US010752803B2

( 12 ) Rectenwald
United States Patent ( 10 ) Patent No.: US 10,752,803 B2
et al . (45 ) Date of Patent : Aug. 25 , 2020
( 54 ) 1K HIGH HARDNESS , HIGH IMPACT (2013.01 ) ; C08G 18/284 ( 2013.01 ) ; C08G
RESISTANCE COATING 18/289 (2013.01 ) ; C08G 18/3893 ( 2013.01 ) ;
C08G 18/758 ( 2013.01 ) ; C08G 18/7887
( 71 ) Applicant: THE SHERWIN -WILLIAMS (2013.01 ) ; C08G 18/791 ( 2013.01 ) ; C08G
COMPANY , Cleveland, OH (US ) 18/792 (2013.01 ) ; C09D 5/00 ( 2013.01 ) ;
C09D 7761 (2018.01 ) ; C09D 7/63 ( 2018.01 ) ;
( 72 ) Inventors : Michael F Rectenwald , Cleveland, OH C09D 175/04 (2013.01 ) ; C08K 3/22 ( 2013.01 ) ;
(US ) ; Brian Makowski , Reminderville, C08K 2003/2241 ( 2013.01 )
OH (US ) ( 58 ) Field of Classification Search
CPC .... COSG 18/12 ; CO8G 18/18 ; CO8G 18/1883 ;
( 73 ) Assignee : The Sherwin - Williams Company , CO8G 18/163 ; COSG 18/242 ; C08G
Cleveland, OH ( US ) 18/289 ; COSG 18/284 ; COSG 18/758 ;
( * ) Notice: Subject to any disclaimer, the term of this COSG 18/791 ; COSG 18/3893 ; C08G
patent is extended or adjusted under 35 18/792 ; C08G 18/7887 ; C08K 3/22 ;
U.S.C. 154 ( b ) by 150 days . COSK 2003/2241 ; CO9D 5/00 ; CO9D
7/61 ; CO9D 7/63 ; CO9D 175/02 ; CO9D
175/04
( 21 ) Appl. No .: 16 /135,252 See application file for complete search history.
( 22 ) Filed : Sep. 19 , 2018 ( 56 ) References Cited
( 65 ) Prior Publication Data U.S. PATENT DOCUMENTS
US 2019/0085202 A1 Mar. 21 , 2019 6,790,903 B1 * 9/2004 Majolo CO9J 201/10
524/506
Related U.S. Application Data 2010/02 16951 A1 * 8/2010 Webster CO8F 283/006
( 60 ) Provisional application No. 62/ 560,234 , filed on Sep. 525/452
19 , 2017 . 2012/0071584 Al * 3/2012 Lutz COSG 18/10
523/428
( 51 ) Int. Ci. * cited by examiner
C08G 18/12 ( 2006.01 )
C08G 18/16 ( 2006.01 ) Primary Examiner Patrick D Niland
C08G 18/18 ( 2006.01 )
C08G 18/24 ( 2006.01 ) ( 57 ) ABSTRACT
CO8G 18/28 ( 2006.01 ) A coating composition can be made by providing an amino
C08G 18/38 ( 2006.01 ) alkoxysilane and, in the substantial absence of water, react
C08G 18/75 ( 2006.01 ) ing at least a portion of the aminoalkoxysilane with at least
C08G 18/78
C08G 18/79
( 2006.01 ) one epoxide -containing compound including an aliphatic
( 2006.01 ) group to yield at least one alkoxysilylamine, and then
C08K 3/22 ( 2006.01 ) reacting the alkoxysilylamine with at least one isocyanate
CO9D 5/00 ( 2006.01 ) reagent containing at least two isocyanate groups to yield a
CO9D 7761 ( 2018.01 ) monomer having plural alkoxysilane groups and, in many
C09D 7763 ( 2018.01 ) embodiments, at least two branched aliphatic groups having
C09D 175/02 ( 2006.01 ) at least six carbon atoms . A coating composition thus formed
C09D 175/04 ( 2006.01 ) exhibits high durability and good flexibility. Also disclosed
( 52) U.S. CI. is a method of applying a coating composition to a substrate
CPC C09D 175/02 (2013.01 ) ; C08G 18/12 and allowing the coating composition to cure , and the cured
(2013.01 ) ; C08G 18/163 ( 2013.01 ) ; C08G coating resulting from such application .
18/18 (2013.01 ) ; C08G 18/1883 ( 2013.01 ) ;
C08G 18/242 (2013.01 ) ; C08G 18/283 47 Claims, No Drawings
 US 10,752,803 B2
1 2
1K HIGH HARDNESS , HIGH IMPACT one another, it has been found that, when 0.5 to 1.5 parts of
RESISTANCE COATING the aminoalkoxysilane are blended with 0.25 to 1.5 parts of
they compound for the kysyme, and
This application claims the benefit of U.S. provisional when the alkoxysilylamine product is blended with 0.05 to
application No. 62 / 560,234 filed on Sep. 19 , 2017 , the 5 0.75 parts of the isocyanate reagent, the resulting coating
entirety of which is hereby incorporated by reference . composition has both satisfactory hardness and desirable
exibilitation ofthecating compostnad
TECHNICAL FIELD exposure of the monomer to ambient water, the siloxane
groups on the monomer become capable of cross -linking
The disclosure relates generally to a coating composition 10 and the coating cures. The coating composition may be
having high hardness and high impact resistance . The dis formulated to have a viscosity that allows easy handling,
closed coating composition is suitable for a variety of uses storage, and application of the composition, and to yield a
including application to interior or exterior surfaces such as cured coating that can have both high hardness and high
wood, drywall, cement, metal , and plaster, or over a primer impact resistance .
coating , and application to metals, composites, and other 15 In an embodiment, at least a portion of an aminoalkox
materials as a protective coating. ysilane is reacted in the substantial absence of water with an
epoxy compound having a branched aliphatic group to form
BACKGROUND akoxysmithalkylanthen being
reacted with an isocyanate reagent containing at least two
Coating compositions are often used in applications to 20 isocyanate groups to yield a monomer having plural alkox
cover interior or exterior surfaces of buildings . Typically, a ysilane groups . For example, 0.5 to 1.5 parts of the amino
user applies a coating composition that cures with exposure alkoxysilane can be blended and reacted with 0.25 to 15
to the ambient environment to form a coating. Coatings parts of the epoxy compound, and the product of this
desirably have a high hardness to inhibit damage. Some reaction can be blended and reacted with 0.05 to 0.75 parts
materials used to impart hardness can cause deterioration of 25 of the isocyanate reagent.
flexibility, which may lead to premature cracking and failure In another embodiment, a portion of an aminoalkoxysi
of the coating. Known coatings compositions may be sol lane is reacted in the substantial absence of water with a first
vent-based or may be aqueous . It is desirable to avoid epoxy compound having a branched aliphatic group and a
organic solvents, which impart a high level of volatile second epoxy compound having a linear aliphatic group to
organic compounds (“ VOCs ” ), such as ethylene glycol , 30 form a mixture of alkoxysilylamines, this mixture then being
formaldehyde, or benzene. reacted with an isocyanate reagent containing at least two
It would be desirable to produce a coating composition isocyanate groups to yield a monomer having plural alkox
that is a single -component (or “ 1K ” ) composition not requir ysilane groups, these alkoxysilane groups again being
ing pre -mixing by the consumer, and that cures to form a capable of curing upon deprotection to form a cured coating .
cured coating that has both high hardness and high impact 35 The components may be reacted with one another in any
resistance . It would be particularly desirable to produce a suitable amounts, but it has been found that when 0.5 to 1.5
coating composition having a low VOC concentration (less parts of the aminoalkoxysilane are blended and reacted with
than 100 grams/ liter ). It would also be desirable for the 0.25 to 1.5 parts of the first epoxy compound and 0.25 to 1.5
coating composition to be suitable for application to interior parts of the second epoxy compound, and when the resulting
or exterior surfaces such as wood , drywall, cement, metal , 40 product is blended with 0.05 to 0.75 parts of the isocyanate
and plaster, or over a primer coating, and suitable for reagent, the cured coating can exhibit both high hardness
application to metals , composites, and other materials as a and high impact resistance .
protective coating. The coating composition should cure at
ambient temperature and without ancillary equipment such DETAILED DESCRIPTION
as ultraviolet lights. 45
The coating compositions described herein can be formu
SUMMARY lated to have certain properties that are desirable in a coating
composition. For example , it is desirable that the coating
In various nonexclusive embodiments, the present appli composition should be a 1K coating composition and that
cation provides a coating composition, a method of making 50 the coating composition has a low VOC content. The coating
a coating composition, a method of applying a coating compositions described herein can be formulated as 1K
composition , and a cured coating. compositions and can be formulated to have a low VOC
A coating composition may be made by providing an content. In exemplary coating compositions, the VOC con
aminoalkoxysilane and , in the substantial absence of water, tent is less than 150 grams/ liter, less than 125 grams/ liter,
reacting at least a portion of the aminoalkoxysilane with at 55 less than 100 grams/ liter, less than 75 grams/ liter, less than
least one epoxide - containing compound including an ali 50 grams/ liter, less than 25 grams/ liter, or essentially zero
phatic group to yield at least one alkoxysilylamine; and VOC content (less than 5 grams/liter ). The composition can
reacting the alkoxysilylamine with at least one isocyanate be a 100 % solids composition , which is contemplated that
reagent containing at least two isocyanate groups to yield a the composition is free or essentially free of solvents . It is
monomer, the monomer being a urea prepolymer with 60 contemplated that solvents may be used if desired in a
moisture reactive siloxane functional groups. These plural coating Compostas provided herein .
alkoxysilane groups enable crosslinking of the composition Additional desirable properties include hardness and
when exposed to ambient water. The composition preferably impact resistance , which are properties that can be mutually
includes a catalytic deprotectant, such as an alkylamine or an difficult to achieve in a coating composition. Exemplary
organotin , in an amount effective to deprotect alkoxy groups 65 coating compositions prepared in accordance with the pres
in the monomer to facilitate such crosslinking. Although the ent disclosure can yield a cured coating having a pencil
reactants may be combined in any suitable ratio relative to hardness of at least H , at least 2H , at least 3H , at least 4H ,
 US 10,752,803 B2
3 4
at least 5H , or at least 6H , as determined by ASTM D5363 wherein R , comprises a branched aliphatic group having at
( 2016 ) . Such coating compositions also can yield a cured least six carbon atoms. An example of a suitable glycidyl
coating having an impact hardness of at least 140 , at least aliphatic ester has the following formula (4 ) :
150 , at least 160 , at least 170 , and at least 180 , as determined
by ASTM D2794 (2016 ) . The coating compositions addi- 5
tionally can be formulated to have a viscosity of 2 to 5 )
4
(
Stokes , for example, 2.5 to 4.5 Stokes , 3 to 4 Stokes , or 3.2
to 3.8 Stokes, at 25 ° C. , the viscosity being determined using
a conventional bubble viscometer.
The reaction paths summarized above begin with an 10
aminoalkoxysilane, by which is contemplated any suitable
compound having alkoxysilyl and amino groups. The
aminoalkoxysilane may have a structure represented by the
following formula ( 1 ) :
The glycidyl aliphatic ester of formula ( 4 ) is available as
15
CARDURATM E10 - P from Hexion , Inc. Without intending
to be bound by any particular theory, it is generally believed
OA10 B1 that just impact the impact resistance of a cured coating
A90 Si - R3 - N formed from the coating composition can be increased by
B2 20 including in the coating composition the residue of the
OA11 glycidyl aliphatic ester of formula (4 ) .
In some aspects of the first approach , another portion of
where Ag , A10 , and Au1 are the same or different and the aminoalkoxysilane is reacted with an epoxy compound
comprise hydrogen or C , -C4 alkyl, with the proviso that at 25 of the following formula ( 5 ) :
least one of A9 , A10 , and A11 comprises C -C4 alkyl, where
B , and B2 are the same or different and comprise hydrogen (5 )
or C1 - C4 alkyl, with the proviso that at least one of B , and A6
B2 is hydrogen, and where Rz is C , -C4 alkyl. In some A5
embodiments , A1 , A2 , and Az each comprises C2 - C4 alkyl. 30 Ag- R2
For example, the aminoalkoxysilane may comprise an
aminopropyl trialkoxysilane, such as aminopropyl A7
trimethoxysilane sold under the trademark DYNASYLAN®
AMMO by Evonik Industries:
(CH3 ) 3 Si– (CH2)3 - NH2 wherein A3 -A, are the same or different and comprise
In some embodiments, a single type of aminoalkoxysilane is 35 hydrogen or a carbon - containing group with one to three
used , and in other embodiments two or more aminoalkox group , and R2, comprises
carbon atoms Ag comprises an ether - containing linking
ysilane forming a mixture of aminoalkoxysilanes may be least two carbon atoms . Ina linear some
aliphatic group having at
embodiments, the com
employed . pound of formula ( 5 ) is a glycidyl aliphatic ether. The
In a first approach at least a portion of the aminoalkox- 40 glycidyl aliphatic ether may, for example , have the follow
ysilane is reacted with an epoxy compound ( epoxide-con ing formula ( 6 ) :
taining compound) of the following formula ( 2 ) :

