U.S. patent application number 17/633604 was filed with the patent office on 2022-09-29 for polyol polymers, methods of preparing such polymers, and coating compositions containing the same.
This patent application is currently assigned to PPG Industries Ohio, Inc.. The applicant listed for this patent is PPG Industries Ohio, Inc.. Invention is credited to Jonathan P. Breon, Paul H. Lamers, Tsukasa Mizuhara, Gobinda Saha, Hongying Zhou.
Application Number | 20220306800 17/633604 |
Document ID | / |
Family ID | 1000006406097 |
Filed Date | 2022-09-29 |
United States Patent
Application |
20220306800 |
Kind Code |
A1 |
Breon; Jonathan P. ; et
al. |
September 29, 2022 |
POLYOL POLYMERS, METHODS OF PREPARING SUCH POLYMERS, AND COATING
COMPOSITIONS CONTAINING THE SAME
Abstract
A polyol polymer is obtained from reactants including: a) a
non-aromatic epoxy functional compound that includes at least 30
weight % of the total solids weight of the reactants; and b) an
aromatic mono-carboxylic acid functional compound, or anhydride
thereof, that is substantially free of non-aromatic ethyl enic
unsaturation. The polyol polymer has ester linkages and hydroxyl
functional groups, Further, if the reactants further include an
aromatic polycarboxylic acid, the aromatic polycarboxylic acid
makes up less than 15 weight % of the total solids weight of the
reactants. A coating composition is also prepared with the polyol
polymer.
Inventors: |
Breon; Jonathan P.;
(Memphis, TN) ; Zhou; Hongying; (Allison Park,
PA) ; Mizuhara; Tsukasa; (Gibsonia, PA) ;
Lamers; Paul H.; (Allison Park, PA) ; Saha;
Gobinda; (Pittsburgh, PA) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
PPG Industries Ohio, Inc. |
Cleveland |
OH |
US |
|
|
Assignee: |
PPG Industries Ohio, Inc.
Cleveland
OH
|
Family ID: |
1000006406097 |
Appl. No.: |
17/633604 |
Filed: |
August 7, 2020 |
PCT Filed: |
August 7, 2020 |
PCT NO: |
PCT/US2020/045505 |
371 Date: |
February 8, 2022 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
|
|
16535859 |
Aug 8, 2019 |
|
|
|
17633604 |
|
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Current U.S.
Class: |
1/1 |
Current CPC
Class: |
C09D 7/65 20180101; C08K
3/013 20180101; C08K 5/0025 20130101; C08K 5/29 20130101; C08K
5/0041 20130101; C09D 167/025 20130101; C09D 7/63 20180101; C08G
63/42 20130101 |
International
Class: |
C08G 63/42 20060101
C08G063/42; C09D 7/65 20060101 C09D007/65; C09D 7/63 20060101
C09D007/63; C09D 167/02 20060101 C09D167/02 |
Claims
1. A polyol polymer obtained from reactants comprising: a) a
non-aromatic epoxy functional compound that comprises at least 30
weight % of the total solids weight of the reactants; and b) an
aromatic mono-carboxylic acid functional compound, or anhydride
thereof, that is substantially free of non-aromatic ethylenic
unsaturation, wherein the polyol polymer comprises ester linkages
and hydroxyl functional groups, and wherein, if the reactants
further comprise an aromatic polycarboxylic acid, the aromatic
polycarboxylic acid comprises less than 15 weight % of the total
solids weight of the reactants.
2. The polymer of claim 1, wherein the non-aromatic epoxy
functional compound comprises a cycloaliphatic diglycidyl ether, a
cycloaliphatic diglycidyl ester, a cycloaliphatic epoxide, or any
combination thereof.
3. The polymer of claim 1, wherein the non-aromatic epoxy
functional compound comprises a hydrogenated bisphenol polyepoxide
or a polyepoxide derived from a hydrogenated bisphenol
compound.
4. The polymer of claim 1, wherein the non-aromatic epoxy
functional compound comprises at least 40 weight % of the total
solids weight of the reactants.
5. The polymer of claim 1, wherein the reactants further comprise a
non-aromatic mono-carboxylic acid.
6. The polymer of claim 5, wherein the non-aromatic mono-carboxylic
acid further comprises a hydroxyl group.
7. The polymer of claim 1, wherein the reactants further comprise a
non-aromatic polycarboxylic acid.
8. The polymer of claim 1, wherein the reactants further comprise
an intramolecular cyclic ester.
9. The polymer of claim 1, wherein the polyol polymer has a
polydispersity index of 3.50 or less.
10. The polymer of claim 1, wherein the polyol polymer has a
hydroxyl value of at least 50 mg KOH/g.
11. The polymer of claim 1, wherein the polyol polymer comprises
carboxylic acid functional groups and epoxy functional groups, and
has an epoxy-to-acid ratio of greater than 0.95.
12. A coating composition comprising: i) a polyol polymer according
to claim 1; and ii) a crosslinker reactive with the polyol
polymer.
13. The coating composition of claim 12, wherein the crosslinker
comprises a polyisocyanate, aminoplast, or a combination
thereof
14. The coating composition of claim 12, further comprising a
non-aqueous solvent.
15. The coating composition of claim 12, further comprising a
colorant.
16. The coating composition of claim 12, wherein the reactants that
form the polyol polymer further comprise a non-aromatic
mono-carboxylic acid.
17. The coating composition of claim 12, wherein the reactants that
form the polyol polymer further comprise a non-aromatic
polycarboxylic acid.
18. The coating composition of claim 12, wherein the reactants that
form the polyol polymer further comprise an intramolecular cyclic
ester.
19. A substrate at least partially coated with a coating formed
from the composition of claim 12.
20. The substrate of claim 19, wherein the coating is formed
directly over a surface of the substrate.
21. A method of forming a polyol polymer comprising: a) reacting
reactants comprising: i) a non-aromatic epoxy functional compound
that comprises at least 30 weight % of the total solids weight of
the reactants; and ii) an aromatic mono-carboxylic acid functional
compound, or anhydride thereof, that is substantially free of
non-aromatic ethylenic unsaturation, wherein the polyol polymer
comprises ester linkages and hydroxyl functional groups, and
wherein, if the reactants further comprise an aromatic
polycarboxylic acid, the aromatic polycarboxylic acid comprises
less than 15 weight % of the total solids weight of the
reactants.
22. The method of claim 21, wherein the reactants of step a)
further comprise a non-aromatic mono-carboxylic acid, a
non-aromatic polycarboxylic acid, or a combination thereof
23. The method of claim 21, further comprising b) reacting a
reaction product from step a) with an intramolecular cyclic ester.
Description
FIELD OF THE INVENTION
[0001] The present invention relates to polyol polymers, methods of
preparing the polymers, coating compositions containing the same,
coatings formed from the coating compositions, and substrates at
least partially coated with such coatings.
BACKGROUND OF THE INVENTION
[0002] Metallic substrates and other substrates having metallic
portions are susceptible to corrosion, especially when exposed to
certain environmental conditions. To prevent or reduce the
corrosion of such substrates, a coating that inhibits corrosion of
these substrates is typically applied over the surface. These
coatings can be applied directly over the substrate as a single
coating layer, or additional coating layers can be applied over the
corrosion inhibiting coating layer to provide other properties
including color, abrasion resistance, and chemical resistance.
While coatings have been developed to reduce corrosion of metallic
containing substrates, it is desirable to provide improved coatings
that more effectively reduce or prevent corrosion and which also
provide other desirable properties such as good appearance.
SUMMARY OF THE INVENTION
[0003] The present invention relates to a polyol polymer obtained
from reactants comprising: a) a non-aromatic epoxy functional
compound that comprises at least 30 weight % of the total solids
weight of the reactants; and b) an aromatic mono-carboxylic acid
functional compound, or anhydride thereof, that is substantially
free of non-aromatic ethylenic unsaturation. The polyol polymer
comprises ester linkages and hydroxyl functional groups. Further,
if the reactants further comprise an aromatic polycarboxylic acid,
the aromatic polycarboxylic acid comprises less than 15 weight % of
the total solids weight of the reactants.
[0004] The present invention further includes a coating composition
comprising the previously described polymer and a crosslinker
reactive with the polymer.
[0005] The present invention also includes a method of forming a
polyol polymer. The method includes reacting reactants comprising:
a) a non-aromatic epoxy functional compound that comprises at least
30 weight % of the total solids weight of the reactants; and b) an
aromatic mono-carboxylic acid functional compound, or anhydride
thereof, that is substantially free of non-aromatic ethylenic
unsaturation. The polyol polymer comprises ester linkages and
hydroxyl functional groups. Further, if the reactants further
comprise an aromatic polycarboxylic acid, the aromatic
polycarboxylic acid comprises less than 15 weight % of the total
solids weight of the reactants.
