U.S. patent application number 17/113549 was filed with the patent office on 2021-03-25 for polymerizable compositions, polymerized compositions, and methods of making and using the same.
The applicant listed for this patent is 3M INNOVATIVE PROPERTIES COMPANY. Invention is credited to Robert S. Clough, Susan E. DeMoss, Michael A. Kropp.
Application Number | 20210087340 17/113549 |
Document ID | / |
Family ID | 1000005255020 |
Filed Date | 2021-03-25 |
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United States Patent
Application |
20210087340 |
Kind Code |
A1 |
Clough; Robert S. ; et
al. |
March 25, 2021 |
POLYMERIZABLE COMPOSITIONS, POLYMERIZED COMPOSITIONS, AND METHODS
OF MAKING AND USING THE SAME
Abstract
A polymerizable composition includes an organoborane-base
complex that is a complex of an organoborane and a base, a
decomplexing agent that at least partially liberates the
organoborane from the organoborane-base complex, a polymerizable
thiol-containing component comprising at least one polymerizable
thiol-containing compound having a plurality of thiol groups in
which the sulfur atom of the thiol group is covalently bonded to
carbon, a hydroperoxide, and a polymerizable
ethylenically-unsaturated component comprising at least one
polymerizable ethylenically-unsaturated compound having a plurality
of ethylenically-unsaturated groups. The combined amounts of the
thiol-containing and ethylenically-unsaturated compounds total at
least 50 percent by weight of all polymerizable material in the
polymerizable composition. The composition may be provide as a
two-part composition. Polymerized reaction product of the
composition and methods of making the composition are also
disclosed.
Inventors: |
Clough; Robert S.; (St.
Paul, MN) ; DeMoss; Susan E.; (Stillwater, MN)
; Kropp; Michael A.; (Cottage Grove, MN) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
3M INNOVATIVE PROPERTIES COMPANY |
St. Paul |
MN |
US |
|
|
Family ID: |
1000005255020 |
Appl. No.: |
17/113549 |
Filed: |
December 7, 2020 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
|
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15756283 |
Feb 28, 2018 |
10889687 |
|
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PCT/US2016/050895 |
Sep 9, 2016 |
|
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17113549 |
|
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62216711 |
Sep 10, 2015 |
|
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Current U.S.
Class: |
1/1 |
Current CPC
Class: |
C08G 75/12 20130101;
C08G 75/045 20130101 |
International
Class: |
C08G 75/12 20060101
C08G075/12; C08G 75/045 20060101 C08G075/045 |
Claims
1. A polymerizable composition comprising: a part A composition
comprising an organoborane-base complex that is a complex of an
organoborane and a base, wherein the organoborane is represented by
the formula B(R.sup.1)(R.sup.2)(R.sup.3) wherein: R.sup.1
represents an alkyl group having from 1 to 10 carbon atoms; and
R.sup.2 and R.sup.3 independently represent: alkyl groups having 1
to 10 carbon atoms; cycloalkyl groups having 3 to 10 carbon atoms;
aryl groups having 6 to 12 carbon atoms; or aryl groups substituted
with alkyl groups having 1 to 10 carbon atoms or cycloalkyl groups
having 3 to 10 carbon atoms; or any two of R.sup.1, R.sup.2, and
R.sup.3 taken together form a divalent alkylene group having from 3
to 7 carbon atoms, and wherein the base is a complexing agent
selected from a compound having one or more amine groups, amidine
groups, hydroxide groups, alkoxide groups, or a combination
thereof; and a part B composition comprising a decomplexing agent
that at least partially liberates the organoborane from the
organoborane-base complex; wherein the polymerizable composition
further comprises: a polymerizable thiol-containing component
comprising at least one polymerizable thiol-containing compound
having a plurality of thiol groups in which the sulfur atom of the
thiol group is covalently bonded to carbon; a hydroperoxide; and a
polymerizable ethylenically-unsaturated component comprising at
least one polymerizable ethylenically-unsaturated compound having a
plurality of ethylenically-unsaturated groups, wherein the combined
amounts of the thiol-containing and ethylenically-unsaturated
compounds total at least 50 percent by weight of all polymerizable
material in the polymerizable composition.
2. The polymerizable composition of claim 1, wherein the
hydroperoxide is an organic hydroperoxide.
3. The polymerizable composition of claim 1, wherein the
hydroperoxide is present in the part B composition.
4. The polymerizable composition of claim 1, wherein upon reaction
a --C--S--C--C-- linkage is formed.
5. The polymerizable composition of claim 1, wherein the base is an
amine comprising at least one primary or secondary amine group.
6. A composition prepared by combining components comprising: a
part A composition comprising an organoborane-base complex that is
a complex of an organoborane and a base, wherein the organoborane
is represented by the formula B(R.sup.1)(R.sup.2)(R.sup.3) wherein:
R.sup.1 represents an alkyl group having from 1 to 10 carbon atoms;
and R.sup.2 and R.sup.3 independently represent: alkyl groups
having 1 to 10 carbon atoms; cycloalkyl groups having 3 to 10
carbon atoms; aryl groups having 6 to 12 carbon atoms; or aryl
groups substituted with alkyl groups having 1 to 10 carbon atoms or
cycloalkyl groups having 3 to 10 carbon atoms; or any two of
R.sup.1, R.sup.2, and R.sup.3 taken together form a divalent
alkylene group having from 3 to 7 carbon atoms, and wherein the
base is a complexing agent selected from a compound having one or
more amine groups, one or more amidine groups, one or more
hydroxide groups, one or more alkoxide groups, or a combination
thereof; and a part B composition comprising a decomplexing agent
that at least partially liberates the organoborane from the
organoborane-base complex, wherein at least one of the part A
composition and the part B composition further comprises: a
polymerizable thiol-containing component comprising at least one
polymerizable thiol-containing compound having a plurality of thiol
groups in which the sulfur atom of the thiol group is covalently
bonded to carbon; a hydroperoxide; and a polymerizable
ethylenically-unsaturated component comprising at least one
polymerizable ethylenically-unsaturated compound having a plurality
of ethylenically-unsaturated groups, wherein the combined amounts
of the thiol-containing and ethylenically-unsaturated compounds
total at least 50 percent by weight of all polymerizable material
in the polymerizable composition.
7. The composition of claim 6, wherein the hydroperoxide is an
organic hydroperoxide.
8. The composition of claim 6, wherein the base is an amine
comprising at least one primary or secondary amine group.
Description
CROSS-REFERENCE TO RELATED APPLICATIONS
[0001] This application is a divisional of U.S. application Ser.
No. 15/756,283, filed Feb. 28, 2018, now pending, which is a
national stage filing under 35 U.S.C. 371 of PCT/US2016/050895,
filed Sep. 9, 2106, which claims the benefit of U.S. Provisional
Application No. 62/216,711, filed Sep. 10, 2015.
BACKGROUND
[0002] There is a need for materials and chemistries that can form
polymers, particularly crosslinked polymers, rapidly under ambient
or mild conditions, particularly in the presence of oxygen.
SUMMARY
[0003] The present disclosure provides compositions, particularly
flowable polymerizable compositions, that include a
thiol-containing compound and an ethylenically-unsaturated compound
that can cure (i.e., polymerize and/or crosslink) under ambient or
mild conditions, particularly in the presence of oxygen (e.g.,
O.sub.2 or a peroxygen compound) to form solids, including
viscoelastic solids. The compositions can be used to form
adhesives, sealants, encapsulants, and potting resins, for example
Such compositions include an organoborane-base complex, especially
those containing a trialkylborane, which can be used in the
presence of oxygen or a peroxygen compound to initiate the curing
(i.e., polymerization and/or crosslinking).
[0004] It is discovered that hydroperoxides as peroxygen compounds
are much more effective than other organic peroxides (e.g., dialkyl
peroxides) in speeding the cure of the thiol-ene compositions in
oxygen (O.sub.2)-limited environments or where the diffusion of
oxygen into the composition is restricted. Examples of such
O.sub.2-limited environments include thick cross-sections, in
highly-filled compositions, and compositions disposed between
impervious substrates. The presence of hydroperoxide greatly
enhances the ability of thiol-ene compositions to uniformly cure in
such environments.
[0005] In addition, it is presently discovered that formulations
containing a high percentage by weight of ether, thioether, and/or
disulfide groups and higher rank sulfur linkages (e.g., trisulfide
and tetrasulfide) may cure slowly relative to other comparable
formulations. This is the case when the structures of the
thiol-containing and/or ethylenically-unsaturated compounds are
predominantly oxygen or sulfur atoms separated by methylene
(--CH.sub.2--), ethylene (--CH.sub.2CH.sub.2--), or propylene
(--CH.sub.2CH(CH.sub.3)--) units and these compounds form the
majority of the formulation.
[0006] In one aspect, the present disclosure provides a
polymerizable composition comprising:
[0007] an organoborane-base complex that is a complex of an
organoborane and a base, wherein the base is a complexing agent
selected from a compound having one or more amine groups, amidine
groups, hydroxide groups, alkoxide groups, or a combination
thereof;
[0008] a decomplexing agent that at least partially liberates the
organoborane from the organoborane-base complex;
[0009] a polymerizable thiol-containing component comprising at
least one polymerizable thiol-containing compound having a
plurality of thiol groups (i.e., mercapto groups) in which the
sulfur atom of the thiol group is covalently bonded to carbon
(i.e., through C--S bonds);
[0010] a hydroperoxide; and
[0011] a polymerizable ethylenically-unsaturated component
comprising at least one polymerizable ethylenically-unsaturated
compound having a plurality of ethylenically-unsaturated
groups;
[0012] wherein the combined amounts of the thiol-containing and
ethylenically-unsaturated compounds total at least 50 percent by
weight of all polymerizable material in the polymerizable
composition.
[0013] In certain embodiments, upon reaction (i.e., curing which
involves polymerizing and/or crosslinking) a --C--S--C--C-- linkage
(e.g., a --CH.sub.2--S--CH.sub.2--CH.sub.2-- or
--CHZ--S--CH.sub.2--CH.sub.2-- linkage where Z is an organic group)
is formed.
[0014] In another aspect, the present disclosure provides a
polymerizable composition comprising:
[0015] a part A composition comprising a organoborane-base complex
that is a complex of an organoborane and a base, wherein the base
is a complexing agent selected from a compound having one or more
amine groups, amidine groups, hydroxide groups, alkoxide groups, or
a combination thereof; and
[0016] a part B composition comprising a decomplexing agent that at
least partially liberates the organoborane from the
organoborane-base complex;
[0017] wherein the polymerizable composition further comprises:
[0018] a polymerizable thiol-containing component comprising at
least one polymerizable thiol-containing compound having a
plurality of thiol groups in which the sulfur atom of the thiol
group is covalently bonded to carbon; [0019] a hydroperoxide; and
[0020] a polymerizable ethylenically-unsaturated component
comprising at least one polymerizable ethylenically-unsaturated
compound having a plurality of ethylenically-unsaturated
groups,
[0021] wherein the combined amounts of the thiol-containing and
ethylenically-unsaturated compounds total at least 50 percent by
weight of all polymerizable material in the polymerizable
composition.
[0022] In certain embodiments, upon reaction a --C--S--C--C--
linkage is formed.
[0023] In yet another aspect, the present disclosure provides a
composition prepared by combining components comprising:
[0024] a part A composition comprising a organoborane-base complex
that is a complex of an organoborane and a base, wherein the base
is a complexing agent selected from a compound having one or more
amine groups, one or more amidine groups, one or more hydroxide
groups, one or more alkoxide groups, or a combination thereof;
and
[0025] a part B composition comprising a decomplexing agent that at
least partially liberates the organoborane from the
organoborane-base complex,
[0026] wherein at least one of the part A composition and the part
B composition further comprises: [0027] a polymerizable
thiol-containing component comprising at least one polymerizable
thiol-containing compound having a plurality of thiol groups in
which the sulfur atom of the thiol group is covalently bonded to
carbon; [0028] a hydroperoxide; and [0029] a polymerizable
ethylenically-unsaturated component comprising at least one
polymerizable ethylenically-unsaturated compound having a plurality
of ethylenically-unsaturated groups,
[0030] wherein the combined amounts of the thiol-containing and
ethylenically-unsaturated compounds total at least 50 percent by
weight of all polymerizable material in the polymerizable
composition.
[0031] In certain embodiments, upon reaction a --C--S--C--C--
linkage is formed.
[0032] The present disclosure further provides a method of making a
composition that includes combining components that include: a part
A composition including an organoborane-base complex, wherein the
base is a complexing agent selected from a compound having one or
more amine groups, amidine groups, hydroxide groups, alkoxide
groups, or a combination thereof; and a part B composition
including a decomplexing agent that at least partially liberates
the organoborane from the organoborane-base complex; and allowing
the part A and part B to react (preferably, to form a polymer that
includes a --C--S--C--C-- linkage (e.g., a
--CH.sub.2--S--CH.sub.2--CH.sub.2-- or
--CHZ--S--CH.sub.2--CH.sub.2-- linkage where Z is an organic
group)).
[0033] Accordingly, in yet another aspect, the present disclosure
provides a method of making a composition, the method
comprising:
[0034] combining components comprising: [0035] a part A composition
comprising a organoborane-base complex that is a complex of an
organoborane and a base, and wherein the base is a complexing agent
selected from a compound having one or more amine groups, amidine
groups, hydroxide groups, alkoxide groups, or a combination
thereof; and [0036] a part B composition comprising a decomplexing
agent that at least partially liberates the organoborane from the
organoborane-base complex; [0037] wherein at least one of the part
A composition and the part B composition further comprises: [0038]
a polymerizable thiol-containing component comprising at least one
polymerizable thiol-containing compound having a plurality of thiol
groups in which the sulfur atom of the thiol group is covalently
bonded to carbon; [0039] a hydroperoxide; and [0040] a
polymerizable ethylenically-unsaturated component comprising at
least one polymerizable ethylenically-unsaturated compound having a
plurality of ethylenically-unsaturated groups, [0041] wherein the
combined amounts of the thiol-containing and
ethylenically-unsaturated compounds total at least 50 percent by
weight of all polymerizable material in the composition; and
[0042] allowing the part A composition and the part B composition
to react to form a polymer.
[0043] As used herein, the term "organic group" means a hydrocarbon
group (with optional elements other than carbon and hydrogen,
including oxygen, nitrogen, sulfur, phosphorus, halogen, and/or
silicon). In some embodiments, the organic group does not include
silicon. The organic group can be monovalent, divalent, trivalent,
or any other desired valency. Example organic groups include an
aliphatic group, cyclic group, or combination of aliphatic and
cyclic groups (e.g., alkaryl and aralkyl groups). The term
"aliphatic group" means a saturated or unsaturated linear or
branched hydrocarbon group. This term is used to encompass
monovalent groups such as alkyl, alkenyl, and alkynyl groups, for
example, as well as corresponding groups with higher valencies. The
term "alkyl group" means a saturated linear or branched hydrocarbon
group including, for example, methyl, ethyl, isopropyl, t-butyl,
heptyl, dodecyl, octadecyl, amyl, 2-ethylhexyl, and the like. The
term "alkenyl group" means an unsaturated, linear or branched
hydrocarbon group other than an aromatic group with one or more
carbon-carbon double bonds, such as a vinyl group. The term
"alkynyl group" means an unsaturated, linear or branched
hydrocarbon group with one or more carbon-carbon triple bonds, such
as an ethynyl group. The term "cyclic group" means a closed ring
hydrocarbon group that is classified as a cycloaliphatic (i.e.,
alicyclic) group, aromatic group, or heterocyclic (e.g., oxygen-,
nitrogen-, or sulfur-containing) group. The term "cycloaliphatic
group" means a cyclic hydrocarbon group having properties
resembling those of aliphatic groups. Cycloaliphatic groups include
monovalent groups such as cycloalkyl groups (i.e., cyclic alkyl
groups such as cyclopropyl, and cyclobutyl, for example, as well as
corresponding groups with higher valencies). The term "aromatic
group" or "aryl group" means a mono- or polynuclear aromatic
hydrocarbon group. The term "heterocyclic group" means a closed
ring hydrocarbon in which one or more of the atoms in the ring is
an element other than carbon (e.g., nitrogen, oxygen, and/or
sulfur). Any of these groups may be substituted or unsubstituted.