(2) 45 (6 )
- R2
A2
AL
-A4 - R1
A3
50 wherein R, comprises a linear aliphatic group having at least
two carbon atoms . An example a glycidyl aliphatic ether has
wherein A1 -Az are the same or different and comprise the following formula ( 7 ) :
hydrogen or a carbon - containing group with one to three
carbon atoms, A4 comprises a carbonyl -containing linking
group , and R , comprises a branched aliphatic group having 55
at least six carbon atoms . In some embodiments, the epox
ide - containing compound of formula ( 2 ) is a glycidyl ali
phatic ester. The glycidyl aliphatic ester may, for example,
have the following formula ( 3 ) : The glycidyl aliphatic ether of formula (7 ) is available as
60 ERISYS® GE - 5 from CVC Thermoset Specialties . Without
intending to be bound by any particular theory, it is generally
( 3 ) believed that the viscosity of a coating composition can be
=O decreased by including therein a residue of the glycidyl
aliphatic ether of formula (7 ) .
Ri 65 Generally, upon reaction of an aminoalkoxysilane with an
epoxy compound, the resulting product or product blend is
reacted with an isocyanate reagent. Any suitable isocyanate
 US 10,752,803 B2
5 6
reagent may be employed. In some embodiments, an iso
cyanate reagent including a single type of isocyanate com NCO
( 11 )
pound is used . In other embodiments , an isocyanate reagent (CH2)6
includes a mixture of isocyanate compounds. Without
intending to be bound by any particular theory, it is generally 5
believed that it is possible to increase the hardness of a cured " ( CH2)6 — NCO .
coating by forming the coating from a coating composition
comprising a residue of an isocyanate reagent. In theory , it OCN- (CH2) 6
is also believed that the viscosity of a coating composition 10
will increase by including therein a residue of an isocyanate
reagent.
In some embodiments, an isocyanate reagent useful for Without intending to be bound by any particular theory, it
making a coating composition includes a compound having is generally believed that the asymmetrical ring structure of
the following formula ( 8 ) : the compound of formula ( 11 ) causes a decrease in viscosity
15 of the resulting coating composition .
In some embodiments, a coating composition is made
using an isocyanate reagent including at least one of ( 8 ) and
NCO
( 8) ( 10 ) , or combinations of ( 8 ) and ( 10 ) .
R5 20
The resulting reaction will form a monomer that is
suitable for use as a coating composition. In some embodi
ments, a coating composition comprises a monomer having
plural alkoxysilane groups, the monomer including at least
one of ( 12 ) and ( 13 ) :
OCN - R4 Ro - NCO 25
( 12 )
Ag0 . OA9,
wherein R4- R , are the same or different and comprise two to OA10
eight carbon atoms. 30
X2
A specific example such isocyanate reagent comprises a OA10 R5
compound of formula ( 9 ) , available as DESMODUR® A90 Si -OA11 OH OA10
N - 3300 , available from Covestro and having the following A90 1
Si
formula : 35 R3 COAL1
N - R R6 - N N. X3
NCO OH OH
(CH2)6 ( 13 )
1
N
40
Ago. PA9
N. X5
OA10 OA10
OCN- (CH2)6 ( CH2)6 — NCO. OA10 RS A90 |
| Si.
45 -0A11 OH
R3 TOA11
AO
R3
Ro - N X6
In some embodiments, an isocyanate reagent useful for X4
1
N - R -N. OH
making a coating composition includes a compound having 50
the following formula ( 10 ) : OH

