U.S. patent application number 09/729718 was filed with the patent office on 2001-12-13 for polymers of 3-butene esters, their preparation and use.
This patent application is currently assigned to Eastman Chemical Company. Invention is credited to Crain, Allen Lynn, Marlow, Chadwick Edward, Webster, Dean Charles.
Application Number | 20010051690 09/729718 |
Document ID | / |
Family ID | 27066872 |
Filed Date | 2001-12-13 |
United States Patent
Application |
20010051690 |
Kind Code |
A1 |
Webster, Dean Charles ; et
al. |
December 13, 2001 |
Polymers of 3-butene esters, their preparation and use
Abstract
The specification describes various polymers having monomer of
formula (I): 1 In formula (I), R1 and R2 are, independently,
hydrogen, a C.sub.1-C.sub.24 alkyl group, an aromatic or
heteroaromatic group, a C.sub.3-C.sub.8 cycloalkyl or
C.sub.2-C.sub.7 heterocycloalkyl group, or a --C(O)R3 group in
which R3 is a C.sub.1-C.sub.24 alkyl group, an aromatic or
heteroaromatic group, a C.sub.3-C.sub.8 cycloalkyl or
C.sub.2-C.sub.7 heterocyclic group; or a --CH.sub.2--C(O)--R4 group
in which R4 is a C.sub.1-C.sub.6 alkyl group. At least one of R1
and R2 is a --C(O)R3 group. The polymer may be a homopolymer or a
copolymer containing other ethylenically unsaturated monomers. The
polymer may be used in a variety of coating compositions such as
inks, adhesives, paints and films. Unique monomers where both R1
and R2 are acetoacetyl groups and novel monomers where R2 is an
acetoacetyl group are also described.
Inventors: |
Webster, Dean Charles;
(Kingsport, TN) ; Crain, Allen Lynn; (Kingsport,
TN) ; Marlow, Chadwick Edward; (Kingsport,
TN) |
Correspondence
Address: |
MORGAN, LEWIS & BOCKIUS
1800 M STREET NW
WASHINGTON
DC
20036-5869
US
|
Assignee: |
Eastman Chemical Company
|
Family ID: |
27066872 |
Appl. No.: |
09/729718 |
Filed: |
December 6, 2000 |
Related U.S. Patent Documents
|
|
|
|
|
|
Application
Number |
Filing Date |
Patent Number |
|
|
09729718 |
Dec 6, 2000 |
|
|
|
09541987 |
Apr 3, 2000 |
|
|
|
6228949 |
|
|
|
|
09541987 |
Apr 3, 2000 |
|
|
|
08956533 |
Oct 23, 1997 |
|
|
|
6121399 |
|
|
|
|
Current U.S.
Class: |
525/328.9 ;
560/112; 560/201; 560/240; 560/261 |
Current CPC
Class: |
C08F 16/26 20130101;
C09D 131/04 20130101; C08F 16/04 20130101; C08F 18/12 20130101;
C09D 129/10 20130101 |
Class at
Publication: |
525/328.9 ;
560/112; 560/201; 560/261; 560/240 |
International
Class: |
C07C 069/76 |
Claims
The claimed invention is:
1. A polymer comprising the free-radical polymerization product of:
a monomer of formula (I): 7where R1 and R2 are, independently,
hydrogen, a C.sub.1-C.sub.24 alkyl group, an aromatic or
heteroaromatic group, a C.sub.3-C.sub.8 cycloalkyl or
C.sub.2-C.sub.7 heterocycloalkyl group, or a --C(O)R3 group; and at
least one of R1 and R2 is a --C(O)R3 group; R3 is a
C.sub.1-C.sub.24 alkyl group, an aromatic or heteroaromatic group,
a C.sub.3-C.sub.8 cycloalkyl or C.sub.2-C.sub.7 heterocyclic group,
or a --CH.sub.2--C(O)-R4 group; R4 is a C.sub.1-C.sub.6 alkyl
group; and optionally, an ethylenically unsaturated monomer.
2. A polymer of claim 1, wherein the ethylenically unsaturated
monomer is at least one selected from the group consisting of an
allylic compound, a vinylic compound, a styrenic compound, an
.alpha.,.beta.-unsaturated compound, an acrylic compound, and an
alkene.
3. A coating composition comprising the polymer of claim 1.
4. A coating composition of claim 3, wherein said coating
composition is an architectural coating, a maintenance coating, an
industrial coating, an automotive coating, a textile coating, an
ink, an adhesive, or a coating for paper, wood, or plastic.