If substituted, the substituents may include halogen, hydroxy,
alkoxy, alkylamino, alkyl, nitro, and the like. A group that may be
the same or different is referred to as being "independently"
something.
[0044] The terms "comprises" and variations thereof do not have a
limiting meaning where these terms appear in the description and
claims. Such terms will be understood to imply the inclusion of a
stated step or element or group of steps or elements but not the
exclusion of any other step or element or group of steps or
elements. By "consisting of" is meant including, and limited to,
whatever follows the phrase "consisting of." Thus, the phrase
"consisting of" indicates that the listed elements are required or
mandatory, and that no other elements may be present. By
"consisting essentially of" is meant including any elements listed
after the phrase, and limited to other elements that do not
interfere with or contribute to the activity or action specified in
the disclosure for the listed elements. Thus, the phrase
"consisting essentially of" indicates that the listed elements are
required or mandatory, but that other elements are optional and may
or may not be present depending upon whether or not they materially
affect the activity or action of the listed elements.
[0045] The words "preferred" and "preferably" refer to embodiments
of the disclosure that may afford certain benefits, under certain
circumstances. However, other embodiments may also be preferred,
under the same or other circumstances. Furthermore, the recitation
of one or more preferred embodiments does not imply that other
embodiments are not useful, and is not intended to exclude other
embodiments from the scope of the disclosure.
[0046] In this application, terms such as "a," "an," and "the" are
not intended to refer to only a singular entity, but include the
general class of which a specific example may be used for
illustration. The terms "a," "an," and "the" are used
interchangeably with the term "at least one."
[0047] The phrases "at least one of" and "comprises at least one
of" followed by a list refers to any one of the items in the list
and any combination of two or more items in the list.
[0048] As used herein, the term "or" is generally employed in its
usual sense including "and/or" unless the content clearly dictates
otherwise.
[0049] The term "and/or" means one or all of the listed elements or
a combination of any two or more of the listed elements.
[0050] Also herein, all numbers are assumed to be modified by the
term "about" and in certain situations by the term "exactly." As
used herein in connection with a measured quantity, the term
"about" refers to that variation in the measured quantity as would
be expected by the skilled artisan making the measurement and
exercising a level of care commensurate with the objective of the
measurement and the precision of the measuring equipment used.
Also, as used herein in connection with a measured quantity, the
term "approximately" refers to that variation in the measured
quantity as would be expected by the skilled artisan making the
measurement and exercising a level of care commensurate with the
objective of the measurement and the precision of the measuring
equipment used.
[0051] Also herein, the recitations of numerical ranges by
endpoints include all numbers subsumed within that range as well as
the endpoints (e.g., 1 to 5 includes 1, 1.5, 2, 2.75, 3, 3.80, 4,
and 5).
[0052] When a group is present more than once in a formula
described herein, each group is "independently" selected, whether
specifically stated or not. For example, when more than one R group
is present in a formula, each R group is independently selected.
Furthermore, subgroups contained within these groups are also
independently selected.
[0053] As used herein, the term "room temperature" refers to a
temperature of 19.degree. C. to 25.degree. C., or more often to a
temperature of 21.degree. C.
[0054] As used herein, the term "thiol group" refers to an --SH
group (i.e., a mercapto group).
[0055] Features and advantages of the present disclosure will be
further understood upon consideration of the detailed description
as well as the appended claims.
DETAILED DESCRIPTION
[0056] Compositions of the present disclosure include an
organoborane-base complex, especially those containing a
trialkylborane, a decomplexing agent, and a hydroperoxide that can
initiate the curing (polymerizing and/or crosslinking) of a
polymerizable composition to form solids, including viscoelastic
solids.
[0057] In particular, the present disclosure provides a
polymerizable composition that includes: an organoborane-base
complex, wherein the base is a complexing agent selected from a
compound having one or more amine groups, amidine groups, hydroxide
groups, alkoxide groups, or a combination thereof; a decomplexing
agent that at least partially liberates the organoborane from the
organoborane-base complex; a hydroperoxide; at least one
polymerizable thiol-containing compound having a plurality of thiol
groups (i.e., mercapto groups) in which the sulfur atom of the
thiol group is covalently bonded to carbon; and at least one
polymerizable ethylenically-unsaturated compound having a plurality
of ethylenically-unsaturated groups. The thiol-containing and the
ethylenically-unsaturated compounds may be polydiorganosiloxanes,
for example.
[0058] The curing reaction involves thiol-ene chemistry or the
addition of a thiol group across carbon-carbon unsaturation, where
the sulfur and hydrogen that add across an individual site of
carbon-carbon unsaturation are not necessarily from the same thiol
group, and the hydrogen may be from other compounds in addition to
those that contain thiol groups. An organoborane-base complex,
especially a trialkylborane-base complex, is used to initiate
polymerizing and/or crosslinking reactions.
[0059] An organoborane, especially a trialkylborane, in the
presence of oxygen or a peroxygen compound is used to initiate
polymerizing and/or crosslinking reactions. The decomplexing agent
reacts with the base to liberate the organoborane from the
organoborane-base complex. In the presence of oxygen, the
trialkylborane reacts with oxygen and subsequently fragments to
generate free radical species some of which initiate the addition
reaction of a thiol with an ethylenically-unsaturated group. The
compounds of the present invention undergo the reaction and afford
polymeric materials, which are typically crosslinked polymeric
materials. The polymers formed can be hydrocarbon-based or
silicone-based. In certain embodiments, the polymers formed upon
reaction include a --C--S--C--C-- linkage (e.g., a
--CH.sub.2--S--CH.sub.2--CH.sub.2-- or
--CHZ--S--CH.sub.2--CH.sub.2-- linkage where Z is an organic
group).
[0060] In certain situations or applications, particularly those
where O.sub.2 may be limited or diffusion of O.sub.2 into the
composition may be restricted, such as thick cross-sections, highly
filled compositions, and between impervious substrates, a peroxygen
compound may be needed to increase the rate of cure, or to increase
the degree of cure in a certain amount of time. Also, compositions
containing a high percentage by weight of ether, thioether, and/or
disulfide groups and higher rank sulfur linkages (e.g., trisulfide
and tetrasulfide) may cure slowly, and a peroxygen compound may be
needed to increase the rate of cure, or to increase the degree of
cure in a certain amount of time. This is the case when the
structures of the thiol-containing and/or ethylenically-unsaturated
compounds are predominantly oxygen or sulfur atoms separated by
methylene (--CH.sub.2--), ethylene (--CH.sub.2CH.sub.2--), or
propylene (--CH.sub.2CH(CH.sub.3)--) units and these compounds form
the majority of the composition. In certain embodiments, the
combined amount of oxygen and sulfur atoms in aliphatic ether,
aliphatic thioether, and aliphatic disulfide groups and higher rank
sulfur linkages in the thiol-containing compounds and
ethylenically-unsaturated compounds of the composition is at least
15 weight percent, at least 20 weight percent, at least 25 weight
percent, or at least 30 weight percent based on the total weight of
the thiol-containing compounds and ethylenically-unsaturated
compounds in the composition. Hydroperoxides are particularly
effective in providing rapid cures or short cure times in these
situations or applications. It should be noted that the
hydroperoxides are not being utilized as conventional thermal free
radical initiators that undergo thermolysis to generate free
radical species, which initiate the thiol-ene reaction. For
example, preferred hydroperoxides are organic hydroperoxides.
Preferred organic hydroperoxides include, e.g., tertiary organic
hydroperoxides (i.e., where the hydroperoxy group (--OOH) is bound
to a tertiary carbon atom), such as tert-butyl hydroperoxide. These
hydroperoxides typically must be heated to over 125.degree. C. in
order to reduce the original amount of the hydroperoxide by 50
percent in 10 hours. Thus, their thermolysis is not suitable for
rapid cures at ambient conditions, i.e., room temperature. Without
wishing to be bound by any particular reaction pathway, it appears
that the hydroperoxide may react or interact with the
organoborane-base complex and/or its freed components to accelerate
the generation of free radical species that initiate the thiol-ene
reaction or polymerization.
[0061] In certain embodiments, the total amount of the
thiol-containing and ethylenically-unsaturated compounds total at
least 50 percent by weight of all polymerizable material in the
composition. In certain embodiments, the amount of the thiol groups
and the amount of ethylenically-unsaturated groups are present in a
molar ratio range of 0.25:1.0 to 4.0:1.0, or 0.33:1.0 to 3.0:1.0,
or 0.5:1.0 to 2.0:1.0, or 0.75:1.0 to 1.33:1.0, or 0.80:1.0 to
1.25:1.0 (thiol groups:ethylenically-unsaturated groups). In
certain embodiments, for example where crosslinking of high
molecular weight polymers that contain an ethylenically-unsaturated
repeating unit, such as 1,2-polybutadiene or unsaturated
polyesters, is desired, the amount of thiol groups and the amount
of ethylenically-unsaturated groups may be present in a molar range
of 0.005:1.0 to 0.20:1.0 (thiol groups:ethylenically-unsaturated
groups).
[0062] The compositions of the present disclosure typically include
at least two parts (i.e., they are multi-part polymerizable
compositions), and preferably, two parts. The at least two-part
compositions according to the present disclosure include a part A
and a part B. Individually, parts A and B have good stability, but
when combined stability is lost and curing is initiated.
[0063] The part A composition includes an organoborane-base
complex. The part B includes a decomplexing agent for the
organoborane-base complex. The polymerizable composition (i.e., the
part A composition and/or the part B composition and/or other
parts) further includes: a thiol-containing component that includes
at least one polymerizable thiol-containing compound having a
plurality of thiol groups in which the sulfur atom of the thiol
group is covalently bonded to carbon; an ethylenically-unsaturated
component that includes at least one polymerizable
ethylenically-unsaturated compound having a plurality of
ethylenically-unsaturated groups; and a hydroperoxide. That is, the
thiol-containing component is in part A, part B, and/or another
part distinct from parts A and B; the ethylenically-unsaturated
component is in part A, part B, and/or another part distinct from
parts A and B, and the hydroperoxide is in part A, part B, and/or
another part distinct from parts A and B. In certain embodiments,
the thiol-containing compound and the ethylenically-unsaturated
compound are separate and distinct compounds. In certain
embodiments, one compound may have both thiol groups and
ethylenically-unsaturated groups.
Organoborane-Base Complex
[0064] The organoborane-base complex is a latent form of an
organoborane which is liberated upon decomplexing the base with a
compound that reacts with the base, such as, for example, an acid.
The free organoborane is an initiator capable of initiating
free-radical polymerization of polymerizable monomer(s) to form a
polymer that can be useful as an adhesive, sealant, encapsulant,
and potting resin, for example.
[0065] The organoborane portion of the organoborane-base complex is
of the following formula (Formula I):
B(R.sup.1)(R.sup.2)(R.sup.3) (I)
wherein R.sup.1, R.sup.2, and R.sup.3 are organic groups (typically
having 30 atoms or less, or 20 atoms or less, or 10 atoms or less).
In certain embodiments of Formula I, R.sup.1 represents an alkyl
group having from 1 to 10 carbon atoms, or from 1 to 6 carbon
atoms, or from 1 to 5 carbon atoms, or from 1 to 4 carbon atoms, or
from 2 to 4 carbon atoms, or from 3 to 4 carbon atoms.
[0066] In certain embodiments of Formula I, R.sup.2 and R.sup.3
independently represent (i.e., they may be the same or different):
alkyl groups having 1 to 10 carbon atoms (or from 1 to 6 carbon
atoms, or from 1 to 5 carbon atoms, or from 1 to 4 carbon atoms, or
from 2 to 4 carbon atoms, or from 3 to 4 carbon atoms); cycloalkyl
groups having 3 to 10 carbon atoms; aryl groups having from 6 to 12
carbon atoms (e.g., phenyl); or aryl groups having from 6 to 12
carbon atoms (e.g., phenyl) substituted with alkyl groups having 1
to 10 carbon atoms (or from 1 to 6 carbon atoms, or from 1 to 5
carbon atoms, or from 1 to 4 carbon atoms, or from 2 to 4 carbon
atoms, or from 3 to 4 carbon atoms), or cycloalkyl groups having 3
to 10 carbon atoms. Any two of R.sup.1, R.sup.2, and R.sup.3 groups
may optionally be part of a ring (e.g., two groups can combine to
form a ring).
[0067] The organoborane initiator is complexed with a basic
complexing agent (i.e., a base that complexes with the
organoborane) to form a stable organoborane-base complex. The
organoborane-base complex may be represented by the formula
(Formula II):
##STR00001##
wherein Cx represents a complexing agent selected from a compound
having one or more amine groups, one or more amidine groups, one or
more hydroxide groups, one or more alkoxide groups, or a
combination thereof; and v is a positive number. The value of v is
selected so as to render the organoborane-base complex stable under
ambient conditions. For example, when the organoborane-base complex
is stored in a capped vessel at about 20.degree. C. to 22.degree.
C. and under otherwise ambient conditions (i.e., the vessel is
capped in an ambient air environment and not under vacuum or an
inert atmosphere), the complex remains useful as an initiator for
at least two weeks. Preferably, the complexes may be readily stored
under these conditions for many months, and up to a year or more.
In certain embodiments the value of v is typically at least 0.1, or
at least 0.3, or at least 0.5, or at least 0.8, or at least 0.9 and
is often up to 4, or up to 3, or up to 2, or up to 1.5, or up to
1.2. In some embodiments, v is in a range of 0.1 to 4, or in a
range of 0.5 to 2, or in a range of 0.8 to 1.2, or in a range of
0.9 to 1.1, or 1.
[0068] In certain embodiments of Formula II, R.sup.4 represents an
alkyl group having from 1 to 10 carbon atoms, or from 1 to 6 carbon
atoms, or from 1 to 5 carbon atoms, or from 1 to 4 carbon atoms, or
from 2 to 4 carbon atoms, or from 3 to 4 carbon atoms.
[0069] In certain embodiments of Formula II, R.sup.5 and R.sup.6,
independently represent (i.e., they may be the same or different):
alkyl groups having 1 to 10 carbon atoms (or from 1 to 6 carbon
atoms, or from 1 to 5 carbon atoms, or from 1 to 4 carbon atoms, or
from 2 to 4 carbon atoms, or from 3 to 4 carbon atoms); cycloalkyl
groups having 3 to 10 carbon atoms; aryl groups having from 6 to 12
carbon atoms (e.g., phenyl); or aryl groups having from 6 to 12
carbon atoms (e.g., phenyl) substituted with alkyl groups having 1
to 10 carbon atoms (or from 1 to 6 carbon atoms, or from 1 to 5
carbon atoms, or from 1 to 4 carbon atoms, or from 2 to 4 carbon
atoms, or from 3 to 4 carbon atoms), or cycloalkyl groups having 3
to 10 carbon atoms. Any two of R.sup.4, R.sup.5, and R.sup.6 groups
may optionally be part of a ring (e.g., two groups can combine to
form a ring).
[0070] Herein, in Formulas I and II, an alkyl group may be straight
chain or branched.
[0071] In certain embodiments, a ring formed by two groups of
R.sup.1, R.sup.2, and R.sup.3 or formed by two groups of R.sup.4,
R.sup.5, and R.sup.6 may be bridged by the boron atom in Formula I
or Formula II.