( 10 ) wherein A9 , A10 , and Au are the same or different and

NCO comprise hydrogen or C -C4 alkyl, with the proviso that at
RS 55 least one of Ag , A10 , and Au comprises C1 - C4 alkyl, Rz is
N. CZ - C4 alkyl, R4- R , are the same or different and comprise
Ro - NCO two to eight carbon atoms , RZ - R, are the same or different
and comprise two to eight carbon atoms , X7 - X , are the same
or different and comprise one the following groups (a ) and
OCN — R1 60 ( b ), and X4 - X are the same or different and comprise one of
groups (a) and ( b ):

wherein Rz - R, are the same or different and comprise two to (

)
a
eight carbon atoms . A specific example of such isocyanate 65
reagent comprises a compound of formula ( 11 ) , available as
DESMODUR® 3900 :
Z2 -A4 - RI
 US 10,752,803 B2
7 8
-continued -continued
(b) ( 15 )

Za -Ag - R2
wherein A includes a carbonyl- containing linking group , R ,
5
A90
R3
OA10
Si- au
Si .

comprises a branched aliphatic group having at least six A4 - R1

carbon atoms, Ag includes an ether -containing linking group ,
and R, comprises a linear aliphatic group having at least two OA10
1
Rs OH
A90R,0410
Si .
OA11
carbon atoms . Exemplary such monomers include ( 14) and 10 A90 - Si -R3OA11
( 15 ) : Ro - N A4 - R1
R1 - A4. N N - R7 OH
( 14 ) OH
15
A, 0 , PA10
Si
R3 OA11
A4 - R]
wherein A4 includes a carbonyl- containing linking group ,
20
QA10 R's OH Ag , A10 , and Au1 are the same or different and comprise
OA10
A90 - Si - OA A90 Si. hydrogen or C , -C4 alkyl, with the proviso that at least one
R3 of A9, A10 , and A11 comprises C2 - C4 alkyl, R , comprises a
R3 COA11 branched aliphatic group having at least six carbon atoms ,
R1 - A4. N - R4 Ro - N A4 - R1 25 Rz is C1 - C4 alkyl, R - R , are the same or different and
comprise two to eight carbon atoms , and R. - R, are the same
OH OH or different and comprise two to eight carbon atoms . Specific
examples include ( 16 ) and ( 17 ) :
( 16 )
0
II
HN
OH

0
=
O

OH OH

)
17
(
NH
OH

0
=
O NH OH

OH
 US 10,752,803 B2
9 10
It is contemplated that the isocyanate in many embodi 0.5 to 1.5 parts, 0.75 to 1.25 parts , or 0.85 to 1.15 parts of
ments should be used in less than a stoichiometric amount an aminoalkoxysilane is blended for reaction with 0.25 to
than needed for complete reaction with the intermediate 1.5 parts, 0.3 to 1.0 parts, or 0.4 to 0.75 parts of a compound
product formed by reaction of the aminoalkoxysilane with of formula (2 ) and 0.25 to 1.5 parts , 0.3 to 1.0 parts, or 0.4
the epoxy compound. The viscosity of the resulting urea 5
to 0.75 parts of a compound of formula ( 5 ) . The mixture of
prepolymer will otherwise be too high in many cases . In alkoxysilylamines can then be reacted with 0.05 to 0.75 , 0.2
exemplary methods including a reaction between amino to 0.6 parts, or 0.3 to 0.5 parts of an isocyanate reagent.
alkoxysilane and a compound of formula (2 ) , 0.5 to 1.5 In an exemplary embodiment, a portion of an amino
parts , 0.75 to 1.25 parts, or 0.85 to 1.15 parts of an alkoxysilane is reacted with a compound of formula ( 4 ) and
aminoalkoxysilane is blended for reaction with 0.25 to 1.5 10
another portion of the aminoalkoxysilane is reacted with a
parts, 0.3 to 1.0 parts, or 0.4 to 0.75 parts of a compound of
formula ( 2 ) . The alkoxysilylamine can be reacted with 0.05 compound of formula (7 ) to yield a mixture alkoxysilylam
to 0.75 , 0.2 to 0.6 parts, or 0.3 to 0.5 parts of an isocyanate ines ; and the mixture alkoxysilylamines is reacted with an
reagent. isocyanate reagent comprising at least one of (9 ) and ( 11 ) to
In exemplary methods including reactions between an yield at least one of a group including formulas ( 16 ) , ( 17 ) ,
aminoalkoxysilane and compounds of formulas ( 2 ) and ( 5 ) , and the following formulas ( 18 ) - ( 19 ) :
( 18 )

HN
OH

OH OH

Si .