DESCRIPTION OF THE INVENTION
[0006] For purposes of the following detailed description, it is to
be understood that the invention may assume various alternative
variations and step sequences, except where expressly specified to
the contrary. Moreover, other than in any operating examples, or
where otherwise indicated, all numbers expressing, for example,
quantities of ingredients used in the specification and claims are
to be understood as being modified in all instances by the term
"about". Accordingly, unless indicated to the contrary, the
numerical parameters set forth in the following specification and
attached claims are approximations that may vary depending upon the
desired properties to be obtained by the present invention. At the
very least, and not as an attempt to limit the application of the
doctrine of equivalents to the scope of the claims, each numerical
parameter should at least be construed in light of the number of
reported significant digits and by applying ordinary rounding
techniques.
[0007] Notwithstanding that the numerical ranges and parameters
setting forth the broad scope of the invention are approximations,
the numerical values set forth in the specific examples are
reported as precisely as possible. Any numerical value, however,
inherently contains certain errors necessarily resulting from the
standard variation found in their respective testing
measurements.
[0008] Also, it should be understood that any numerical range
recited herein is intended to include all sub-ranges subsumed
therein. For example, a range of "1 to 10" is intended to include
all sub-ranges between (and including) the recited minimum value of
1 and the recited maximum value of 10, that is, having a minimum
value equal to or greater than 1 and a maximum value of equal to or
less than 10.
[0009] In this application, the use of the singular includes the
plural and plural encompasses singular, unless specifically stated
otherwise. In addition, in this application, the use of "or" means
"and/or" unless specifically stated otherwise, even though "and/or"
may be explicitly used in certain instances. Further, in this
application, the use of "a" or "an" means "at least one" unless
specifically stated otherwise. For example, "a" polymer, "a"
coating composition, "a" crosslinker, and the like refer to one or
more of any of these items.
[0010] As indicated, the polymer of the present invention comprises
a polyol polymer obtained from reactants comprising at least a
non-aromatic epoxy functional compound and an aromatic
mono-carboxylic acid functional compound which is substantially
free of non-aromatic ethylenic unsaturation.
[0011] As used herein, a "polyol polymer" refers to a polymer
having two or more, such as three or more, hydroxyl functional
groups. The term "polymer" refers to oligomers and homopolymers
(e.g., prepared from a single monomer species), copolymers (e.g.,
prepared from at least two different monomer species), terpolymers
(e.g., prepared from at least three different monomer species) and
graft polymers. The term "resin" is used interchangeably with
"polymer."
[0012] A "non-aromatic epoxy functional compound" refers to a
linear, branched, or cyclic compound having epoxy functional groups
and which is free of aromatic groups. As used herein, the term
"aromatic" refers to a conjugated cyclic hydrocarbon structure with
a stability (due to delocalization) that is significantly greater
than that of a hypothetical localized structure. Further, the term
"linear" refers to a compound having a straight chain, the term
"branched" refers to a compound having a chain with a hydrogen
replaced by a substituent such as an alkyl group that branches or
extends out from a straight chain, and the term "cyclic" refers to
a closed ring structure. Thus, the epoxy functional compound is an
aliphatic compound, i.e. a non-aromatic linear, branched, or cyclic
structure that contains saturated carbon bonds.
[0013] Non-limiting examples of suitable non-aromatic epoxy
functional compounds include a cycloaliphatic diglycidyl ether, a
cycloaliphatic diglycidyl ester, a cycloaliphatic epoxide, or a
combination thereof. A "cycloaliphatic diglycidyl ether" refers to
a non-aromatic cyclic compound comprising one or more ether groups
and at least two epoxy functional groups, such as for example
hydrogenated bisphenol A epoxide. A "cycloaliphatic diglycidyl
ester" refers to a non-aromatic cyclic compound comprising one or
more esters groups and at least two epoxy functional groups, such
as for example 1,2-cyclohexanedicarboxylic acid,
1,2-bis(2-oxiranylmethyl) ester. A "cycloaliphatic epoxide" refers
to a non-aromatic cyclic compound comprising one or more epoxy
functional groups and which does not include glycidyl ester or
glycidyl ether groups, such as for example
3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexane carboxylate,
bis((3,4-epoxycyclohexyl)methyl)adipate, or a combination
thereof.
[0014] As indicated, the non-aromatic epoxy functional compound can
be selected from compounds prepared from a hydrogenated bisphenol
polyepoxide or a polyepoxide derived from a hydrogenated bisphenol
compound. For example, the non-aromatic epoxy functional compound
can comprise a cycloaliphatic diglycidyl ether formed from a
hydrogenated bisphenol polyepoxide or a polyepoxide derived from a
hydrogenated bisphenol compound.
[0015] The non-aromatic epoxy functional compound can also comprise
additional functional groups. For example, the non-aromatic epoxy
functional compound can also comprise ester groups, ether groups,
nitro groups, nitrile groups, keto functional groups (also referred
to as ketone functional groups), aldo functional groups (also
referred to as aldehyde functional groups), amine groups, hydroxyl
groups, thiol groups, carbamate groups, amide groups, urea groups,
isocyanate groups (including blocked isocyanate groups),
ethylenically unsaturated groups, and combinations thereof
Alternatively, the non-aromatic epoxy functional compound can also
be free of (i.e., does not contain) any one of the previously
described additional functional groups.
[0016] As used herein, "ethylenically unsaturated" refers to a
group having at least one carbon-carbon double bond. Non-limiting
examples of ethylenically unsaturated groups include, but are not
limited to, (meth)acrylate groups, vinyl groups, other alkenyl
groups, and combinations thereof. As used herein, the term
"(meth)acrylate" refers to both the methacrylate and the
acrylate.
[0017] The non-aromatic epoxy functional compound can comprise at
least 30 weight %, at least 40 weight %, at least 50 weight %, or
at least 60 weight %, based on the total solids weight of the
reactants used to form the polyol polymer. The non-aromatic epoxy
functional compound can comprise up to 90 weight %, up to 80 weight
%, up to 70 weight %, or up to 65 weight %, based on the total
solids weight of the reactants used to form the polyol polymer. The
non-aromatic epoxy functional compound can also comprise an amount
within a range, such as for example, of from 30 weight % to 90
weight %, or from 40 weight % to 80 weight %, or from 50 weight %
to 70 weight %, or from 60 weight % to 70 weight %, based on the
total solids weight of the reactants used to form the polyol
polymer.
[0018] As previously described, the polyol polymer is also prepared
with an aromatic mono-carboxylic acid functional compound that is
substantially free of non-aromatic ethylenic unsaturation. As used
herein, an "aromatic mono-carboxylic acid functional compound"
refers to a compound that includes a cyclically conjugated
hydrocarbon with a stability that is significantly greater than
that of a hypothetical localized structure and which also includes
a single carboxylic acid group or the ester or anhydride of the
acid.
[0019] As indicated, the aromatic mono-carboxylic acid functional
compound is substantially free of non-aromatic ethylenic
unsaturation. The aromatic mono-carboxylic acid functional compound
can also be essentially free or completely free of non-aromatic
ethylenic unsaturation. The term "non-aromatic ethylenic
unsaturation" refers to carbon-carbon double bonds that do not form
a part of a cyclically conjugated hydrocarbon aromatic group.
Further, the terms "substantially free of non-aromatic ethylenic
unsaturation" means that the mixture of reactants contains less
than 1000 parts per million (ppm) of compounds containing
non-aromatic ethylenic unsaturation, "essentially free of
non-aromatic ethylenic unsaturation" means that the mixture of
reactants contains less than 100 ppm of compounds containing
non-aromatic ethylenic unsaturation, and "completely free of
non-aromatic ethylenic unsaturation" means that the mixture of
reactants contains less than 20 parts per billion (ppb) of
compounds containing non-aromatic ethylenic unsaturation.
[0020] The aromatic mono-carboxylic acid functional compound can
also comprise additional functional groups. For example, the
aromatic mono-carboxylic acid functional compound can also comprise
any of the additional functional groups previously described
provided that the aromatic mono-carboxylic acid functional compound
is substantially free, essentially free, or completely free of
non-aromatic ethylenic unsaturation. Alternatively, the aromatic
mono-carboxylic acid functional compound is free of (i.e., does not
contain) any of the previously described additional functional
groups.
[0021] Non-limiting examples of aromatic monoacids that can be used
to prepare the polymer include benzoic acid, 4-tert-butylbenzoic
acid, hydroxybenzoic acids such as 4-hydroxybenzoic acid, salicylic
acid, naphthoic acids, amino benzoic acids such as 4-aminobenzoic
acid, nitrobenzoic acids such as 4-nitrobenzoic acid,
3,5-dinitrobenzoic acid, phenylpropanoic acid, mandelic acid,
3-benzoylpropanoic acid, anthranilic acid, nicotinic acid,
picolinic acid, anhydrides of such acids, and combinations
thereof.
[0022] The aromatic mono-carboxylic acid functional compound can
comprise at least 10 weight %, at least 15 weight %, at least 20
weight %, at least 25 weight %, or at least 30 weight %, based on
the total solids weight of the reactants used to form the polyol
polymer. The aromatic mono-carboxylic acid functional compound can
comprise up to 45 weight %, up to 40 weight %, or up to 35 weight
%, based on the total solids weight of the reactants used to form
the polyol polymer. The aromatic mono-carboxylic acid functional
compound can also comprise an amount within a range, such as for
example, of from 10 weight % to 45 weight %, or from 15 weight % to
40 weight %, or from 15 weight % to 35 weight %, or from 20 weight
% to 35 weight %, based on the total solids weight of the reactants
used to form the polyol polymer.