[0072] In certain embodiments of Formula II, R.sup.4 represents an
alkyl group having from 1 to 10 carbon atoms; R.sup.5 and R.sup.6
independently represent alkyl groups having 1 to 10 carbon atoms or
aryl groups having 6 to 12 carbon atoms; Cx represents a complexing
agent selected from a compound having one or more amine groups,
amidine groups, hydroxide groups, alkoxide groups, or a combination
thereof; and v is a positive number such as in a range of 0.1 to 4,
in a range of 0.5 to 2, in a range of 0.8 to 1.2, or 0.9 to 1.1, or
1.
[0073] In certain embodiments, the organoborane-base complex does
not include a thiol group.
[0074] Among preferred organoboranes of the organoborane-base
complexes are trimethylborane, triethylborane, tri-n-propylborane,
tri-isopropylborane, tri-n-butylborane, tri-isobutylborane, and
tri-sec-butylborane.
[0075] Useful basic complexing agents (Cx) include, for example,
amines, amidines, hydroxides, and/or alkoxides. Sufficient
complexing agent is provided to ensure stability of the
organoborane-base complex under ambient conditions. Insufficient
complexing agent could leave free organoborane, a material that
tends to be pyrophoric. In practice, to ensure stability of the
complex at ambient conditions, the compound that serves as the
complexing agent is often in excess, i.e., some of the compound is
free or not complexed in the composition. The amount of excess
basic complexing agent is chosen to ensure stability of the complex
under ambient conditions while still achieving desired performance
such as cure rate of the polymerizable composition and mechanical
properties of the cured composition. For example, there may be up
to 100 percent molar excess, or up to 50 percent molar excess, or
up to 30 percent molar excess of the basic complexing agent
relative to the organoborane. Often, there is 10 to 30 percent
molar excess of the basic complexing agent relative to the
organoborane.
[0076] Useful basic complexing agents include, for example, amine
compounds, amidine compounds, hydroxides, alkoxides, or
combinations thereof. The amine compounds have a primary amine
group and/or a secondary amine group. The amidine compounds have an
amidine group. The hydroxides and alkoxides are salts having
hydroxide and alkoxide groups, respectively, such as shown in
Formula VIII hereinbelow.
[0077] Amine complexing agents (Cx) may be provided by a wide
variety of materials having one or more primary or secondary amine
groups, including blends of different amines Amine complexing
agents may be a compound with a single amine group or may be a
polyamine (i.e., a material having multiple amine (i.e., amino)
groups such as two or more primary, secondary, or tertiary amine
groups). Suitable polyamines have at least one amine group that is
a primary and/or secondary amine group.
[0078] In one embodiment, the amine complexing agent may be a
primary or secondary monoamine represented by the following formula
(Formula III):
##STR00002##
wherein: R.sup.7 and R.sup.8 are independently selected from the
group consisting of hydrogen, and organic groups, preferably alkyl
groups having 1 to 10 carbon atoms, alkylcycloalkyl groups (i.e.,
an alkyl substituted with an cycloalkyl or a cycloalkyl substituted
with an alkyl), alkylaryl (i.e., an alkyl substituted with an aryl)
groups in which the amine group is not directly attached to the
aryl structure, and polyoxyalkylene groups. The organic groups may
include substituents, particularly hydroxyl or alkoxy substituents.
Alternatively, R.sup.7 and R.sup.8 together with the nitrogen atom
to which they are attached may be joined to form a 4 to 7-membered
heterocyclic ring. The heterocyclic ring can include additional
heteroatoms such as oxygen, sulfur, or nitrogen in addition to the
nitrogen atom joining R.sup.7 and R.sup.8. In some embodiments, the
complexing agent of Formula (III) is a primary amine (i.e., one but
not both of R.sup.7 or R.sup.8 is hydrogen). Particular examples of
amines of Formula (III) include ammonia, ethylamine, butylamine,
hexylamine, octylamine, benzylamine, piperidine, pyrrolidine,
3-methoxypropylamine, and polyoxyalkylene monoamines (e.g., as
marketed under the trade designation JEFFAMINE by Huntsman Corp.,
Salt Lake City, Utah). Specific examples include JEFFAMINE M715 and
JEFFAMINE M2005 polyoxyalkylene monoamines.
[0079] In another embodiment, the amine may be a polyamine such as
those represented by the following formula (Formula IV):
##STR00003##
wherein R.sup.7 and R.sup.8 are as defined above and R.sup.9 is a
divalent organic group, preferably a divalent alkylene,
cycloalkylene, alkylene-arylene-alkylene, or
alkylene-heterocyclic-alkylene group. An alkylene refers to a
divalent radical of an alkane and typically has 1 to 10 carbon
atoms. An arylene refers to a divalent radical of an aromatic group
and often has 6 to 12 carbon atoms. Examples of arylene groups
include phenylene and diphenylene. The divalent organic group
R.sup.9 can optionally include a group of formula --NR.sup.a--, an
oxy group, a carbonyl group, or a combination thereof between two
alkylene groups. Group R.sup.a is typically hydrogen or an alkyl
group. Preferably, compounds of Formula (IV) have at least one
primary amine group. Examples of these polyamines are
dimethylaminopropylamine, and aminopropylmorpholine.
[0080] Still other suitable polyamines are alkanediamines, which
may be branched or linear, and having the following formula
(Formula V):
##STR00004##
wherein x is a whole number greater than or equal to 1, more
preferably 2 to 12, and each R.sup.10 is independently a hydrogen
or an alkyl group. Examples of alkanediamines include
1,2-ethanediamine, 1,3-propanediamine, 1,5-pentanediamine,
1,6-hexanediamine, 1,12-dodecanediamine,
2-methyl-1,5-pentanediamine, and 3-methyl-1,5-pentanediamine.
[0081] Still other amine complexing agents are various
alkanepolyamines having three or more amine groups such as, for
example, triethylenetetraamine or diethylenetriamine, or compounds
having a heterocyclic group such as, for example,
4-(dimethylamino)pyridine.
[0082] Other useful polyamines also include
polyoxyalkylenepolyamines. Suitable polyoxyalkylenepolyamines are
reported, for example, in U.S. Pat. No. 5,621,143 (Pocius).
Preferred polyoxyalkylenepolyamines may be represented by the
following formulae (Formula VI and Formula VII):
H.sub.2NR.sup.11O(R.sup.12O).sub.w(R.sup.13O).sub.u(R.sup.12O).sub.yR.su-
p.11NH.sub.2 (VI)
(i.e., polyoxyalkylenediamines); or
[H.sub.2NR.sup.11O(R.sup.12O).sub.w].sub.zR.sup.14 (VII)
wherein R.sup.11, R.sup.12, and R.sup.13 represent alkylene groups
(i.e., an alkylene is a divalent radical of an alkane) having 1 to
10 carbon atoms, which may be the same or may be different. In
certain embodiments, R.sup.11 is an alkylene group having 2 to 4
carbon atoms such as ethylene, n-propylene, isopropylene,
n-butylene or isobutylene. In certain embodiments, R.sup.12 and
R.sup.13 are alkylene groups having 2 or 3 carbon atoms such as
ethylene, n-propylene, or isopropylene. The R.sup.N group is a
z-valent organic group (e.g., a residue of a polyol used to prepare
the polyoxyalkylenepolyamine), preferably having from 1 to 18
carbon atoms. The R.sup.14 group may be branched or linear, and
substituted or unsubstituted (although substituents should
preferably not interfere with oxyalkylation reactions). The value
of w is typically greater than or equal to 1, or, in certain
embodiments, 1 to 50, or 1 to 20. The values of u and y are
typically both greater than or equal to 0. The value of z is
typically greater than or equal to 2, or, in certain embodiments, 3
or 4 (so as to provide, respectively, polyoxyalkylenetriamines and
polyoxyalkylenetetraamines). It is preferred that the values of w,
u, y, and z be chosen such that the resulting complex is a liquid
at room temperature, as this simplifies handling and mixing
thereof.
[0083] Usually, the polyoxyalkylenepolyamine is itself a liquid.
For the polyoxyalkylenepolyamine, molecular weights of less than
5000 grams/mole may be used, although molecular weights of 1000
grams/mole or less are more preferred, and molecular weights of 140
to 1000 grams/mole are most preferred. Examples of
polyoxyalkylenepolyamines include, but are not limited to,
poly(ethylene oxide)diamine, poly(propylene oxide)diamine,
poly(propylene oxide)triamine, diethylene glycol dipropylamine,
triethylene glycol dipropylamine, poly(tetramethylene
oxide)diamine, poly(ethylene oxide-co-propylene oxide)diamine, and
poly(ethylene oxide-co-propylene oxide)triamine Examples of
suitable commercially available polyoxyalkylenepolyamines include
those marketed under the trade designation JEFFAMINE by Huntsman
Corporation such as the D-, ED-, and EDR-series diamines (e.g.,
D-400, D-2000, D-5000, ED-600, ED-900, ED-2001, and EDR-148), and
the T-series triamines (e.g., T-403), as well as DCA-221 from Dixie
Chemical Co., Pasadena, Tex.
[0084] As reported in U.S. Pat. No. 5,616,796 (Pocius et al.), the
polyamine may also include the condensation reaction product of
diprimary-amine-terminated material (i.e., the two terminal groups
are primary amine groups) and one or more materials containing at
least two groups that are reactive with primary amines.
[0085] In certain embodiments, the amine may be an aziridine.
Aziridines are not preferred, however, because there may be
stability issues with such compounds.
[0086] Suitable hydroxide and/or alkoxide complexing agents (Cx)
are reported, for example, in U.S. Pat. No. 6,486,090 (Moren).
Preferred hydroxide and/or alkoxide complexing agents may be
represented by the formula (Formula VIII):
(R.sup.15O.sup.(-)).sub.nM.sup.(m+) (VIII)
wherein:
[0087] R.sup.15 is independently selected from hydrogen or an
organic group (e.g., alkyl group);
[0088] M.sup.(m+) represents a countercation with a charge m+
(e.g., sodium, potassium, tetraalkylammonium, or combinations
thereof);
[0089] n is an integer greater than zero such as 1 to 6 or 1 to 4
or 1 to 3; and
[0090] m is an integer greater than zero such as 1 to 6 or 1 to 4
or 1 to 3. Preferably, the variables n and m are equal.
[0091] "Amidines" are compounds having at least one N.dbd.C--N unit
in its structure. Exemplary amidine complexing agents (Cx) are
reported in U.S. Pat. No. 6,410,667 (Moren). Other amidine
complexing agents include, for example,
N,N,N',N'-tetramethylguanidine; 1,8-diazabicyclo[5.4.0]undec-7-ene;
1,5-diazabicyclo[4.3.0]non-5-ene; 2-methylimidazole; and
2-methylimidazoline.
[0092] The organoborane-base complex may be readily prepared using
known techniques, as described, for example, in U.S. Pat. No.
5,616,796 (Pocius et al.), U.S. Pat. No. 5,621,143 (Pocius), U.S.
Pat. No. 6,252,023 (Moren), U.S. Pat. No. 6,410,667 (Moren), and
U.S. Pat. No. 6,486,090 (Moren).
[0093] Organoborane-amine complexes are available from suppliers
such as BASF and AkzoNobel. TEB-DAP
(triethylborane-1,3-diaminopropane (or 1,3-propanediamine)
complex), TnBB-MOPA (tri-n-butylborane-3-methoxypropylamine)
complex, TEB-DETA (triethylborane-diethylenetriamine) complex,
TnBB-DAP (tri-n-butylborane-1,3-diaminopropane complex), and
TsBB-DAP (tri-sec-butylborane-1,3-diaminopropane) are all available
from BASF (Ludwigshafen, Germany). TEB-HMDA
(triethylborane-hexamethylene diamine (or 1,6-hexanediamine or
1,6-diaminohexane) complex) is available from AkzoNobel (Amsterdam,
The Netherlands).
[0094] The organoborane-base complex is generally employed in an
effective amount, which is an amount large enough to permit
reaction (i.e., curing by polymerizing and/or crosslinking) to
readily occur to obtain a polymer of sufficiently high molecular
weight for the desired end use. If the amount of organoborane
produced is too low, then the reaction may be incomplete. On the
other hand, if the amount is too high, then the reaction may
proceed too rapidly to allow for effective mixing and use of the
resulting composition. Useful rates of reaction will typically
depend at least in part on the method of applying the composition
to a substrate. Thus, a faster rate of reaction may be accommodated
by using a high speed automated industrial applicator rather than
by applying the composition with a hand applicator or by manually
mixing the composition.
[0095] Within these parameters, an effective amount of the
organoborane-base complex is an amount that preferably provides at
least 0.003 percent by weight of boron, or at least 0.008 percent
by weight of boron, or at least 0.01 percent by weight of boron. An
effective amount of the organoborane-base complex is an amount that
preferably provides up to 1.5 percent by weight of boron, or up to
0.5 percent by weight of boron, or up to 0.3 percent by weight of
boron. The percent by weight of boron in a composition is based on
the total weight of the polymerizable material.
[0096] Alternatively stated, an effective amount of the
organoborane-base complex is at least 0.1 percent by weight, or at
least 0.5 percent by weight. An effective amount of the
organoborane-base complex is up to 10 percent by weight, or up to 5
percent by weight, or up to 3 percent by weight. The percent by
weight of boron in a composition is based on the total weight of
the polymerizable material.
Decomplexing Agents
[0097] As used herein, the term "decomplexing agent" refers to a
compound capable of at least partially liberating (i.e., liberating
at least some organoborane from its complexing agent) the
organoborane from its complexing agent, thereby enabling initiation
of the reaction (curing by polymerizing and/or crosslinking) of the
polymerizable material of the composition. Decomplexing agents may
also be referred to as "activators" or "liberators" and these terms
may be used synonymously herein. The choice of decomplexing agent
typically depends on the specific organoborane-base complex
used.
[0098] Compounds that react quickly with the base or the
organoborane-base complex under mild temperatures are particularly
effective decomplexing agents. These may include mineral acids,
Lewis acids, carboxylic acids, acid anhydrides, acid chlorides,
sulfonyl chlorides, phosphonic acids, isocyanates, aldehydes,
1,3-dicarbonyl compounds, acrylates, and epoxies.
[0099] In certain embodiments, the decomplexing agent may be
attached to solid particles such as silica, titanium dioxide,
alumina, calcium carbonate, and carbon black.
[0100] In certain embodiments, if the organoborane is complexed
with an amine, a suitable decomplexing agent is an amine-reactive
compound. The amine-reactive compound liberates organoborane by
reacting with the amine, thereby removing the organoborane from
chemical attachment with the amine. A wide variety of materials may
be used to provide the amine-reactive compound including
combinations of different materials. Desirable amine-reactive
compounds are those materials that can readily form reaction
products with amines at or below room temperature so as to provide
a composition such as an adhesive that can be easily used and cured
under ambient conditions.
[0101] General classes of useful amine-reactive compounds include
mineral acids (e.g., hydrochloric acid, sulfuric acid, phosphoric
acid, and silicic acid), Lewis acids (e.g., SnCl.sub.4 or
TiCl.sub.4), carboxylic acids, acid anhydrides (i.e., organic
compounds that have two acyl groups bound to the same oxygen atom),
acid chlorides, sulfonyl chlorides, phosphonic acids, phosphinic
acids, isocyanates, aldehydes, 1,3-dicarbonyl compounds, acrylates,
and epoxies. Compounds that react quickly with amines at mild
temperatures, such as acids, acid anhydrides, acid chlorides,
sulfonyl chlorides, and isocyanates, are particularly effective
decomplexing agents. Since the thiol group is also reactive with
some of these compounds, care should be taken in the separation of
reactive components into different parts of the 2-part
compositions.