5. A method of making a vinyl polymer comprising the step of:
polymerizing under free-radical conditions: a monomer of formula
(I): 8where R1 and R2 are, independently, hydrogen, a
C.sub.1-C.sub.24 alkyl group, an aromatic or heteroaromatic group,
a C.sub.3-C.sub.8 cycloalkyl or C.sub.2-C.sub.7 heterocycloalkyl
group, or a --C(O)R3 group; and at least one of R1 and R2 is a
--C(O)R3 group; R3 is a C.sub.1-C.sub.24 alkyl group, an aromatic
or heteroaromatic group, a C.sub.3-C.sub.8 cycloalkyl or
C.sub.2-C.sub.7 heterocyclic group, or a --CH.sub.2--C(O)-R4 group;
R4 is a C.sub.1-C.sub.6 alkyl group; and, optionally, an
ethylenically unsaturated monomer.
6. The method of claim 5 wherein the free-radical polymerization
step is a semi-batch solution, or emulsion free-radical
polymerization step.
7. The method of claim 5 wherein the ethylenically unsaturated
monomer is at least one selected from the group consisting of an
allylic compound, a vinylic compound, a styrenic compound, an
.alpha.,.beta.-unsaturated compound, an acrylic compound and an
alkene.
8. A monomer of the formula (I): 9where R1 is a C.sub.1-C.sub.24
alkyl group or an aromatic or heteroaromatic group and R is a
--C(O)R3 group; R3 is a C.sub.1-C.sub.24 alkyl group, an aromatic
or heteroaromatic group, a C.sub.3-C.sub.8 cycloalkyl or
C.sub.2-C.sub.7 heterocyclic group; or a --CH.sub.2--C(O)-R4 group;
and R4 is a C.sub.1-C.sub.6 alkyl group.
9. A monomer of claim 8, wherein R1 is a methyl group and R2 is
selected from the group consisting of an acetoacetyl group and an
acetyl group.
10. A monomer of the formula (I): 10where R1 and R2 are both an
acetoacetyl group.
11. An enamine functional polymer comprising the reaction product
of an amine selected from the group consisting of ammonia, a
primary amine, and a secondary amine and an acetoacetoxy
functionalized polymer wherein said acetoacetoxy polymer comprises
the free- radical polymerization product of: a monomer of formula
(I): 11where R1 and R2 are, independently, hydrogen, a
C.sub.1-C.sub.24 alkyl group, an aromatic or heteroaromatic group,
a C.sub.3-C.sub.8 cycloalkyl or C.sub.2-C.sub.7 heterocycloalkyl
group, or a --C(O)R3 group; R3 is a C.sub.1-C.sub.24 alkyl group;
an aromatic, heteroaromatic, C.sub.3-C.sub.8 cycloalkyl or
C.sub.2-C.sub.7 heterocyclic group; or a --CH.sub.2--C(O)-R4; and
R4 is a C.sub.1-C.sub.6 alkyl group; wherein at least one of R1 and
R2 is an acetoacetoxy group; and, optionally, an ethylenically
unsaturated monomer.
12. A polymer of claim 11, wherein the ethylenically unsaturated
monomer is at least one selected from the group consisting of an
allylic compound, a vinylic compound, a styrenic compound, an
.alpha.,.beta.-unsaturated compound, an acrylic compound, and an
alkene.
13. A coating composition comprising the polymer of claim 11.
14. A coating composition of claim 13, wherein said coating
composition is an architectural coating, a maintenance coating, an
industrial coating, an automotive coating, a textile coating, an
ink, an adhesive, or a coating for paper, wood, or plastic.
15. A method of preparing the enamine functional polymer of claim
11, comprising the step of reacting an amine selected from the
group consisting of ammonia, a primary amine and a secondary amine,
and the free-radical polymerization product of: a monomer of
formula (I): 12where R1 and R2 are, independently, hydrogen, a
C.sub.1-C.sub.24 alkyl group, an aromatic or heteroaromatic group,
a C.sub.3-C.sub.8 cycloalkyl or C.sub.2-C.sub.7 heterocycloalkyl
group, or a --C(O)R3 group; R3 is a C.sub.1-C.sub.24 alkyl group,
an aromatic or heteroaromatic group, a C.sub.3-C.sub.8 cycloalkyl
or C.sub.2-C.sub.7 heterocyclic group, or a --CH.sub.2--C(O)-R4
group; and R4 is a C.sub.1-C.sub.6 alkyl group; wherein at least
one of R1 and R2 is an acetoacetoxy group; and, optionally, an
ethylenically unsaturated monomer.