[0023] The reactants that form the polyol polymer may further
comprise an aromatic polycarboxylic acid provided that the aromatic
polycarboxylic acid is less than 15 weight %, less than 10 weight
%, less than 5 weight % or less than 1 weight %, based on the total
solids weight of the reactants used to form the polyol polymer. The
reactants that form the polyol polymer can also be substantially
free, essentially free, or completely free of an aromatic
polycarboxylic acid. That is, the reactants that form the polyol
polymer may be substantially free of aromatic polycarboxylic acids
in which the mixture of reactants contain less than 1000 ppm of
aromatic polycarboxylic acids, essentially free of aromatic
polycarboxylic acids in which the mixture of reactants contain less
than 100 ppm of aromatic polycarboxylic acids, and completely free
of aromatic polycarboxylic acids in which the mixture of reactants
contain less than 20 ppb of aromatic polycarboxylic acids.
[0024] As used herein, an "aromatic polycarboxylic acid" refers to
a compound that includes a cyclically conjugated hydrocarbon with a
stability that is significantly greater than that of a hypothetical
localized structure and which also includes a two or more
carboxylic acid groups or the anhydride of the acid. Non-limiting
examples of aromatic polycarboxylic acids include terephthalic
acid, isophthalic acid, orthophthalic acid, trimellitic acid,
anhydrides of such acids, and combinations thereof.
[0025] The aromatic polycarboxylic acid can also comprise
additional functional groups. For example, the aromatic
polycarboxylic acid can also comprise any of the additional
functional groups previously described. Alternatively, the aromatic
polycarboxylic acid is free of (i.e., does not contain) any of the
previously described additional functional groups.
[0026] The polyol polymer can also be prepared with additional
reactants. For example, the reactants that form the polyol polymer
may further comprise non-aromatic carboxylic acids such as
non-aromatic mono-carboxylic acids, non-aromatic polycarboxylic
acids, anhydrides of such acids, and combinations thereof.
[0027] As used herein, a "non-aromatic mono-carboxylic acid" refers
to a straight, branched, or cyclic structure that contains
saturated carbon bonds, a single carboxylic acid, or anhydride
thereof, and which is free of aromatic groups. Further, a
"non-aromatic polycarboxylic acid" refers to a straight, branched,
or cyclic structure that contains saturated carbon bonds, two or
more carboxylic acids, or anhydrides thereof, and which is free of
aromatic groups.
[0028] The non-aromatic mono-carboxylic acid and/or non-aromatic
polycarboxylic acid can also comprise additional functional groups.
For example, the non-aromatic mono-carboxylic acid and/or
non-aromatic polycarboxylic acid can also comprise any of the
additional functional groups previously described. For example, the
non-aromatic mono-carboxylic acid and/or non-aromatic
polycarboxylic acid can also comprise hydroxyl functional groups.
Alternatively, the non-aromatic mono-carboxylic acid and/or
non-aromatic polycarboxylic acid are free of (i.e., does not
contain) any of the previously described additional functional
groups.
[0029] Non-limiting examples of non-aromatic mono-carboxylic acids
include cycloaliphatic carboxylic acids such as cyclohexane
carboxylic acid, C.sub.1-C.sub.18 linear or branched carboxylic
acids such as acetic acid, propanoic acid, butanoic acid, hexanoic
acid, heptanoic acid, and octanoic acid, anhydrides of such acids,
and combinations thereof
[0030] Non-limiting examples of non-aromatic polycarboxylic acids
include 1,4-cyclohexanedicarboxylic acid,
1,3-cyclohexanedicarboxylic acid, decahydronaphthalene dicarboxylic
acid, 1,3-cyclopentanedicarboxylic acid,
1,1-cyclopropanedicarboxylic acid, hexahydrophthalic acid, succinic
acid, acipic acid, azelaic acid, citric acid, anhydrides of such
acids, and combinations thereof.
[0031] When used to form the polyol polymer, the non-aromatic
mono-carboxylic acid and/or non-aromatic polycarboxylic acid can
each independently comprise at least 1 weight %, at least 3 weight
%, or at least 5 weight %, based on the total solids weight of the
reactants used to form the polyol polymer. The non-aromatic
mono-carboxylic acid and/or non-aromatic polycarboxylic acid can
each independently comprise up to 25 weight %, up to 15 weight %,
or up to 10 weight %, based on the total solids weight of the
reactants used to form the polyol polymer. The non-aromatic
mono-carboxylic acid and/or non-aromatic polycarboxylic acid can
also each independently comprise an amount within a range, such as
for example, of from 1 weight % to 25 weight %, or from 3 weight %
to 15 weight %, or from 5 weight % to 15 weight %, or from 5 weight
% to 10 weight %, based on the total solids weight of the reactants
used to form the polyol polymer.
[0032] Other additional reactants that can be used to form the
polyol polymer include intramolecular cyclic esters. An
"intramolecular cyclic ester" refers to a cyclic ring in which an
ester linkage is part of the ring structure. The intramolecular
cyclic ester can comprise, for example, a cyclic mono-ester or
di-ester. Non-limiting examples of intramolecular cyclic esters
include a lactone, lactide, glycolide, or a combination thereof. A
"lactone" refers to a cyclic ester having a ring structure with two
or more carbon atoms and a single oxygen atom with a ketone group
in one of the carbons adjacent to the other oxygen. A "lactide"
refers to a cyclic di-ester obtained from two or more molecules of
lactic acid, and a "glycolide" refers to a cyclic ester obtained by
dehydration of two water molecules from two glycolic acid
molecules. Non-limiting examples of suitable lactones include
.epsilon.-caprolactone, .beta.-propiolactone,
.gamma.-butyrolactone, .delta.-valerolactone, and combinations
thereof. Non-limiting examples of suitable lactides include
L-lactide, D-lactide, DL-lactide, and combinations thereof.
[0033] When used to form the polyol polymer, the intramolecular
cyclic ester can comprise at least 1 weight %, at least 3 weight %,
or at least 5 weight %, based on the total solids weight of the
reactants used to form the polyol polymer. The intramolecular
cyclic ester can comprise up to 50 weight %, or up to 40 weight %,
or up to 30 weight %, or 20 weight %, or up to 15 weight %, or up
to 10 weight %, based on the total solids weight of the reactants
used to form the polyol polymer. The intramolecular cyclic ester
can comprise an amount within a range, such as for example, of from
1 weight % to 50 weight %, or from 3 weight % to 40 weight %, or
from 5 weight % to 30 weight %, or from 5 weight % to 20 weight %,
based on the total solids weight of the reactants used to form the
polyol polymer.
[0034] The present invention is also directed to a method of
preparing the previously described polyol polymer. The method can
comprise mixing and reacting all the desired reactants at the same
time to form the polyol polymer. Alternatively, the reactants can
be reacted in a stepwise manner by first mixing and reacting only a
portion of the reactants to form a preliminary reaction product and
then mixing and reacting the remaining reactants with the
preliminary reaction product to form the polyol polymer. For
example, the polyol polymer can be prepared by first reacting
reactants comprising the non-aromatic epoxy functional compound and
the aromatic mono-carboxylic acid functional compound which is
substantially free of non-aromatic ethylenic unsaturation to form a
preliminary reaction product, and then reacting the preliminary
reaction product with additional reactants such as an
intramolecular cyclic ester.
[0035] Various types of reaction aids can also be added to the
reaction mixture including, but not limited to, catalysts.
Non-limiting examples of catalysts include triphenylphosphine,
ethyltriphenylphosphonium iodide, butyl stannoic acid, and
combinations thereof
[0036] The reactants and other optional components can also be
combined and reacted in a liquid medium such as a non-aqueous
liquid medium. As used herein, the term "non-aqueous" refers to a
liquid medium comprising less than 50 weight % water, based on the
total weight of the liquid medium. In accordance with the present
invention, such non-aqueous liquid mediums can comprise less than
40 weight % water, or less than 30 weight % water, or less than 20
weight % water, or less than 10 weight % water, or less than 5%
water, based on the total weight of the liquid medium. The solvents
that make up more than 50 weight % of the liquid medium include
organic solvents. Non-limiting examples of suitable organic
solvents include polar organic solvents e.g. protic organic
solvents such as glycols, glycol ether alcohols, alcohols; and
ketones, glycol diethers, esters, and diesters. Other non-limiting
examples of organic solvents include aromatic and aliphatic
hydrocarbons.
[0037] The resulting polyol polymer of the present invention
comprises ester linkages and hydroxyl functional groups. The polyol
polymer can also comprise other linkages and functional groups. For
example, the polyol polymer can also comprise ether linkages and/or
any of the additional functional groups previously described such
as epoxy functional groups and/or carboxylic acid functional
groups.