[0102] Since the concentration of thiol groups is often greater
than the concentration of primary or secondary amines in the basic
complexing agent, proper selection of the decomplexing agent is
desired for proper cure of the composition. In addition, strong
acids, such as many mineral acids, may degrade the components of
the polymerizable composition before or after reaction, and also
can degrade or corrode substrates that the composition may contact.
Many Lewis acids are quite reactive with thiol groups, and generate
strong acids upon reaction with thiols or water (moisture) that can
lead to degradation or corrosion. Owing to these facts, carboxylic
acids, acid anhydrides, aldehydes, isocyanates, phosphonic acids,
and 1,3-dicarbonyl compounds, such as barbituric acid, dimedone,
and their derivatives, are the more versatile and preferred
decomplexing agents.
[0103] Useful carboxylic acids include those having the general
formula R.sup.19--CO.sub.2H, wherein R.sup.19 represents hydrogen
or a monovalent organic group. Preferably R.sup.19 is an aliphatic
group having 1 to 20 (preferably 1 to 8) carbon atoms, or an aryl
group having 6 to 10 (preferably 6 to 8) carbon atoms. The
aliphatic groups may comprise a straight chain or they may be
branched, and may be saturated or unsaturated. The aryl groups may
contain substituents such as alkyl, alkoxy, or halogen groups.
Suitable acids of this type include acrylic acid, methacrylic acid,
acetic acid, nonanoic acid, benzoic acid, and p-methoxybenzoic
acid.
[0104] Useful carboxylic acids also include those having the
general formula R.sup.20--CO.sub.2H, wherein R.sup.20 may be a
straight or branched chain, saturated or unsaturated aliphatic
group of from 9 to 36 carbon atoms, preferably from 11 to 24 carbon
atoms, and more preferably from 15 to 24 carbon atoms.
[0105] Yet other carboxylic acids useful as the amine-reactive
compound include dicarboxylic acids and carboxylic acid esters.
Such compounds may be represented by the following formula (Formula
IX):
##STR00005##
wherein:
[0106] R.sup.21 is hydrogen, a monovalent organic group (typically
having 18 atoms or less, or 8 atoms or less), or a multivalent
organic group (typically having 30 atoms or less, or 10 atoms or
less);
[0107] R.sup.22 is a multivalent (i.e., (q+2)-valent) organic group
(typically having 8 atoms or less, or 4 atoms or less);
[0108] R.sup.23 is hydrogen or a monovalent organic group
(typically having 18 atoms or less, or 8 atoms or less); and
[0109] q is 0, 1, or 2, and the value of p is greater than or equal
to one, preferably 1 to 4, more preferably 1 or 2.
[0110] In some embodiments, the carboxylic acids can be represented
by the formula (Formula X):
##STR00006##
wherein:
[0111] R.sup.21 is as defined above and r is greater than or equal
to one, preferably 1 to 4, more preferably 1 or 2; and
[0112] R.sup.24 is a single bond or a divalent organic group
(preferably having from 1 to 40 carbon atoms, more preferably from
1 to 10 carbon atoms or 1 to 6 carbon atoms). The organic group is
often an alkylene or alkene-diyl (divalent radical of an alkene) or
an arylene.
[0113] When R.sup.21 is hydrogen and r is one, the resulting
compounds of Formula (X) are dicarboxylic acids. In some
embodiments, R.sup.21 is an alkyl and r is equal to 1. In other
embodiments, R.sup.21 is an alkylene and r is equal to 2. Useful
dicarboxylic acids include oxalic acid, malonic acid, succinic
acid, glutaric acid, adipic acid, maleic acid, fumaric acid,
phthalic acid, isophthalic acid, terephthalic acid, and dimer
acid.
[0114] Other useful monofunctional or polyfunctional carboxylic
acids are those that contain thioester groups or amide groups, and
those that are reactive via thiol-ene chemistry, such as
thioglycolic acid, 3-mercaptopropanoic acid, and the previously
mentioned (meth)acrylic acid.
[0115] Polydiorganosiloxanes that contain carboxylic acid groups
are also useful, such as Shin-Etsu Chemical Co. Ltd. X-22-3710 that
has a carboxylic acid group at one of the terminal ends of the
silicone chain, and X-22-162C that has a carboxylic acid group at
each of the two termini, when the polyfunctional thiol and
ethylenically-unsaturated compounds are polydiorganosiloxanes.
[0116] Compounds that easily generate carboxylic acids upon
reaction with water or moisture, i.e., are easily hydrolyzed by
water to form carboxylic acids, such as vinyltriacetoxysilane and
(meth)acryloxypropyltriacetoxysilane are also useful.
[0117] Also preferred as amine-reactive compounds that can serve as
decomplexing agents are materials having at least one anhydride
group, such materials preferably represented by one of the
following formulae (Formula XI and Formula XII):
##STR00007##
[0118] R.sup.25 and R.sup.26 are organic groups which independently
may be aliphatic, cycloaliphatic, or aromatic. Preferred aliphatic
and cycloaliphatic groups include 1 to 17 carbon atoms, more
preferably 2 to 9 carbon atoms. The aliphatic and cycloaliphatic
groups can be saturated or unsaturated. Preferred aromatic groups
include phenyl, optionally substituted with 1 to 4 carbon atom
aliphatic groups.
[0119] R.sup.27 is a divalent organic group that completes a cyclic
structure with the anhydride group to form, for example, a 5- or
6-membered ring. R.sup.27 may be aliphatic, cycloaliphatic,
aromatic, or a combination. The aliphatic and cycloaliphatic groups
can be saturated or unsaturated. Preferably, R.sup.27 is an
aliphatic group having 2 to 20, more preferably 2 to 12 carbon
atoms. The R.sup.27 group may also contain heteroatoms such as
oxygen or nitrogen provided that any heteroatom is not adjacent to
the anhydride functionality. The R.sup.27 group may also be part of
a cycloaliphatic or aromatic fused ring structure, either of which
may be optionally substituted with aliphatic groups. R.sup.27 may
be substituted with one or more carboxylic acid groups, any two of
which, when on adjacent carbons (i.e., covalently bonded carbons)
can be cyclized to form another anhydride group.
[0120] Suitable anhydrides of Formula (XI) are propionic anhydride,
methacrylic anhydride, hexanoic anhydride, decanoic anhydride,
lauric anhydride, and benzoic anhydride. Suitable anhydrides of
Formula (XII) are maleic anhydride, succinic anhydride,
methylsuccinic anhydride, 2-octen-1-ylsuccinic anhydride,
2-dodecen-1-ylsuccinic anhydride, dodecenylsuccinic anhydride
(mixture of isomers), cyclohexanedicarboxylic anhydride,
cis-5-norbornene-endo-2,3-dicarboxylic anhydride,
methyl-5-norbornene-2,3-dicarboxylic anhydride, phthalic anhydride,
trimellitic anhydride, and pyromellitic anhydride. The presence of
an ethylenically-unsaturated group in the anhydride-functional
amine reactive compound, such as would be the case for maleic
anhydride, may permit the same to react with the other
thiol-containing or ethylenically-unsaturated components.
[0121] Other useful amine-reactive compounds having at least one
anhydride group are copolymers of maleic anhydride, such as the
copolymers of maleic anhydride and styrene, the copolymers of
maleic anhydride and ethylene or .alpha.-olefins, and the
copolymers of maleic anhydride and (meth)acrylates. Also, polymeric
materials in which maleic anhydride has been grafted onto the
polymer to form, for example, succinic anhydride-functional
polymers are suitable. Polydiorganosiloxanes that contain
anhydrides are also useful, such as Gelest, Inc. succinic
anhydride-terminated polydimethylsiloxane, DMS-Z21, when the
polyfunctional thiol and ethylenically-unsaturated compounds are
polydiorganosiloxanes.
[0122] Suitable aldehydes useful as the amine-reactive compounds
that serve as decomplexing agents may include those represented by
the formula (Formula XIII):
##STR00008##
wherein R.sup.28 is a monovalent organic group such as, for
example, an alkyl group having 1 to 10 carbon atoms (in some
embodiments, 1 to 4 carbon atoms), or an aryl group having 6 to 10
carbon atoms (in some embodiments, 6 to 8 carbon atoms). In this
formula, the alkyl groups may be straight or branch-chained, and
may contain substituents such as halogen, hydroxy, and alkoxy. The
aryl groups may contain substituents such as halogen, hydroxy,
alkoxy, alkyl, and nitro. One preferred R.sup.28 group is aryl.
Exemplary compounds of this type include: benzaldehyde; o-, m- and
p-nitrobenzaldehyde; 2,4-dichlorobenzaldehyde; p-tolylaldehyde; and
3-methoxy-4-hydroxybenzaldehyde. Blocked aldehydes such as acetals
and dialdehydes, may also be used.
[0123] Other suitable decomplexing agents may include
1,3-dicarbonyl compounds (e.g., beta-ketones), for example, as
described in U.S. Pat. No. 6,849,569 (Moren). Exemplary
1,3-dicarbonyl compound decomplexing agents include methyl
acetoacetate, ethyl acetoacetate, t-butyl acetoacetate,
2-methacryloyloxyethyl acetoacetate, diethylene glycol
bis(acetoacetate), polycaprolactone tris(acetoacetate),
polypropylene glycol bis(acetoacetate), poly(styrene-co-allyl
acetoacetate), N,N-dimethylacetoacetamide, N-methylacetoacetamide,
acetoacetanilide, ethylene bis(acetoacetamide), polypropylene
glycol bis(acetoacetamide), acetoacetamide, and acetoacetonitrile.
Preferable 1,3-dicarbonyl compounds are dimedone, barbituric acid
and their derivatives (e.g., 1,3-dimethyl barbituric acid,
1-phenyl-5-benzyl barbituric acid, and 1-ethyl-5-cyclohexyl
barbituric acid).
[0124] Examples of suitable isocyanate decomplexing agents include,
but are not limited to, polyfunctional isocyanates, such as
isophorone diisocyanate, hexamethylene diisocyanate, methylene
diphenyl diisocyanate, toluene diisocyanate, and their prepolymers.
Additionally, 2-isocyanatoethyl methacrylate alone or its
copolymers with, e.g., other (meth)acrylates are suitable
decomplexing agents.
[0125] Examples of suitable phosphonic acid decomplexing agents
include vinylphosphonic acid, phenylphosphonic acid,
methylphosphonic acid, and octadecylphosphonic acid.
[0126] Preferred compounds capable of decomplexing the
organoborane-amine complex include, for example, a carboxylic acid,
an acid anhydride, an aldehyde, an isocyanate, a phosphonic acid,
or a 1,3-dicarbonyl.
[0127] In the cases when the organoborane is complexed to an
amidine, alkoxide, or hydroxide, suitable decomplexing agents are
the same as described above for amine complexing agents. When the
organoborane is complexed to an alkoxide, hydroxide, or amidine,
which is protic, i.e., at least one of the nitrogen atoms are
substituted with hydrogen, the preferred decomplexing agents
include, for example, a carboxylic acid, an acid anhydride, an
isocyanate, a phosphonic acid, or a 1,3-dicarbonyl. When the
organoborane is complexed to an amidine, which is aprotic (i.e.,
none of the nitrogen atoms are substituted with hydrogen), the
preferred decomplexing agents include, for example, a carboxylic
acid, an acid anhydride, a phosphonic acid, or a
1,3-dicarbonyl.
[0128] The decomplexing agent is typically used in an effective
amount (i.e., an amount effective to promote reaction (i.e., curing
by polymerizing and/or crosslinking) by liberating the initiator
from its complexing agent, but without materially adversely
affecting desired properties of the ultimate composition). As
recognizable to one of ordinary skill in the art, too much of the
decomplexing agent may cause reaction to proceed too quickly.
However, if too little decomplexing agent is used, the rate of
reaction may be too slow and the resulting polymers may not be of
adequate molecular weight for certain applications. A reduced
amount of decomplexing agent may be helpful in slowing the rate of
reaction if it is otherwise too fast. Thus, within these
parameters, the decomplexing agent is typically provided in an
amount such that the molar ratio of amine-, amidine-, hydroxide-,
or alkoxide-reactive groups in the decomplexing agent(s) to amine,
amidine, hydroxide or alkoxide groups in the complexing agent(s) is
in the range of 0.5:1.0 to 10.0:1.0. For better performance,
preferably the ratio of amine-, amidine-, hydroxide-, or
alkoxide-reactive groups in the decomplexing agent(s) to amine,
amidine, hydroxide, or alkoxide groups in the complexing agent(s)
is in the range of 0.5:1.0 to 4.0:1.0, preferably 1.0:1.0.
Hydroperoxide
[0129] Polymerizable compositions according to the present
disclosure include at least one hydroperoxide. In multi-part
compositions, the hydroperoxide can be in Part A, Part B, or in any
other part. In some embodiments, the hydroperoxide is not in the
same part as the organoborane-base complex. Examples of suitable
hydroperoxides include hydrogen peroxide and organic hydroperoxides
(e.g., hydrocarbyl hydroperoxides).
[0130] While organic peroxides generally may be useful additives
for decreasing the cure time in applications that require
relatively thick coating (e.g., coating thickness greater than 0.25
mm, or greater than 0.50 mm, or greater than 1.00 mm),
hydroperoxides (e.g., organic hydroperoxides) unexpectedly are much
more effective at increasing the rate of cure than other peroxides
such as, for example, dialkyl peroxides. Combinations of more than
one hydroperoxide (e.g., hydrogen peroxide and/or organic
hydroperoxide(s)) may also be used.
[0131] In some preferred embodiments, the hydroperoxide is a
tertiary hydroperoxide, i.e., an organic hydroperoxide where the
hydroperoxy group (--OOH) is bound to a tertiary carbon atom. In
some embodiments the organic hydroperoxide comprises a
tertiary-hydrocarbyl (including cyclic, branched, and/or linear
alkyl groups, and/or aryl groups) hydroperoxide, preferably having
from 4 to 15 carbon atoms.
[0132] Exemplary organic hydroperoxides include tertiary
hydroperoxides (e.g., isopropylcumyl hydroperoxide, cumyl
hydroperoxide, tert-butyl hydroperoxide, tert-amyl hydroperoxide,
and 1,1,3,3-tetramethylbutyl hydroperoxide), available from Akzo
Nobel NV, Amsterdam, The Netherlands, under the trade designation
TRIGONOX. Additional hydroperoxides include
trans-5-phenyl-4-pentenyl hydroperoxide, alkane hydroperoxides
(e.g., propane hydroperoxide, n-octane hydroperoxide, isohexane
hydroperoxide, isopentane hydroperoxide, cyclohexane hydroperoxide,
cyclopentane hydroperoxide, methylcyclohexane hydroperoxide,
decalin hydroperoxide, and tetralin hydroperoxide), toluene
hydroperoxide, diphenylmethyl hydroperoxide, triphenylmethyl
hydroperoxide, trinaphthylmethyl hydroperoxide, cymene
hydroperoxide, and phenylethyl hydroperoxide.
[0133] Typically, the hydroperoxide is included in compositions
according to the present disclosure in at least an effective amount
(i.e., to provide sufficient degree of cure in a timeframe suitable
for the intended application), although other amounts may also be
used. For example, in a 2-part system, the amount of hydroperoxide
may be higher in one part, so that when mixed, the diluted
concentration is as desired. In some embodiments, the molar ratio
of hydroperoxy groups (--OOH) provided by the hydroperoxide to
boron atoms provided by the organoborane is from about 0.2 to 1.0,
and in some embodiments from 0.4 to 0.8.
Polymerizable Ethylenically-Unsaturated Compounds
[0134] Suitable polymerizable ethylenically-unsaturated compounds
are those compounds (e.g., monomer, oligomer, polymerizable
polymer) that include a plurality of ethylenically-unsaturated
groups. Such compounds are often referred to as
"polyfunctional".
