about 85 mole %, not more than about 80 mole %,
not more than about 75 mole %, not more than about 70 mole %, not
more than about 65 mole %, not more than about 60 mole %, not more
than about 55 mole %, not more than about 50 mole %, or not more
than about 45 mole %. In some embodiments, the acid component of
the polyester polyol may comprise not more than 10 mole %, not more
than about 5 mole %, not more than about 2 mole %, or not more than
about 1 mole percent of residues other than adipic acid.
[0045] In some embodiments, the acid component of the polyester
polyol may comprise residues of isophthalic acid. When present, the
acid component may comprise isophthalic acid residues in an amount
of at least about 5 mole %, at least about 10 mole %, at least
about 15 mole %, at least about 20 mole %, at least about 25 mole
%, at least about 30 mole %, at least about 35 mole %, at least
about 40 mole %, at least about 45 mole %, or at least about 50
mole % and/or not more than about 95 mole %, not more than about 90
mole %, not more than about 85 mole %, not more than about 80 mole
%, not more than about 75 mole %, not more than about 70 mole %,
not more than about 65 mole %, not more than about 60 mole %, not
more than about 55 mole %, not more than about 50 mole %, or not
more than about 45 mole %. In some embodiments, the acid component
of the polyester polyol may comprise not more than 10 mole %, not
more than about 5 mole %, not more than about 2 mole %, or not more
than about 1 mole percent of residues other than isophthalic acid.
In some embodiments, the acid component may comprise not more than
95, not more than about 90, or not more than about 85 mole percent
of isophthalic acid.
[0046] In some embodiments, the polyester polyol may have an acid
component that comprises at least about 10 mole percent of residues
of adipic acid and at least about 10 mole percent of residues of
isophthalic acid and a diol component that comprises at least about
10 mole percent of residues of diethylene glycol and at least 10
mole percent of residues of TACD. In some embodiments, the
polyester polyol may have an acid component comprising about 30 to
about 60 mole percent of residues of adipic acid and about 40 to
about 70 mole percent of residues of isophthalic acid, based on the
total moles of said acid component and a diol component comprising
about 20 to about 75 mole percent of residues of diethylene glycol
and about 20 to about 75 mole percent of residues of
2,2,4,4-tetramethyl-1,3-cyclobutanediol (TMCD), based on the total
moles of said diol component.
[0047] In some embodiments, the polyester polyol may have an acid
component comprising about 5 to about 100 mole percent of residues
of a dicarboxyl monomer selected from the group consisting of
1,4-cyclohexanedicarboxylic acid, adipic acid, isophthalic acid,
and hexahydrophthalic acid, based on the total moles of said acid
component, and wherein said diol component further comprises about
5 to about 95 mole percent of residues of said at least one diol
monomer is selected from the group consisting of
1,4-cyclohexanedimethanol, neopentyl glycol, and combinations
thereof, based on the total moles of said diol component, with the
remaining residues of the diol component comprising TACD.
[0048] In some embodiments, the polyester polyol may have a
hydroxyl number in the range of from about 15 to about 120 mg KOH/g
and a glass transition temperature in the range of from about
-25.degree. C. to 30.degree. C. The polyester polyol may have a
hydroxyl number of about 15 to about 50 mg KOH/g and a glass
transition temperature of about 10 to 55.degree. C., or about 20 to
55.degree. C. In other embodiments, the polyester polyol may have a
Tg of -25.degree. C. to 20.degree. C., a hydroxyl number of 15 to
70 mg KOH/g, and a number average molecular weight of 1500 to 9000
g/mole. In other embodiments, the polyester polyol may have a Tg of
0 to 70.degree. C., a hydroxyl number of 15 to 60 mg KOH/g, and a
number average molecular weight of 2000 to 5500 g/mole.
[0049] In some embodiments, the acid component of the polyester
polyol may comprise lower amounts of certain acids, as compared to
conventional polyols. For example, in some embodiments, the acid
component of the polyester polyol may comprise not more than 25
mole %, not more than about 20 mole %, not more than about 15 mole
%, not more than about 10 mole %, not more than about 8 mole %, not
more than about 5 mole %, not more than about 3 mole %, not more
than about 2 mole %, not more than about 1 mole %, or not more than
about 0.5 mole % of residues of aromatic dicarboxyl monomers,
including, but not limited to, terephthalic acid or dimethyl
terephthalate, based on the total moles of the acid component.
[0050] The resulting polyester polyol may exhibit certain
properties that make it particularly useful in adhesive
compositions as described herein. For example, in some embodiments,
the polyester polyol may have a hydroxyl functionality of 2.1 or
less. The hydroxyl functionality of a polyol can be calculated
according to the following formula: OH functionality=Mn*N/56100,
wherein Mn is the number average molecular weight of the polyester
polyol (measured by gel permeation chromatography (GPC) using
polystyrene equivalent molecular weight), N is the hydroxyl number
of the polyester polyol, measured according to ASTM E222-17. In
some embodiments, the polyester polyol may have a hydroxyl
functionality of less than 2.1, not more than about 2.05, not more
than about 2.01, not more than about 2.0, or not more than about
1.99. In some cases, the polyester polyol as described herein may
be thermoplastic and may not be thermosetting. The polyester polyol
may not have a hydroxyl functionality greater than 2.1, at least
about 2.2, at least about 2.25, at least about 2.3, at least about
2.35, at least about 2.4, at least about 2.45, or at least about
2.5.
[0051] According to some embodiments, the polyester polyol as
described herein may have a glass transition temperature (Tg) in
the range of from -70.degree. C. to 150.degree. C., determined by
Differential Scanning calorimetry (DSC) using a TA DSC 2920 from
Thermal Analyst Instrument at a scan rate of 20.degree. C./min.
[0052] The polyester polyol may have a Tg of at least about -70, at
least about -65, at least about -60, at least about -55, at least
about -50, at least about -45, at least about -40, at least about
-35, at least about -30, at least about -25, at least about -20, at
least about -15, at least about -10, at least about -5, at least
about 0, at least about 5, at least about 10, at least about 15, at
least about 20, or at least about 25.degree. C. and/or not more
than about 150, not more than about 145, not more than about 140,
not more than about 135, not more than about 130, not more than
about 125, not more than about 120, not more than about 115, not
more than about 110, not more than about 105, not more than about
100, not more than about 95, not more than about 90, not more than
about 85, not more than about 80, not more than about 75, not more
than about 70, not more than about 65, not more than about 60, not
more than about 55, not more than about 50, not more than about 45,
not more than about 40, not more than about 35, not more than about
30, not more than about 25, or not more than about 20.degree.
C.
[0053] The glass transition temperature (Tg) of polyester polyol
may be from -70.degree. C. to 120.degree. C., from -60.degree. C.
to -20.degree. C., from -40.degree. C. to -10.degree. C., from
-30.degree. C. to 10.degree. C., from -30.degree. C. to 20.degree.
C., from -10.degree. C. to 20.degree. , from 0.degree. C. to
30.degree. C., from 20.degree. C. to 50.degree. C., from 30.degree.
C. to 60.degree. C., from 40.degree. C. to 70.degree. C., from
50.degree. C. to 80.degree. C., or from 60.degree. C. to
100.degree. C., or from -30 to 30.degree. C., from -30 to
55.degree. C., from -25 to 30.degree. C., from -25 to 25.degree.
C., from -25 to 25.degree. C., from -25 to -20.degree. C., from -20
to 20.degree. C., from -15 to 15.degree. C., from -15 to 25.degree.
C., from -5 to 75.degree. C., from 0 to 70.degree. C., from 0 to
65.degree. C., from 0 to 60.degree. C., from 0 to 55.degree. C.,
from 10 to 55.degree. C., from -10 to 35.degree. C., from
-70.degree. C. to 100.degree. C., from -60.degree. C. to
-10.degree. C., from -50.degree. C. to -10.degree. C., from
-40.degree. C. to -10.degree. C., from -30.degree. C. to
-10.degree. C., from 0.degree. C. to 100.degree. C., from
10.degree. C. to 80.degree. C., from 20.degree. C. to 70.degree.
C., from 30.degree. C. to 70.degree. C., from 40.degree. C. to
70.degree. C.
[0054] In some embodiments, the polyester polyol may have a
Brookfield viscosity, measured according to ASTM D3236 using a
Brookfield DV-1 Prime viscometer Thermosel.TM. and spindle 27 at
the specified temperature (AMETEK Brookfield, Middleborough, Mass.,
US), in the range of from about 0.01 to 200 Pas, at 130.degree. C.
In some cases, the viscosity of the polyester polyol at 130.degree.
C. may be at least about 0.01, at least about 0.05, at least about
0.1, at least about 0.5, at least about 1, at least about 1.5, at
least about 2, at least about 2.5, at least about 3, at least about
3.5, at least about 4, at least about 4.5, at least about 5, at
least about 5.5, at least about 6, at least about 6.5, at least
about 7, at least about 7.5, at least about 8, at least about 9, at
least about 10, and/or not more than about 50, not more than about
45, not more than about 40, not more than about 35, not more than
about 30, not more than about 27, not more than about 25, not more
than about 20, or not more than about 18 Pas. In some cases, the
Brookfield viscosity of the polyester polyol may be from 0.01 to 50
Pas, from 0.1 to 40 Pas, from 1 to 35 Pas, or from 10 to 25
Pas.
[0055] In some embodiments, the polyester polyol may have a
hydroxyl number in the range of from 5 to 300 mg KOH/g, and/or an
acid number of not more than 50 mg KOH/g. Acid number is determined
by the titration method in accordance with ASTM D974. Hydroxyl
number is determined by ASTM E222-17.
[0056] In some embodiments, the polyester polyol may have a
hydroxyl number of at least about 5 mg KOH/g, at least about 10 mg
KOH/g, at least about 15 mg KOH/g, 20 mg KOH/g, 25 mg KOH/g, 30 mg
KOH/g, 35 mg KOH/g, 40 mg KOH/g, 45 mg KOH/g, 50 mg KOH/g, 55 mg
KOH/g, 60 mg KOH/g, 65, mg KOH/g, or 70 mg KOH/g. Additionally, or
in the alternative, the polyester polyol may have a hydroxyl number
of not more than about 300 mg KOH/g, not more than about 250 mg
KOH/g, not more than about 200 mg KOH/g, not more than about 150 mg
KOH/g, not more than about 100 mg KOH/g, not more than about 75 mg
KOH/g, not more than about 70 mg KOH/g, not more than about 65 mg
KOH/g, not more than about 60 mg KOH/g, not more than about 55 mg
KOH/g, not more than about 50 mg KOH/g, not more than about 45 mg
KOH/g, or not more than about 40 mg KOH/g.
[0057] In some embodiments, the hydroxyl number of the polyester
polyol may be from about 10 to about 300, from about 10 to about
200, from about 10 to about 180, or from about 10 to about 150, or
from about 10 to about 120, or from about 10 to about 100, or from
about 15 to about 100, from about 25 to about 300, from about 25 to
about 200, from about 25 to about 180, or from about 25 to about
150, or from about 25 to about 120, or from about 25 to about 100,
or from 30 to about 300, from about 30 to about 200, from about 30
to about 180, or from about 30 to about 150, or from about 30 to
about 120, or from about 30 to about 100, or from about 50 to about
300, from about 50 to about 200, from about 50 to about 180, or
from about 50 to about 150, or from about 50 to about 120, or from
about 50 to about 100 mgKOH/g.