16. A method of preparing the enamine functional polymer of claim I
1, comprising the steps of: reacting an amine selected from the
group consisting of ammonia, a primary amine and a secondary amine,
and a monomer of formula (I): 13where R1 and R2 are, independently,
hydrogen, a C.sub.1-C.sub.24 alkyl-group, an aromatic or
heteroaromatic group, a C.sub.3-C.sub.8 cycloalkyl or
C.sub.2-C.sub.7 heterocycloalkyl group, or a --C(O)R3 group; R3 is
a C.sub.1-C.sub.24 alkyl group, an aromatic or heteroaromatic
group, a C.sub.3-C.sub.8 cycloalkyl or C.sub.2-C.sub.7 heterocyclic
group, or a --CH.sub.2--C(O)--R4 group; and R4 is a C.sub.1-C.sub.6
alkyl group; wherein at least one of R1 and R2 is an acetoacetoxy
group; and polymerizing the resulting monomer and, optionally, an
ethylenically unsaturated monomer.
17. A coated article comprising a substrate coated with a coating
composition of claim 3.
18. A coated article comprising a substrate coated with a coating
composition of claim 13.
Description
BACKGROUND OF THE INVENTION
[0001] 1. Field of the Invention
[0002] The present invention relates to polymers resulting from
polymerizing ethylenically unsaturated esters derived from
3,4-epoxy-1-butene or epoxybutene. The polymers may be homopolymers
or copolymers containing other ethylenically unsaturated monomers.
The polymers of the invention may be used in a variety of coating
compositions such as inks, adhesives, paints, and films.
[0003] 2. Description of the Related Art
[0004] The ring opening chemistry of epoxides is well known. (Evans
et al., J. Chem. Soc. 248 (1949)). Opening an epoxide ring with a
nucleophile can create one hydroxyl moiety or, depending on
reaction conditions, two hydroxyl moieties. The hydroxyl groups can
undergo further reaction. The hydroxyl groups can, for example, be
converted to esters by reaction with carboxylic acids. Hydroxyl
groups can also be converted to acetoacetic esters. (Clemens, R.
J., Chemical Reviews, 86:241-318 (1986); Witzeman, J. S., U.S. Pat.
No. 5,051,529 (1991)).
[0005] Reacting an epoxide group with an acid anhydride can yield a
disubstituted ester derivative (U.S. Pat. No. 5,623,086). Reacting
an epoxide with an alcohol results in the formation of a hydroxy
ether and is well known in the literature. The remaining hydroxyl
group may be further derivatized using, for example, carboxylic
acids or anhydrides to form esters using methods well known to
those skilled in the art.
[0006] The ring opening reaction of 3,4-epoxy-1-butene or
epoxybutene with hydroxide base yields an ethylenically unsaturated
diol, 3-butene-1,2-diol, having the following structure: 2
[0007] The two hydroxyl moieties provide a possible means by which
firther functionality may be added to the polymer. For example,
U.S. Pat. No. 2,504,082 describes the synthesis of the propenyl
ester of 1-hydroxy-2-methoxy-3-butene. U.S. Pat. No. 4,916,255
describes the synthesis of the methacrylate ester of
1-hydroxy-2-methoxy-3-butene.
[0008] However, the polymerization of ethylenically unsaturated
esters such as allyl esters has proven difficult.
Homopolymerization of allyl esters such as allyl acetate is
sluggish and results in a low molecular weight polymer. Allyl
esters will also only copolymerize with a few selected unsaturated
monomers such as vinyl esters or maleic anhydride. (C. E.
Schildknecht, Allyl Compounds and Their Polymers,
Wiley-Interscience, 1973).
[0009] Similarly, only a few monomers are known that will
copolymerize effectively with vinyl esters. For a number of
applications, particularly coatings, poly(vinyl acetate) needs to
be modified with other monomers to provide a lower glass transition
temperature, T.sub.g. Vinyl esters such as vinyl neodecanoate have
been shown to be usefuil in lowering the T.sub.g of poly(vinyl
acetate), but are expensive. Other vinyl esters that have also been
shown usefull in reducing the T.sub.g of poly(vinyl acetate)
include butyl acrylate and 2-ethyl hexyl acrylate. Copolymers of
vinyl acetate and butyl acrylate are heterogeneous due to the
differences in reactivity (e.g., C. Pichot, M. F. Llauro, Q. T.