[0135] Many types of ethylenically-unsaturated groups are feasible
including internal and terminal ethylenically-unsaturated groups.
However, the unsaturation associated with aromaticity, e.g., in a
benzene ring is not suitable. Alkenyl and alkynyl groups are
useful. The groups can be unconjugated or conjugated with other
carbon-carbon, carbon-oxygen, or carbon-nitrogen unsaturation, such
as in the case of 1,3-dienes, fumarate esters, and maleate
esters.
[0136] In general, terminal ethylenically-unsaturated groups, such
as vinyl, allyl, and ethynyl groups, are more reactive and, thus,
preferred when relatively fast cure rates are desired under ambient
conditions (the exception being norbornenes, which are highly
reactive, and maleimides, which are moderately reactive, thus, also
preferred). Preferred ethylenically-unsaturated compounds include
vinyls, allyls, ethynyls, norbornenyls, and maleimides. Vinyls
include, but are not limited to, vinyl ethers, vinyl silicones
(i.e., polydiorganosiloxanes with vinyl groups covalently bonded to
silicon), N-vinyl amides, vinyl aliphatics (e.g., 1,9-decadiene),
vinyl aromatics (e.g., divinylbenzene), vinyl esters,
(meth)acrylates, and (meth)acrylamides. Allyls include, but are not
limited to, allyl ethers, allyl esters, allyl carbamates, allyl
amines, allyl amides (which include allyl imides, allyl
isocyanurates, and allyl ureas), allyl cyanurates, and
allyltriazines.
[0137] Exemplified polyfunctional ethylenically-unsaturated
compounds include vinyl ethers, vinyl silicones, vinyl aliphatics,
(meth)acrylates, allyl ethers, allyl esters, and allyl amides
(allyl isocyanurate).
[0138] Suitable polyfunctional allyl ethers include
trimethylolpropane diallyl ether, pentaerythritol tetraallyl ether
(also referred to as allyl pentaerythritol), dipentaerythritol
hexaallyl ether, trimethylolpropane triallyl ether, ethylene glycol
diallyl ether, and diethylene glycol diallyl ether.
[0139] Suitable polyfunctional allyl amides (i.e., N-allyl amides)
include N,N'-diallyltartramide, 1,3-diallyl urea, and triallyl
isocyanurate, as well as N,N'-diallylamides synthesized from
allylamine and dicarboxylic acids or their acid chlorides, and
N,N-diallylamides synthesized from diallylamine and carboxylic
acids or their acid chlorides. Preferred polyfunctional allyl amide
is triallyl isocyanurate.
[0140] Suitable ethylenically-unsaturated compounds include
polyfunctional (meth)acrylate monomers. As used herein the terms
"(meth)acrylate" and "(meth)acrylic" and the plural forms thereof
are meant to include acrylate and/or methacrylate species of the
designated compound. For example, the term "ethyl (meth)acrylate"
is meant to include ethyl acrylate and/or ethyl methacrylate.
Suitable (meth)acrylic acid derivatives are, for example, the
(meth)acrylic esters of polyhydric alcohols.
[0141] Suitable di(meth)acrylates include 1,3-butylene glycol
di(meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,6-hexanediol
di(meth)acrylate, 1,6-hexanediol mono acrylate monomethacrylate,
ethylene glycol di(meth)acrylate, alkoxylated aliphatic
di(meth)acrylate, alkoxylated cyclohexanedimethanol
di(meth)acrylate, alkoxylated hexanediol di(meth)acrylate,
alkoxylated neopentyl glycol di(meth)acrylate, caprolactone
modified neopentyl glycol hydroxypivalate di(meth)acrylate,
cyclohexanedimethanol di(meth)acrylate, diethylene glycol
di(meth)acrylate, dipropylene glycol di(meth)acrylate, ethoxylated
(10) bisphenol A di(meth)acrylate, ethoxylated (3) bisphenol A
di(meth)acrylate, ethoxylated (30) bisphenol A di(meth)acrylate,
ethoxylated (4) bisphenol A di(meth)acrylate, ethoxylated (4)
bisphenol A di(meth)acrylate, hydroxypivalaldehyde modified
trimethylolpropane di(meth)acrylate, neopentyl glycol
di(meth)acrylate, polyethylene glycol (200) di(meth)acrylate,
polyethylene glycol (400) di(meth)acrylate, polyethylene glycol
(600) di(meth)acrylate, propoxylated neopentyl glycol
di(meth)acrylate, tetraethylene glycol di(meth)acrylate,
tricyclodecanedimethanol di(meth)acrylate, triethylene glycol
di(meth)acrylate, and tripropylene glycol di(meth)acrylate.
[0142] Suitable tri(meth)acrylates include glycerol
tri(meth)acrylate, trimethylolpropane tri(meth)acrylate,
ethoxylated tri(meth)acrylates (for example, ethoxylated (3)
trimethylolpropane tri(meth)acrylate, ethoxylated (6)
trimethylolpropane tri(meth)acrylate, ethoxylated (9)
trimethylolpropane tri(meth)acrylate, ethoxylated (15)
trimethylolpropane tri(meth)acrylate, ethoxylated (20)
trimethylolpropane tri(meth)acrylate), pentaerythritol
tri(meth)acrylate, propoxylated tri(meth)acrylates (for example,
propoxylated (3) glyceryl tri(meth)acrylate, propoxylated (5.5)
glyceryl tri(meth)acrylate, propoxylated (3) trimethylolpropane
tri(meth)acrylate, propoxylated (6) trimethylolpropane
tri(meth)acrylate), trimethylolpropane tri(meth)acrylate, and
tris(2-hydroxyethyl)isocyanurate tri(meth)acrylate, which is also
referred to as tris(2-(meth)acryloyloxyethyl)isocyanurate.
[0143] Suitable higher functionality (meth)acrylic compounds
include ditrimethylolpropane tetra(meth)acrylate, dipentaerythritol
penta(meth)acrylate, ethoxylated (4) pentaerythritol
tetra(meth)acrylate, pentaerythritol tetra(meth)acrylate, and
caprolactone modified dipentaerythritol hexa(meth)acrylate.
[0144] Suitable oligomeric polymerizable (meth)acrylic compounds
include urethane (meth)acrylates, polyester (meth)acrylates,
polybutadiene (including hydrogenated polybutadiene)
(meth)acrylates, and epoxy (meth)acrylates.
[0145] Suitable (meth)acrylates include (meth)acrylic acid esters
of polyhydric alcohols, such as, for example, ethylene glycol,
diethylene glycol, polyethylene glycol, trimethylolpropane,
triethylene glycol, tetraethylene glycol, dipropylene glycol,
tripropylene glycol, tetrapropylene glycol, pentapropylene glycol
and polypropylene glycol; ethoxylated or propoxylated
diphenylolpropane and hydroxy-terminated polyurethanes.
[0146] Suitable ethylenically-unsaturated compounds include
polyfunctional (meth)acrylamide monomers. As used herein the terms
"(meth)acrylamide" and the plural form thereof are meant to include
acrylamide and/or methacrylamide species of the designated
compound.
[0147] Suitable polyfunctional (meth)acrylamides include
1,4-bis((meth)acryoyl)piperazine, bis-(meth)acrylamide (also
referred to as N,N'-methylenedi(meth)acrylamide),
N,N'-(1,2-dihydroxyethylene)bis(meth)acrylamide, as well as
polyfunctional (meth)acrylamides that can be formed from reaction
of (meth)acrylic acid or its acid chloride with primary and/or
secondary amines, such as 1,3-diaminopropane,
N,N'-dimethyl-1,3-diaminopropane, 1,4-diaminobutane,
polyamidoamines, and polyoxyalkylenepolyamines.
[0148] Suitable polyfunctional vinyl ethers include
1,4-cyclohexanedimethanol divinyl ether, diethylene glycol divinyl
ether, triethylene glycol divinyl ether, poly(ethylene glycol)
divinyl ether, and butanediol divinyl ether.
[0149] Suitable polyfunctional vinyl polydiorganosiloxanes (also
referred to as vinyl silicones) include vinyl-terminated
polydimethylsiloxanes, such as Gelest, Inc. DMS-V21, DMS-V22,
DMS-V31, DMS-V35, and DMS-V42; and vinyl-terminated
diphenylsiloxane-dimethylsiloxane copolymers, such as Gelest, Inc.
PDV-0325, PDV-0331, PDV-0525, PDV-1625, PDV-1631, and PDV-1635; and
polydimethylsiloxanes containing vinyl groups bonded to silicon
atoms internal along the polymer chain and not at its termini, and
referred to as vinylmethylsiloxane-dimethylsiloxane copolymers,
trimethylsiloxy terminated, such as Gelest, Inc. VDT-131, VDT-153,
VDT-431, VDT-731, and VDT-954; and polydimethylsiloxanes that
contain vinyl groups both internally and at the termini, and
referred to as vinylmethylsiloxane-dimethylsiloxane copolymers,
vinyl terminated, such as Gelest Inc. VDV-0131.
[0150] Suitable polyfunctional vinyl aliphatics include
1,9-decadiene, and 1,2,4-trivinylcyclohexane, and polybutadiene,
wherein some of the 1,3-butadiene has been incorporated by
1,2-addition.
[0151] Suitable polyfunctional allyl esters include diallyl
succinate, diallyl adipate, diallyl isophthalate, diallyl
phthalate, and triallyl trimellitate.
[0152] Suitable norbornenes include 2,5-norbornadiene,
5-vinyl-2-norbornene, 5-ethylidene-2-norbornene,
5-methylene-2-norbornene, dicyclopentadiene, terpolymers of
ethylene, propylene, and a diene monomer, in which the diene
monomer is 2,5-norbornadiene, 5-vinyl-2-norbornene,
5-ethylidene-2-norbornene, 5-methylene-2-norbornene, or
dicyclopentadiene, and (bicycloheptenyl)ethyl-terminated
polydimethylsiloxanes, such as Gelest, Inc. DMS-NB25 and
DMS-NB32.
[0153] Suitable polyfunctional maleimides include bismaleimides,
which are synthesized by the reaction of maleic anhydride and
aliphatic or aromatic primary amines, such as 1,4-diaminobutane,
1,6-diaminohexane, 4,4'-methylenedianiline, 4,4'-oxydianiline,
phenylenediamines, and polyamidoamines.
[0154] Various combinations of the polymerizable
ethylenically-unsaturated compounds may be used. Preferred
combinations include miscible mixtures. It is noted that vinyl
silicones and (bicycloheptenyl)ethyl-terminated
polydimethylsiloxanes, however, may not be miscible with others
listed herein. Further, when the ethylenically-unsaturated compound
is a polydiorganosiloxane, typically the thiol-containing compound
is also a polydiorganosiloxane.
Thiol-Containing Compounds
[0155] Suitable polymerizable thiol-containing compounds are those
compounds (e.g., monomer, oligomer, polymerizable polymer (i.e.,
prepolymer) that include a plurality of thiol groups (--SH groups
also referred to as mercapto groups) in which the sulfur atom of
the thiol group is covalently bonded to carbon (i.e., through C--S
bonds). Such compounds are often referred to as "polyfunctional"
thiols or polythiols.
[0156] Examples of suitable polythiols include aliphatic monomeric
polythiols (ethane dithiol, hexamethylene dithiol, decamethylene
dithiol, tolylene-2,4-dithiol, and the like), aromatic monomeric
polythiols (benzene-1,2-dithiol, benzene-1,3-dithiol,
benzene-1,4-dithiol, and the like), and some polymeric polythiols
such as a thiol-terminated ethylcyclohexyl dimercaptan polymer, and
the like.
[0157] Other useful polythiols are described in U.S. Pat. No.
6,605,687 (Gross et al.), and include dimercaptodiethyl sulfide,
1,6-hexanedithiol, 1,8-dimercapto-3,6-dithiaoctane,
propane-1,2,3-trithiol,
1,2-bis[(2-mercaptoethyl)thio]-3-mercaptopropane,
tetrakis(7-mercapto-2,5-dithiaheptyl)methane, and trithiocyanuric
acid.
[0158] Preferred polythiols useful in the present disclosure
include polythiols formed from the esterification of polyols with
thiol-containing carboxylic acids or their derivatives. Examples of
polythiols formed from the esterification of polyols with
thiol-containing carboxylic acids or their derivatives include
those made from the esterification reaction between thioglycolic
acid or 3-mercaptopropionic acid and several polyols to form the
mercaptoacetates or mercaptopropionates, respectively.
[0159] Examples of the polythiol compounds preferred because of
relatively low odor level include, but are not limited to, esters
of thioglycolic acid (HS--CH.sub.2COOH), .alpha.-mercaptopropionic
acid (HS--CH(CH.sub.3)--COOH) and .beta.-mercaptopropionic acid,
also referred to as 3-mercaptopropionic acid
(HS--CH.sub.2CH.sub.2COOH) with polyhydroxy compounds (polyols)
such as diols (e.g., glycols), triols, tetraols, pentaols, hexaols,
and the like. Specific examples of such polythiols include, but are
not limited to, ethylene glycol bis(thioglycolate), ethylene glycol
bis(.beta.-mercaptopropionate), trimethylolpropane
tris(thioglycolate), trimethylolpropane
tris(.beta.-mercaptopropionate) and ethoxylated versions,
pentaerythritol tetrakis(thioglycolate), pentaerythritol
tetrakis(.beta.-mercaptopropionate), and
tris(hydroxyethyl)isocyanurate tris(.beta.-mercaptopropionate).
[0160] Suitable materials are commercially available under the
trade designations THIOCURE PETMP (pentaerythritol
tetra-3-mercaptopropionate), TMPMP (trimethylolpropane
tri(3-mercaptopropionate), ETTMP (ethoxylated-trimethylolpropane
tri-3-mercaptopropionate) such as ETTMP 1300 and ETTMP 700, GDMP
glycol di(3-mercaptopropionate), TMPMA (trimethylolpropane
trimercaptoacetate), TEMPIC
(tris[2-(3-mercaptopropionyloxy)ethyl]), and PPGMP (propylene
glycol 3-mercaptopropionate) from Bruno Bock Chemische Fabrik GmbH
& Co. KG. A specific example of a polymeric polythiol is
polypropylene-ether glycol bis(.beta.-mercaptopropionate), which is
prepared from polypropylene-ether glycol (e.g., PLURACOL P201,
Wyandotte Chemical Corp.) and .beta.-mercaptopropionic acid by
esterification.
[0161] Other useful polythiols can be formed from the addition of
hydrogen sulfide (H.sub.2S) (or its equivalent) across
carbon-carbon double bonds. For example, dipentene and
triglycerides which have been reacted with H.sub.2S (or its
equivalent). Specific examples include dipentene dimercaptan and
those polythiols available under the trade designations
POLYMERCAPTAN 358 (mercaptanized soybean oil), and POLYMERCAPTAN
805C (mercaptanized castor oil) from Chevron Phillips Chemical Co.
LLP. At least for some applications, the preferred polythiols are
POLYMERCAPTAN 358 and 805C since they are produced from largely
renewable materials, i.e., the triglycerides, soybean oil and
castor oil, and have relatively low odor in comparison to many
thiols. Useful triglycerides have at least 2 sites of unsaturation,
i.e., carbon-carbon double bonds, per molecule on average, and
sufficient sites are converted to result in at least 2 thiols per
molecule on average. In the case of soybean oil, this requires a
conversion of approximately 42 percent or greater of the
carbon-carbon double bonds, and in the case of castor oil this
requires a conversion of approximately 66 percent or greater of the
carbon-carbon double bonds. Typically, higher conversion is
preferred, and POLYMERCAPTAN 358 and 805C can be obtained with
conversions greater than approximately 60 percent and 95 percent,
respectively.