( 19 )

HN
OH

Si

II

OH OH

Si
 US 10,752,803 B2
11 12
-continued
)
20
(
||
HN
??

?? ??

( 21 )

NH
??

N ??

??

22
(
)

NH
??

??

??
 US 10.752.803 B2
13 14
-continued
( 23 )

??? OH
NH

OH

OH

(24)

N NH
OH

OH

OH
" Si.

( 25 )

NH
OH

II
OH

OH
 US 10,752,803 B2
15 16
-continued
(26)

NH
OH

moon OH

mang
27

NH

mpton
C
=
O

OH

Si .

An embodiment of a coating composition comprises at

east of161718-27) . 45 29
(
)
In a second reaction pathway, a portion of aminoalkox
yanis rated with compound of formu 2 ) and
another portion of the amiakyslane is reacted with
compound of formula ( 5 ) to yield a mixture of alkoxysily CN NC
lamines. 50
In some embodiments, the aminoalkoxysilane is reacted
with a blend of compounds of formula (4 ) and formula (7 )
to form an intermediate product mixture. The compounds of
formulas (4 ) and ( 7 ) may be used in any amounts relative to
one another. In some embodiments, equal amounts of (4 ) 55
and (7 ) are employed.
Upon reaction of the aminoalkoxysilane with the epoxy
compounds, the resulting mixture of alkoxysilylamines is
blended with an isocyanate reagent. In some embodiments, The isocyanate compound according to formula ( 29 ) is
an isocyanate reagent useful for making a coating compo available as DESMODUR® W.
60
sition includes a compound having the following formula In an aspect, a portion of an aminoalkoxysilane is reacted
( 28 ) : with a compound of formula (2 ) and another portion of the
OCN — R10 — NCO (28 ) aminoalkoxysilane is reacted with a compound of formula
( 5 ) to yield a mixture of alkoxysilylamines; and the mixture
wherein R10 comprises a linear, branched , cyclic , or bicyclic alkoxysilylamines is reacted with an isocyanate reagent
aliphatic group having at least seven carbon atoms. An 65 having
example of a suitable isocyanate reagent comprises a com
comprising a compound of formula (28) to yield a monomer
plural alkoxysilane groups , the monomer comprising
pund formula (29) at least one compound according to formula (30 ) :
 US 10,752,803 B2
17 18
-continued
( 30 ) (b )
OA10 -Ag - R2
Si -OA11 AgO .
OA10
AO 1 5
Si
R3 R3 OA11
X N - R10 - N N X2
10
OH OH

wherein A9 , A10 , and Au1 are the same or different and wherein A4 includes a carbonyl- containing linking group , R1
comprise hydrogen or C , -C4 alkyl, with the proviso that at comprises a branched aliphatic group having at least six
least one of A9 , A10 , and A11 comprises C -C4 alkyl, Rz is 15 carbon atoms , Ag includes an ether -containing linking group ,
C1 - C4 alkyl, Rio comprises a linear, branched , cyclic , or and R2 comprises a linear aliphatic group having at least two
bicyclic aliphatic group having at least seven carbon atoms, carbon atoms . An embodiment of a coating composition
and X , and X , are the same or different and comprise one the comprises at least one compound according to formula ( 30) .
following groups ( a ) and (b ): In an embodiment, a portion of an aminoalkoxysilane is
20 reacted with a compound of formula (4 ) and another portion
of the aminoalkoxysilane is reacted with a compound of
( a) formula (7 ) to yield a mixture alkoxysilylamines ; and the
ZA -A4 - R1 mixture alkoxysilylamines is reacted with an isocyanate
reagent comprising the compound of formula (29 ) to yield at
least one selected from (31 ) , (32 ) , and ( 33 ) :
( 31 )

HO .

( 32 )

me OH

Si
??.
 US 10,752,803 B2
19 20
-continued
( 33 )

OH ?? .

Si

An embodiment of a coating composition comprises at formula (7 ) to yield a mixture alkoxysilylamines ; and the
least one of ( 31 ) , ( 32 ) , and (33 ) . mixture alkoxysilylamines is reacted with an isocyanate
In an aspect , at least a portion of an aminoalkoxysilane is 20 reagent comprising at least one compound selected from
reacted with a compound of formula ( 2 ) to yield an alkox formulas (9 ), ( 11), and (29 ) to yield at least one of ( 16 ) - (27 )
ysilylamine, and the alkoxysilylamine is reacted with an and (31 ) - (33 ) .
isocyanate reagent comprising at least one of ( 8 ) , ( 10 ) , and In an aspect , at least a portion of an aminoalkoxysilane is
( 28 ) to yield at least one of the following formula (34 ) and reacted with a compound of formula ( 5 ) to yield an alkox
formulas ( 14) and ( 15 ) : 25
ysilylamine , and the alkoxysilylamine is reacted with an
isocyanate reagent comprising at least one of ( 8 ) , ( 10 ) , and
(28 ) to yield at least one compound of ( 35 ) , ( 36 ) , and ( 37 ) :
( 34)
OA10 30
( 35 )
OA11 OA10 OA10
A90 A9O . 1 A90