Pham, J. Polym. Sci.: Polym. Chem. Ed, 19, 2619-2633 (1981)).
However, monomers that will copolymerize well with vinyl esters
such as vinyl acetate and result in polymers with functional groups
available for post-polymerization are not known in the art.
[0010] Therefore, a need exists in the art for functionalized
ethylenically unsaturated esters which may be used as monomers and
undergo facile polymerization. Moreover, the needed monomers should
not only be able to form high molecular weight polymers but also be
able to copolymerize with a variety of other ethylenically
unsaturated monomers. It would also be desirable that such a
functionalized ethylenically unsaturated monomer contain
functionality capable of surviving polymerization and undergoing
further post-polymerization reaction.
SUMMARY OF THE INVENTION
[0011] The invention provides a polymer formed by the
polymerization of a monomer of formula (I): 3
[0012] In formula (I), at least one of R1 and R2 is an ester group.
The monomer of formula (I) may be homopolymerized. The monomer may
also be copolymerized with other ethylenically unsaturated
monomers. The invention also provides coating compositions
containing such polymers.
[0013] The invention further provides a method of making a polymer
containing a monomer of formula (I). The method involves the
polymerization, such as free-radical polymerization, of a monomer
of formula (I) with either itself or with another ethylenically
unsaturated monomer.
[0014] The invention further provides a monomer of formula (I) of
which at least one of R1 and R2 is an acetoacetyl group as well as
monomers of formula (I) of which R1 is a methyl group and R2 is
either an acetoacetyl or an acetyl group.
[0015] The invention still further provides a enamine finctional
polymer resulting from the reaction of an amine and the
polymerization product of a monomer of formula (I) and, optionally,
an ethylenically unsaturated monomer. In formula (I), at least one
of R1 and R2 is an acetoacetyl group. The invention also provides a
method of making the enamine functional polymers.
DETAILED DESCRIPTION OF THE INVENTION
[0016] One embodiment of the invention is a polymer resulting from
polymerization of a monomer of formula (I): 4
[0017] and, optionally, an ethylenically unsaturated monomer.
Mixtures of these monomers together or with other ethylenically
unsaturated monomers may be used to prepare polymers of the
invention. Preferably, the polymerization is a free-radical
polymerization.
[0018] In formula (I), R1 and R2 are, independently, hydrogen, a
C.sub.1-C.sub.24 alkyl group, an aromatic or heteroaromatic group,
a C.sub.3-C.sub.8 cycloalkyl or C.sub.2-C.sub.7 heterocycloalkyl
group, or a --C(O)R3 group. R3 is a C.sub.1-C.sub.24 alkyl group,
an aromatic or heteroaromatic group, a C.sub.3-C.sub.8zycloalkyl or
C.sub.2-C.sub.7 heterocyclic group, or a --CH.sub.2--C(O)-R4 group
where R4 is a C.sub.1-C.sub.6 alkyl group. In the monomers of
formula (I), at least one of R1 and R2 is a --C(O)R3 group forming
an ester. Preferably, when R1 and R2 both a --C(O)R3 group, R3 is a
--CH.sub.2--C(O)-R4 where R4 is methyl group, i.e. an acetoacetyl
group. When R1 is a methyl group, preferably, R2 is either an
acetyl group or an acetoacetyl group.
[0019] The alkyl group of R1, R2 and R3 may be a linear or branched
alkyl group. Preferably, the alkyl group is a C.sub.1-C.sub.12
alkyl group. More preferably, the alkyl group is, for example, a
methyl, ethyl, propyl, isopropyl, butyl, isobutyl, t-butyl, pentyl,
neopentyl or hexyl group. The alkyl group of R4 may also be a
linear or branched alkyl group. Preferably, R4 is a C.sub.1-C.sub.4
alkyl group. More preferably, R4 is, for example, a methyl, ethyl,
or propyl group.
[0020] Preferred aromatic and heteroaromatic groups described here
include, but are not limited to, phenyl, furanyl, pyrrolyl,
isopyrrolyl, thienyl, napthyl, pyridinyl, pyranyl, and benzyl.
Preferred cycloalkyl groups described here are C.sub.3-C.sub.6
cycloalkyl groups. More preferably, the cycloalkyl group is, for
example, a cyclopropyl, cyclopentyl, or cyclohexyl group. The
heterocycloalkyl groups described here are preferably
C.sub.2-C.sub.5 heterocycloalkyl groups. More preferably, the
heterocycloalkyl groups is, for example, an oxiranyl, aziridinyl,
imidazolidinyl, pyrazolidinyl, piperidinyl, piperazinyl, or
morpholinyl group.