[0162] Other useful polythiols can be formed from the ring-opening
reaction of epoxides with H.sub.2S (or its equivalent). Preferred
polythiols of this type include those available under the trade
designations POLYMERCAPTAN 407 (mercaptohydroxy soybean oil) from
Chevron Phillips Chemical Co. LLP, and CAPCURE, specifically
CAPCURE 3-800 (a polyoxyalkylene triol with mercapto end groups of
the structure
R[O(C.sub.3H.sub.6O).sub.n--CH.sub.2--CH(OH)--CH.sub.2SH].sub.3
wherein R represents an aliphatic hydrocarbon group having 1-12
carbon atoms and n is an integer from 1 to 25), formerly from BASF,
Inc. (and now Gabriel Performance Products, Ashtabula, Ohio), and
GPM-800, which is equivalent to CAPCURE 3-800, and from Gabriel
Performance Products.
[0163] Other useful polythiols of this type include those derived
from the reaction of H.sub.2S (or its equivalent) with the glycidyl
ethers of bisphenol A epoxy resins, bisphenol F epoxy resins, and
novolak epoxy resins. A preferred polythiol of this type is QX11,
derived from bisphenol A epoxy resin, from Japan Epoxy Resins (JER)
under the trade designation EPOMATE. Other polythiols suitable
include those available under the trade designations EPOMATE QX10
and QX20 from JER.
[0164] Other useful polythiols are polysulfides that contain thiol
groups such as those available under the trade designations THIOKOL
LP-2, LP-3, LP-12, LP-31, LP-32, LP-33, LP-977, and LP-980 from
Toray Fine Chemicals Co., Ltd.
[0165] Still other useful polythiols include polythioether
oligomers and polymers such as those described in U.S. Provisional
Pat. Appln. No. 62/116,019 (DeMoss et al.) entitled "Cold Tolerant
Sealants and Components Thereof", filed Feb. 13, 2015, and
references included therein.
[0166] Another type of polythiol, thiol-containing silicones is
preferred when the ethylenically-unsaturated compound is a
polydiorganosiloxane. Polydimethylsiloxanes in which some of the
methyl groups have been replaced by mercaptoalkyl groups are
preferred. Specific examples include those available under the
trade designations SMS-022 and SMS-042 (from Gelest Inc.), as well
as KF-2001 and KF-2004 (from Shin-Etsu Chemical Co. Ltd. (Tokyo,
Japan)), in which some silicon atoms internal to the polymer chain,
i.e., not at the termini, are substituted with mercaptoalkyl
groups. Another preferred silicone is Shin-Etsu Chemical Co. Ltd.
X-22-167B, in which both terminal silicon atoms are substituted
with mercaptoalkyl groups.
[0167] Various combinations of the polymerizable thiol-containing
compounds may be used. Preferred combinations include miscible
mixtures. It is noted that thiol-containing silicones, however, may
not be miscible with other thiol containing compounds listed
herein.
[0168] It is noted that thiol-containing silicones (i.e.,
polydiorganosiloxanes) may not be suitable for combination (or
mixture) with many of the ethylenically-unsaturated compounds due
to their lack of miscibility with these compounds and their high
price. However, in the case where the ethylenically-unsaturated
compound is also a silicone (i.e., polydiorganosiloxane), the
thiol-containing polydiorganosiloxanes are preferred due to their
miscibility with these ethylenically-unsaturated
polydiorganosiloxanes and the lack of miscibility of the
non-silicone polythiols with these silicones that contain the
ethylenically-unsaturated groups.
[0169] Exemplary thiol-containing compounds include those prepared
from esterification of polyols with thiol-containing carboxylic
acids or their derivatives, those prepared from a ring-opening
reaction of epoxides with H.sub.2S (or its equivalent), those
prepared from the addition of H.sub.2S (or its equivalent) across
carbon-carbon double bonds, polysulfides, polythioethers, and
polydiorganosiloxanes. Specifically, these include the
3-mercaptopropionates (also referred to as
.beta.-mercaptopropionates) of ethylene glycol and
trimethylolpropane (the former from Evans Chemetrics, now part of
Bruno Boch, the latter from Sigma-Aldrich); POLYMERCAPTAN 805C
(mercaptanized castor oil); CAPCURE 3-800 (a polyoxyalkylene triol
with mercapto end groups of the structure
R[O(C.sub.3H.sub.6O).sub.n--CH.sub.2--CH(OH)--CH.sub.2SH].sub.3
wherein R represents an aliphatic hydrocarbon group having 1-12
carbon atoms and n is an integer from 1 to 25); THIOKOL LP-3
polysulfide; and GELEST SMS-022 and SMS-042 (polydimethylsiloxanes
in which some of the methyl groups have been replaced by
mercaptoalkyl groups).
[0170] In certain embodiments, the weight percent (wt. %) of the
thiol-containing compound is at least 1 wt. %, or at least 10 wt.
%, or at least 20 wt. %, or at least 30 wt. %, or at least 40 wt. %
of the total weight of the thiol-containing and
ethylenically-unsaturated compounds. In certain embodiments, the
weight percent of the thiol-containing compound is up to 99 wt. %,
or up to 90 wt. %, or up to 80 wt. %, or up to 70 wt. %, or up to
60 wt. % of the total weight of the thiol-containing and
ethylenically-unsaturated compounds. In certain embodiments, the
weight percent of the ethylenically-unsaturated compound is at
least 1 wt. %, or at least 10 wt. %, or at least 20 wt. %, or at
least 30 wt. %, or at least 40 wt. % of the total weight of the
thiol-containing and ethylenically-unsaturated compounds. In
certain embodiments, the weight percent of the
ethylenically-unsaturated compound is up to 99 wt. %, or up to 90
wt. %, or up to 80 wt. %, or up to 70 wt. %, or up to 60 wt. % of
the total weight of the thiol-containing and
ethylenically-unsaturated compounds.
[0171] In certain embodiments, the amount of the thiol groups from
the thiol-containing compounds and the amount of
ethylenically-unsaturated groups from the ethylenically-unsaturated
compounds are present in a molar ratio range of 0.25:1.0 to
4.0:1.0, or 0.33:1.0 to 3.0:1.0, or 0.5:1.0 to 2.0:1.0, or 0.75:1.0
to 1.33:1.0, or 0.80:1.0 to 1.25:1.0 (thiol
groups:ethylenically-unsaturated groups). In some specific
embodiments, the molar ratio is preferably 0.5:1.0 to 2.0:1.0. In
certain embodiments, for example where crosslinking of high
molecular weight polymers that contain an ethylenically-unsaturated
repeating unit, such as 1,2-polybutadiene or unsaturated
polyesters, is desired, the amount of thiol groups and the amount
of ethylenically-unsaturated groups may be present in a molar range
of 0.005:1.0 to 0.20:1.0 (thiol groups:ethylenically-unsaturated
groups).
Optional Additives
[0172] Compositions according to the present disclosure (whether
multi-part or unitary) can include other optional additives. These
optional additives can be, e.g., in Part A, Part B, or in any other
part.
[0173] Peroxygen compounds other than hydroperoxides may be useful
additives for adjusting or customizing the cure profile (i.e., the
degree of cure vs. time). Examples of useful peroxygen compounds
are organic peroxides, other than organic hydroperoxides, that have
half-lives of 10 hours at temperatures of approximately 90.degree.
C. or greater, such as 1,1-di(tert-butylperoxy)cyclohexane,
tert-amylperoxy 2-ethylhexy carbonate, tert-amyl peroxyacetate,
2,2-di(tert-butylperoxy)butane, tert-butylperoxy isopropyl
carbonate, dicumyl peroxide,
tert-butylperoxy-3,5,5-trimethylhexanoate,
2,5-dimethyl-2,5-di(tert-butylperoxy)hexane, di-tert-butyl
peroxide, 2,5-dimethyl-2,5-di(tert-butylperoxy)hexyne-3, and
tert-butyl cumyl peroxide. In certain embodiments, the various
compositions according to the present disclosure are free of
peroxygen compounds other than hydroperoxides (e.g., organic
hydroperoxides and/or hydrogen peroxide).
[0174] Another particularly useful additive is a thickener, such as
medium (e.g., 40,000 grams/mole) molecular weight polybutyl
methacrylate that may generally be incorporated in an amount of up
to 50 percent by weight, based on the total weight of the
polymerizable monomers. Thickeners may be employed to increase the
viscosity of the resulting composition to a more easily applied
viscous syrup-like consistency.
[0175] Yet another particularly useful additive is an elastomeric
material. These materials can improve the fracture toughness of
compositions made therewith, which can be beneficial when, for
example, bonding stiff, high yield strength materials (e.g., metal
substrates that do not mechanically absorb energy as easily as
other materials, such as flexible polymeric substrates). Such
additives can generally be incorporated in an amount of up to 50
percent by weight, based on the total weight of the
composition.
[0176] Core-shell polymers can also be added to modify spreading
and flow properties of the composition. These enhanced properties
may be manifested by a reduced tendency for the composition to
leave an undesirable "string" upon dispensing from a syringe-type
applicator, or sag or slump after having been applied to a vertical
surface. Accordingly, use of more than 20 percent by weight, based
on total weight of the composition, of a core-shell polymer
additive may be desirable for achieving improved sag-slump
resistance. Core-shell polymers can also improve the fracture
toughness of compositions made therewith, which can be beneficial
when, for example, bonding stiff, high yield strength materials
(e.g., metal substrates that do not mechanically absorb energy as
easily as other materials, such as flexible polymeric
substrates).
[0177] Small amounts of inhibitors, such as hydroquinone monomethyl
ether, 2,6-di-(tert-butyl-1,2-dihydroxybenzene,
2,6-di-(tert-butyl)-4-methyl-phenol, pyrogallic acid, and tris
(N-nitroso-N-phenylhydroxylamine) aluminum salt may be used in
polymerizable compositions, for example, to prevent reaction or
reduce degradation of the polymerizable monomers during storage.
Inhibitors may be added in an amount that does not materially
affect the rate of curing or the ultimate properties of polymers
made therewith. Accordingly, inhibitors are generally useful in
amounts of 100-30,000 parts per million (ppm) based on the total
weight of polymerizable monomers in a polymerizable
composition.
[0178] Other possible additives include UV absorbers and light
stabilizers, flame retardants, plasticizers, adhesion promoters,
non-reactive diluents, non-reactive colorants, tackifiers, fillers
(e.g., carbon black, hollow glass/ceramic beads, silica, titanium
dioxide, calcium carbonate, solid glass/ceramic spheres,
electrically and/or thermally conductive particulate, such as metal
particles, graphite, alumina trihydrate (also referred to as
aluminum hydroxide), alumina, boron nitride, and silicon carbide,
glass/ceramic fiber, carbon fiber, antistatic compounds, and
chalk), and the like. The various optional additives are employed
in any amount, but generally amounts that do not significantly
adversely affect the curing process or the desired properties of
polymers made therewith.
Combinations
[0179] Multi-part compositions according to the present disclosure
are provided as at least a part A composition (part A) and a part B
composition (part B), with these parts being mixed prior to use of
the composition (e.g., application of the composition to a
substrate). In this way, activation of the organoborane can be
delayed until parts A and B are combined.
[0180] More specifically, compositions of the present disclosure
are multi-part polymerizable compositions that include at least two
parts: a part A composition that includes an organoborane-base
complex; and a part B composition that includes a decomplexing
agent. These two parts are kept separate until reaction is desired.
The polymerizable components can be in part A, part B, or another
part distinct from parts A and B. The polymerizable
ethylenically-unsaturated component and the thiol-containing
component can be separate or together in part A, part B, or another
part distinct from parts A and B. The hydroperoxide can be in part
A, part B, or another part distinct from parts A and B. Various
combinations can be envisioned.
[0181] For a two-part composition in which part A includes an
organoborane-base complex and part B includes a decomplexing agent,
the following combinations of the polymerizable
ethylenically-unsaturated component and the thiol-containing
component can be created:
[0182] (1) the polymerizable thiol-containing and
ethylenically-unsaturated components are only in Part A;
[0183] (2) the polymerizable thiol-containing and
ethylenically-unsaturated components are only in Part B;
[0184] (3) all of the polymerizable thiol-containing component is
in Part A and all of the polymerizable ethylenically-unsaturated
component is in Part B;
[0185] (4) all of the polymerizable ethylenically-unsaturated
component is in Part A and all of the polymerizable
thiol-containing component is in Part B;
[0186] (5) each of Part A and Part B include a portion of the
polymerizable thiol-containing component and a portion of the
polymerizable ethylenically-unsaturated component;
[0187] (6) Part A includes a portion of the polymerizable
thiol-containing component and all of the polymerizable
ethylenically-unsaturated component, and Part B includes a portion
of the polymerizable thiol-containing component;
[0188] (7) Part A includes all of the polymerizable
thiol-containing component and a portion of the polymerizable
ethylenically-unsaturated component, and Part B includes a portion
of the polymerizable ethylenically-unsaturated component;
[0189] (8) Part A includes a portion of the polymerizable
thiol-containing component, and Part B includes a portion of the
polymerizable thiol-containing component and all of the
polymerizable ethylenically-unsaturated component; and
[0190] (9) Part A includes a portion of the polymerizable
ethylenically-unsaturated component, and Part B includes a portion
of the polymerizable ethylenically-unsaturated component and all of
the polymerizable thiol-containing component.
[0191] In certain situations compatibility between the
organoborane-base complex or the decomplexing agent and the
polymerizable components as it relates to the stability of the
components needs to be considered when determining the various
combinations. In addition, compatibility of the polymerizable
components (i.e., the polyfunctional thiol-containing compounds and
the polyfunctional ethylenically-unsaturated compounds) needs to be
considered.
[0192] Two-part compositions are preferred due to cost
considerations, as is long shelf life.
[0193] When a two-part composition is used, in addition to
separating the organoborane-base complex from the decomplexing
agent, stability of the combinations with the other components
should be considered. For example, preferred stable combinations
include: an organoborane-base complex with a vinyl ether, vinyl
aliphatic, allyl ether, or allyl amide; and a polythiol with a
decomplexing agent selected from a carboxylic acid, acid anhydride,
1,3-dicarbonyl, isocyanate, aldehyde, or phosphonic acid. More
preferred combinations include: an organoborane-base complex with a
vinyl ether, vinyl aliphatic, allyl ether, or allyl amide; and a
polythiol with a decomplexing agent selected from a carboxylic
acid, acid anhydride, 1,3-dicarbonyl, or phosphonic acid. For
longer shelf life, an organoborane-base complex is preferably not
in the same part with an acrylate, methacrylate, acrylamide,
methacrylamide, or allyl ester. In some embodiments, the
hydroperoxide is in a different part than the organoborane-base
complex. For longer shelf-life, the hydroperoxide is preferably in
a different part than the organoborane-base complex.
Methods
[0194] For multi-part compositions such as those described in the
present disclosure to be most easily used in commercial and
industrial environments, the ratio at which the various parts are
combined should be a convenient whole number. This facilitates
application of the composition with conventional, commercially
available dispensers. Such dispensers are shown in U.S. Pat. No.
4,538,920 (Drake) and U.S. Pat. No. 5,082,147 (Jacobs) and are
available from ConProTec, Inc., Salem, N.H., under the trade
designation MIXPAC, and are sometimes described as dual
syringe-type applicators.
[0195] Typically, for two-part compositions, such dispensers use a
pair of tubular receptacles arranged side-by-side with each tube
being intended to receive one of the two parts of the composition.