[0038] The polyol polymer prepared from the reactants described
above can have a hydroxyl value of at least 50 mg KOH/g, at least
75 mg KOH/g, or at least 100 mg KOH/g. The polyol polymer prepared
from the reactants described above can also have a hydroxyl value
of up to 300 mg KOH/g, at least 250 mg KOH/g, or at least 200 mg
KOH/g. The polyol polymer product prepared from the reactants
described above can further have a hydroxyl value within a range of
from 50 to 300 mg KOH/g, or from 75 to 250 mg KOH/g, or from 100 to
200 mg KOH/g.
[0039] The hydroxyl value is determined by esterification of the
sample with excess acetic anhydride. The excess acetic anhydride is
converted to acetic acid by hydrolysis and titrated
potentiometrically with standard potassium hydroxide. The volume
difference of titrate potassium hydroxide between a blank (no
reaction) and the sample corresponds to the acid content of the
sample, from which the hydroxyl number is calculated as the number
of milligrams of potassium hydroxide needed to neutralize the acid
in one gram of the sample. The hydrolyzing solution used in the
determination is a mixture of dimethylformamide, pyridine, and
distilled water, and the acetylating reagent is a mixture of acetic
anhydride and dichloroethane with p-toluene sulphonic acid as the
catalyst.
[0040] The polyol polymer prepared from the reactants can comprise
a weight average molecular weight of less than 10,000 g/mol, less
than 8,000 g/mol, less than 6,000 g/mol, or less than 5,000 g/mol.
The weight average molecular weight is determined by Gel Permeation
Chromatography using a Waters 2695 separation module with a Waters
410 differential refractometer (RI detector) and polystyrene
standards in which tetrahydrofuran (THF) is used as the eluent at a
flow rate of 1 ml min.sup.-1 and two PL Gel Mixed C columns used
for separation.
[0041] The polyol polymer prepared from the reactants can have a
polydispersity index (PDI) of at least 1.05, at least 1.2, or at
least 1.3. The polyol polymer prepared from the reactants can have
a PDI of up to 3.50, up to 2.5, or up to 1.8. The polyol polymer
prepared from the reactants can also have a PDI within a range such
as, for example, of from 1.05 to 3.50, or from 1.2 to 2.5, or from
1.3 to 1.8. The PDI values represent a ratio of the weight average
molecular weight (Mw) to the number average molecular weight (Mn)
of the polymer (i.e., Mw/Mn). The weight average molecular weight
and polydispersity index and the number average molecular weight
are determined by gel permeation chromatography as previously
described with respect to the weight average molecular weight.
[0042] The polyol polymer prepared from the reactants can also
comprise a particular equivalent ratio of functional groups. For
instance, when the polyol polymer comprises epoxy and carboxylic
acid functional groups, the equivalent ratio of epoxy functional
groups to acid functional groups is from 0.95:5.0, or from 1.10 to
2.0, or from 1.15 to 1.5.
[0043] The present invention is also directed to a coating
composition that comprises the polyol polymer and a crosslinker(s)
reactive with one or more functional groups of the polyol polymer.
It is appreciated that the polyol polymer in the coating
composition acts as a film-forming resin. As used herein, a
"film-forming resin" refers to a self-supporting continuous film on
at least a horizontal surface of a substrate upon removal of any
diluents or carriers present in the composition or upon curing. The
terms "curable", "cure", and the like, as used in connection with a
coating composition, means that at least a portion of the
components that make up the coating composition are polymerizable
and/or crosslinkable. The coating composition of the present
invention can be cured at ambient conditions, with heat, or with
other means such as actinic radiation. The term "actinic radiation"
refers to electromagnetic radiation that can initiate chemical
reactions. Actinic radiation includes, but is not limited to,
visible light, ultraviolet (UV) light, X-ray, and gamma radiation.
Further, "ambient conditions" refers to the conditions of the
surrounding environment (e.g., the temperature, humidity, and
pressure of the room or outdoor environment in which the substrate
is located such as, for example, at a temperature of 23.degree. C.
and at a relative humidity in the air of 35% to 75%).
[0044] The coating composition can comprise one or more of the
polyol polymers previously described. For instance, the coating
composition can comprise at least one polyol polymer that is not
prepared with an intramolecular cyclic ester and at least one
polyol polymer that is prepared with an intramolecular cyclic
ester.
[0045] The polyol polymer can comprise at least 15 weight %, at
least 20 weight %, at least 25 weight %, or at least 30 weight %,
based on the total weight of the coating composition. The polyol
polymer can comprise up to 80 weight %, up to 70 weight %, up to 60
weight %, or up to 50 weight %, based on the total weight of the
coating composition. The polyol polymer can comprise an amount
within a range such as, for example, from 15 to 80 weight %, or
from 20 to 70 weight %, or from 25 to 60 weight %, or from 30 to 50
weight %, based on the total weight of the coating composition.
[0046] As previously described, the coating composition comprises a
crosslinker(s) reactive with one or more functional groups of the
polyol polymer. As used herein, the term "crosslinker" refers to a
molecule comprising two or more functional groups that are reactive
with other functional groups and which is capable of linking two or
more monomers or polymer molecules through chemical bonds such as
during a curing process. Thus, the coating composition comprises a
crosslinker having functional groups that are reactive with at
least some of the functional groups on the polyol polymer.
[0047] Non-limiting examples of crosslinkers include carbodiimides,
polyhydrazides, aziridines, epoxy resins, alkylated carbamate
resins, (meth)acrylates, isocyanates, blocked isocyanates,
polyacids, polyamines, polyamides, aminoplasts such as
melamine-formaldehyde resins, hydroxyalkyl ureas, hydroxyalkyl
amides, and any combination thereof. For instance, the crosslinker
can comprise a polyisocyanate, aminoplast, or a combination thereof
that is reactive with at least the hydroxyl functional groups on
the polyol polymer.
[0048] It is appreciated that the coating composition can include a
single type or multiple types of crosslinkers. For instance, the
coating composition can comprise at least two different types of
crosslinkers that are reactive with the same functional groups or
different functional groups on the polyol polymer. The coating
composition can also comprise at least two different types of
crosslinkers that are reactive with different types of polyol
polymers when used as previously described.
[0049] The coating composition can also comprise additional
components. For example, the coating composition can also comprise
additional film-forming resins. The additional resins can include
any of a variety of thermoplastic and/or thermosetting resins known
in the art. As used herein, the term "thermosetting" refers to
resins that "set" irreversibly upon curing or crosslinking, wherein
the polymer chains are joined together by covalent bonds. This
property is usually associated with a cross-linking reaction often
induced, for example, by heat or radiation. Curing or crosslinking
reactions also may be carried out under ambient conditions. Once
cured, a thermosetting resin will not melt upon the application of
heat and is insoluble in solvents. As noted, the additional resins
can also include a thermoplastic resin. As used herein, the term
"thermoplastic" refers to resins that include polymeric components
that are not joined by covalent bonds and, thereby, can undergo
liquid flow upon heating.
[0050] The additional resins can be selected from, for example,
(meth)acrylic polymers, polyurethanes, polyester polymers,
polyamide polymers, polyether polymers, polysiloxane polymers,
epoxy resins, vinyl resins, copolymers thereof, and mixtures
thereof. Thermosetting resins typically comprise reactive
functional groups. The reactive functional groups can include, but
are not limited to, carboxylic acid groups, amine groups, epoxide
groups, alkoxy groups, hydroxyl groups, thiol groups, carbamate
groups, amide groups, urea groups, isocyanate groups (including
blocked isocyanate groups), and combinations thereof.
[0051] Coating compositions containing thermosetting resins are
typically reacted with a crosslinker. As such, when additional
film-forming resins are used in the coating composition, the
coating composition can comprise additional crosslinkers that are
reactive with the additional film-forming resins and/or the
crosslinker reactive with the polyol polymer can also be reactive
with the additional film-forming resin. Non-limiting examples of
such crosslinkers include any of the crosslinkers previously
described. The thermosetting resins can also have functional groups
that are reactive with themselves; in this manner, such resins are
self-crosslinking.
[0052] The coating compositions can also comprise a colorant. As
used herein, "colorant" refers to any substance that imparts color
and/or other opacity and/or other visual effect to the composition.
The colorant can be added to the coating in any suitable form, such
as discrete particles, dispersions, solutions, and/or flakes. A
single colorant or a mixture of two or more colorants can be used
in the coatings of the present invention.
[0053] Example colorants include pigments (organic or inorganic),
dyes and tints, such as those used in the paint industry and/or
listed in the Dry Color Manufacturers Association (DCMA), as well
as special effect compositions. A colorant may include, for
example, a finely divided solid powder that is insoluble, but
wettable, under the conditions of use. A colorant can be organic or
inorganic and can be agglomerated or non-agglomerated. Colorants
can be incorporated into the coatings by use of a grind vehicle,
such as an acrylic grind vehicle, the use of which will be familiar
to one skilled in the art.