[0058] Additionally, or in the alternative, the polyester polyol
can have a hydroxyl number of about 10 to about 60 mg KOH/g, about
10 to about 55 mg KOH/g, about 10 to about 50 mg KOH/g, about 10 to
about 45 mg KOH/g, about 15 to about 60 mg KOH/g, about 15 to about
55 mg KOH/g, about 15 mg KOH/g to about 55 mg KOH/g, or about 15 to
about 50 mg KOH/g, about 15 to about 45 mg KOH/g, about 15 to about
35 mg KOH/g, or about 15 to about 30 mg KOH/g.
[0059] In some embodiments, the polyester polyol may have an acid
number of not more than about 30 mg KOH/g, not more than about 25
mg KOH/g, not more than about 20 mg KOH/g, not more than about 15
mg KOH/g, not more than about 10 mg KOH/g, or not more than about 5
mg KOH/g. In some embodiments, the acid number of the polyester
polyol may be from 0 to about 30, from about 3 to about 25, from 3
to about 15, or from 3 to about 12, or from about 5 to about 25,
from 5 to about 15, or from 5 to about 12, or from about 8 to about
25, from 8 to about 15, or from 8 to about 12 mgKOH/g. In some
embodiments, the polyester polyol may have an acid number from
about 0.5 to about 9.0, or from about 0.5 to about 8.0, or about
0.5 to about 7.0, or about 0.5 to about 6.0, or about 0.5 to about
5.0, or about 0.5 to about 4.0, or about 0.5 to about 3.0, or about
0.5 to about 2.
[0060] Equivalent ratio of OH/COOH of the polyester polyols
described herein denotes the ratio of total OH equivalents/total
COOH equivalents. In certain embodiments, the equivalent ratio
(OH/COOH) of a polyester polyol as described herein may be from 1
to 3, or 1.1 to 3, or 1 to 2, or 1.1 to 2, or 1 to 1.5, or 1.1 to
1.5, or 1.0 to 1.3 or, 1.1 to 1.3. The polyester polyol may have an
equivalent ratio of at least about 1, at least about 1.1, at least
about 1.2, at least about 1.3, at least about 1.4, at least about
1.5, at least about 1.6, at least about 1.7, at least about 1.8, or
at least about 1.9 and/or not more than about 3, not more than
about 2.9, not more than about 2.8, not more than about 2.7, not
more than about 2.6, not more than about 2.5, not more than about
2.4, not more than about 2.3, or not more than about 2.2.
[0061] In some embodiments, the number average molecular weight
(Mn) of the polyester polyol may be from 500 to 10,000, or from 500
to 9,000, or from 500 to 8,000, or from 500 to 7,000, or from 500
to 6,000, or from 500 to 5,000, or from 500 to 4,000, or from 500
to 3,000, or from 1,000 to 10,000, or from 1,000 to 9,000, or from
1,000 to 8,000, or from 1,000 to 7,000, or from 1,000 to 6,000, or
from 1,000 to 5,000, or from 1,000 to 4,000, or from 1,000 to
3,000, or from 2,000 to 7,000, or from 2,000 to 6,000, or from
2,000 to 5,000, or from 2,000 to 4,000, or from 3,000 to 7,000, or
from 3,000 to 6,000, or from 3,000 to 5,000 g/mole.
[0062] The Mn of the polyester polyol may be at least about 500, at
least about 750, at least about 1000, at least about 1050, at least
about 1100, at least about 1150, at least about 1200, at least
about 1250, at least about 1300, at least about 1350, at least
about 1400, at least about 1450, at least about 1500, at least
about 1550, at least about 1600, at least about 1650, at least
about 1700, at least about 1750, at least about 1800, at least
about 1850, at least about 1900, at least about 1950, at least
about 2000, at least about 2100, at least about 2200, at least
about 2300, at least about 2400, at least about 2500, at least
about 2600, at least about 2700, at least about 2800, at least
about 2900, at least about 3000, at least about 3100, at least
about 3200, at least about 3300, at least about 3400, at least
about 3500, at least about 3600, at least about 3700, at least
about 3800, at least about 3900, at least about 4000, at least
about 4100, at least about 4200, at least about 4300, at least
about 4400, or at least about 4500 g/mole.
[0063] Additionally, or in the alternatively, the Mn of the
polyester polyol may be not more than about 10,000, not more than
about 9900, not more than about 9800, not more than about 9700, not
more than about 9600, not more than about 9500, not more than about
9400, not more than about 9300, not more than about 9200, not more
than about 9100, not more than about 9000, not more than about
8900, not more than about 8800, not more than about 8700, not more
than about 8600, not more than about 8500, not more than about
8400, not more than about 8300, not more than about 8200, not more
than about 8100, not more than about 8000, not more than about
7900, not more than about 7800, not more than about 7700, not more
than about 7600, not more than about 7500, not more than about
7400, not more than about 7300, not more than about 7200, not more
than about 7100, not more than about 7000, not more than about
6900, not more than about 6800, not more than about 6700, not more
than about 6600, not more than about 6500, not more than about
6400, not more than about 6300, not more than about 6200, not more
than about 6100, not more than about 6000, not more than about
5900, not more than about 5800, not more than about 5700, not more
than about 5600, or not more than about 5500 g/mole.
[0064] The weight average molecular weight (Mw) of the polyester
polyol may be from 1,000 to 100,000, from 1,500 to 50,000, or from
1,500 to 15,000, or from 1,500 to 12,000, or from 2,000 to 10,000
g/mole. Molecular weights are measured by gel permeation
chromatography (GPC) using polystyrene equivalent molecular
weight.
[0065] In some embodiments, the Mw of the polyester polyol may be
from 500 to 10,000, or from 500 to 9,000, or from 500 to 8,000, or
from 500 to 7,000, or from 500 to 6,000, or from 500 to 5,000, or
from 500 to 4,000, or from 500 to 3,000, or from 1,000 to 10,000,
or from 1,000 to 9,000, or from 1,000 to 8,000, or from 1,000 to
7,000, or from 1,000 to 6,000, or from 1,000 to 5,000, or from
1,000 to 4,000, or from 1,000 to 3,000, or from 2,000 to 7,000, or
from 2,000 to 6,000, or from 2,000 to 5,000, or from 2,000 to
4,000, or from 3,000 to 7,000, or from 3,000 to 6,000, or from
3,000 to 5,000 g/mole.
[0066] The Mw of the polyester polyol may be at least about 500, at
least about 750, at least about 1000, at least about 1050, at least
about 1100, at least about 1150, at least about 1200, at least
about 1250, at least about 1300, at least about 1350, at least
about 1400, at least about 1450, at least about 1500, at least
about 1550, at least about 1600, at least about 1650, at least
about 1700, at least about 1750, at least about 1800, at least
about 1850, at least about 1900, at least about 1950, at least
about 2000, at least about 2100, at least about 2200, at least
about 2300, at least about 2400, at least about 2500, at least
about 2600, at least about 2700, at least about 2800, at least
about 2900, at least about 3000, at least about 3100, at least
about 3200, at least about 3300, at least about 3400, at least
about 3500, at least about 3600, at least about 3700, at least
about 3800, at least about 3900, at least about 4000, at least
about 4100, at least about 4200, at least about 4300, at least
about 4400, or at least about 4500 g/mole.
[0067] Additionally, or in the alternatively, the Mw of the
polyester polyol may be not more than about 10,000, not more than
about 9900, not more than about 9800, not more than about 9700, not
more than about 9600, not more than about 9500, not more than about
9400, not more than about 9300, not more than about 9200, not more
than about 9100, not more than about 9000, not more than about
8900, not more than about 8800, not more than about 8700, not more
than about 8600, not more than about 8500, not more than about
8400, not more than about 8300, not more than about 8200, not more
than about 8100, not more than about 8000, not more than about
7900, not more than about 7800, not more than about 7700, not more
than about 7600, not more than about 7500, not more than about
7400, not more than about 7300, not more than about 7200, not more
than about 7100, not more than about 7000, not more than about
6900, not more than about 6800, not more than about 6700, not more
than about 6600, not more than about 6500, not more than about
6400, not more than about 6300, not more than about 6200, not more
than about 6100, not more than about 6000, not more than about
5900, not more than about 5800, not more than about 5700, not more
than about 5600, or not more than about 5500 g/mole.
[0068] In some embodiments, the polyester polyol may have an
inherent viscosity (IV) less than longer-chain polyesters. For
example, in some embodiments, the polyester polyol may have an IV
of not more than about 0.4 dL/g, measured in a 60/40 (wt/wt)
phenol/tetrachloroethane at a concentration of 0.5 g/100 mL at
25.degree. C. In some embodiments, the polyester polyol may have an
IV of at least about 0.01, at least about 0.05, at least about
0.10, at least about 0.15, at least about 0.20, at least about
0.25, at least about 0.30 dL/g and/or not more than about 0.50, not
more than about 0.45, not more than about 0.40, not more than about
0.35, not more than about 0.30, not more than about 0.25, or not
more than about 0.20 dL/g.
[0069] In some embodiments, a method for making a polyester polyol
is provided that includes reacting at least one dicarboxyl monomer
with at least one diol comprising
2,2,4,4-tetraalkyl-1,3-cyclobutanediol (TACD) to form a polyester
polyol as described herein. During the reacting step, the reaction
medium may be heated so that the highest average temperature of the
reaction medium reached is at least about 200, at least about 205,
at least about 210, at least about 215, at least about 220, at
least about 225, at least about 230, at least about 235, at least
about 240, or at least about 245 and/or not more than about 300,
not more than about 290, not more than about 280, not more than
about 270, not more than about 265, not more than about 260, not
more than about 255, not more than about 250, or not more than
about 240.degree. C.
[0070] Despite being conducted at lower-than-expected temperatures,
the reaction medium used to form the polyester polyol may comprise
little or no azeotroping solvent such as, for example, A150. In
some cases, the reaction for forming the polyester polyol may be
carried out in the presence of not more than 20, not more than
about 15, not more than about 10, not more than about 8, not more
than about 5, not more than about 3, not more than about 2, not
more than about 1, or not more than about 0.5 weight percent of an
azeotroping solvent, based on the total weight of the reaction
medium.
[0071] All or a portion of the reaction may take place under vacuum
so that, for example, the pressure can be at least about 5, at
least about 10, at least about 15, at least about 20, or at least
about 25 torr and/or not more than about 500, not more than about
450, not more than about 400, not more than about 350, not more
than about 300, not more than about 250, not more than about 200,
not more than about 150, not more than about 100, or not more than
about 75 torr. The reaction pressure can be in the range of from
about 5 to about 200 torr, about 10 to about 150 torr, or about 20
to about 100 torr.
[0072] In some embodiments, the reaction used to form the polyester
polyol may be carried out in the presence of at least one catalyst.
In some cases, the catalyst may be present in an amount of at least
about 0.1, at least about 0.5, at least about 1, at least about
1.5, or at least about 2 weight percent and/or not more than about
20, not more than about 15, not more than about 10, not more than
about 5, or not more than about 3 weight percent, based on the
total weight of the reaction medium.
[0073] In some embodiments, the catalyst may be present in the
reaction medium in an amount of at least about 5, at least about
10, at least about 15, at least about 20, at least about 30, at
least about 40, at least about 45, at least about 50, or at least
about 55 parts per million by weight (ppmw) and/or not more than
about 1000, not more than about 900, not more than about 800, not
more than about 700, not more than about 600, not more than about
500, not more than about 450, not more than about 400, not more
than about 350, not more than about 300, not more than about 250
ppmw, based on the total weight of the reaction medium.