Two plungers, one for each tube, are simultaneously advanced (e.g.,
manually or by a hand-actuated ratcheting mechanism) to evacuate
the contents of the tubes into a common, hollow, elongated mixing
chamber that may also contain a static mixer to facilitate blending
of the two parts. The blended composition is extruded from the
mixing chamber, typically onto a substrate. Once the tubes have
been emptied, they can be replaced with fresh tubes and the
application process continued.
[0196] The ratio at which the parts of the composition are combined
is controlled by the diameter of the tubes. Each plunger is sized
to be received within a tube of fixed diameter, and the plungers
are advanced into the tubes at the same speed. A single dispenser
is often intended for use with a variety of different compositions
and the plungers are sized to deliver the parts of the composition
at a convenient mix ratio. For two-part compositions, some common
mix ratios are 1:1, 1:2, 1:4, and 1:10 volume:volume.
[0197] If the parts of the composition are combined in an odd mix
ratio (e.g., 3.5:100), then the ultimate user would probably
manually weigh the parts of the composition. Thus, for best
commercial and industrial utility and for ease of use with
currently available dispensing equipment, the parts, particularly
two parts, of the composition should be capable of being combined
in a common whole number mix ratio such as, for example, 1:1, 1:2,
1:4, and 1:10.
[0198] Once the parts have been combined, the composition should
preferably be used within a period of time less than or equal to
the work-life of the composition. Once the parts are combined,
e.g., part A and part B, the reaction occurs under mild conditions,
and preferably under ambient conditions. In this context, "mild
conditions" include 0.degree. C. to 50.degree. C., 10.degree. C. to
50.degree. C., 19.degree. C. to 50.degree. C., or 19.degree. C. to
40.degree. C., or 19.degree. C. to 30.degree. C., or 19.degree. C.
to 25.degree. C. Ambient conditions include room temperature. If
desired, heat could be applied to accelerate the reaction.
[0199] Once the parts are combined, e.g., part A and part B, the
reaction occurs within hours, and often within minutes. For
example, the time for curing the composition can typically range
from seconds to 12 hours under ambient conditions. Post-curing at
an elevated temperature may also be used if desired. Although
relatively quick reaction (polymerization and/or crosslinking) can
occur within 12 hours, certain embodiments do not cure that
quickly. Such compositions are useful in situations that do not
require such rapid cure.
Select Embodiments of the Present Disclosure
[0200] Embodiment 1. A polymerizable composition comprising: [0201]
an organoborane-base complex that is a complex of an organoborane
and a base, wherein the base is a complexing agent selected from a
compound having one or more amine groups, amidine groups, hydroxide
groups, alkoxide groups, or a combination thereof; [0202] a
decomplexing agent that at least partially liberates the
organoborane from the organoborane-base complex; [0203] a
polymerizable thiol-containing component comprising at least one
polymerizable thiol-containing compound having a plurality of thiol
groups in which the sulfur atom of the thiol group is covalently
bonded to carbon; [0204] a hydroperoxide; and [0205] a
polymerizable ethylenically-unsaturated component comprising at
least one polymerizable ethylenically-unsaturated compound having a
plurality of ethylenically-unsaturated groups; [0206] wherein the
combined amounts of the thiol-containing and
ethylenically-unsaturated compounds total at least 50 percent by
weight of all polymerizable material in the polymerizable
composition.
[0207] Embodiment 2. The polymerizable composition of embodiment 1,
wherein the hydroperoxide is an organic hydroperoxide.
[0208] Embodiment 3. The polymerizable composition of embodiment 1
or 2, wherein upon reaction a --C--S--C--C-- linkage is formed.
[0209] Embodiment 4. The polymerizable composition of any one of
embodiments 1 to 3, wherein the polymerizable composition is free
of any thiol-containing compound having a polymerizable
ethylenically-unsaturated group.
[0210] Embodiment 5. The polymerizable composition of any one of
embodiments 1 to 4, wherein the organoborane-base complex does not
include a thiol group.
[0211] Embodiment 6. The polymerizable composition of any one of
embodiments 1 to 5, wherein the organoborane is represented by the
formula B(R.sup.1)(R.sup.2)(R.sup.3) wherein: [0212] R.sup.1
represents an alkyl group having from 1 to 10 carbon atoms; and
[0213] R.sup.2 and R.sup.3 independently represent: [0214] alkyl
groups having 1 to 10 carbon atoms; [0215] cycloalkyl groups having
3 to 10 carbon atoms; [0216] aryl groups having 6 to 12 carbon
atoms; or aryl groups substituted with alkyl groups having 1 to 10
carbon atoms or cycloalkyl groups having 3 to 10 carbon atoms,
[0217] or any two of R.sup.1, R.sup.2, and R.sup.3 taken together
form a divalent alkylene group having from 3 to 7 carbon atoms.
[0218] Embodiment 7. The polymerizable composition of any one of
embodiments 1 to 6, wherein the base is an amine comprising at
least one primary or secondary amine group.
[0219] Embodiment 8. The polymerizable composition of any one of
embodiments 1 to 7, wherein the decomplexing agent comprises at
least one of a carboxylic acid, an acid anhydride, an aldehyde, an
isocyanate, a phosphonic acid, or a 1,3-dicarbonyl compound.
[0220] Embodiment 9. The polymerizable composition of any one of
embodiments 1 to 8, wherein the polymerizable composition is a
multi-part polymerizable composition.
[0221] Embodiment 10. The polymerizable composition of embodiment
9, wherein the multi-part polymerizable composition comprises:
[0222] a part A composition comprising the organoborane-base
complex; and [0223] a part B composition comprising the
decomplexing agent, [0224] wherein the thiol-containing compound is
in the part A composition, the part B composition, or another part
distinct from the part A composition and the part B composition;
[0225] wherein the hydroperoxide is in the part A composition, the
part B composition, or another part distinct from the part A
composition and the part B composition; and [0226] wherein the
polymerizable ethylenically-unsaturated compound is in the part A
composition, the part B composition, or another part distinct from
the part A composition and the part B composition.
[0227] Embodiment 11. The polymerizable composition of any one of
embodiments 1 to 10, wherein the thiol-containing component
comprises at least one polymerizable thiol-containing compound
selected from those prepared from a ring-opening reaction of
epoxides with H.sub.2S, those prepared by addition of H.sub.2S
across carbon-carbon double bonds, poly sulfides, polythioethers,
polydimethylsiloxanes in which some of the methyl groups have been
replaced by mercaptoalkyl groups, and those prepared by
esterification of polyols with thiol-containing carboxylic acids or
their derivatives.
[0228] Embodiment 12. The polymerizable composition of any one of
embodiments 1 to 11, wherein the polymerizable
ethylenically-unsaturated compound is selected from polyfunctional
vinyl ethers, vinyl silicones, vinyl aliphatics, (meth)acrylates,
allyl ethers, allyl esters, and allyl amides.
[0229] Embodiment 13. The polymerizable composition of any one of
embodiments 1 to 12, wherein the amount of the thiol groups in the
thiol-containing component and the amount of the polymerizable
ethylenically-unsaturated groups in the polymerizable
ethylenically-unsaturated component are in a molar ratio range of
0.25:1.0 to 4.0:1.0.
[0230] Embodiment 14. The polymerizable composition of any one of
embodiments 1 to 13, wherein the molar ratio of hydroperoxy groups
to boron atoms is from 0.2 to 1.0.
[0231] Embodiment 15. A polymerizable composition comprising:
[0232] a part A composition comprising a organoborane-base complex
that is a complex of an organoborane and a base, wherein the base
is a complexing agent selected from a compound having one or more
amine groups, amidine groups, hydroxide groups, alkoxide groups, or
a combination thereof; and [0233] a part B composition comprising a
decomplexing agent that at least partially liberates the
organoborane from the organoborane-base complex; [0234] wherein the
polymerizable composition further comprises: [0235] a polymerizable
thiol-containing component comprising at least one polymerizable
thiol-containing compound having a plurality of thiol groups in
which the sulfur atom of the thiol group is covalently bonded to
carbon; [0236] a hydroperoxide; and [0237] a polymerizable
ethylenically-unsaturated component comprising at least one
polymerizable ethylenically-unsaturated compound having a plurality
of ethylenically-unsaturated groups, [0238] wherein the combined
amounts of the thiol-containing and ethylenically-unsaturated
compounds total at least 50 percent by weight of all polymerizable
material in the polymerizable composition.
[0239] Embodiment 16. The polymerizable composition of embodiment
15, wherein the hydroperoxide is an organic hydroperoxide.
[0240] Embodiment 17. The polymerizable composition of embodiment
15 or 16, wherein the hydroperoxide is present in the part B
composition.
[0241] Embodiment 18. The polymerizable composition of any one of
embodiments 15 to 17, wherein upon reaction a --C--S--C--C--
linkage is formed.
[0242] Embodiment 19. The polymerizable composition of any one of
embodiments 15 to 18, wherein the organoborane is represented by
the formula B(R.sup.1)(R.sup.2)(R.sup.3) wherein: [0243] R.sup.1
represents an alkyl group having from 1 to 10 carbon atoms; and
[0244] R.sup.2 and R.sup.3 independently represent: [0245] alkyl
groups having 1 to 10 carbon atoms; [0246] cycloalkyl groups having
3 to 10 carbon atoms; [0247] aryl groups having 6 to 12 carbon
atoms; or [0248] aryl groups substituted with alkyl groups having 1
to 10 carbon atoms or cycloalkyl groups having 3 to 10 carbon
atoms; [0249] or any two of R.sup.1, R.sup.2, and R.sup.3 taken
together form a divalent alkylene group having from 3 to 7 carbon
atoms.
[0250] Embodiment 20. The polymerizable composition of any one of
embodiments 15 to 19, wherein the base is an amine comprising at
least one primary or secondary amine group.
[0251] Embodiment 21. A composition prepared by combining
components comprising: [0252] a part A composition comprising a
organoborane-base complex that is a complex of an organoborane and
a base, wherein the base is a complexing agent selected from a
compound having one or more amine groups, one or more amidine
groups, one or more hydroxide groups, one or more alkoxide groups,
or a combination thereof; and [0253] a part B composition
comprising a decomplexing agent that at least partially liberates
the organoborane from the organoborane-base complex, [0254] wherein
at least one of the part A composition and the part B composition
further comprises: [0255] a polymerizable thiol-containing
component comprising at least one polymerizable thiol-containing
compound having a plurality of thiol groups in which the sulfur
atom of the thiol group is covalently bonded to carbon; [0256] a
hydroperoxide; and [0257] a polymerizable ethylenically-unsaturated
component comprising at least one polymerizable
ethylenically-unsaturated compound having a plurality of
ethylenically-unsaturated groups, [0258] wherein the combined
amounts of the thiol-containing and ethylenically-unsaturated
compounds total at least 50 percent by weight of all polymerizable
material in the polymerizable composition.
[0259] Embodiment 22. The composition of embodiment 21, wherein the
hydroperoxide is an organic hydroperoxide.
[0260] Embodiment 23. The composition of embodiment 21 or 22,
wherein the organoborane is represented by the formula
B(R.sup.1)(R.sup.2)(R.sup.3) wherein: [0261] R.sup.1 represents an
alkyl group having from 1 to 10 carbon atoms; and [0262] R.sup.2
and R.sup.3 independently represent: [0263] alkyl groups having 1
to 10 carbon atoms; [0264] cycloalkyl groups having 3 to 10 carbon
atoms; [0265] aryl groups having 6 to 12 carbon atoms; or [0266]
aryl groups substituted with alkyl groups having 1 to 10 carbon
atoms or cycloalkyl groups having 3 to 10 carbon atoms; [0267] or
any two of R.sup.1, R.sup.2, and R.sup.3 taken together form a
divalent alkylene group having from 3 to 7 carbon atoms.
[0268] Embodiment 24. The composition of any one of embodiments 21
to 23, wherein the base is an amine comprising at least one primary
or secondary amine group.
[0269] Embodiment 25. A method of making a composition, the method
comprising:
[0270] combining components comprising: [0271] a part A composition
comprising a organoborane-base complex that is a complex of an
organoborane and a base, and wherein the base is a complexing agent
selected from a compound having one or more amine groups, amidine
groups, hydroxide groups, alkoxide groups, or a combination
thereof; and [0272] a part B composition comprising a decomplexing
agent that at least partially liberates the organoborane from the
organoborane-base complex; [0273] wherein at least one of the part
A composition and the part B composition further comprises: [0274]
a polymerizable thiol-containing component comprising at least one
polymerizable thiol-containing compound having a plurality of thiol
groups in which the sulfur atom of the thiol group is covalently
bonded to carbon; [0275] a hydroperoxide; and [0276] a
polymerizable ethylenically-unsaturated component comprising at
least one polymerizable ethylenically-unsaturated compound having a
plurality of ethylenically-unsaturated groups, [0277] wherein the
combined amounts of the thiol-containing and
ethylenically-unsaturated compounds total at least 50 percent by
weight of all polymerizable material in the composition; and
[0278] allowing the part A composition and the part B composition
to react to form a polymer.
[0279] Embodiment 26. The method of embodiment 25, wherein the
hydroperoxide is an organic hydroperoxide.
[0280] Objects and advantages of this disclosure are further
illustrated by the following non-limiting examples, but the
particular materials and amounts thereof recited in these examples,
as well as other conditions and details, should not be construed to
unduly limit this disclosure.
EXAMPLES
[0281] Unless otherwise noted, all parts, percentages, ratios, etc.
in the Examples and the rest of the specification are by
weight.
Preparation of
4,13-dithia-7,10-dioxa-2,15-dimethylhexadecyl-1,15-diene (DMDO-CMP
Diene)
[0282] Into a 500-mL four-neck, round bottom flask fitted with a
stirrer, thermometer, chilled water condenser and a pressure
equalizing addition funnel was added 206.54 grams of a 20% aqueous
solution of sodium hydroxide (1.033 moles). To this was added,
dropwise with stirring, 94.08 grams of
1,8-dimercapto-3,6-dioxaoctane (DMDO, 0.51 moles, obtained from
Arkema, Inc., King of Prussia, Pa.), and the mixture then allowed
to cool to approximately 21.degree. C. 3-chloro-2-methyl-1-propene
(CMP, 96.4 grams, 1.065 moles) was added drop wise with vigorous
stirring, and stirring continued for another 2 hours. The mixture
was then held at 21.degree. C. for approximately 16 hours, after
which 150 grams of a clear layer was decanted. NMR analysis
confirmed the decanted layer to be DMDO-CMP diene, the structure of
which is shown below.
##STR00009##
Preparation of Polythioether CMPDP
[0283] Into a 100-mL round bottom flask equipped with an air-driven
stirrer, thermometer, and a dropping funnel, was added 36.68 grams
(0.20 moles) DMDO and 4.17 grams (0.0127 moles) of a diglycidyl
ether of bisphenol F (obtained as EPALLOY 8220 from Emerald
Performance Materials, LLC, Cuyahoga Falls, Ohio). To this mixture
was added 0.02 grams of triethylenediamine, obtained as DABCO from
Air Products & Chemicals, Inc., Allentown, Pa. The system was
flushed with nitrogen, then mixed and heated for 1.5 hours at
60-70.degree. C. 23.92 grams (0.082 moles) DMDO-CMP Diene was
added, followed by approximately 0.01 grams VAZO 52. With
continuous stirring, an additional 0.13 gram of
2,2'-azobis(2,4-dimethyl-pentanenitrile) (obtained as VAZO 52 from
E.I. du DuPont de Nemours and Company) was added, the mixture
maintained at 60.degree. C. for another 4.5 hrs.