[0054] Example pigments and/or pigment compositions include, but
are not limited to, carbazole dioxazine crude pigment, azo,
monoazo, diazo, naphthol AS, benzimidazolone, isoindolinone,
isoindoline and polycyclic phthalocyanine, quinacridone, perylene,
perinone, diketopyrrolo pyrrole, thioindigo, anthraquinone,
indanthrone, anthrapyrimidine, flavanthrone, pyranthrone,
anthanthrone, dioxazine, triarylcarbonium, quinophthalone pigments,
diketo pyrrolo pyrrole red ("DPPBO red"), titanium dioxide, carbon
black, and mixtures thereof. The terms "pigment" and "colored
filler" can be used interchangeably.
[0055] Example dyes include, but are not limited to, those that are
solvent and/or aqueous based such as phthalo green or blue, iron
oxide, bismuth vanadate, anthraquinone, and perylene and
quinacridone.
[0056] Example tints include, but are not limited to, pigments
dispersed in water-based or water miscible carriers such as
AQUA-CHEM 896 commercially available from Degussa, Inc., and
CHARISMA COLORANTS and MAXITONER INDUSTRIAL COLORANTS commercially
available from Accurate Dispersions Division of Eastman Chemical,
Inc.
[0057] Other non-limiting examples of components that can be used
with the coating compositions of the present invention include
plasticizers, abrasion resistant particles, fillers including, but
not limited to, micas, talc, clays, and inorganic minerals,
anti-oxidants, hindered amine light stabilizers, UV light absorbers
and stabilizers, surfactants, flow and surface control agents,
thixotropic agents, organic cosolvents, reactive diluents,
catalysts, reaction inhibitors, additional corrosion-inhibitors,
and other customary auxiliaries.
[0058] The components that form the coating composition can also be
combined and/or mixed in a liquid medium. For example, the polyol
polymer, crosslinker reactive with the polyol polymer, and optional
other components previously described can be combined and mixed in
a non-aqueous liquid medium.
[0059] After forming the coating composition of the present
invention, the composition can be applied to a wide range of
substrates known in the coatings industry. For example, the coating
composition of the present invention can be applied to automotive
substrates and components (e.g. automotive vehicles including, but
not limited to, cars, buses, trucks, trailers, etc.), industrial
substrates, aircraft and aircraft components, marine substrates and
components such as ships, vessels, and on-shore and off-shore
installations, storage tanks, windmills, nuclear plants, packaging
substrates, wood flooring and furniture, apparel, electronics,
including housings and circuit boards, glass and transparencies,
sports equipment, including golf balls, stadiums, buildings,
bridges, and the like. These substrates can be, for example,
metallic or non-metallic.
[0060] Metallic substrates include, but are not limited to, tin,
steel (including electrogalvanized steel, cold rolled steel,
hot-dipped galvanized steel, steel alloys, or blasted/profiled
steel, among others), aluminum, aluminum alloys, zinc-aluminum
alloys, steel coated with a zinc-aluminum alloy, and aluminum
plated steel. As used herein, blasted or profiled steel refers to
steel that has been subjected to abrasive blasting and which
involves mechanical cleaning by continuously impacting the steel
substrate with abrasive particles at high velocities using
compressed air or by centrifugal impellers. The abrasives are
typically recycled/reused materials and the process can efficiently
removal mill scale and rust. The standard grades of cleanliness for
abrasive blast cleaning is conducted in accordance with BS EN ISO
8501-1.
[0061] Further, non-metallic substrates include polymeric and
plastic substrates including polyester, polyolefin, polyamide,
cellulosic, polystyrene, polyacrylic, poly(ethylene naphthalate),
polypropylene, polyethylene, nylon, EVOH, polylactic acid, other
"green" polymeric substrates, poly(ethylene terephthalate) (PET),
polycarbonate, polycarbonate acrylobutadiene styrene (PC/ABS),
polyamide, wood, veneer, wood composite, particle board, medium
density fiberboard, cement, stone, glass, paper, cardboard,
textiles, leather, both synthetic and natural, and the like. It is
appreciated that the coating compositions can be applied to various
areas of any of the previously described substrates to form a
continuous solid coating such as over the body and edges of a
substrate and which provides the superior properties described
herein.
[0062] The coating compositions of the present invention can be
applied by any means standard in the art, such as electrocoating,
spraying, electrostatic spraying, dipping, rolling, brushing, and
the like. The coatings formed from the coating compositions of the
present invention can be applied to a dry film thickness of 5 to
300 microns, 20 to 150 microns, or 35 to 70 microns.
[0063] The coating composition can be applied to a substrate to
form a monocoat. As used herein, a "monocoat" refers to a single
layer coating system that is free of additional coating layers.
Thus, the coating composition can be applied directly to a
substrate without any intermediate coating layer and cured to form
a single layer coating, i.e. a monocoat. The coating composition
can also be applied directly over a pretreated substrate as a
monocoat. For example, the substrate can be pretreated with an iron
phosphate treatment, zinc phosphate treatment, zirconium treatment,
titanium treatment, or silane treatment.
[0064] Alternatively, the coating composition can be applied to a
substrate as a first coating layer along with additional coating
layers, such as a second coating layer, to form a multi-layer
coating system. It is appreciated that the multi-layer coating can
comprise multiple coating layers such as three or more, or four or
more, or five or more, coating layers. For example, the previously
described coating composition of the present invention can be
applied to a substrate as a primer layer and second and third
coating layers, and, optionally, additional coatings layers, can be
applied over the primer layer as basecoats and/or topcoats. As used
herein, a "primer" refers to a coating composition from which an
undercoating may be deposited onto a substrate in order to prepare
the surface for application of a protective or decorative coating
system. A "basecoat" refers to a coating composition from which a
coating is deposited onto a primer and/or directly onto a
substrate, optionally, including components (such as pigments) that
impact the color and/or provide other visual impact, and which may
be overcoated with a protective and decorative topcoat.
[0065] The additional coating layers, such as a second and third
coating layer, can be formed from a coating composition that
includes a film-forming resin that is the same or different from
the first coating layer. The additional coating layers can be
prepared with any of the film-forming resins, crosslinkers,
colorants, and/or other components previously described. Further,
each coating composition can be applied as a dry-on-dry process
where each coating composition is dried or cured to form a coating
layer prior to application of another composition coating.
Alternatively, all or certain combinations of each coating
composition described herein can be applied as a wet-on-wet process
and dried or cured together.
[0066] It was found that coatings formed form the coating
compositions of the present invention comprising the polyol polymer
provided improved corrosion resistance and good viscosity at low
levels of VOC's. The coatings formed form the coating compositions
of the present invention comprising the polyol polymer also
provided fast property development (e.g., Konig hardness) while
maintaining good appearance and improved 20 degree gloss.
[0067] The following examples are presented to demonstrate the
general principles of the invention. The invention should not be
considered as limited to the specific examples presented. All parts
and percentages in the examples are by weight unless otherwise
indicated.
EXAMPLE 1
Preparation of a Polyester Polyol
[0068] A polyester polyol according to the present invention was
prepared from the components listed in Table 1.
TABLE-US-00001 TABLE 1 Ingredients Parts by weight Charge 1 EPONEX
.TM. 1510.sup.1 1000.00 Dimethylol Propionic Acid 125.36 Benzoic
Acid 342.39 Ethyltriphenylphosphonium iodide (ETPPI) 7.34 Triphenyl
phosphite 7.34 Charge 2 Butyl acetate 370.61 .sup.1A hydrogenated
bisphenol-A epoxy functional resin, commercially available from
Hexion Specialty Chemicals.
[0069] Charge 1 was added to a 3000 mL, 4-necked flask equipped
with a motor driven stainless steel stir blade, a water-cooled
condenser, a nitrogen blanket, and a heating mantle with a
thermometer connected through a temperature feedback control
device. The reaction mixture was heated to 120.degree. C. At
120.degree. C., the reaction mixture was exothermal up to
150.degree. C. After exotherm, the reaction mixture was held at
150.degree. C. until an acid value of less than 0.2 mg KOH/g was
obtained with a Metrohm 888 Titrando using a 0.1 N KOH solution in
methanol as the reagent (3.about.4 hours). The reaction mixture was
then cooled to 85.degree. C. and Charge 2 was added to the reaction
mixture. The final resin was stirred at 60.degree. C. for 30
minutes and poured out. The weight average molecular weight of the
polyester polyol was 994 g/mol and solids content was 80%.
[0070] The weight average molecular weight was determined by Gel
Permeation Chromatography using a Waters 2695 separation module
with a Waters 410 differential refractometer (RI detector) and
polystyrene standards. Tetrahydrofuran (THF) was used as the eluent
at a flow rate of 1 ml min.sup.-1, and two PL Gel Mixed C columns
were used for separation.
EXAMPLE 2
Preparation of a Polyester Polyol
[0071] A polyester polyol according to the present invention was
prepared from the components listed in Table 2.