R3 R3 "OA11 N.
OA11
Ag- R2
OA10 RE
N - R10 - N A4 - RI
4,0–$I 1–0.4
Ri — A4 'N

OH ??
35
,
OA11 OH
A.O
OA10
R3 R3 OA11
/
R2 - Ag N - R4 Ro - N N. Ag- R2
wherein A4 includes a carbonyl - containing linking group , 40
Ay , A10 , and All are the same or different and comprise ?? OH
hydrogen or C - C4 alkyl, with the proviso that at least one (36 )
of A9 , A10 , and A11 comprises C1 - C4 alkyl, R , comprises a QA10
branched aliphatic group having at least six carbon atoms, A90
Rz is C1 - C4 alkyl, and Rio comprises a linear, branched , 45
cyclic , or bicyclic aliphatic group having at least seven N 'NR3AgOA11
- R2
RS
carbon atoms. An embodiment of a coating composition OA10 ??
AgO . OA10
/
Si .
comprises at least one of ( 14 ) , ( 15 ) , and (34 ) . A90 - Si- OA11 R3 OA11
In an embodiment, at least a portion of an aminoalkox 1
ysilane is reacted with a compound of formula (4 ) to yield 50 R3
Ro - N Ag- R2
an alkoxysilylamine , and the alkoxysilylamine is reacted R2 - Ag N -R -N.
with an isocyanate reagent comprising at least one of ( 9 ) , OH
( 11 ) , and ( 29 ) to yield at least one of ( 16 ) , ( 17 ) , and ( 31 ) . OH
An embodiment of a coating composition comprises at ( 37 )
least one of ( 16 ) , ( 17 ) , and (31 ) . 55
In an aspect , a portion of an aminoalkoxysilane is reacted OA10
with a compound of formula ( 2 ) and another portion of the A90 Si —OA1 A90 ,
OA10
1
aminoalkoxysilane is reacted with a compound of formula
( 5 ) to yield a mixture alkoxysilylamines ; and the mixture OA11
alkoxysilylamines is reacted with an isocyanate reagent 60 R3
comprising at least one compound selected from formulas R2- Ag N - R10 - N Ag- R2
( 8 ) , ( 10 ) , and ( 28 ) to yield at least one ( 12 ) , ( 13 ) , and (30 ) .
An embodiment of a coating composition comprises at least ?? OH
one of ( 12 ) , ( 13 ) , and (30 ) .
In an embodiment, a portion of an aminoalkoxysilane is 65
reacted with a compound of formula ( 4 ) and another portion wherein Ag comprises an ether - containing linking group , A. ,
of the aminoalkoxysilane is reacted with a compound of A10 , and A11 are the same or different and comprise hydro
 US 10,752,803 B2
21 22
gen or C , -C4alkyl, with the proviso that at least one of Ag , Any suitable alkylamine may be provided in the coating
Alo, and Aji comprises C.-C. alkyl, R, comprises a linear composition . Exemplary secondary and tertiary amines
aliphatic group having at least two carbon atoms, Rz is include di- and trimethyl amine, di and triethyl amine, di
C1 - C4 alkyl, R4-Ro are the same or different and comprise and tripropyl amine , di- and tributyl amine, di- and tripentyl
two to eight carbon atoms, Rz - R, are the same or different
and comprise two to eight carbon atoms, and R10 comprises
5 amine , di- and trihexyl amine , n - ethylmethylamine, n -eth
propylaminenethylbutylaminen-ethylpentylamin ,
a linear, branched , cyclic , or bicyclic aliphatic group having n -methylpropylamine, n -propylbutylamine, n -pentylpro
at least seven carbon atoms. An embodiment of a coating pylamine, butylmethylamine, -butylpentylamin , n -bu
composition comprises at least one of ( 35 ) , ( 36 ) , and ( 37 ).
tylhexylamine, n - pentylhexylamine, n - isopropylmethylam
In an embodiment, at least a portion of an aminoalkox 10 ine , n -methylisobutylamine, ethylisobutylamine, diisobutyl
ysilane is reacted with a compound of formula (7 ) to yield amine , and dispropylamine. exemplary coating com
an alkoxysilylamine , and the alkoxysilylamine is reacted positions , the alkylamine can be included in an amount of
with an isocyanate reagent comprising at least one com 0.15 wt % based on the total amount of the coating com
pound selected from formulas ( 9 ) , ( 11 ) , and (29 ) to yield at
position .
least one compound selected from formulas ( 20) , (24 ) , and
( 33 ) . An embodiment of a coating composition comprises at 15 Any suitable organotin may be provided in the coating
least one compound selected from formulas ( 20) , (24 ) , and composition . Exemplary organotins include tributyltin com
( 33 ) . pounds such as tributyltin hydride, trimethyltin compounds
Insofar as the present application discloses aspects other such as trimethyltin hydride, tricyclohexyltin compounds
than the method for preparing the coating composition, it such as tricyclohexyltin hydride, tripropyltin compounds
should be noted that the above reactions are not limiting , 20 such as tripropyltin hydride, dibutyltin compounds such as
however, because there are other ways to create the above dibutyltin laurate and dibutyltin bis ( 2 - ethylhexanoate ), and
described monomers . dimethyltin compounds such as dimethyltin dineodecanoate.
The coating composition has long -term shelf stability and A deprotecting catalyst may be included in a coating
is capable of forming siloxane bonds effectively. It is gen composition in any amount that is catalytically effective to
erally believed
composition , thethat ,duringgroups
alkoxy a process
at leastofpartially
curing thehydrolyze
coating 25 deprotect alkoxy groups of the monomer when the monomer
is exposed to ambient water . In exemplary coating compo
when exposed to water in air. As these hydrolysis reactions sitions , a deprotecting catalyst can be included in an amount
occur, the alkoxy groups convert to silanol groups. It is also
believed that at least a portion of the silanol groups cross toof 0.1
1.1
to 1.7 wt % , 0.3 to 1.5 wt % , 0.5 to 1.3 wt % , or 0.7
wt % , based on the total amount of the coating
link together to form siloxane linkages . The hydrolysis
reactions may also produce water and one or more types of 30 composition .
The coating composition may include other functional
alcohol , which may evaporate from the coating composition .
While alcohol may be considered VOC , it is generally ingredients in amounts intended for their effective purposes.
believed that the amount of alcohol produced during the For example, the coating composition may contain a colo
curing process is substantially lower than the amounts of rant, such as a pigment such as titanium dioxide . The
VOCs that are produced during curing of an organic solvent- 35 colorant may be present any amount suitable to impart
based coating composition. color and covering effect to the finished coating; for
It is generally believed that the monomers may, in some example , when the pigment is titanium dioxide, it may be
instances, include hydrophobic structures that slow the present in an amount ranging from 5 to 30 % by weight of the
progress of a hydrolysis reaction between water and the composition. Other suitable pigments include any suitable
alkoxy groups. To speed curing of the composition, a 40 pigment particles, such as azo pigments, anazurite, alumi
catalytic deprotectant may be provided in a coating compo num silicate, aluminum potassium silicate , aluminum paste ,
sition in an amount that is catalytically effective to deprotect anthraquinone pigments, amongxide, barium metabo
alkoxy groups of the heretofore described when the mono rate, barium sulfate, calcium carbonate , calcium metaborate ,
mer is exposed to ambient water. Exemplary catalytic depro calcium metasilicate , carbon black , chromium oxides , clay,
tectants include at least one of alkylamines or organotins. In 45 copper oxides , copper oxychloride, dioxazine pigments,
some embodiments, catalytic deprotectants can accelerate feldspar, hansa yellows , iron oxides such as yellow and red
the production of the silanol groups during curing of the iron oxides, isoindoline pigments , kaolinite , lithopone , mag
coating composition . nesium silicates , metallic flakes, mica , napthol pigments
For example, without intending to be bound by any such as napthol reds, nitroso pigments, nepheline syenite,
particular theory, it is believed that an alkylamine, such as 50 perinone pigments, perylene pigments, polycyclic pigments,
dibutylamine, may catalytically deprotect the alkoxy groups pyrropyrrol pigments, pthalocyanines such as copper ptha
according to the following reaction : locyanine blue and copper pthalocyanine green , quinacri
dones such as quinacridone violets , quinophthalone pig
ments, scates, sulfides , ta , titanum oxide, ultramarine,
H3CO
55 zinc chromate , zinc oxide , and zinc phosphate. In addition,
Ir pearlescents , optical brighteners, ultraviolet stabilizers, and
R - Si - OCH3 H3CO the like may be employed.
The coating composition also may include any one or
H3CO more of dispersants, surfactants, wetting agents, synergists ,
: NH
H3CO + -NH . 60 and rheology modifiers. Any suitable dispersant, such as any
one or more of anionic dispersants, cationic dispersants,
R - Si - OH amphoteric dispersants , or nonionic dispersants may be used
H3CO in conjunction with a pigment vehicle. Other known disper
sants believed to be suitable include NUOSPERSE® 657
65 and NUOSPERSE? FA 196 available from Elementis Spe
cialties , DISPERBYK 108 available from Altana AG , and
SOLSPERSETM M387 available from Lubrizol Corporation .
 US 10,752,803 B2
23 24
Similarly, any suitable wetting agents such as any one or quantity comprising of 0.02 g of dibutyltin dilaurate was
more of anionic wetting agents, cationic wetting agents, added as a deprotectant catalyst .
amphoteric wetting agents, or nonionic wetting agents may
be used . An exemplary synergist is SOLSPERSETM 5000 Example 3
available from Lubrizol Corporation . Exemplary rheology 5
modifiers include SUSPENO 201 - MS available from Poly Example 2 was repeated, except that 7.4 g of DESMO
Resyn , Inc. and AEROSIL® available from Evonik Indus DUR® 3900 was added to 50.5 g of Compound 1 for a molar
tries. ratio of 1 : 1 : 0.33 .
Once formed , the coating composition may be applied
immediately to a substrate, but the coating composition also 10 Example 4
may be dispensed into a suitable container, such as a paint
can , and sealed . It is believed that the coating composition An alkoxysilylamine was produced by reacting 50.0 g of
will have a shelf life of at least several months.
Amethod of applying a coating composition can comprise DYNASYLAN® AMMO and 42.9 g of ERISYS® GE - 5 in
a flask , and mixing and reacting the contents of the flask for
applying the coating composition to a substrate, and allow- 15 2 hr at 65 ° C. to form Compound 2 .
ing the coating composition to cure . Once applied to the
substrate, the coating composition will cure as the compo DUR® Example 4 was prepared by adding 18.5 g of DESMO
sition crosslinks. The curing process does not require addi 1 : 1 : 0.5 3900
(AMMO
to 69.0 g of Compound 2. The molar ratio was
:ERISYS : DESMODUR ). A quantity of 0.1
tional equipment (e.g. , a UV source ), but rather, it is
believed that the curing occurs when the coating composi- 20 g of dibutyl amine was added as a deprotectant catalyst.
tion is exposed to air containing water. Example 5
The coating composition may be employed for any suit
able purpose . In some embodiments, the coating composi Example 4 was repeated, except that 6.8 g of DESMO
tion may be applied to interior or exterior surfaces such as
wood, drywall, cement, metal, and plaster, or over a primer 25 ratio
DUR®of3900 was added to 63.4 g of Compound 2 for a molar
1 : 1 : 0.2 , A quantity of 0.1 g of dibutyl amine was
coating. In certain embodiments, the coating composition
may be applied to metals, composites, and other materials as added as a deprotectant catalyst .
a protective coating . In other embodiments, the coating Example 6 [ MXR - 306-19 ]
composition may be applied to a surface in order to impart An alkoxysilylamine was produced by reacting 736.0 g of
dry - erase characteristics. For example, the surface may be a 30 DYNASYLAN® AMMO , 509.6 g of CARDURATM E10 - P,
wall , which may have paint or a primer already applied to and 318.4 g of ERISYS® GE - 5 in a flask , and mixing and
the surface of the wall , over which the coating can be applied reacting the contents of the flask for 3 hr at 65 ° C. The
to form a dry -erase surface. The coating composition may be mixture was cooled to room tem iture and 107.4 g of
applied with brush , roller, sponge , or spray gun , or other DESMODUR® W was added to yield a monomer having
conventional painting tool . The cured coating may have any 35 plural alkoxysilane groups. The molar ratio was 1 : 0.5 : 0.5 :
suitable thickness, such as a thickness ranging from 0.05-2 0.2 ( AMMO : CARDURA :ERISYS :DESMODUR ). A quan
mm with preferred thickness around 0.1 mm . tity of 16.7 g of dibutyl amine was added as a deprotectant
catalyst.
EXAMPLES These formulations were evaluated for viscosity ( rating
40 from A = thin to Z -thick ). Subsequently, these formulations
Example 1 were coated onto 2 mil Bond- Rite panels and tested for
pencil hardness (ASTM D5363 (2016 ) ) and impact hardness
An alkoxysilylamine was produced by reacting 36.1 g of ( ASTM D2794 (2016 ) ) . The following results were
DYNASYLAN® AMMO and 50.6 g of CARDURATM obtained .
Cardura Erisys Desmodur Desmodur Desmodur Dibutyltin Dibutyl Pencil Impact
Example AMMO E- 10 GE - 5 3300 3900 Dilaurate amine Viscosity Hardness Hardness
1 1 1 0.5 > Z9
2 1 1 0.5 <1 % > Z9 4H
3 1 1 0.333 <1 % Z7-28 4H
4 1 1 0.5 <1 % Z3-24 4H
5 1 1 0.2 1% I-T H 160
6 1 0.5 0.5 0.2 1% 4H 172