[0074] Any suitable type of catalyst may be used, although in some
embodiments, the catalyst may not be or comprise a tin-containing
catalyst. In some embodiments, the catalyst may comprise not more
than about 5, not more than about 4, not more than about 3, not
more than about 2, not more than about 1, or not more than about
0.5 mole percent tin, based on the total weight of the catalyst, or
it may include no tin. The catalyst may instead comprise titanium
or other metal in an amount of at least about 1, at least about 2,
at least about 5, at least about 10, or at least about 25 mole
percent and/or not more than about 90, not more than about 85, not
more than about 80, not more than about 75, or not more than about
70 mole percent, based on the total moles of the catalyst. In some
embodiments, the catalyst can comprise titanium isopropoxide.
[0075] Polyester polyols according to embodiments of the present
invention may be particularly suitable for use in a variety of
adhesive compositions and, in particular, for use in polyurethane
adhesive compositions. Polyurethane is formed by reacting a
polyester polyol having hydroxyl functionality with an isocyanate
having two or more isocyanate functional groups. In some cases, at
least a portion of this reaction can occur prior to use of the
adhesive so that, for example, the adhesive composition comprises
an isocyanate-containing polyurethane prepolymer. Alternatively, or
in addition, the reaction may occur while the adhesive is being
applied so that the polyurethane polymer is being formed in situ on
the substrate. Various embodiments of specific types of adhesive
compositions are discussed herein.
[0076] The amount of polyester polyol in the adhesive composition
may vary depending on the specific application. In some
embodiments, the polyester may be present in the adhesive
composition (or a precursor thereto) in an amount of at least about
2, at least about 5, at least about 10, at least about 15, at least
about 20, at least about 25, at least about 30, at least about 35,
or at least about 40 weight percent and/or not more than about 90,
not more than about 85, not more than about 80, not more than about
75, not more than about 70, not more than about 65, not more than
about 60, not more than about 55, not more than about 50, or not
more than about 45 weight percent, based on the total weight of the
adhesive composition.
[0077] The polyester polyol may be present in the adhesive
composition alone, or in combination with one or more other polyols
including, but not limited to, various other polyester polyols or
polyether polyols. In some embodiments, particularly when the
adhesive is a hot melt adhesive, the composition may include a
blend of two or more polyols. In some cases, the polyols other than
the TMCD-containing polyol may be polyester polyols, polyether
polyols, or combinations thereof.
[0078] When present in a blend, the polyester polyol comprising
residues of TMCD can be present in the composition in an amount of
at least about 5, at least about 10, at least about 15, at least
about 20, at least about 25, at least about 30, at least about 35,
at least about 40, at least about 45, at least about 50, at least
about 55, at least about 60, at least about 65, at least about 70
and/or not more than about 95, not more than about 90, not more
than about 85, not more than about 80, not more than about 75, not
more than about 70, not more than about 65, or not more than about
60 weight percent, based on the total weight of the active
components. As used herein, the term "active components" refers to
the components of an adhesive composition such as the polyol,
isocyanate, and additives but does not include solvents or any
inert components.
[0079] In some embodiments, hot melt adhesives as described herein
may include at least one amorphous polyester polyol, a
semi-crystalline polyester polyol, and/or a polyether polyol, in
combination with the polyester polyol comprising residues of TMCD
described herein. Examples of amorphous polyols include, but are
not limited to, high Tg amorphous polyols such as, Dynacoll 7100
(commercially available from Evonik), Stepanpol PN-110
(commercially available from Stephan), and HS 2F-136P and HS
2F-306P (commercially available from Hokoku Corporation). High Tg
amorphous polyester polyols may be present in the adhesive blend in
an amount of at least about 5, at least about 10, at least about 15
weight percent and/or not more than about 50, not more than about
45, not more than about 40, not more than about 35, or not more
than about 30 weight percent, based on the total weight of the
composition.
[0080] Additionally, or in the alternative, the adhesive blend may
also comprise at least one low Tg amorphous polyester polyol.
Examples of such a polyester polyol include, but are not limited
to, Dynacoll 7200 (commercially available from Evonik). Such
polyols may be present in the composition in the same amount as
described previously and may be used alone or in combination with a
higher Tg amorphous polyester.
[0081] In some embodiments, the adhesive blend may further comprise
a semi-crystalline polyester polyol in combination with the
TMCD-containing polyester polyol described herein. Examples of such
polyester polyols can include, but are not limited to, Dynacoll
7300 series polyols (commercially available from Evonik) PC-205P-30
(commercially available from Stepan), and HS 2H-351A and HS2H-350S
(commercially available from Hokoku Corporation). The amount of
semi-crystalline polyester polyol may be 0, or at least about 5, at
least about 10, at least about 15, at least about 20, at least
about 25, at least about 30, at least about 35 and/or not more than
about 55, not more than about 50, not more than about 45, not more
than about 40, not more than about 35, not more than about 30, or
not more than about 25 weight percent, based on the total weight of
the composition. These ranges may also apply to the amount of the
TMCD-containing polyester polyol described herein in an adhesive
composition.
[0082] Additionally, or in the alternative, the adhesive
composition may comprise at least one polyether polyol. Examples of
suitable polyether polyols include, but are not limited to, Voranol
2120 and 2000LM (commercially available from Dow Chemical). In some
embodiments, the polyether polyol may be used in an amount of 0, or
at least about 5, at least about 10, at least about 15, at least
about 20, at least about 25, at least about 30, at least about 35
and/or not more than about 55, not more than about 50, not more
than about 45, not more than about 40, not more than about 35, not
more than about 30, or not more than about 25 weight percent, based
on the total weight of the composition.
[0083] In some embodiments, the adhesive composition may only
include the polyester polyol including TMCD residues as described
herein. In some cases, the adhesive composition may comprise not
more than about 20, not more than about 15, not more than about 10,
not more than about 5, not more than about 3, not more than about
2, not more than about 1, or not more than about 0.5 weight percent
of polyols other than the TMCD-containing polyol described herein,
based on the total weight of the adhesive composition.
[0084] The adhesive composition may also include at least one
isocyanate. The isocyanate may comprise a diisocyanate and may be
present in the adhesive composition (or a precursor thereto) in an
amount of at least about 0.1, at least about 0.5, at least about 1,
at least about 1.5, at least about 2, at least about 2.5, at least
about 5, at least about 8, at least about 10, at least about 15
and/or not more than about 50, not more than about 45, not more
than about 40, not more than about 35, not more than about 30, not
more than about 25, not more than about 20, not more than about 15,
not more than about 10, not more than about 8, not more than about
5, not more than about 3, not more than about 1.5, not more than
about 1, or not more than about 0.5 weight percent, based on the
total weight of the adhesive composition (or its precursor).
[0085] Suitable isocyanates may be difunctional or multifunctional
isocyanates having, for example, two or more isocyanate functional
groups. Such isocyanates may be aromatic or aliphatic. Examples of
aliphatic isocyanates include isophorone diisocyanate (IPDI),
hexamethylene diisocyanate (HDI), tetramethylene diisocyanate,
methylene bis(4-cyclohexylisocyanate) (HMDI), m-xylylene
diisocyanate, p-xylylene diisocyanate,
1,3-bis(isocyanatomethyl)cyclohexane,
1,4-bis(isocyanatomethyl)cyclohexane, cyclohexylene diisocyanate,
1,3-bis(1-isocyanato-1-methylethyl)benzene, HDI trimer, HDI biuret,
HDI uretdione, IPDI trimer, and mixtures thereof. The isocyanate
may also comprise dimers or trimers of any of the above compounds.
Examples of aromatic isocyanates include methylenediphenyl
diisocyanate (MDI), polymeric MDI (PMDI), toluene diisocyanate
(TDI), naphthalene diisocyanate, 4,4'-stilbene diisocyanate, and
mixtures thereof.
[0086] According to some embodiments, the isocyanate may be
selected from the group consisting of isophorone diisocyanate
(IPDI), hexamethylene diisocyanate (HDI), tetramethylene
diisocyanate, methylene bis(4-cyclohexylisocyanate) (HMDI),
m-xylylene diisocyanate, p-xylylene diisocyanate,
1,3-bis(isocyanatomethyl)cyclohexane,
1,4-bis(isocyanatomethyl)cyclohexane, cyclohexylene diisocyanate,
1,3-bis(1-isocyanato-1-methylethyl)benzene, methylenediphenyl
diisocyanate (MDI), polymeric MDI (PMDI), toluene diisocyanate
(TDI), naphthalene diisocyanate, 4,4'-stilbene diisocyanate, and
mixtures thereof. In some embodiments, the isocyanate is selected
from the group consisting of hexamethylene diisocyanate (HDI)
trimer, isophorone diisocyanate (IPDI) trimer, and combinations
thereof. In other embodiments, the isocyanate is selected from the
group consisting of 2,4'-methylene diphenyl diisocyanate (2,4-MDI),
4,4'-methylene diphenyl diisocyanate (4,4-MDI), and combinations
thereof.
[0087] In some embodiments, modified isocyanates may be used. For
example, in some embodiments, the isocyanate may be modified with
acrylic groups. Modified isocyanates can include modified
methylenediphenyl diisocyanate selected from the group consisting
of a carbodiimide-modified methylenediphenyl diisocyanate, an
allophanate-modified methylenediphenyl diisocyanate, a
biuret-modified methylenediphenyl diisocyanate, and combinations
thereof.
[0088] In some embodiments, the adhesive composition can have an R
value in the range of from 0.5 to 4. As used herein, the "R" value
is the equivalent ratio of isocyanate groups to hydroxyl groups in
a composition. In some embodiments, the R value can be at least
about 0.75, at least about 0.90, at least about 1, at least about
1.1, at least about 1.2, at least about 1.3, at least about 1.4, at
least about 1.5, at least about 1.6, at least about 1.7, at least
about 1.8, at least about 1.9, or at least about 2 and/or not more
than about 4, not more than about 3.9, not more than about 3.8, not
more than about 3.7, not more than about 3.6, not more than about
3.5, not more than about 3.4, not more than about 3.3, not more
than about 3.2, not more than about 3.1, or not more than about
3.
[0089] The adhesive composition may also include one or more other
components such as, for example, a tackifier. The tackifier may
help improve the adhesive properties, including but not limited to
the viscosity, wetting behavior, adhesion, particularly to low
energy surfaces, and viscoelastic behavior of the finished adhesive
composition. The tackifier resin selected may vary depending on the
exact curable composition and the balance of properties needed in
an application, such as peel strength, shear strength, and
tack.
[0090] Tackifier resins that may be present in the adhesive
compositions described herein may include, but are not limited to,
cycloaliphatic hydrocarbon resins, C5 hydrocarbon resins, C5/C9
hydrocarbon resins, aromatically modified C5 resins (commercially
available as Piccotac.TM. resins, Eastman Chemical Company, Tenn.,
US), C9 hydrocarbon resins (commercially available as Picco.TM.
resins, Eastman), pure monomer resins (e.g., copolymers of styrene
with alpha-methyl styrene, vinyl toluene, para-methyl styrene,
indene, and methyl indene) (commercially available as Kristalex.TM.
resins, Eastman), DCPD resins, dicyclopentadiene based/containing
resins, cyclo-pentadiene based/containing resins, terpene resins
(commercially available as Sylvares.TM. resins, Ariz. Chem
Holdings, LP, Jacksonville, Fla., US), terpene phenolic resins,
terpene styrene resins, esters of rosin (commercially available as
Permalyn.TM. resins, Eastman), esters of modified rosins, liquid
resins of fully or partially hydrogenated rosins, fully or
partially hydrogenated rosin esters (commercially available as
Foral.TM. and Foralyn.TM. resins, Eastman), fully or partially
hydrogenated modified rosin resins, fully or partially hydrogenated
rosin alcohols, fully or partially hydrogenated C5 resins, fully or
partially hydrogenated C5/C9 resins, fully or partially
hydrogenated DCPD resins (commercially available as Escorez.RTM.