TABLE-US-00002 TABLE 2 Ingredients Parts by weight Charge 1
Polyester of Example 1 500.00 PURALACT .RTM. B3 lactide .sup.2
109.03 Butyl stannoic acid 1.14 Triphenyl phosphite 1.14 Charge 2
Butyl acetate 25.00 .sup.2 An intramolecular cyclic di-ester
monomer based on L-lactide, commercially available from
CORBION.
[0072] Charge 1 was added to a 1000 mL, 4-necked flask equipped
with a motor driven stainless steel stir blade, a water-cooled
condenser, a nitrogen blanket, and a heating mantle with a
thermometer connected through a temperature feedback control
device. The reaction mixture was heated to 70.degree. C. and held
at 70.degree. C. for 30 minutes. Then, the reaction mixture was
heated to 130.degree. C. The reaction mixture was held at
150.degree. C. until IR spectroscopy showed the absence of the
characteristic lactide band (936 cm-1) using a Thermo Scientific
Nicolet iS5 FT-IR. The reaction mixture was cooled to 85.degree. C.
and Charge 2 was added to the reaction mixture. The final resin was
stirred at 60.degree. C. for 30 minutes and poured out. The weight
average molecular weight of the polyester polyol was 1328 g/mol and
the solids content was 80%. The weight average molecular weight was
determined according to Example 1.
EXAMPLE 3
Preparation of a Polyester Polyol
[0073] A polyester polyol according to the present invention was
prepared from the components listed in Table 3.
TABLE-US-00003 TABLE 3 Ingredients Parts by weight Charge 1 EPONEX
.TM. 1510.sup.1 600.00 Dimethylol Propionic Acid 75.22
4-Tertbutylbenzoic Acid 299.82 Ethyltriphenylphosphonium iodide
(ETPPI) 4.40 Triphenyl phosphite 4.40 Charge 2 Butyl acetate
240.00
[0074] Charge 1 was added to a 3000 mL, 4-necked flask equipped
with a motor driven stainless steel stir blade, a water-cooled
condenser, a nitrogen blanket, and a heating mantle with a
thermometer connected through a temperature feedback control
device. The reaction mixture was heated to 120.degree. C. At
120.degree. C., the reaction mixture was exothermal up to
180.degree. C. After exotherm, the reaction mixture was held at
150.degree. C. until an acid value of less than 0.2 mg KOH/g was
obtained with a Metrohm 888 Titrando using a 0.1 N KOH solution in
methanol as the reagent (3.about.4 hours). The reaction mixture was
then cooled to 85.degree. C. and Charge 2 was added to reaction
mixture. The final resin was stirred at 60.degree. C. for 30
minutes and poured out. The weight average molecular weight of the
polyester polyol was 1053 g/mol and the solids content was 80%. The
weight average molecular weight was determined according to Example
1.
EXAMPLE 4
Preparation of a Polyester Polyol
[0075] A polyester polyol according to the present invention was
prepared from the components listed in Table 4.
TABLE-US-00004 TABLE 4 Ingredients Parts by weight Charge 1 EPONEX
.TM. 1510.sup.1 400.00 Dimethylol Propionic Acid 50.15
4-Tertbutylbenzoic Acid 199.88 Ethyltriphenylphosphonium iodide
(ETPPI) 2.94 Triphenyl phosphite 2.94 Charge 2 Butyl acetate 240.00
Charge 3 PURALACT .RTM. B3 Lactide 161.64 Butyl stannoic acid 0.84
Triphenyl phosphite 0.84 Charge 4 Butyl acetate 35.92
[0076] Charge 1 was added to a 2000 mL, 4-necked flask equipped
with a motor driven stainless steel stir blade, a water-cooled
condenser, a nitrogen blanket, and a heating mantle with a
thermometer connected through a temperature feedback control
device. The reaction mixture was heated to 120.degree. C. At
120.degree. C., the reaction mixture was exothermal up to
183.degree. C. After exotherm, the reaction mixture was held at
150.degree. C. until an acid value of less than 0.2 mg KOH/g was
obtained with a Metrohm 888 Titrando using a 0.1 N KOH solution in
methanol as the reagent (3.about.4 hours). Charge 2 was added to
the reaction mixture and the reaction mixture was cooled to
100.degree. C. At 100.degree. C., Charge 3 was added to reaction
mixture. The reaction mixture was then heated to 130.degree. C. and
held at 130.degree. C. until IR spectroscopy showed the absence of
the characteristic lactide band (936 cm-1) using the Thermo
Scientific Nicolet iS5 FT-IR. Then the reaction mixture was cooled
to 85.degree. C. and Charge 4 was added to the reaction mixture.
The final resin was stirred at 60.degree. C. for 30 minutes and
poured out. The weight average molecular weight of the polyester
polyol was 1380 g/mol and the solids content was 80%. The weight
average molecular weight was determined according to Example 1.
EXAMPLE 5
Preparation of a Polyester Polyol
[0077] A polyester polyol according to the present invention was
prepared from the components listed in Table 5.
TABLE-US-00005 TABLE 5 Ingredients Parts by weight Charge 1 EPONEX
.TM. 1510.sup.1 600.00 Benzoic Acid 136.96 Adipic acid 81.95
Ethyltriphenylphosphonium iodide (ETPPI) 4.09 Triphenyl phosphite
4.09 Charge #2 Butyl acetate 206.77
[0078] Charge 1 was added to a 3000 mL, 4-necked flask equipped
with a motor driven stainless steel stir blade, a water-cooled
condenser, a nitrogen blanket, and a heating mantle with a
thermometer connected through a temperature feedback control
device. The reaction mixture was heated to 120.degree. C. At
120.degree. C., the reaction mixture was exothermal up to
157.degree. C. After exotherm, the reaction mixture was held at
150.degree. C. until an acid value of less than 0.2 mg KOH/g was
obtained with a Metrohm 888 Titrando using a 0.1 N KOH solution in
methanol as the reagent (3.about.4 hours). The reaction mixture was
then cooled to 85.degree. C. and Charge 2 was added to the reaction
mixture. The final resin was stirred at 60.degree. C. for 30
minutes and poured out. The weight average molecular weight of the
polyester polyol was 2357 g/mol and the solids content was 80%. The
weight average molecular weight was determined according to Example
1.
EXAMPLE 6
Preparation of a Polyester Polyol
[0079] A polyester polyol according to the present invention was
prepared from the components listed in Table 6.
TABLE-US-00006 TABLE 6 Ingredients Parts by weight Charge 1 EPONEX
.TM. 1510.sup.1 600.00 Benzoic acid 136.96 Cyclohexane dicarboxylic
acid 96.55 Ethyltriphenylphosphonium iodide (ETPPI) 4.09 Triphenyl
phosphite 4.09 Charge 2 Butyl acetate 210.46
[0080] Charge 1 was added to a 3000 mL, 4-necked flask equipped
with a motor driven stainless steel stir blade, a water-cooled
condenser, a nitrogen blanket, and a heating mantle with a
thermometer connected through a temperature feedback control
device. The reaction mixture was heated to 120.degree. C. At
120.degree. C., the reaction mixture was exothermal up to
177.degree. C. After exotherm, the reaction mixture was held at
150.degree. C. until an acid value of less than 0.2 mg KOH/g was
obtained with a Metrohm 888 Titrando using a 0.1 N KOH solution in
methanol as the reagent (3.about.4 hours). The reaction mixture was
then cooled to 85.degree. C. and Charge 2 was added to reaction
mixture. The final resin was stirred at 60.degree. C. for 30
minutes and poured out. The weight average molecular weight of the
polyester polyol was 2187 g/mol and the solids content was 80%. The
weight average molecular weight was determined according to Example
1.
COMPARATIVE EXAMPLE 7
Preparation of a Polyester Polyol
[0081] A polyester polyol was prepared from the components listed
in Table 7.
TABLE-US-00007 TABLE 7 Ingredients Parts by weight Charge 1
Trimethylpentanediol 379.16 4-methylhexahydrophthalic anhydride
436.22 Charge 2 EPONEX .TM. 1510.sup.1 600.00
Ethytriphenylphosphonium iodide (ETPPI) 0.30 Butyl acetate
342.86
[0082] Charge 1 was added to a 3000 mL, 4-necked flask equipped
with a motor driven stainless steel stir blade, a water-cooled
condenser, a nitrogen blanket, and a heating mantle with a
thermometer connected through a temperature feedback control
device. The reaction mixture was heated to 120.degree. C. At
120.degree. C., the reaction mixture was exothermal up to
164.degree. C. After exotherm, the reaction mixture was held at
150.degree. C. until the acid value was around 173.34 mg KOH/g as
determined with a Metrohm 888 Titrando using a 0.1 N KOH solution
in methanol as the reagent (1.about.2 hours). The reaction mixture
was then cooled to 100.degree. C. and Charge 2 was added into the
reaction mixture. Next, the reaction mixture was held at
150.degree. C. until an acid value of less than 10 mg KOH/g was
obtained with a Metrohm 888 Titrando using a 0.1 N KOH solution in
methanol as the reagent (.about.16 hours). The reaction mixture was
cooled to 60.degree. C. and poured out. The weight average
molecular weight of the polyester polyol was 2772 g/mol and the
solids content was 80%. The weight average molecular weight was
determined according to Example 1.