55
E10 - Pin a flask , and mixing and reacting the contents of the Without intending to be bound by any particular theory, it
flask for 3 hr at 65 ° C. to form Compound 1 . is generally believed that the coating composition of
Example 1 was prepared by adding 6.8 g of DESMO Example 6 had acceptable viscosity and provided a cured
DUR® 3300 to 30 g of Compound 1. The molar ratio of coating having a balance of hardness and flexibility to due
these components was 1 : 1 : 0.5 (AMMO :CARDURA : DES- 60 toDURATM
the relative amounts of DYNASYLAN® AMMO , CAR
E10 - P, and ERISYS® GE - 5 , and DESMODUR®
MODUR) . W used to make the coating composition .
Example 2 All methods described herein can be performed in any
suitable order unless otherwise indicated herein or otherwise
65 clearly contradicted by context. The use of any and all
Example 1 was repeated, except that DESMODUR® examples , or language describing an example ( e.g. , " such
3900 was used in place of DESMODUR , 3300. A small as ” ) provided herein , is intended to illuminate the invention
 US 10,752,803 B2
25 26
and does not pose a limitation on the scope of the invention .
Any statement herein as to the nature or benefits of the OA10
(1 )
invention or of the preferred embodiments is not intended to Bi
be limiting . This invention includes all modifications and A90 — Si - R3 - N
equivalents of the subject matter recited herein as permitted 5 B2
by applicable law . Moreover, any combination of the above OA11
described elements in all possible variations thereof is
encompassed by the invention unless otherwise indicated where Ag , A10 , and Au are the same or different and
herein or otherwise clearly contradicted by context. The 10
comprise hydrogen or C , -C4 alkyl, with the proviso that at
description herein of any reference or patent, even if iden least one of A9 , A10 , and Aji comprises C2 - C4 alkyl, where
tified as “ prior," is not intended to constitute a concession B , and B2 are the same or different and comprise hydrogen
that such reference or patent is available as prior art against or C , -C4 alkyl, with the proviso that at least one of B , and
the present invention . No unclaimed language should be B2 is hydrogen, and where Rz is C1 - C4 alkyl.
deemed to limit the invention in scope . Any statements or 15 7. The method according to claim 1 , said compound of
suggestions herein that certain features constitute a compo formula ( 2 ) being a glycidyl aliphatic ester.
nent of the claimed invention are not intended to be limiting 8. The method according to claim 7 , said glycidyl ali
unless reflected in the appended claims . Neither the marking phatic ester having the following formula ( 3 ) :
of the patent number on any product nor the identification of
the patent number in connection with any service should be 20
deemed a representation that all embodiments described (3 )
herein are incorporated into such product or service .
What is claimed is : Ri
1. A method of making a coating composition, the method 25
comprising :
providing an aminoalkoxysilane ; wherein Ry comprises a branched aliphatic group having at
in the substantial absence of water, reacting at least a least six carbon atoms .
portion of said aminoalkoxysilane with a compound of 30 9. The method according to claim 8 , said glycidyl ali
the following formula (2 ) : phatic ester having the following formula ( 4 ) :