5000-series resin, ExxonMobil Chemical Company, Texas, US), fully
or partially hydrogenated dicyclopentadiene based/containing
resins, fully or partially hydrogenated cyclo-pentadiene
based/containing resins, fully or partially hydrogenated
aromatically modified C5 resins, fully or partially hydrogenated C9
resins (commercially available as Regalite.TM. resins, Eastman),
fully or partially hydrogenated pure monomer resins (e.g.,
copolymers or styrene with alpha-methyl styrene, vinyl toluene,
para-methyl styrene, indene, and methyl indene) (commercially
available as Regalrez.TM. resins, Eastman), fully or partially
hydrogenated C5/cycloaliphatic resins (commercially available as
Eastotac.TM. resins, Eastman), fully or partially hydrogenated
C5/cycloaliphatic/styrene/C9 resins, fully or partially
hydrogenated cycloaliphatic resins, and mixtures thereof.
[0091] When present, the tackifier may also include, for example,
rosin esters, such as glycerol rosin ester, pentaerythritol rosin
ester, and hydrogenated rosin resins, and hydrocarbon resins.
[0092] In some embodiments, the adhesive composition may include at
least about 5, at least about 10, at least about 15, at least about
20, or at least about 25 and/or not more than about 50, not more
than about 45, not more than about 40, not more than about 35, not
more than about 30, or not more than about 25 weight percent of at
least one tackifier. In some cases, the adhesive composition may
comprise less than about 5, less than about 3, less than about 2,
less than about 1, or less than about 0.5 weight percent of
tackifiers, based on the total weight of the composition.
[0093] Additionally, or in the alternative, the adhesive
composition may further comprise one or more reactive or
non-reactive vinyl polymers to further improve the desirable
properties such as cure time, bond strength, cohesion, and
mechanical strength. Examples of such vinyl polymers include
homopolymers and copolymers of ethylenically unsaturated monomers
selected from the group comprising methyl acrylate, methyl
methacrylate, ethyl acrylate, ethyl methacrylate, butyl acrylate,
butyl methacrylate, isobutyl acrylate, isobutyl methacrylate,
2-ethylhexyl methacrylate, 2-ethylhexyl acrylate, isoprene, octyl
acrylate, octyl methacrylate, iso-octyl acrylate, iso-octyl
methacrylate, isobornyl (meth)acrylate, cyclohexyl (meth)acrylate,
hydroxymethyl (meth)acrylate, hydroxyethyl (meth)acrylate,
hydroxypropyl (meth)acrylate, hydroxylbutyl (meth)acrylate,
acetoacetoxy ethyl methacrylate, acetoacetoxy ethyl acrylate,
methyl 2-(hydroxymethyl)acrylate, ethyl 2-(hydroxymethyl)acrylate,
isopropyl 2-(hydroxymethyl)acrylate, n-butyl
2-(hydroxymethyl)acrylate, t-butyl 2-(hydroxymethyl)acrylate, vinyl
ester such as vinyl acetate, vinyl alcohol, vinyl ether, styrene,
alkylstyrene, butadiene, and acrylonitrile. The reactive vinyl
polymers can have functionalities such as, for example, hydroxyl,
acetoacetate, and carbamate that are reactive toward isocyanates,
or they may have isocyanate functionality that is moisture curable.
The vinyl polymers may be used in various adhesive formulations
including solvent-borne, solventless, and hot melt types.
[0094] In some embodiments, the adhesive of the present invention
may further comprise one or more catalysts or activating agents
selected from the group comprising dibutyl tin dilaurate, dibutyl
tin diacetate, dioctyl tin diacetate,
1,8-diazabicyclo-[5.4.0]undec-7-ene (DBU),
1,5-diazabicyclo[4.3.0]non-5-ene (DBN),
1,5,7-triazabicyclo[4.4.0]dec-5-ene (TBD),
7-methyl-1,5,7-triazabicyclo[4.4.0]dec-5-ene (MTBD),
1,1,3,3-tetramethylguanidine (TMG), 1,4-diazabicyclo[2.2.2]octane
(DABCO), 2,2'-di morpholinodieethylether (DMDEE), and combinations
thereof.
[0095] In some embodiments, the adhesive composition may be a two
part or two-pack (also called a two-component or 2K) adhesive
system. Such systems include two separate components or portions,
one including the polyol and the other including the isocyanate.
These components are stored separately, then combined just prior to
or during application of the adhesive, at which point the polyol
and isocyanate react to form a polyurethane in situ. Such reactions
can occur at room temperature or at an elevated temperature. One or
both of the components may include other compounds such as, for
example, solvents or other additives.
[0096] In some embodiments, the polyol may be pre-reacted with an
isocyanate to provide an isocyanate-terminated polyurethane
prepolymer. The polyurethane prepolymer may be prepared by bulk
polymerization or solution polymerization. The reaction may be
carried out under anhydrous conditions to prevent crosslinking of
the isocyanate groups by moisture. The polyurethane prepolymer may
comprise residues of at least one polyester polyol as described
herein and at least one isocyanate.
[0097] This isocyanate-functional prepolymer, present in one
component of the adhesive, may then be reacted further with a
polyol, in another component, when part of a two-component (2K)
adhesive composition. In some embodiments, one or both parts of the
2K adhesive may further include at least one solvent. A 2K
solvent-borne adhesive can be used in applications for, for
example, flexible packaging, textile, auto interior, wood working,
assembly of electronic components, and potting for electronics.
[0098] Examples of suitable solvents can include, but are not
limited to, ethyl acetate, n-butyl acetate, isobutyl acetate,
t-butyl acetate, n-propyl acetate, isopropyl acetate, methyl
acetate, ethanol, n-propanol, isopropanol, sec-butanol, isobutanol,
ethylene glycol monobutyl ether, propylene glycol n-butyl ether,
propylene glycol methyl ether, propylene glycol monopropyl ether,
dipropylene glycol methyl ether, diethylene glycol monobutyl ether,
ethyl-3-ethoxypropionate, xylene, toluene, acetone, methyl amyl
ketone, methyl isoamyl ketone, methyl ethyl ketone, cyclopentanone,
and cyclohexanone.
[0099] When a solvent is present, the adhesive may have a solids
content of at least about 10, at least about 15, at least about 20,
at least about 25, at least about 30, at least about 35, at least
about 40, or at least about 45 weight percent and/or less than
about 90, not more than about 85, not more than about 80, not more
than about 75, not more than about 70, not more than about 65, not
more than about 60, not more than about 55, not more than about 50,
or not more than about 45 percent, based on the total weight of the
adhesive composition.
[0100] Alternatively, the isocyanate-terminated polyurethane
prepolymer may react with moisture (added or in the environment) at
the time the adhesive is applied. Such moisture-cure adhesive
compositions may be considered one-part (1K) adhesive compositions.
Although not wishing to be bound by theory, it is assumed that, in
such moisture-cure systems, the isocyanate functionality of the
polyurethane prepolymer first reacts with water to yield an amine
functional compound, which then further reacts with the isocyanate
group on another polymer molecule. A 1K moisture-cure adhesive can
have utility in, for example, auto exterior, building and
construction, textiles, wood working, assembly of electronic
components, and potting for electronics.
[0101] In some embodiments, the adhesive composition can be a hot
melt adhesive or a reactive hot melt adhesive composition. When the
adhesive is a hot melt, it may comprise a solventless or solid
composition and may be heated during all or a portion of its
application. When the adhesive composition is solventless, it may
have a solids content of at least about 90, at least about 92, at
least about 95, at least about 97, at least about 99, or at least
about 99.5 weight percent, based on the total weight of the
adhesive. Solventless adhesives may be in the form of pellets,
powders, sticks, or other masses solid at room temperature and
pressure.
[0102] When the adhesive composition is a hot melt (or reactive hot
melt) adhesive, it may be applied by heating the adhesive to a
temperature of at least about 50, at least about 55, at least about
60, at least about 65, at least about 70, at least about 75, at
least about 80, at least about 85, at least about 90, at least
about 95, at least about 100, at least about 105, at least about
110, at least about 115, at least about 120, at least about 125, at
least about 130, at least about 135, or at least about 140.degree.
C. and/or not more than about 200, not more than about 195, not
more than about 190, not more than about 185, not more than about
180, not more than about 175, not more than about 170, not more
than about 165, not more than about 160, not more than about 155,
or not more than about 150.degree. C. Hot melt adhesive
compositions according to embodiments of the invention can be
single component or two-component adhesives. Typical methods of
applying the hot melt adhesive include, but are not limited to, a
roll coater, sprayer, or a glue gun.
[0103] Adhesive compositions as described herein may have enhanced
properties as compared to adhesives formulated with conventional
polyols. For example, adhesive compositions according to
embodiments of the present invention may have both greater initial
bond strength (offline bond strength), as well as higher levels of
both thermal and chemical resistance. This makes the adhesives
suitable for a variety of end use applications, from woodworking to
electronics to flexible packaging and automotive finishes. Such
adhesives exhibit high offline bond strength, quickly reach
substrate failure, have a high chemical and thermal resistance,
while avoiding polyols including certain monomers, while achieving
these properties with various isocyanates and on multiple laminate
structures.
[0104] In some embodiments, adhesive compositions as described
herein may have an offline bond strength in the range of from 100
to 1000 grams per inch (g/in). Offline Bond Strength is measured
according to ASTM F904-16 immediately after lamination according to
the procedure described in Example 3. The offline bond strength
exhibited by the present invention can be at least about 150, at
least about 200, at least about 250, at least about 300, at least
about 350, at least about 400, at least about 450, at least about
500, or at least about 550 and/or not more than about 1000, not
more than about 950, not more than about 900, not more than about
850, not more than about 800, not more than about 750, not more
than about 700, not more than about 650, or not more than about 600
g/in.
[0105] In some embodiments, the offline bond strength of the
adhesive composition can be at least about 5, at least about 10, at
least about 15, at least about 20, at least about 25, at least
about 30, at least about 35, at least about 40, at least about 45,
at least about 50, at least about 55, at least about 60, at least
about 65, at least about 70, at least about 75, at least about 80
percent, or at least about 90 percent higher than an identical
adhesive composition formed with a polyester polyol having an acid
component comprising 58 mole % adipic acid (AD) and 42 mole %
isophthalic acid (IPA) and a diol component comprising 25 mole %
diethylene glycol (DEG) and 75 mole % ethylene glycol with a
hydroxyl number of 24 KOH/g, and a glass transition temperature of
-21.degree. C., all other components of said adhesive composition
being the same.
[0106] Alternatively, or in addition, the offline bond strength of
the adhesive composition can be at least about 5, at least about
10, at least about 15, at least about 20, at least about 25, at
least about 30, at least about 35, at least about 40, at least
about 45, at least about 50, at least about 55, at least about 60,
at least about 65, at least about 70, at least about 75, at least
about 80 percent, or at least about 90 percent higher than an
identical adhesive composition formed with a polyester polyol that
has an acid component comprising 50 mole % terephthalic acid (TPA)
and 50 mole % isophthalic acid (IPA) and a diol component
comprising 52 mole % neopentyl glycol (NPG) and 48 mole % ethylene
glycol with a hydroxyl number of 45 mg KOH/g, a glass transition
temperature of 50.degree. C., and a melt viscosity of 130.degree.