EXAMPLE 8
Preparation of a Polyester Polyol
[0083] A polyester polyol according to the present invention was
prepared from the components listed in Table 8.
TABLE-US-00008 TABLE 8 Ingredients Parts by weight Charge 1 EPONEX
.TM. 1510.sup.1 600.00 Benzoic acid 119.84 Adipic acid 112.72
Ethyltriphenylphosphonium iodide (ETPPI) 3.90 Triphenyl phosphite
4.40 Charge 2 Butyl acetate 218.18
[0084] Charge 1 was added to a 3000 mL, 4-necked flask equipped
with a motor driven stainless steel stir blade, a water-cooled
condenser, a nitrogen blanket, and a heating mantle with a
thermometer connected through a temperature feedback control
device. The reaction mixture was heated to 120.degree. C. At
120.degree. C., the reaction mixture was exothermal up to
187.degree. C. After exotherm, the reaction mixture was held at
150.degree. C. until an acid value of less than 0.2 mg KOH/g was
obtained with a Metrohm 888 Titrando using a 0.1 N KOH solution in
methanol as the reagent (3.about.4 hours). Then the reaction
mixture was cooled to 85.degree. C. and Charge 2 was added into the
reaction mixture. The final resin was stirred at 60.degree. C. for
30 minutes and poured out. The weight average molecular weight of
the polyester polyol was 4033 g/mol and the solids content was 80%.
The weight average molecular weight was determined according to
Example 1.
EXAMPLE 9
Preparation of a Polyester Polyol
[0085] A polyester polyol according to the present invention was
prepared from the components listed in Table 9.
TABLE-US-00009 TABLE 9 Ingredients Parts by weight Charge 1 EPONEX
.TM. 1510.sup.1 600.00 Benzoic acid 119.84 Cyclohexane dicarboxylic
acid 132.77 Ethyltriphenylphosphonium iodide (ETPPI) 3.90 Triphenyl
phosphite 4.40 Charge 2 Butyl acetate 218.18
[0086] Charge 1 was added to a 3000 mL, 4-necked flask equipped
with a motor driven stainless steel stir blade, a water-cooled
condenser, a nitrogen blanket, and a heating mantle with a
thermometer connected through a temperature feedback control
device. The reaction mixture was heated to 120.degree. C. At
120.degree. C., the reaction mixture was exothermal up to
192.degree. C. After exotherm, the reaction mixture was held at
150.degree. C. until an acid value of less than 0.2 mg KOH/g was
obtained with a Metrohm 888 Titrando using a 0.1 N KOH solution in
methanol as the reagent (3.about.4 hours). Then the reaction
mixture was cooled to 85.degree. C. and Charge 2 was added into
reaction mixture. The final resin was stirred at 60 .degree. C. for
30 minutes and poured out. The weight average molecular weight t of
the polyester polyol was 3245 g/mol and the solids content was 80%.
The weight average molecular weight was determined according to
Example 1.
COMPARATIVE EXAMPLE 10
Preparation of a Polyester Polyol
[0087] A polyester polyol according to the present invention was
prepared from the components listed in Table 10.
TABLE-US-00010 TABLE 10 Ingredients Parts by weight Charge 1 EPONEX
.TM. 1510.sup.1 600.00 Benzoic acid 119.84 Terephthalic acid 128.14
Ethyltriphenylphosphonium iodide (ETPPI) 3.90 Triphenyl phosphite
4.40 Charge 2 Butyl acetate 218.18
[0088] Charge 1 was added to a 3000 mL, 4-necked flask equipped
with a motor driven stainless steel stir blade, a water-cooled
condenser, a nitrogen blanket, and a heating mantle with a
thermometer connected through a temperature feedback control
device. The reaction mixture was heated to 120.degree. C. At
120.degree. C., the reaction mixture was exothermal up to
168.degree. C. After exotherm, the reaction mixture was held at
150.degree. C. until an acid value of less than 0.2 mg KOH/g was
obtained with a Metrohm 888 Titrando using a 0.1 N KOH solution in
methanol as the reagent (3.about.4 hours). Then the reaction
mixture was cooled to 85.degree. C. and Charge 2 was added into the
reaction mixture. The final resin was stirred at 60.degree. C. for
30 minutes and poured out. The weight average molecular weight of
the polyester polyol was 5010 g/mol and the solids content was 80%.
The weight average molecular weight was determined according to
Example 1.
[0089] After three days of storage at ambient temperature, the
resin began to develop crystallinity (haze). The polyester polyol
resin therefore showed poor stability.
EXAMPLE 11
Polyester Polyol Properties
[0090] The polyester polyols described in Examples 1-10 were tested
for various properties which are listed in Table 11.
TABLE-US-00011 TABLE 11 Viscosity .sup.3 Mn .sup.4 Mw .sup.4
Example (centipoise) (g/mol) (g/mol) PDI .sup.5 Example 1 370 731
994 1.36 Example 2 490 923 1328 1.44 Example 3 590 811 1053 1.30
Example 4 615 1018 1871 1.36 Example 5 710 1018 2357 2.31 Example 6
770 945 2187 2.31 Comparative Example 7 2370 1271 2772 2.18 Example
8 1370 1405 4033 2.87 Example 9 2500 1360 3245 2.39 Comparative
Example 10 4760 1416 5010 3.54 .sup.3 Viscosity was determined at
50.degree. C. and 75 RPM using BYK Cap 2000+ high torque viscometer
with Number 2 spindle and the viscosity of the resins of Examples
8-10 were determined at 50.degree. C. and 10 RPM using BYK Cap
2000+ high torque viscometer with Number 2 spindle. .sup.4 Number
average molecular weight (Mn) and weight average molecular weight
(Mw) were determined by gel permeation chromatography according to
the description in Example 1. .sup.5 Polydispersity index (PDI) is
the weight average molecular weight of each resin divided by the
number average molecular weight of the resin.
[0091] As shown in Table 11, the polyester polyol of Comparative
Example 10, which had 15 weight % of an aromatic diacid (based on
the total solids weight of the reactants used to form the polyester
polyol), exhibited the highest viscosity and considerably higher
PDI than the polyester polyols of the present invention that were
formed with aliphatic and cycloaliphatic diacids.
EXAMPLES 12-18
Preparation of Coating Compositions
[0092] Various coating compositions were prepared in three stages
as described below.
[0093] Part A: A milled pigment mixture was first prepared from the
components listed in Table 12.
TABLE-US-00012 TABLE 12 Ex. Ex. Ex. Ex. Ex. Ex. Comp. Components 12
13 14 15 16 17 Ex. 18 Polyester Example 1 37.23 -- -- -- -- -- --
Polyester Example 2 -- 40.42 -- -- -- -- -- Polyester Example 3 --
-- 39.65 -- -- -- -- Polyester Example 4 -- -- -- 40.28 -- -- --
Polyester Example 5 -- -- -- -- 37.40 -- -- Polyester Example 6 --
-- -- -- -- 36.54 -- Comparative Polyester -- -- -- -- -- -- 38.48
Example 7 n-butyl acetate 9.98 9.76 10.39 10.06 9.67 9.89 9.54
Sunfast Green 7 .sup.6 0.78 0.77 0.78 0.77 0.75 0.76 0.73 Mapico
Yellow 1050A.sup.7 5.20 5.17 5.18 5.13 4.99 5.08 4.87 R-960-38 TiO2
.sup.8 0.69 0.69 0.69 0.68 0.67 0.68 0.65 Monolite Green 860 .sup.9
0.49 0.49 0.49 0.48 0.47 0.48 0.46 Hostaperm Yellow H3G .sup.10
1.58 1.57 1.57 1.56 1.51 1.54 1.48 Heucophos ZP-10 .sup.11 2.92
2.90 2.90 2.88 2.79 2.84 2.73 Disperbyk .RTM.-163 .sup.12 0.88 0.87
0.88 0.87 0.84 0.86 0.82 .sup.6 Green phthalocyanine organic
pigment, commercially available from Sun Chemical. .sup.7Yellow
ferric oxide hydrate inorganic pigment, commercially available from
Huntsman. .sup.8 Rutile titanium dioxide inorganic pigment,
commercially available from The Chemours Company. .sup.9 Green
phthalocyanine organic pigment, commercially available from
Heubach. .sup.10 Yellow benzimidazolone organic pigment,
commercially available from Clariant. .sup.11 Zinc phosphate
inorganic pigment, commercially available from Heubach. .sup.12
Wetting and dispersing additive, commercially available form
BYK-Chemie GmbH.
[0094] In the first stage, the listed pigments in Table 12 were
dispersed in a mixture comprising the corresponding polyester
polyol, dispersants, and solvents to form a pre-mill mixture. The
pre-mill mixture was then milled with a Lau 200 Disperser for 120
minutes and demonstrated a Hegman value of greater than 7, as
determined by ASTM D1210-05.
[0095] Part B: The milled pigment mixtures were then agitated and
letdown with the additional components listed in Table 13.