1,2,4-Trivinylcyclohexane (0.81 grams, 0.005 moles, obtained from
BASF Corp., Florham Park, N.J.) was then added, along with an
additional 0.02 gram of VAZO 52, and maintained at 60.degree. C.
for another 1.5 hrs. Triethylene glycol divinyl ether (14.44 grams,
0.07 moles, obtained as RAPI-CURE DVE-3 from Ashland Specialty
Ingredients, Wilmington, Del.) was then added dropwise to the flask
over 15 minutes, keeping the temperature at approximately
70.degree. C. Additional VAZO 52 was added in approximately 0.01
gram increments over approximately 16 hours for a total of about
0.4 grams. The temperature was raised to 100.degree. C. and the
material degassed for approximately 10 minutes. The resultant
polythioether had a molecular weight of approximately 3200
grams/mole with 2.2 theoretical thiol functionality.
[0284] Additional materials used in the Examples are listed in
Table 1 (below).
TABLE-US-00001 TABLE 1 CHEMICAL NAME OR ABBREVIATION DESCRIPTION
AND SUPPLIER APE Allyl pentaerythritol (i.e., pentaerythritol
tetra-allyl ether), available from Perstorp Specialty Chemicals AB
(Skane, Sweden) 2,5-bis(t-butylperoxy)-
2,5-bis(tert-butylperoxy)-2,5-dimethylhexane, 2,5-dimethylhexane
LUPEROX 101 available from Arkema Inc. (King of Prussia, PA USA)
t-butyl hydroperoxide tert-butyl hydroperoxide, 5.0-6.0M in nonane
available from Sigma-Aldrich (Milwaukee, WI USA) t-butyl
peroxy-3,5,5- tert-butyl peroxy-3,5,5-trimethylhexanoate, available
trimethylhexanoate from ACROS Organics (Antwerp, Belgium) Cumene
hydroperoxide Cumene hydroperoxide from Lucidol Division, Pennwalt
Corp (Buffalo, NY USA); now part of Arkema, Inc. DEGDVE Di(ethylene
glycol) divinyl ether available from Sigma- Aldrich
2,5-di(t-butylperoxy)-
2,5-di(tert-butylperoxy)-2,5-dimethyl-3-hexyne
2,5-dimethyl-3-hexyne available from Sigma-Aldrich Dicumyl peroxide
Dicumyl peroxide available from Sigma-Aldrich DDSA
Dodecenylsuccinic anhydride available from Sigma- Aldrich GPM-800
Multi-functional thiol, having on average roughly 3 thiol groups
per molecule, thiol equivalent weight of approximately 277,
available from Gabriel Performance Products (Ashtabula, OH).
Equivalent material to CAPCURE 3-800 from BASF (Florham Park, NJ,
USA). LP-3 Multi-functional thiol polysulfide, THIOKOL LP-3,
available from Toray Fine Chemicals Co., Ltd. (Chiba, Japan) MOPA
3-methoxypropylamine available from Sigma-Aldrich Nonanoic acid
Nonanoic acid available from Sigma-Aldrich TEGDVE Tri(ethylene
glycol) divinyl ether available from Sigma-Aldrich TnBB-MOPA
Tri-n-butylborane-3-methoxypropylamine complex (with between 6 to 9
wt. percent free 3- methoxypropylamine per BASF; NMR indicated
approximately 12 wt. percent free 3- methoxypropylamine), available
from BASF (Florham Park, NJ, USA)
[0285] Peroxides used in the Examples are listed in Table 2
(below).
TABLE-US-00002 TABLE 2 EXAMPLE or COMPARATIVE EXAMPLE PEROXIDE USED
1, 3, 5, CEF, CEG cumene hydroperoxide 2, 4 t-butyl hydroperoxide
CEA, CEH t-butyl peroxy-3,5,5-trimethylhexanoate CEB, CEI dicumyl
peroxide CEC, CEJ, CEM 2,5-di(t-butylperoxy)-2,5-dimethyl-3-hexyne
CED, CEK 2,5-bis(t-butylperoxy)-2,5-dimethylhexane (LUPEROX 101)
CEE, CEL none
Examples 1-2 and Comparative Examples CEA-CEE
[0286] Examples 1-2 and Comparative Examples CEA-CEE involved the
same 2-part thiol-ene composition, except for the presence or
absence of a peroxide, and the identity of the peroxide. Part A
included diethylene glycol divinyl ether (DEGDVE), triethylene
glycol divinyl ether (TEGDVE), and
tri-n-butylborane:3-methoxypropylamine complex (TnBB-MOPA). Part B
included CMPDP, GPM-800, dodecenyl anhydride (DDSA), and optionally
a peroxide. If present, the amount of peroxide added corresponded
to approximately 0.75 moles of the --O--O-- group per mole
TnBB-MOPA.
[0287] The components of Part A were weighed into a glass vial and
mixed to provide a liquid mixture. The components of Part B were
weighed into a max 10, DAC plastic mixing cup at room temperature.
The dimensions of the inner, cylindrical cavity of the max 10
mixing cup were approximately 26 mm in diameter by 27 mm in height.
The cup was capped and contents mixed at 2000 rpm for 1 minute with
a centrifugal mixer (SpeedMixer, model DAC 150.1 FVZ-K from
FlackTek Inc., Landrum, S.C.), which provided a viscous, flowable
liquid. The weights of the components in Part B are reported in
Table 3. In the case of Example 2, the weight of peroxide reported
is the approximate weight of the t-butyl peroxide excluding the
nonane solvent. This peroxide was added to the formulation as a
solution in nonane (i.e., it was used as received from
Sigma-Aldrich). Then, Part A was weighed into the max 10 mixing cup
that contained Part B (at room temperature). The amount of Part A
transferred to the mixing cup was such that it provided the amounts
of the individual components as reported in Table 3. The actual
amounts weighed initially into the glass vial for Part A were in
excess of the amounts delivered to Part B by approximately 10
percent. After addition of Part A to Part B, the composition was
immediately mixed at 2000 rpm for 1 minute with the SpeedMixer DAC
150.1 FVZ-K, and then the contents observed. The contents of the
cups had leveled and filled the bottom of the cups to a depth of
approximately 1.0 cm.
TABLE-US-00003 TABLE 3 PART A, grams PART B, grams TnBB- GPM-
EXAMPLE DEGDVE TEGDVE MOPA CMPDP 800 DDSA Peroxide 1 0.129 0.173
0.197 4.267 0.289 0.468 0.088 2 0.130 0.177 0.196 4.284 0.281 0.448
0.050 CEA 0.128 0.176 0.198 4.273 0.302 0.464 0.123 CEB 0.130 0.175
0.201 4.284 0.279 0.450 0.148 CEC 0.133 0.177 0.200 4.268 0.275
0.450 0.079 CED 0.131 0.175 0.198 4.271 0.278 0.464 0.077 CEE 0.134
0.178 0.195 4.288 0.270 0.479 0.000
[0288] In the case of Examples 1 and 2, the contents of the cups
cured to a uniform, solid material within 5 minutes after the
mixing together of Parts A and B. Comparative Examples A-E did not
cure to a uniform, solid material within 5 minutes. Comparative
Example B was a viscous liquid, and Comparative Examples A, C, D,
and E formed a skin (i.e., a thin elastomeric solid film or layer)
on the top surface of the composition with viscous liquid below.
After 19 hours, Comparative Examples A-E still had not cured to a
uniform, solid material. All had a skin layer on the top surface,
which may have increased in thickness relative to the 5 minute
mark, but the bulk of the composition was a viscous liquid-like
material.
Comparative Example F (CEF)
[0289] Comparative Example F was similar to Example 1, except that
no organoborane-amine complex (TnBB-MOPA) was initially present in
the composition, and no compounds with at least two
ethylenically-unsaturated groups (DEGDVE, TEGDVE) were present.
This was done to demonstrate that the rapid and uniform cures seen
in Example 1 (and Example 2) were not the result of oxidative
coupling of thiols to form disulfide linkages, but rather required
the multi-functional ethylenically-unsaturated compounds and curing
via thiol-ene reaction.
[0290] CMPDP, GPM-800, dodecenyl anhydride (DDSA), and cumene
hydroperoxide were weighed into a max 10, DAC plastic mixing cup
(at room temperature), and mixed at 2000 rpm for 1 minute with a
centrifugal mixer (SpeedMixer, model DAC 150.1 FVZ-K), and then the
contents observed. Initially, the contents was a viscous liquid,
and it remained a viscous liquid for approximately 2 hours, at
which time TnBB-MOPA was weighed into the cup and mixed at 2000 rpm
for 1 minute with the centrifugal mixer. The contents were checked
periodically up to 12 days after the addition of the TnBB-MOPA, and
the contents remained a viscous liquid and no skin layer formed on
the top surface. The weights of the components are reported in
Table 4.
TABLE-US-00004 TABLE 4 GPM- Cumene TnBB- CMPDP, 800, DDSA,
Hydroperoxide, MOPA, EXAMPLE grams grams grams grams grams CEF
4.271 0.274 0.457 0.083 0.192
Comparative Example G (CEG)
[0291] Comparative Example G was similar to Example 1, and the same
procedure was followed to prepare the example, except no
organoborane-amine complex (TnBB-MOPA) was present in the
composition and 3-methoxypropylamine (MOPA) was added to Part A.
This was done to demonstrate that the rapid and uniform cures seen
in Example 1 (and Example 2) were not the result of initiation by
radical species that might potentially be generated from
unanticipated redox reaction between free amine, i.e.,
3-methoxypropylamine, and cumene hydroperoxide. After combining
Part A, which was a liquid, and Part B, and mixing in a max 10, DAC
plastic mixing cup, the contents was observed. Initially, the
contents was a viscous liquid. The contents was checked
periodically up to 2 days, and the contents remained a viscous
liquid, and no skin layer formed on the top surface. The weights of
the components are reported in Table 5.
TABLE-US-00005 TABLE 5 PART B, grams PART A, grams GPM- Cumene
EXAMPLE DEGDVE TEGDVE MOPA CMPDP 800 DDSA Hydroperoxide CEG 0.133
0.183 0.052 4.269 0.275 0.461 0.087
Examples 3-4 and Comparative Examples CEH-CEL
[0292] Examples 3-4 and Comparative Examples CEH-CEL involved the
same 2-part thiol-ene composition, except for the presence or
absence of a peroxide, and the identity of the peroxide. Part A
included diethylene glycol divinyl ether (DEGDVE), and
tri-n-butylborane:3-methoxypropylamine complex (TnBB-MOPA). Part B
included LP-3, GPM-800, dodecenyl anhydride (DDSA), and optionally
a peroxide. If present, the amount of peroxide added corresponded
to approximately 0.75 moles of the --O--O-- group per mole
TnBB-MOPA.
[0293] The components of Part A were weighed into a glass vial and
mixed to provide a liquid mixture. The components of Part B were
weighed into a max 10, DAC plastic mixing cup (at room
temperature), and mixed at 2000 rpm for 1 minute with a centrifugal
mixer (SpeedMixer, model DAC 150.1 FVZ-K from FlackTek Inc.,
Landrum, S.C. USA), which provided a viscous, flowable liquid. The
weights of the components in Part B are reported in Table 5. In the
case of Example 10, the weight of peroxide reported is the
approximate weight of the t-butyl peroxide excluding the nonane
solvent. This peroxide was added to the formulation as a solution
in nonane (i.e., it was used as received from Sigma-Aldrich). Then
Part A was weighed into the max 10 mixing cup that contained Part B
(at room temperature). The amount of Part A transferred to the
mixing cup was such that it provided the amounts of the individual
components as reported in Table 6. The actual amounts weighed
initially into the glass vial for Part A were in excess of the
amounts delivered to Part B by approximately 10 percent. After
addition of Part A to Part B, the composition was immediately mixed
at 2000 rpm for 1 minute with the SpeedMixer DAC 150.1 FVZ-K, and
then the contents observed. The contents of the cups had leveled
and filled the bottom of the cups to a depth of approximately 1.0
cm.
TABLE-US-00006 TABLE 6 PART A, grams PART B, grams TnBB- GPM-
EXAMPLE DEGDVE MOPA LP-3 800 DDSA Peroxide 3 0.745 0.200 3.657
0.521 0.383 0.083 4 0.740 0.199 3.654 0.522 0.384 0.050 CEH 0.748
0.198 3.655 0.535 0.389 0.122 CEI 0.752 0.199 3.655 0.522 0.391
0.148 CEJ 0.747 0.198 3.653 0.535 0.384 0.071 CEK 0.741 0.196 3.651
0.521 0.384 0.076 CEL 0.742 0.199 3.652 0.520 0.384 0.000
[0294] In the case of Examples 3 and 4, the contents of the cups
cured to a uniform, solid material within 2 minutes after the
mixing together of Parts A and B. Comparative Examples CEH-CEL all
remained viscous liquids and did not cure to a uniform, solid
material within 2 minutes. After 55 minutes, Comparative Examples
CEH-CEL all had formed a skin (i.e., a thin elastomeric solid film
or layer) on the top surface of the composition with viscous liquid
below. After 2 days, Comparative Examples CEH-CEL still had not
cured to a uniform, solid material. All had a skin layer on the top
surface, which may have increased in thickness relative to the 55
minute mark, but the bulk of the composition was a viscous
liquid.
Example 5 and Comparative Example M
[0295] Example 5 and Comparative Example M involved the same 2-part
thiol-ene composition, except that the peroxide was cumene
hydroperoxide in Example 5 and
2,5-di(t-butylperoxy)-2,5-dimethyl-3-hexyne in Comparative Example
M. Part A included allyl pentaerythritol (APE), and
tri-n-butylborane:3-methoxypropylamine complex (TnBB-MOPA). Part B
included GPM-800, nonanoic acid, and the peroxide. The amount of
peroxide added corresponded to approximately 0.745 moles of the
--O--O-- group per mole TnBB-MOPA.
[0296] The components of Part A were weighed into a glass vial and
mixed to provide a liquid mixture. The components of Part B were
weighed into a max 10, DAC plastic mixing cup (at room
temperature), and mixed at 2000 rpm for 1 minute with a centrifugal
mixer (SpeedMixer, model DAC 150.1 FVZ-K), which provided a liquid.
The weights of the components in Part B are reported in Table 6.
Then Part A was weighed into the max 10 mixing cup that contained
Part B (at room temperature). The amount of Part A transferred to
the mixing cup was such that it provided the amounts of the
individual components as reported in Table 7. The actual amounts
weighed initially into the glass vial for Part A were in excess of
the amounts delivered to Part B by approximately 10 percent. After
addition of Part A to Part B, the composition was immediately mixed
at 2000 rpm for 1 minute with the SpeedMixer DAC 150.1 FVZ-K, and
then the contents observed. The contents of the cups had leveled
and filled the bottom of the cups to a depth of approximately 1.0
cm.
TABLE-US-00007 TABLE 7 PART A, grams PART B, grams TnBB- GPM-
Nonanoic EXAMPLE APE MOPA 800 Acid Peroxide 5 1.132 0.088 4.221
0.066 0.037 CEM 1.130 0.088 4.221 0.066 0.027
[0297] In the case of Example 5, 4 minutes after the mixing
together of Parts A and B, a skin layer formed on top surface of
the composition with viscous liquid underneath, and then in an
additional minute the entire contents of the cup gelled. After 4
hours, the contents had firmed to a rubbery material throughout. In
Comparative Example CEM, a skin layer formed after 12-22 minutes
with a flowable liquid underneath. After 2 days, the skin layer had
thickened to roughly 1 mm in thickness, and a flowable, viscous
liquid was underneath.
[0298] All cited references, patents, and patent applications in
the above application for letters patent are herein incorporated by
reference in their entirety in a consistent manner. In the event of
inconsistencies or contradictions between portions of the
incorporated references and this application, the information in
the preceding description shall control. The preceding description,
given in order to enable one of ordinary skill in the art to
practice the claimed disclosure, is not to be construed as limiting
the scope of the disclosure, which is defined by the claims and all
equivalents thereto.
* * * * *