C. at 60 Pa, all other components being the same.
[0107] Adhesive compositions as described herein may have a 24-hour
bond strength, measured as described in Example 4, in the range of
from about 200 to about 3000 g/in. The 24-hour bond strength of the
adhesive composition can be at least about 250, at least about 300,
at least about 350, at least about 400, at least about 450, at
least about 500, at least about 550, at least about 600, at least
about 650, at least about 700, at least about 750, at least about
800, at least about 850, at least about 900, at least about 950, at
least about 1000, at least about 1050, at least about 1100, at
least about 1150, or at least about 1200 and/or not more than about
3000, not more than about 2500, not more than about 2000, not more
than about 1500, not more than about 1000, not more than about 950,
not more than about 900, not more than about 850, not more than
about 800, not more than about 750, or not more than about 700
g/in.
[0108] In some embodiments, the 24 hour bond strength of the
adhesive composition can be at least about 5, at least about 10, at
least about 15, at least about 20, at least about 25, at least
about 30, at least about 35, at least about 40, at least about 45,
at least about 50, at least about 55, at least about 60, at least
about 65, at least about 70, at least about 75, at least about 80
percent, or at least about 90 percent higher than an identical
adhesive composition formed with a polyester polyol having an acid
component comprising 58 mole % adipic acid (AD) and 42 mole %
isophthalic acid (IPA) and a diol component comprising 25 mole %
diethylene glycol (DEG) and 75 mole % ethylene glycol with a
hydroxyl number of 24 KOH/g, and a glass transition temperature of
-21.degree. C., all other components of said adhesive composition
being the same.
[0109] Additionally, or in the alternative, the 24 hour bond
strength of the adhesive composition can be at least about 5, at
least about 10, at least about 15, at least about 20, at least
about 25, at least about 30, at least about 35, at least about 40,
at least about 45, at least about 50, at least about 55, at least
about 60, at least about 65, at least about 70, at least about 75,
at least about 80 percent, or at least about 90 percent higher than
an identical adhesive composition formed with a polyester polyol
that has an acid component comprising 50 mole % terephthalic acid
(TPA) and 50 mole % isophthalic acid (IPA) and a diol component
comprising 52 mole % neopentyl glycol (NPG) and 48 mole % ethylene
glycol with a hydroxyl number of 45 mg KOH/g, a glass transition
temperature of 50.degree. C., and a melt viscosity of 130.degree.
C. at 60 Pa, all other components being the same.
[0110] In some embodiments, the adhesive composition may have a
chemical resistance, measured as described in Example 5, in the
range of 200 to 1000 g/in, measured after boil-in-bag with 1:1:1
food simulant. The adhesive composition can have a chemical
resistance after boil-in-bag with 1:1:1 food simulant can be at
least about 250, at least about 300, at least about 350, at least
about 400, at least about 450, or at least about 500 and/or not
more than about 1000, not more than about 950, not more than about
900, not more than about 850, not more than about 800, not more
than about 750, not more than about 700, not more than about 650,
or not more than about 600 g/in.
[0111] Such a chemical resistance may be at least about 5, at least
about 10, at least about 15, at least about 20, at least about 25,
at least about 30, at least about 35, at least about 40, at least
about 45, at least about 50, at least about 55, at least about 60,
at least about 65, at least about 70, at least about 75, at least
about 80 percent, or at least about 90 percent higher than an
identical adhesive composition formed with a polyester polyol
having an acid component comprising 58 mole % adipic acid (AD) and
42 mole % isophthalic acid (IPA) and a diol component comprising 25
mole % diethylene glycol (DEG) and 75 mole % ethylene glycol with a
hydroxyl number of 24 KOH/g, and a glass transition temperature of
-21.degree. C., all other components of said adhesive composition
being the same.
[0112] Alternatively, or in addition, the chemical resistance of
the adhesive composition can be at least about 5, at least about
10, at least about 15, at least about 20, at least about 25, at
least about 30, at least about 35, at least about 40, at least
about 45, at least about 50, at least about 55, at least about 60,
at least about 65, at least about 70, at least about 75, at least
about 80 percent, or at least about 90 percent higher than an
identical adhesive composition formed with a polyester polyol that
has an acid component comprising 50 mole % terephthalic acid (TPA)
and 50 mole % isophthalic acid (IPA) and a diol component
comprising 52 mole % neopentyl glycol (NPG) and 48 mole % ethylene
glycol with a hydroxyl number of 45 mg KOH/g, a glass transition
temperature of 50.degree. C., and a melt viscosity of 130.degree.
C. at 60 Pa, all other components being the same.
[0113] In some embodiments, the adhesive composition may exhibit a
thermal resistance of 200 to 800 g/in at 90.degree. C., measured as
described in Example 6. The thermal resistance of the adhesive
composition can be at least about 250, at least about 300, at least
about 350, at least about 400, at least about 450, at least about
500 and/or not more than about 800, not more than about 750, not
more than about 700, not more than about 650, not more than about
600, or not more than about 550 g/in.
[0114] Such a thermal resistance may be at least about 5, at least
about 10, at least about 15, at least about 20, at least about 25,
at least about 30, at least about 35, at least about 40, at least
about 45, at least about 50, at least about 55, at least about 60,
at least about 65, at least about 70, at least about 75, at least
about 80 percent, or at least about 90 percent higher than an
identical adhesive composition formed with a polyester polyol
having an acid component comprising 58 mole % adipic acid (AD) and
42 mole % isophthalic acid (IPA) and a diol component comprising 25
mole % diethylene glycol (DEG) and 75 mole % ethylene glycol with a
hydroxyl number of 24 KOH/g, and a glass transition temperature of
-21.degree. C., all other components of said adhesive composition
being the same.
[0115] Additionally, or in the alternatively, the adhesive
composition can exhibit a thermal resistance that is at least about
5, at least about 10, at least about 15, at least about 20, at
least about 25, at least about 30, at least about 35, at least
about 40, at least about 45, at least about 50, at least about 55,
at least about 60, at least about 65, at least about 70, at least
about 75, at least about 80 percent, or at least about 90 percent
higher than an identical adhesive composition formed with a
polyester polyol that has an acid component comprising 50 mole %
terephthalic acid (TPA) and 50 mole % isophthalic acid (IPA) and a
diol component comprising 52 mole % neopentyl glycol (NPG) and 48
mole % ethylene glycol with a hydroxyl number of 45 mg KOH/g, a
glass transition temperature of 50.degree. C., and a melt viscosity
of 130.degree. C. at 60 Pa, all other components being the same
[0116] In some cases, the adhesive composition may exhibit a time
to achieve substrate failure of less than 24 hours, measured as
described in Example 4. The time to achieve substrate failure is
the amount of time required for the adhesive to cure at 50.degree.
C. before substrate failure occurs. In some cases, the time to
substrate failure is not more than 20, 15, 12, 10, 5, or 2 hours,
and sometimes it occurs without curing the adhesive (offline peel
testing).
[0117] In some embodiments, the adhesive composition may exhibit
one or more of the above properties. For example, the adhesive
composition may have an offline bond strength within one or more of
the above ranges, as well a 24-hour bond strength, offline bond
strength, chemical resistance, thermal resistance, and time to
substrate failure within one or more of the above ranges. In some
cases, the adhesive composition exhibits values within the above
ranges for one, two, three, four, or five of the above
properties.
[0118] In some embodiments, adhesive compositions formed as
described herein may exhibit a lower reduction in bond strength
than would be expected from a conventional adhesive. For example,
in some embodiments, the adhesive composition comprising
CHDM-containing polyester polyols can have a reduction in bond
strength of not more than 50, not more than about 45, not more than
about 40, not more than about 35, not more than about 30, or not
more than about 25 percent, measured according to the following
formula: (Bond Strength Before Curing-Bond Strength After
Curing)/(Bond Strength Before Curing), expressed as a percentage.
As described herein, the bond strength after curing measured for
the reduction in bond strength is measured after 2 weeks of curing
at a temperature of 85.degree. C. and 85% relative humidity.
[0119] Additionally, the adhesive compositions described herein may
reach a bond strength of 75 psi in less than 20, less than 18, less
than 16, less than 12, less than 10, or less than 8 minutes of
curing at room temperature.
[0120] In some embodiments, the bond strength of the adhesive
composition described herein may be greater than about 90, at least
about 95, at least about 100, at least about 110, at least about
120, at least about 130, at least about 140, at least about 150, at
least about 160, at least about 170, at least about 180, at least
about 190, at least about 200, at least about 210, at least about
220, at least about 230, at least about 240, at least about 250, at
least about 260, at least about 270, at least about 280, at least
about 290, or at least about 300 psi, measured after curing the
adhesive at room temperature for 2 weeks and then heating to
82.degree. C. for 30 minutes.
[0121] Further, in some embodiments, the adhesive compositions
described herein are visually transparent or translucent, rather
than opaque.
[0122] Additionally, in some embodiments, the adhesive composition
can include a Zahn #2 viscosity of less than about 25 seconds, less
than about 24 seconds, less than about 23, less than about 22, less
than about 21, less than about 20, less than about 19, less than
about 18, less than about 17, less than about 16, or less than
about 15 seconds. The adhesive composition may also have a pot life
of at least about 6, at least about 6.5, at least about 7, at least
about 7.5, at least about 8, at least about 8.5, at least about 9,
or at least about 9.5 hours.
[0123] According to embodiments of the present invention, there is
provided a method of using the adhesive compositions described
herein. The method comprises contacting a surface of at least one
layer or substrate with at least a portion of an adhesive
composition, then adhering another layer or substrate to the first
via the adhesive layer. The adhesive composition used to form the
adhesive layer may be any adhesive composition as described herein
and can, in some cases, be a 1K or 2K adhesive composition.
[0124] Additionally, there is provided a laminated article formed
from an adhesive described herein comprising a first substrate
presenting a first surface, a second substrate presenting a second
surface, and an adhesive layer disposed between and partially in
contact with at least one of the first and second surfaces. Each of
the first and second layers may comprise a material selected from
the group consisting of polyethylene terephthalate, polypropylene,
aluminum-coated or aluminum-laminated polyethylene terephthalate,
low density polyethylene, and combinations thereof. In some cases,
the first and second layers may be the same, while, in other
embodiments, the first and second substrates or layers may be
different (or formed from different materials).
[0125] In some embodiments, one or both of the first and second
layers may have a thickness of at least about 0.5, at least about
1, at least about 1.5, or at least about 2 mil and/or not more than
about 10, not more than about 8, not more than about 5, not more
than about 3, not more than about 2, or not more than about 1.5
mil. The laminated article may further comprise a third, fourth,
fifth, or even sixth layer, each separated from and in contact
with, at least one additional adhesive layer, at least one of which
is formed from an adhesive composition as described herein.
[0126] In some embodiments, the laminated article, or film, may be
used to form another article such as, for example, a package,
pouch, bag, or other type of container for holding and storing at
least one substance, such as, for example, an edible item. The
package, pouch, bag, or other container may then be filled with at
least one substance, such as, for example, a foodstuff, beverage,
or other edible substance, which can then be sealed within the
interior volume of the package. As discussed previously, such a
package may exhibit enhanced chemical and thermal resistance to
delamination or other types of failure, due to the enhanced
performance of the adhesive used to form the laminate.
[0127] In another embodiment, there is provided a laminated article
comprising a first substrate presenting a first surface, a second
substrate presenting a second surface, and an adhesive layer
disposed between and in contact with at least a portion of the
first and second surfaces. The substrates may be selected from the
group consisting of polymers (including, but not limited to,
polymeric foams and thicker or rigid polymeric substrates such as
polycarbonate), wood, metal, fabric, leather, and combinations
thereof. The first and second substrates may be formed from the
same material or each may be formed from a different material.