A2 4
(
)
AL

AA3
-A4 - R1

wherein A1 -Az are the same or different and comprise 40

35

hydrogen or a carbon -containing group with one to three

carbon atoms, A4 comprises a carbonyl -containing linking 10. The method according to claim 1 , said isocyanate
group , and R¡ comprises a branched aliphatic group having reagent comprising at least one of ( 8 ) and ( 10 ) :
at least six carbon atoms , the reaction yielding an alkoxysi 45
lylamine; and
reacting said alkoxysilylamine with an isocyanate reagent NCO
(8 )
containing at least two isocyanate groups to yield a RS
monomer having plural alkoxysilane groups and at
least two branched aliphatic groups having at least six
carbon atoms . 50
2. The method according to claim 1 , 0.5 to 1.5 parts of
said aminoalkoxysilane being blended with 0.25 to 1.5 parts OCN — R4 R6 - NCO
of said compound of formula ( 2 ) .
3. The method of claim 2 , said alkoxysilylamine being ( 10 )
reacted with 0.05 to 0.75 parts of said isocyanate reagent. 55 NCO
4. The method according to claim 1 , further comprising Rg
providing a catalytic deprotectant in an amount catalytically
effective to deprotect alkoxy groups when said monomer is Ro - NCO
exposed to ambient water, said catalytic deprotectant com
prising at least one of an alkylamine and an organotin 60
compound OCN — R7
5. The method according to claim 4 , said catalytic depro
tectant comprising at least one of dibutylamine and dibu
tyltin dilaurate.
6. The method according to claim 1 , said aminoalkoxysi- 65 wherein R4- R , are the same or different and comprise two to
lane having a structure represented by the following formula eight carbon atoms , and R -R, are the same or different and
(1): comprise two to eight carbon atoms .
 US 10,752,803 B2
27 28
11. The method according to claim 10 , said isocyanate -continued
reagent comprising at least one of ( 9 ) and ( 11 ) : ( 15 )
A90 OA10
(9) 5 Si
NCO SOA11
( CH2) 6 'N A4 - R1
|
OA10 RS OH A90 OA10
Si
10 A90 - Si -OAj] OA11
OCN— (CH2) 6 ( CH2 )6 — NCO R3 Ro - N N A4 - R1
R1 - A4 N N - R7 OH
( 11 )
NCO OH
( CH2) 6 15

( CH2)6 — NCO.

OCN— (CH2) 20

12. The method according to claim 1 , said monomer

comprising at least one of ( 14 ) and ( 15 ) : 25

( 14)
A90
OA10 30
Si.
R3 OA11 wherein A4 includes a carbonyl -containing linking group ,
A4 - R1 Ag , A10 , and A11 are the same or different and comprise
OA10 R's hydrogen or C1 - C4 alkyl, with the proviso that at least one
1 OH
OA10 35 of A9, A10 , and Au comprises C1 - C4 alkyl, R , comprises a
A90 - Si -OAU A90 1
Si branched aliphatic group having at least six carbon atoms ,
R3
R3
OA11 Rz is C -C4 alkyl, R4 -Ro are the same or different and
N - R4 Ro - N N
comprise two to eight carbon atoms , and RZ - R, are the same
R1- A4. A4 - R1 or different and comprise two to eight carbon atoms .
40
OH OH 13. The method according to claim 12 , said monomer
comprising at least one of ( 16 ) and ( 17 ) :

( 16 )
=
O
C

HN
OH

N
OH OH
 US 10,752,803 B2
29 30
-continued
)
(
17
NH
OH

0
=
O
N.

OH
OH

14. The method according to claim 1 , further including -continued

adding a pigment. ( 15 )
15. The method according to claim 14 , the pigment A90
OA10
including titanium dioxide . 45
Si
16. A coating composition prepared by the method OA11
according to claim 1 . A4 - RI
17. A coating composition comprising at least one of ( 14 ) OA10 Rg OH A90 Si1
OA10
and ( 15) : 50
A90 - Si -OA11 R3 COA11
R3 Ro - N N. A4 - R1
( 14) R1 - A4 N N -R OH
OA10 55 OH
A90 .
Si
R3 TOA11
A4 - R1 wherein A4 includes a carbonyl - containing linking group ,
R's
Ag , A10 , and Au are the same or different and comprise
OA10 OH
OA10 60 hydrogen or C1 - C4 alkyl, with the proviso that at least one
A90 - Si- OAU AO .
Si .
of A9, A10 , and A11 comprises C2 - C4 alkyl, R , comprises a
R3 OA11 branched aliphatic group having at least six carbon atoms ,
Rz is CZ - C4 alkyl, R4-Ro are the same or different and
Ri - A4 N - R4 R6 - N N A4 - R1 comprise two to eight carbon atoms , and R, R , are the same
65 or different and comprise two to eight carbon atoms .
OH OH 18. The coating composition according to claim 17 ,
comprising at least one of ( 16 ) and ( 17 ) :
 US 10,752,803 B2
31 32
( 16 )

HN
OH

N N
OH OH

Si Si .