TABLE-US-00013 TABLE 13 Ex. Ex. Ex. Ex. Ex. Ex. Comp. Components 12
13 14 15 16 17 Ex. 18 n-butyl acetate 5.44 6.18 5.42 6.52 9.31 7.59
10.92 Flow additive.sup.13 0.58 0.58 0.58 0.57 0.56 0.57 0.54
BYK-3455 .sup.14 0.17 0.17 0.17 0.17 0.17 0.17 0.16 Tinuvin .RTM.
292 .sup.15 1.17 1.16 1.16 1.15 1.12 1.14 1.09 Tinuvin .RTM. 1130
.sup.16 0.58 0.58 0.58 0.58 0.56 0.57 0.55 Dibutyltin dilaurate
0.03 0.03 0.03 0.03 0.03 0.03 0.03 .sup.13Acrylic based flow
additive, commercially available from BASF. .sup.14 Wetting and
leveling additive, commercially available form BYK-Chemie GmbH.
.sup.15 Hindered amine light stabilizer, commercially available
from BASF. .sup.16 UVA light stabilizer, commercially available
from BASF.
[0096] Part C: Next, a polyisocyanate was added as listed in Table
14.
TABLE-US-00014 TABLE 14 Ex. Ex. Ex. Ex. Ex. Ex. Comparative
Components 12 13 14 15 16 17 Ex. 18 GXH-1080 .sup.17 32.27 28.65
29.54 28.28 29.18 31.28 26.95 .sup.17 Solvated polyisocyanate,
commercially available from PPG.
EXAMPLE 19
Preparation and Evaluation of Coatings
[0097] Each of the coatings composition of Examples 12-18 were
sprayed between 65-80 microns of a dry-film thickness over an iron
phosphate pretreated cold rolled steel with a deionized water rinse
treatment and a non-chrome phosphate free rinse treatment. The
coatings were flashed for 10 minutes at ambient temperature and
humidity conditions, then baked at 60.degree. C. for 20 minutes.
The coating properties of each formed coating are listed in Table
15.
TABLE-US-00015 TABLE 15 Ex. 12 Ex. 13 Ex. 14 Ex. 15 Ex. 16 Ex. 17
Comp. Ex. 18 Viscosity Stage 80 80 85 80 78 83 83 1 + 2 (cP)
.sup.18 % Volume Solids .sup.19 61.29 60.65 61.36 60.2 58.12 59.54
56.93 V.O.C. .sup.20 2.84 2.89 2.83 2.9 3.07 2.97 3.16 20.degree.
Gloss .sup.21 86.3 84.5 85.5 86.3 85.6 86.4 84.9 Appearance/Popping
.sup.22 Good/Low Very Good/ Very Good/ Best/None Good/None
Good/None Good/None Very Low Very Low Konig @ 2 hour. 68 71 75 75
44 27 N/A (tacky) (sec.) .sup.23 Konig @ 24 hour. 149 146 145 147
135 115 87 (sec.) .sup.23 20 Deg. Gloss after 64.7 73.4 71.6 75.9
66.3 70.6 44.8 4000 hrs. .sup.24 Scraped Scribe 6.92 8.25 8.36 7.98
6.70 9.17 10.19 Creep (mm) after 360 hrs. .sup.25 .sup.18 Viscosity
at 23.degree. C. was determined using a BYK Cap 2000+ high torque
viscometer with a Number 2 spindle at 750 RPM. .sup.19 Volume of
non-volatile matter measured in accordance with ASTM
D2697-03(2014). .sup.20 Amount of volatile organic compounds
measured in accordance with ASTM D3960-05(2018). .sup.21 Specular
gloss measured in accordance with ASTM D523-14(2018). .sup.22
Visual rating of relative coating smoothness and density of solvent
pops on a 4 .times. 12 sq. inch coating sample. .sup.23 Konig
method of pendulum hardness measuring dampening from 6 to 3 degrees
according to ASTM D4366-95. .sup.24 Gloss of a coating after
exposure to accelerated weathering conditions measured in
accordance with SAE J2527. .sup.25 Corrosion resistance of a
coating measured in accordance with ASTM B117-16 and ASTM
D1654-08(2016)e1.
[0098] As shown in Table 15, the liquid coatings containing the
polyester polyols of the present invention demonstrated good
viscosity at low levels of VOC's as compared to Comparative Example
18. The liquid coatings containing the polyester polyols of the
present invention also demonstrated faster early property
development (2 and 24 hr. Konig hardness) while maintaining good
appearance and improved 20 degree gloss retention after 4000 hrs.
of accelerated weathering as compared to Comparative Example 18.
The liquid coatings containing the polyester polyols of the present
invention further exhibited improved corrosions resistance as
compared to Comparative Example 18.
[0099] The present invention is also directed to the following
clauses.
[0100] Clause 1: A polyol polymer obtained from reactants
comprising: a) a non-aromatic epoxy functional compound that
comprises at least 30 weight % of the total solids weight of the
reactants; and b) an aromatic mono-carboxylic acid functional
compound, or anhydride thereof, that is substantially free of
non-aromatic ethylenic unsaturation, wherein the polyol polymer
comprises ester linkages and hydroxyl functional groups, and
wherein, if the reactants further comprise an aromatic
polycarboxylic acid, the aromatic polycarboxylic acid comprises
less than 15 weight % of the total solids weight of the
reactants.
[0101] Clause 2: The polymer of clause 1, wherein the non-aromatic
epoxy functional compound comprises a cycloaliphatic diglycidyl
ether, a cycloaliphatic diglycidyl ester, a cycloaliphatic epoxide,
or any combination thereof.
[0102] Clause 3: The polymer of clause 1, wherein the non-aromatic
epoxy functional compound comprises a hydrogenated bisphenol
polyepoxide or a polyepoxide derived from a hydrogenated bisphenol
compound.
[0103] Clause 4: The polymer of any one of clauses 1-3, wherein the
non-aromatic epoxy functional compound comprises at least 40 weight
% of the total solids weight of the reactants.
[0104] Clause 5: The polymer of any one of clauses 1-4, wherein the
reactants further comprise a non-aromatic mono-carboxylic acid.
[0105] Clause 6: The polymer of clause 5, wherein the non-aromatic
mono-carboxylic acid further comprises a hydroxyl group.
[0106] Clause 7: The polymer of any one of clauses 1-6, wherein the
reactants further comprise a non-aromatic polycarboxylic acid.
[0107] Clause 8: The polymer of any one of clauses 1-7, wherein the
reactants further comprise an intramolecular cyclic ester.
[0108] Clause 9: The polymer of any one of clauses 1-8, wherein the
polyol polymer has a polydispersity index of 3.50 or less.
[0109] Clause 10: The polymer of any one of clauses 1-9, wherein
the polyol polymer has a hydroxyl value of at least 50 mg
KOH/g.
[0110] Clause 11: The polymer of any one of clauses 1-10, wherein
the polyol polymer comprises carboxylic acid functional groups and
epoxy functional groups, and has an epoxy-to-acid ratio of greater
than 0.95.
[0111] Clause 12: A coating composition comprising: i) a polyol
polymer according to any one of clauses 1-11; and ii) a crosslinker
reactive with the polyol polymer.
[0112] Clause 13: The coating composition of clause 12, wherein the
crosslinker comprises a polyisocyanate, aminoplast, or a
combination thereof
[0113] Clause 14: The coating composition of clauses 12 or 13,
further comprising a non-aqueous solvent.
[0114] Clause 15: The coating composition of any one of clauses
12-14, further comprising a colorant.
[0115] Clause 16: A substrate at least partially coated with a
coating formed from the composition of any one of clauses
12-15.
[0116] Clause 17: The substrate of clause 16, wherein the coating
is formed directly over a surface of the substrate.
[0117] Clause 18: A method of forming a polyol polymer comprising:
a) reacting reactants comprising: i) a non-aromatic epoxy
functional compound that comprises at least 30 weight % of the
total solids weight of the reactants; and ii) an aromatic
mono-carboxylic acid functional compound, or anhydride thereof,
that is substantially free of non-aromatic ethylenic unsaturation,
wherein the polyol polymer comprises ester linkages and hydroxyl
functional groups, and wherein, if the reactants further comprise
an aromatic polycarboxylic acid, the aromatic polycarboxylic acid
comprises less than 15 weight % of the total solids weight of the
reactants.
[0118] Clause 19: The method of clause 18, wherein the polyol
polymer is a polyol polymer as described in any one of clauses
1-11.
[0119] Clause 20: The method of clauses 18 or 19, wherein the
reactants of step a) further comprise a non-aromatic
mono-carboxylic acid, a non-aromatic polycarboxylic acid, or a
combination thereof.
[0120] Clause 21: The method of any one of clauses 18-20, further
comprising b) reacting a reaction product from step a) with an
intramolecular cyclic ester.
[0121] Whereas particular embodiments of this invention have been
described above for purposes of illustration, it will be evident to
those skilled in the art that numerous variations of the details of
the present invention may be made without departing from the
invention as defined in the appended claims.
* * * * *