[0128] In some embodiments, the first and second substrates may
have different thicknesses such that, for example, one substrate is
relatively thick (e.g., 0.25 inches or more), while the other is
relative thin (e.g., not more than 30 mils). Such differences in
thickness may occur when, for example, an adhesive composition is
used to adhere an outer decorative or functional layer to a base
substrate. In some cases, the ratio of the thickness of the thinner
substrate to the thicker substrate can be at least about 0.0001:1,
at least about 0.0005:1, at least about 0.001:1, at least about
0.005:1, at least about 0.01:1, at least about 0.05:1, at least
about 0.1:1, at least about 0.5:1, or at least about 0.75:1.
[0129] Examples of suitable end use applications for adhesives as
described herein can include, but are not limited to, woodworking,
automotive, textile, appliances, electronics, book-binding, and
packaging.
[0130] It is contemplated that compositions useful in the invention
can possess at least one of the Tg ranges described herein and at
least one of the monomer ranges for the compositions described
herein unless otherwise stated. It is also contemplated that
compositions useful in the invention can possess at least one of
the inherent viscosity ranges described herein, at least one of the
Tg ranges described herein, and at least one of the monomer ranges
for the compositions described herein, unless otherwise stated.
[0131] The following examples further illustrate how the polyesters
in the invention can be made and evaluated, and how the
polyurethane adhesives can be made and evaluated and are intended
to be purely exemplary of the invention and are not intended to
limit the scope thereof. Unless indicated otherwise, parts are
parts by weight, temperature is in degrees C. (Celsius) or is at
room temperature, and pressure is at or near atmospheric.
EXAMPLES
Example 1
[0132] A 12-L round bottom kettle with a four-neck lid was equipped
with a mechanical stirrer, a thermocouple, a heated partial
condenser (100.degree. C.), a Dean-Stark trap, and a chilled
condenser (15.degree. C.). The kettle was charged with
2,2,4,4-tetramethylcyclobutane-1,3-diol (TMCD) (1890 g), diethylene
glycol (DEG g), isophthalic acid (IPA) (2558 g), adipic acid (AD)
(1098 g). The mixture was allowed to react under a nitrogen
blanket. The temperature was increased from room temperature to
140.degree. C. over 80 minutes. Once at 140.degree. C., the
temperature was then increased from 140 to 250.degree. C. over 4
hours. Once the maximum temperature was reached, the acid catalyst,
titanium isopropoxide (3.7 g), was added to reaction, vacuum of 28
torr was applied and the temperature was held until a low acid
number was achieved. The polyester polyol was sampled for acid
number and achieved an acid number of 1.6. Then, the polyester
polyol was allowed to cool to 190.degree. C. before being poured
into aluminum pans to further cool and a solid product
collected.
[0133] Several polyester polyols having various compositions were
synthesized using the same procedure. The compositions of each of
these polyols are listed in Table 1, where AD is adipic acid, IPA
is isophthalic acid, DEG is diethylene glycol. All monomers are
reported in mole %, where the diacids total 100 mole % and the
diols total 100 mole %. Table 1 also lists the respective polyol
properties, in which Mn is the number average molecular weight
(g/mol), Mw is weight average molecular weight (g/mol), OHN is the
hydroxyl number (mg KOH/g) and AN is the acid number (mg
KOH/g).
TABLE-US-00001 TABLE 1 AD IPA DEG TMCD Sample (mol %) (mol %) (mol
%) (mol %) OHN AN M.sub.n M.sub.w Polyol A1 33 67 79 21 21 3 5,700
13,000 Polyol B1 58 42 79 21 19 2 4,800 14,000 Polyol C1 33 67 50
50 20 1 6,600 16,000 Polyol D1 58 42 50 50 17 0 6,600 16,000 Polyol
E1 45 55 65 35 19 0 6,300 15,000 Polyol F1 58 42 75 25 18 2 7,100
17,000 Polyol G1 58 42 60 40 19 1 6,000 16,000 Polyol Z 58 42 25 75
10 2 8,000 22,000
Example 2
[0134] A 12-L round bottom kettle with a four-neck lid was equipped
with a mechanical stirrer, a thermocouple, a heated partial
condenser (100.degree. C.), a Dean-Stark trap, and a chilled
condenser (15.degree. C.). The kettle was charged with
2,2,4,4-tetramethylcyclobutane-1,3-diol (TMCD) (1890 g), diethylene
glycol (DEG g), isophthalic acid (IPA) (2558 g), adipic acid (AD)
(1098 g). The mixture was allowed to react under a nitrogen
blanket. The temperature was increased from room temperature to
140.degree. C. over 80 minutes. Once at 140.degree. C., the
temperature was increased from 140 to 250.degree. C. over 4 hours.
Then the acid catalyst, titanium isopropoxide (3.7 g), was added to
reaction, vacuum of 28 torr was applied and the temperature held
until the polyol had an acid number of 1.6. The resulting polyester
polyol was allowed to cool to 190.degree. C. before being poured
into aluminum pans, wherein it was further cooled and collected as
a solid product.
[0135] Several polyester polyols having various compositions were
synthesized using the same procedure. The compositions of each of
these polyols are listed in Table 2, where AD is adipic acid, IPA
is isophthalic acid, DEG is diethylene glycol. All monomers are
reported in mol%, where the diacids total 100% and the diols total
100%. Table 2 also lists glass transition temperature (T.sub.g) and
the hydroxyl number (OHN) of the respective polyols.
[0136] Glass transition temperature was determined using a TA
Instruments Q2000 Differential Scanning calorimeter with the RCS-90
cooler and purged with 50 mL/m in N2. The sample was cooled to
-55.degree. C. then heated at 20.degree. C./min to 205.degree. C.
It then equilibrated at 200.degree. C. and held isothermally for 2
minutes. The sample was then cooled again to -55.degree. C. at
20.degree. C./min then equilibrated at -50.degree. C. and held
isothermally for 30 seconds. Finally, the sample was heated again
at 20.degree. C./min to 205.degree. C.
[0137] Viscosity was determined using a Brookfield DV-1+ viscometer
that used a S28 spindle and ran at 100 rpm with 13.6% torque.
TABLE-US-00002 TABLE 2 Viscosity AD IPA DEG TMCD T.sub.g Weight %
25.degree. C. Polyol (mol %) (mol %) (mol %) (mol %) OHN (.degree.
C.) Solids (cP) Polyol-A1 33 67 79 21 21 -5 -- -- Polyol-B1 58 42
79 21 19 -23 -- -- Polyol-C1 33 67 50 50 21 11 -- -- Polyol-C2 33
67 50 50 20 13 60 700 Polyol-D1 58 42 50 50 17 -8 -- -- Polyol-E1
45 55 65 35 19 -7 -- -- Polyol-F1 58 42 75 25 18 -20 -- --
Polyol-G1 58 42 60 40 19 -15 -- -- Polyol-Z 58 42 25 75 10 4 -- --
Polyol-C4 33 67 50 50 63 -3 -- -- Polyol-C5 33 67 50 50 102 -16 --
-- Polyol-A2 33 67 79 21 19 -4 -- -- Polyol-D2 58 42 50 50 20 -8 --
-- Polyol-C3 33 67 50 50 21 10 -- --
Example 3
[0138] Polyol-A2 described in Example 2 was weighed into an 8 oz
glass jars that has a Teflon lid with Urethane Grade Ethyl Acetate,
making a polyol solution of 60 wt % solids. The jar was closed and
sealed with electrical tape and rolled over night to allow for
complete mixing. When ready to coat, the polyol solution, the
hardener, ethyl acetate, and an adhesion promoter was combined into
another 8 oz glass jar and rolled to mix, making an adhesive
formulation with 40 wt % solids and an isocyanate/OH index of
2.
[0139] The adhesive formulation was coated onto PET1 using a TMI
Automatic Drawdown Machine, Model KCC-101 and a Meyer rod #1 at 30
ft/min. The coated PET1 was placed in an oven at 65.degree. C. for
1 minute. The second film, CPP, after treated by a corona treater
at a watt density of 10 KWf.sup.2/m, is then placed on top of the
coated PET1, and the structure is laminated using a laminator
(Scotch.RTM. TL806 Smart Thermal Laminator, Office Depot). This
results in a laminated film with a (dry) coat weight of about 4 gsm
(grams per square meter). See Table 3, below, for further details
on the types of substrates.
[0140] Polyol-A1, pre-diluted with Urethane Grade Ethyl Acetate to
60 wt % solids, was poured into a plastic bucket. HDI trimer,
pre-diluted with Urethane Grade Ethyl Acetate to 20 wt % solids,
ethyl acetate, and additional components, such as an adhesion
promoter, were poured into the same bucket, and mixed into an
adhesive formulation of 39 wt % solids. It had an isocyanate/OH
index of 2 and a Zahn #2 viscosity of 22 seconds.
[0141] The adhesive formulation was then poured into the gravure
pan of a Faustel LabMaster pilot line laminator. The adhesive
formulation was coated onto PET-Al with a gravure coating roll of
120 LPI/15 BCM at a line speed of 50 ft/min. The coated PET-Al was
then sent through a 10 ft dryer, heated to 175.degree. F. After the
coated PET-Al leaves the dryer, CPP pretreated by corona, was
placed on top of the coated PET-Al and put through a laminating
roll heated to 170.degree. F. and under 65 psi of pressure.
[0142] Next the viscosity of the adhesive compositions was measured
with a #2 Zahn cup according to ASTM D4212 "Standard Test Method
for Viscosity by Dip-Type Viscosity Cups." Table 3 below summarizes
specifics regarding each of the tested substrates, monomers, and
hardeners. Tables 4 and 5 below summarize the results of testing of
the above adhesive compositions.
TABLE-US-00003 TABLE 3 Flexible Substrates (Films): PET1
Polyethylene terephthalate, 1 mil (Mitsubishi), surface treated by
supplier, used for hand laminations PET2 Polyethylene
terephthalate, 1 mil (Neologic Solutions), corona treated prior to
use, used for machine laminations CPP1 Cast polypropylene, 2 mil
(Neologic), corona treated prior to use, used for hand laminations
CPP2 Cast polypropylene, 2 mil (Berry), corona treated prior to
use, used for machine laminations PET-Al Al foil/PET laminate, 32
micron (Neologic solutions), corona treated prior to use, used for
machine laminations LDPE Low density polyethylene, 1.5 mil (Berry),
corona treated prior to use, used for machine laminations Monomers:
AD adipic acid IPA isophthalic acid TMCD
2,2,4,4-tetramethyl-1,3-cyclobutanediol DEG diethylene glycol
Isocyanate Hardeners: HDI Trimer hexamethylene diisocyanate trimer
IPDI Trimer isophorone diisocyanate trimer
TABLE-US-00004 TABLE 4 AD IPA DEG TMCD EG T.sub.g Polyol (mol %)
(mol %) (mol %) (mol %) (mol %) OHN AN M.sub.n M.sub.w (.degree.