( 17 )

NH
OH

ye
0
=
O

=
O
OH

OH

40
19. The coating composition according to claim 17 , wherein A1 -Az are the same or different and comprise
further comprising a pigment. hydrogen or a carbon -containing group with one to three
20. The coating composition according to claim 19 , the carbon atoms , A4 comprises a carbonyl -containing linking
pigment including titanium dioxide .
21. A method of applying a coating composition, the 45 group , and R , comprises a branched aliphatic group having
method comprising applying the coating composition at least six carbon atoms,
according to claim 17 to a substrate , and allowing the
coating composition to cure . (5 )
22. A cured coating comprising a cross -linked product of A6
the coating composition according to claim 17 .
23. A method of making a coating composition, the
method comprising:
providing an aminoalkoxysilane;
in the substantial absence of water, reacting a portion of
said aminoalkoxysilane with a compound of the fol
50

55
A5.

A A7
Ag - R2

lowing formula ( 2 ) and reacting another portion of said

aminoalkoxysilane with a compound of the following wherein A3 -A, are the same or different and comprise
formula (5 ) : hydrogen or a carbon -containing group with one to three
carbon atoms, Ag comprises an ether - containing linking
60 group, and R, comprises a linear aliphatic group having at
(2) least two carbon atoms , the reactions between said amino
A1 A2 alkoxysilane and said compounds of formulas (2 ) and ( 5 )
yielding a mixture of alkoxysilylamines ; and
AL - R1
reacting said mixture of alkoxysilylamines with an iso
A3 65 cyanate reagent containing at least two isocyanate
groups to yield a monomer having plural alkoxysilane
groups .
 US 10,752,803 B2
33 34
24. The method according to claim 23, 0.5 to 1.5 parts of wherein R2 comprises a linear aliphatic group having at least
said aminoalkoxysilane being blended with 0.25 to 1.5 parts two carbon atoms.
of said compound of formula ( 2 ) and 0.25 to 1.5 parts of said 34. The method according to claim 33 , said glycidyl
compound of formula ( 5 ) . aliphatic ether having the following formula (7 ) :
25. The method of claim 24 , said mixture of alkoxysily- 5
lamines being reacted with 0.05 to 0.75 parts of said
isocyanate reagent. (7 )
26. The method according to claim 23 , further comprising
providing a catalytic deprotectant in an amount catalytically
effective to deprotect alkoxy groups when said monomer is
exposed to ambient water, said catalytic deprotectant com 10
prising at least one of an alkylamine and an organotin. 35. The method according to claim 23 , said isocyanate
27. The method according to claim 26 , said catalytic reagent comprising a compound according to formula ( 28 ) :
deprotectant comprising at least one of dibutylamine and OCN — R10 NCO ( 28 )
dibutyltin dilaurate.
28. The method according to claim 23 , said aminoalkox- 15 wherein R10 comprises a linear, branched,cyclic, or bicyclic
ysilane having a structure represented by the following aliphatic group having at least seven carbon atoms.
formula ( 1 ) : 36. The method according to claim 35 , said isocyanate
reagent comprising a compound of formula ( 29 ) :
(1) 20
OA10 (29)
B1
A90 — Si -R3
B2
OA11 OCN NCO .
25

where Ag , A10 , and A11 are the same or different and 37. The method according to claim 23 , said monomer
comprise hydrogen or C -C4 alkyl, with the proviso that at comprising at least one compound according to formula
least one of A9 , A10 , and A11 comprises C1 - C4 alkyl, where (30 ) :
B , and B2 are the same or different and comprise hydrogen
or C , -C4 alkyl, with the proviso that at least one of B , and 30
B2 is hydrogen, and where Rz is C -C4 alkyl. (30)
29. The method according to claim 23 , said compound of
formula (2 ) being a glycidyl aliphatic ester. OA10
30. The method according to claim 29 , said glycidyl A90 /OA10
aliphatic ester having the following formula (3 ) : 35 A90 — Si - OA11 Si.
(3 ) R3 R3
OA11
X7 . N - R10 - N X8
Ri 40
OH OH
wherein R , comprises a branched aliphatic group having at
least six carbon atoms. wherein A9 , A10 , and Au1 are the same or different and
31. The method according to claim 30 , said glycidyl comprise hydrogen or C.-C. alkyl, with the proviso that at
aliphatic ester having the following formula (4 ) : 45
least one of A9 , A10 , and Au comprises CZ - C4 alkyl, Rz is
CZ - C4 alkyl, R10 comprises a linear, branched, cyclic , or
bicyclic aliphatic group having at least seven carbon atoms ,
and X , and X , are the same or different and comprise one the

of 50
following groups ( a) and ( b ):

( a)

32. The method according to claim 23 , said compound of

55 ?---
-A4 - R1
(b )
formula ( 5 ) being a glycidyl aliphatic ether.
33. The method according to claim 32 , said glycidyl
aliphatic ether having the following formula ( 6 ) : 60
ta--A3 - R2

wherein A includes a carbonyl -containing linking group , R1

( 6)
comprises a branched aliphatic group having at least six
0 - R2 carbon atoms , Ag includes an ether -containing linking group ,
and R, comprises a linear aliphatic group having at least two
65 carbon atoms .
38. The method according to claim 37 , said monomer
comprising at least one of ( 31 ) , ( 32 ) , and ( 33 ) :
 US 10,752,803 B2
35 36

aman
( 31 )

OH

phongo
( 32 )

Si Si

mogu
BE
( 33 )

39. The method according to claim 23 , further including wherein A9 , A10 , and Au are the same or different and
adding a pigment. comprise hydrogen or C , -C4 alkyl, with the proviso that at
40. The method according to claim 39 , the pigment 50 least one of A9 , A10 , and A11 comprises C1 - C4 alkyl, Rz is
including titanium dioxide . CZ - C4 alkyl, R10 comprises a linear, branched , cyclic , or
41. A coating composition prepared by the method bicyclic aliphatic group having at least seven carbon atoms ,
according to claim 23 . and X , and X , are the same or different and comprise one the
42. A coating composition comprising at least one com following groups ( a) and ( b ):
55
pound according to formula (30) :
( 30 ) ( a)
OA10
A90 — Si - OAU A90
OA10
60
LA -A4 - R1
(b )

X
R3
N - R10 - N Xe
COA11
E -Ag - R2

65 wherein A4 includes a carbonyl - containing linking group , R?

OH OH comprises a branched aliphatic group having at least six
carbon atoms , Ag includes an ether -containing linking group ,
 US 10,752,803 B2
37 38
and R2 comprises a linear aliphatic group having at least two 43. The coating composition according to claim 42 ,
carbon atoms . comprising at least one of ( 31 ) , (32 ) , and ( 33 ):
(31 )

mu ?? .

( 32)

OH HO .

Si

( 33 )

OH ?? ,

N
H

Si

50 44. The coating composition according to claim 42 ,

further comprising a pigment.
45. The coating composition according to claim 44 , the
pigment including titanium dioxide .
46. A method of applying a coating composition, the
55 method comprising applying the coating composition
according to claim 42 to a substrate , and allowing the
coating composition to cure .
47. A cured coating comprising a cross - linked product of
the coating composition according to claim 42 .