C.) Polyol-A1 33 67 79 21 0 21 3 5,700 13,000 -5 Polyol-B1 58 42 79
21 0 19 2 4,800 14,000 -23 Polyol-C1 33 67 50 50 0 21 2 5,600
13,000 11 Polyol-C2 33 67 50 50 0 20 2 6,600 16,000 13 Polyol-D1 58
42 50 50 0 17 0 6,600 16,000 -8 Polyol-E1 45 55 65 35 0 19 0 6,300
15,000 -7 Polyol-F1 58 42 75 25 0 18 2 7,100 17,000 -20 Polyol-G1
58 42 60 40 0 19 1 6,000 16,000 -15 Polyol-Z 58 42 25 75 0 10 2
8,000 22,000 4 Polyol-A2 33 67 79 21 0 19 0 4,500 13,000 -4
Polyol-D2 58 42 50 50 0 20 0 6,600 16,000 -8 Polyol-C3 33 67 50 50
0 21 1 6,200 15,000 10 Control-H 58 42 25 0 75 24 1 4,000 11,000
-21 Control-2 29 71 69 0 31 17 1 5,500 15,500 -6
TABLE-US-00005 TABLE 5 Polyol Isocyanate Final wt % Zahn # 2 Coat
Weight Isocyanate Substrate Lamination Descriptor Hardener Solids
Cup (sec) (gsm) Index Type Coating Method Control-H HDI Trimer 40
24 4.0 2 PET-Al/CPP2 Machine Control-2 HDI Trimer 37 22. 3.7 2
PET-Al/CPP2 Machine Polyol-B1 HDI Trimer 41 22 4.2 2 PET-Al/CPP2
Machine Polyol-F1 HDI Trimer 36 22 3.7 2 PET-Al/CPP2 Machine
Polyol-G1 HDI Trimer 41 21 4.2 2 PET-Al/CPP2 Machine Polyol-D1 HDI
Trimer 41 23 4.4 2 PET-Al/CPP2 Machine Polyol-Z HDI Trimer 36 22
3.7 2 PET-Al/CPP2 Machine Polyol-A1 HDI Trimer 39 22 3.6 2
PET-Al/CPP2 Machine Polyol-C1 HDI Trimer 38 22 4.1 2 PET-Al/CPP2
Machine Polyol-C2 HDI Trimer 38 21 4.2 2 PET-Al/CPP2 Machine
Polyol-C2 HDI Trimer 38 21 4.2 2 PET2/CPP2 Machine Polyol-C2 HDI
Trimer 38 21 4.3 2 PET-Al/LDPE Machine Polyol-C2 HDI Trimer 38 21
4.0 2 PET2/LDPE Machine Polyol-A2 HDI Trimer 40 -- 4.0 1.4
PET1/CPP1 Hand Polyol-A2 IPDI Trimer 40 -- 4.0 1.4 PET1/CPP1 Hand
Polyol-A2 HDI Trimer 40 -- 4.0 2 PET1/CPP1 Hand Polyol-D2 HDI
Trimer 40 -- 4.0 1.4 PET1/CPP1 Hand Polyol-D2 IPDI Trimer 40 -- 4.0
1.4 PET1/CPP1 Hand Polyol-D2 HDI Trimer 40 -- 4.0 2 PET1/CPP1 Hand
Polyol-C3 HDI Trimer 40 -- 4.0 1.4 PET1/CPP1 Hand Polyol-C3 HDI
Trimer 40 -- 4.0 2.0 PET1/CPP1 Hand
Example 4
[0143] Several adhesives were formulated with various polyols as
described in Example 3. The offline peel strength for each was
tested according to the following procedure. T-peel testing was
done according to ASTM F904-16 "Standard Test Method for Comparison
of Bond Strength or Ply Adhesion of Similar Laminates Made from
Flexible Materials" using an MTS Criterion Model 42, 100 Newton
load-cell. The samples were cured at 50.degree. C. for either 24
hours, 1 week or 2 weeks before testing. A film direction of the
coating direction was used. The film was separated by a t-peel test
in the direction of the coating. A minimum of three samples of each
composition were tested and the average and standard deviation
reported. Off-line peel strength was measured by taking laminated
samples directly off the laminator (0-5 min after lamination) for
T-peel testing.
[0144] Table 6, below, summarizes the offline peel strength test
for adhesives formed with polyester polyols having increasing
amounts of TMCD. The laminates were all machine laminated between
PET-Al and CPP2. The adhesive had an isocyanate index of 2.
TABLE-US-00006 TABLE 6 Offline Iso- Peel Standard Mol % cyanate
Strength Deviation Failure Polyol TMCD* Hardener (g/in) (g/in)
Mechanism Control-H 0 HDI Trimer 53 -- Cohesive Polyol-B1 10.5 HDI
Trimer 25 -- Cohesive Polyol-F1 12.5 HDI Trimer 31 -- Cohesive
Polyol-G1 20 HDI Trimer 23 -- Cohesive Polyol-D1 25 HDI Trimer 92
-- Cohesive Polyol-Z 37.5 HDI Trimer 492 22 Cohesive *This is the
mole % TMCD considering both diacids and diols
[0145] Table 7, below, summarizes the results of a 24 hour bond
strength test for adhesives formed with polyester polyols having
increasing amounts of TMCD. The laminates were all machine
laminated between PET-Al and CPP2. The adhesives had an isocyanate
index of 2.
TABLE-US-00007 TABLE 7 24 hr Iso- Peel Standard Mol % cyanate
Strength Deviation Failure Polyol TMCD* Hardener (g/in) (g/in)
Mechanism Control-H 0 HDI Trimer 409 -- Cohesive Polyol-B1 10.5 HDI
Trimer 505 -- Cohesive Polyol-F1 12.5 HDI Trimer 236 -- Cohesive
Polyol-G1 20 HDI Trimer 288 -- Cohesive Polyol-D1 25 HDI Trimer 696
-- Cohesive Polyol-Z 37.5 HDI Trimer 2952 273 Substrate *This is
the mole % TMCD considering both diacids and diols
[0146] Table 8, below, summaries the impact that the Tg of the
polyol has on the offline peel strength of the adhesive. All
samples were machine laminated between PET-Al and CPP2 using an
adhesive composition with an isocyanate index of 2.
TABLE-US-00008 TABLE 8 Offline Iso- Peel Standard T.sub.g cyanate
Strength Deviation Failure Polyol (.degree. C.) Hardener (g/in)
(g/in) Mechanism Control-H -21 HDI Trimer 53 -- Cohesive Polyol-B1
-23 HDI Trimer 25 -- Cohesive Polyol-A1 -5 HDI Trimer 212 --
Cohesive Polyol-Z 4 HDI Trimer 492 22 Cohesive Polyol-C1 11 HDI
Trimer 528 -- Cohesive
[0147] Table 9, below, summaries the impact that the Tg of the
polyol has on the 24 hour peel strength of the adhesive. All
samples were machine laminated between PET-Al and CPP2 using an
adhesive composition with an isocyanate index of 2.
TABLE-US-00009 TABLE 9 24 hr Iso- Peel Standard T.sub.g cyanate
Strength Deviation Failure Polyol (.degree. C.) Hardener (g/in)
(g/in) Mechanism Control-H -21 HDI Trimer 409 -- Cohesive Polyol-B1
-23 HDI Trimer 505 -- Cohesive Polyol-A1 -5 HDI Trimer 792 --
Elongation Polyol-Z 4 HDI Trimer 2,952 273 Substrate Polyol-C1 11
HDI Trimer 2,084 -- Substrate
[0148] Table 10 summarizes the time until Substrate Failure of
several machine laminated articles between PET-Al and CPP2, and
Table 11 summarizes data for several other substrates. Substrate
failure was determined by visual inspection of the article after
peel testing. Control-H failed via the adhesive layer and did not
exhibit any substrate failure.
TABLE-US-00010 TABLE 10 Isocyanate Cure Time until Polyol Hardener
Substrate Failure Control-H HDI Trimer Did not achieve Polyol-A1
HDI Trimer 1 week Polyol-C1 HDI Trimer 24-hours Polyol-Z HDI Trimer
24-hours
TABLE-US-00011 TABLE 11 Iso- Sub- 24 hr Peel Standard cyanate
strate Strength Deviation Failure Polyol Hardener Type (g/in)
(g/in) Mechanism Polyol- HDI PET-Al/ 2405 210 Substrate C2 Trimer
CPP2 Polyol- HDI PET2/ 2676 152 Substrate C2 Trimer CPP2 Polyol-
HDI PET-Al/ 1202 56 Substrate C2 Trimer LDPE Polyol- HDI PET2/ 1175
283 Substrate C2 Trimer LDPE
[0149] Table 12 summarizes the results of a Two-Week Peel Strength
test for several adhesive compositions including an HDI Trimer. All
samples were hand Laminated between PET1 and CPP1, with the
adhesive having an isocyanate index of 1.4.
TABLE-US-00012 TABLE 12 Iso- Iso- 1 Week Peel Standard cyanate
cyanate Strength Deviation Failure Polyol Hardener Index (g/in)
(g/in) Mechanism Polyol- HDI 1.4 1084 337 Substrate C3 Trimer
Polyol- HDI 2.0 945 260 Substrate C3 Trimer Polyol- HDI 1.4 940 82
Substrate D2 Trimer Polyol- HDI 2.0 892 88 Substrate D2 Trimer
[0150] Table 13 is a summary of Two-Week Peel Strength test with
adhesives formed with IPDI Trimer and HDI Trimer as the isocyanate
components. All samples were hand Laminated between PET1 and CPP1.
The adhesive had an isocyanate Index of 1.4.
TABLE-US-00013 TABLE 13 Iso- Two Week Peel Standard cyanate
Strength Deviation Failure Polyol Hardener (g/in) (g/in) Mechanism
Polyol-A2 HDI Trimer 857 44 Substrate Polyol-A2 IPDI Trimer 927 56
Substrate Polyol-D2 HDI Trimer 806 14 Substrate Polyol-D2 IPDI
Trimer 736 134 Substrate
Example 5
[0151] Several adhesive compositions were formed as discussed
above. Then, laminates were formed using the adhesive composition
and then sealed to form pouches. To form a pouch, a 9''.times.12''
(23 cm.times.30.5 cm) sheet of laminate was folded over to give a
double layer of about 9''.times.6'' (23 cm.times.15.25 cm) such
that the polyethylene or polypropylene film of one layer was in
contact with the polyethylene or polypropylene film of the other
layer. The inner film layer was either be polyethylene or
polypropylene. PET2 and PET-Al were used as the outer film layer.
The edges were trimmed on a paper cutter to give a folded piece
about 5''.times.7'' (12.7 cm.times.17.8 cm). Two long sides and one
short side were heat sealed at the edges to give a finished pouch
with an interior size of 4''.times.6'' (10.2 cm.times.15.2 cm). The
heat sealing was then carried out at 177.degree. C. (350.degree.
F.) for one second at a hydraulic pressure of 276 kPa (40 psi).
[0152] The chemical resistance of each pouch was tested according
to the following procedure. The pouches were filled through the
open side with 100.+-.5 ml of "1:1:1 sauce" (blend of equal parts
by weight of ketchup, vinegar, and vegetable oil). During filling,
splashing the sauce onto the heat seal area was avoided as this can
cause the heat seal to fail during the testing. After filling, the
top of the pouch was sealed in a manner that minimizes air
entrapment inside of the pouch. The pouches were then held at
100.degree. C. (boiling in water) for 1 hour. The food simulant was
removed by cutting one side of the sealed pouch. The contents were
dumped out and the pouch rinsed with deionized water. Strips were
cut out of the pouch (3''.times.1'') to be tested for Peel
Strength. Peel strength was tested within 0.5 hours after the pouch
was removed from the heated bath and was performed as described in
Example 4.
[0153] Table 14 below summarizes the results of chemical resistance
Testing with a 1:1:1 food simulant. All samples were machine
laminated between PET-Al and CPP2.
TABLE-US-00014 TABLE 14 Iso- Peel Strength Standard Polyol cyanate
on PET-Al/CPP Deviation Failure Descriptor Hardener (g/in) (g/in)
Mechanism Control- HDI 81 11 Adhesive 2 Trimer Polyol- HDI 636 237
Cohesive/ A1 Trimer Partial Substrate Polyol- HDI 738 144 Cohesive/
C1 Trimer Partial Substrate
[0154] Table 15 summarizes the results of additional chemical
resistance testing performed as above, but with 50 wt% ethyl
alcohol in the pouch. All samples were machine laminated between
PET-Al and CPP2.
TABLE-US-00015 TABLE 15 Iso- Peel Strength Standard Polyol cyanate
on PET-Al/CPP Deviation Failure Descriptor Hardener (g/in) (g/in)
Mechanism Control-2 HDI Trimer 15 1 Cohesive Polyol-A1 HDI Trimer
576 41 Cohesive Polyol-C1 HDI Trimer 508 56 Cohesive
Example 6
[0155] Several adhesive compositions were formed as discussed
above. Then, laminates were formed and tested for thermal
resistance according to the following procedure.
[0156] T-peel testing was done as described in Example 3 except
with a Thermocraft Lab-Temp Heating Chamber set to 90.degree. C.
The sample was put into the grips of the MTS Criterion Model 42
instrument and then enclosed in the heating chamber. It was
equilibrated at the elevated temperature for 2 minutes. Keeping the
sample in the heating chamber, the sample was pulled in the
direction of the coating. A minimum of three samples of each
composition were tested and the average and standard deviation
reported
[0157] Table 16 below summarizes the results of thermal resistance
bond strength testing for several adhesives. All samples were
machine laminated between PET-Al and CPP2.
TABLE-US-00016 TABLE 16 Iso- Peel Strength Standard cyanate on
PET-Al/CPP Deviation Failure Polyol Hardener (g/in) (g/in)
Mechanism Control-2 HDI Trimer 182 8 Adhesive Polyol-A1 HDI Trimer
306 26 Cohesive Polyol-C1 HDI Trimer 320 17 Adhesive
Example 7
[0158] A 12 L round bottom flask sitting in a heating mantle was
fitted with a stir shaft, a thermal couple, a nitrogen inlet, and a
condenser. The condenser was maintained at 100-105.degree. C. using
a circulation bath. The volatiles coming out of the first condenser
was condensed with a cold water chilled condenser then collected in
a graduated cylinder. The flask was kept under a nitrogen blanket
throughout the reaction. An amount of 3374 g
2,2,4,4-tetramethyl-1,3-cyclobutanediol, 2652 g
1,4-cyclohexanedicarboxylic acid (65% cis), 672 g adipic acid, and
6.6 g FASCAT.RTM. 4102 were charged into the flask. The mixture was
then heated to 240.degree. C. and maintained at such temperature
till the condensate stopped coming out. Another 6.6 gram of
FASCAT.RTM. 4102 was then added to the reaction. The mixture was
then subjected to a vacuum of 20 torr until the acid number was
around 2.0 mgKOH/g. The product was then poured into an aluminum
pan, cooled to room temperature.
[0159] Next, a 2-L kettle reactor with a four-neck lid was equipped
with a mechanical stirrer, a thermocouple, a heated partial
condenser (115.degree. C.), a Dean-Stark trap, and a chilled
condenser (15.degree. C.). Hexahydrophthalic anhydride (HHPA)
(817.8 g) and TMCD (559.9 g) were added to the reactor. The mixture
was slowly heated to 150.degree. C. The reaction was exothermic and
reached ca. 180.degree. C. When the exotherm was complete, the
temperature was set to 215.degree. C. and ca. 20 mL of water was
taken off. To the reaction mixture was added neopentyl glycol
(217.7 g) and Fascat 4100 (1.5 g). The temperature was slowly
increased to 230.degree. C. When the acid number was less than 2
mgKOH/g, the reaction was stopped and the polyester polyol was
poured out.
[0160] Several polyester polyol resins were synthesized according
to this method. The compositions of each of these polyester polyols
are listed in Table 17 and 18, and the polyester polyol properties
are listed in Table 19, in which CHDA is
1,4-cyclohexanedicarboxylic acid, IPA is isophthalic acid, HHPA is
hexahydrophthalic anhydride, CHDM is 1,4-cyclohexanedimethanol, NPG
is neopentyl glycol, and TMP is trimethylolpropane.
TABLE-US-00017 TABLE 17 Polyol CHDA Adipic acid IPA HHPA Polyol K
2652 672 Polyol L 2651.6 672.24 Polyol M 2754.9 584.56 Polyol N
817.83 Polyol O 809.42 Polyol P 772.59 Polyol Q 772.59 Polyol R
15945 Polyol S 319.97 Polyol T 315.67
TABLE-US-00018 TABLE 18 Polyol TMCD CHDM NPG TMP BDO Polyol K 3374
Polyol L 3273.3 100.94 Polyol M 3175.1 98.2 Polyol N 559.92 217.74
Polyol O 632.76 152.33 Polyol P 329.27 493.9 Polyol Q 416.74 408.57
Polyol R 8426.6 6997.7 444.06 Polyol S 64.17 185.34 Polyol T 66.86
193.14
TABLE-US-00019 TABLE 19 Melt vicosity OHN, AN, Tg, at 130.degree.
C., Polyol mgKOH/g mgKOH/g .degree. C. Pa s Mn Mw Dynacoll 41 1 50
68 7150 Dynacoll 36 1 28 10 7130 Polyol K 41 2 48 36 3441 7297
Polyol L 35 2 46 73 4065 8918 Polyol M 37 2 49 70 3626 7831 Polyol
N 31 2 57 37 2961 6868 Polyol O 25 4 63 80 2501 6442 Polyol P 25 2
53 51 3700 8115 Polyol Q 43 1 52 25 2501 5834 Polyol R 33 3 58 59
3373 8764 Polyol S 45 3 52 74 2839 5764 Polyol T 46 3 55 54 2574
2394
Example 5
[0161] Several urethane prepolymers were synthesized according to
the following general procedure. A 1-Liter kettle reactor with a
four-neck lid was equipped with a heating mantle, a mechanical
stirrer, a thermocouple, a chilled condenser, nitrogen inlet and
bubbler. To the reactor was charged, 125 g Dow Voranol 2120, 100 g
Evonik Dynacoll 7360, 50 g Evonik Dynacoll 7380, 125 g Evonik
Dynacoll 7250, 70.8 g Evonik Vestplast 508, 35.4 g Lubrizol
Pearlbond 521, and 100 grams of a polyester polyol (a TMCD
polyester polyol or a control polyol). The mixture was heated to
120.degree. C. and mixed before being dried at the same temperature
under high vacuum for at least 2 hours. After cooling down to
90.degree. C., the amount of 4,4'-MDI as listed in Table 20 was
charged in one portion. The mixture was then stirred at 95.degree.
C. under high vacuum for 2 hours. The mixture was heated to
120.degree. C., 0.7 g 2,2'-dimorpholinildiethylether was charged
then the product was degassed for 0.5 hours. Finally, the
prepolymer was stored in sealed metal cans at room temperature.
TABLE-US-00020 TABLE 20 Prepolymer Polyol MDI, g Prepolymer
appearance C-1 Dynacoll 7150 74.45 opaque C-2 Dynacoll 7130 71.82
opaque A Polyol K 75.06 translucent B Polyol L 71.62 translucent C
Polyol M 72.42 translucent D Polyol N 70.00 translucent E Polyol O
68.78 translucent F Polyol P 68.38 translucent G Polyol Q 74.45
translucent H Polyol R 70.81 translucent I Polyol S 75.66 opaque J
Polyol T 76.07 opaque
[0162] Several properties of the adhesive compositions were tested
as described below. Open time was measured according to the
following procedure. The prepolymer was heated up to 140.degree. C.
then applied onto silicon paper as a 500 microns thick film. Strips
of paper were pressed onto the film at certain intervals. When the
film became tack-free, the paper strips were removed. The open time
was determined by the time when no fibers were torn apart from the
paper.
[0163] Setting time was measured according to the following
procedure. A shear module was prepared with a bonding area of 25 mm
by 25 mm. After fixing the upper end in a single location, a 1
kg-weight was hung at the bottom of the module, and the time for
the module to stop moving was determined as the settling time.
[0164] The softening point of the adhesive was determined by ring
and ball method ASTM D6493-11) (2015).
[0165] The melt viscosity of the adhesives was measured using a
Brookfield Thermosel, RVDV-1 Prime. Shear strength was measured as
follows: A shear module was prepared having a bonding area of 25 mm
by 25 mm. Adhesive was cured at room temperature using prescribed
conditions. The testing machine conformed to requirements of and
have the capabilities of the machine prescribed in ASTM D1002. At
least three lap shear samples were prepared tested.
[0166] Green strength for several of the adhesives was measured as
follows. A shear module was prepared with a bonding area of 25 mm
by 25 mm. Immediately applied 500 g weight on top of the bonding
area for 30 seconds. The shear strength was then measured at 1 min,
2 min, 5 min, 10 min, and 15 min after the start of the
compression. At least three lap shear samples were prepared in each
case and measured.
[0167] Tables 21 through 25 summarizes the evaluation of the
adhesive compositions based on TMCD polyester polyols of the above
properties. Table 21 shows the results of several of the above
tests, while Table 22 summarizes the green strength at various
times. Table 23 summarizes the results after a 2-week cure, and
Table 24 shows the bond strength of two-week cured samples which
were then heated to 82.degree. C. for 30 minutes before being
tested (to illustrate heat resistance). Finally, Table 25 shows
tensile strength and percent elongation of several samples.
TABLE-US-00021 TABLE 21 Viscosity at Set Open Softening 120.degree.
C., Prepolymer Time, s Time, s point, .degree. C. Pa s C-1 50 35 15
C-2 35 35 65 29.8 A 50 35 9.4 B 85 60 71 9.3 D 60 35 72 7.6 E 75 15
74 16.4 F 90 55 75 7.4 G 110 70 72 6.6 H 80 35 72 9.7 I 64 19.9 J
66 15
TABLE-US-00022 TABLE 22 Prepolymer 1 min 2 min 5 min 10 min 15 min
C-1 3 16 49 67 68 C-2 5 27 62 68 A 4 31 76 84 B 1 17 77 84 D 2 39
77 82 100 E 1 29 79 85.0 F 1 5 69 83 G 1 4 64 74 H 1 29 84 88
TABLE-US-00023 TABLE 23 PP Beech, Aluminum, (untreated), PVC,
Prepolymer psi psi psi psi C-1 156.8 160.9 44.4 355.7 A 355.8 177.5
54.3 335.8 D 290.1 178.9 157 260.4 F 360.9 153.5 61.3 274.6 H 308.9
166.3 55.2 222.1
TABLE-US-00024 TABLE 24 PP Beech, Aluminum, (untreated), PVC,
Prepolymer psi psi psi psi C-1 16.5 13.5 2.9 24.8 A 64.4 20.9 5.2
34.2 D 58.1 19.0 10.1 25.9 F 24.4 7.7 3.5 15.2 H 57.5 13.2 3.1
23.3
TABLE-US-00025 TABLE 25 Prepolymer Tensile strength, psi Elongation
% C-1 1833 846% C-2 1550 1120% A 1966 690% B 2297 842% D 1448 739%
E 1177 712% F 1451 760% G 2412 856% H 2565 782% I 1907 920%
* * * * *