[0021] In addition, an alkyl group, aromatic or heteroaromatic
group, or a cycloalkyl or heterocyclic group may be substituted
with groups such as, but not limited to, nitro, bromo, chloro,
fluoro, hydroxy, and alkoxy groups. An aromatic or heteroaromatic
group or cycloalkyl or heterocycle may also be substituted with a
C.sub.1-C.sub.4 alkyl group. Possible heteroatoms for
heteroaromatic groups include nitrogen, oxygen, and sulfur.
[0022] The ethylenically unsaturated monomer can be any monomer
which contains at least one ethylenically unsaturated group
allowing it to be copolymerized with monomers of formula (I). Such
monomers include, for example, allylic compounds, vinylic
compounds, styrenic compounds, .alpha.,.beta.-unsaturated
compounds, alkenes, acrylic compounds and the like. Examples of
suitable ethylenically unsaturated monomers include, but are not
limited to, vinyl acetate, vinyl pivalate, vinyl neodecanoate,
vinyl neononanoate, vinyl crotonate, vinyl 2-ethyl hexanoate, vinyl
propionate, 4-vinyl-1,3-dioxolan-2-one; ethylene, epoxy butene;
vinyl chloride, vinyl methacrylate; allyl alcohol, allyl chloride,
allyl acetate, allyl methacrylate, di-allylmalonate; dimethyl
maleate, diethyl maleate, di-n-butyl maleate, di-octyl maleate,
maleic anhydride; 3-butene-1,2-diacetate,
3-butene-1,2-dipropionate, 3-butene-1,2-dibutyrate,
3-butene-1,2-dibenzoate; dimethyl itaconate, itaconic anhydride;
crotonic acid and its esters, for example, C.sub.1-C.sub.18 alkyl
crotonates; acrylonitrile; acrylamide, methacrylamide, butyl
acrylamide, ethyl acrylamide; acrylic acid; methyl acrylate, ethyl
acrylate, ethylhexyl acrylate, propyl acrylate, butyl acrylate,
isobutyl acrylate, hydroxy ethyl acrylate, hydroxy propyl acrylate,
lauryl acrylate, octyl acrylate, iso-octyl acrylate; methacrylic
acid; methyl methacrylate, ethyl methacrylate, ethylhexyl
methacrylate, propyl methacrylate, butyl methacrylate, isobutyl
methacrylate, hydroxy ethyl methacrylate, hydroxy propyl
methacrylate, octyl methacrylate, glycidyl methacrylate,
carbodiimide methacrylate, methoxybutenyl methacrylate, isobomyl
methacrylate, hydroxybutenyl methacrylate, isopropenyl
methacrylate, iso-octyl methacrylate, cylcoaliphaticepoxy
methacrylate; ethylformamide; styrene and a-methyl styrene.
Preferably the ethylenically unsaturated monomer is the vinyl
ester, vinyl acetate.
[0023] Another embodiment of the invention is a method of making a
polymer of the invention. The method involves polymerizing,
preferably under free-radical polymerization conditions, a monomer
of formula (I) as described above and, optionally, an ethylenically
unsaturated monomer, also as described above. Free radical
polymerization of monomer (I) is achieved under conditions known by
those skilled in the art. The polymerization is conducted in the
presence of a free radical generating initiator. The free radical
polymerization process may be a bulk, solution, emulsion, or
suspension process. Preferably, the free radical polymerization
process is a semi-batch solution or emulsion process.
[0024] The free radical generating initiator may be any
conventional free radical polymerization initiator. Examples of
suitable initiators include, but are not limited to, azo(bis
isobutyronitrile), benzoyl peroxide, di-t-butyl peroxide, t-butyl
peroctoate, t-amyl-peroxy-2-ethyl hexanoate, and the like.
Quantitative conversion of monomer (I) to the corresponding polymer
can be improved by using a more active free radical initiator, i.e.
one with a shorter half-life, conducting the polymerization at a
higher temperature, or using a higher concentration of
initiator.
[0025] If a solvent is used to carry out the polymerization
process, solvents which can solubilize both monomer (I) and the
resulting polymer are preferred. Examples of suitable solvents
include, but are not limited to, xylene, toluene, methyl amyl
ketone, ethyl ethoxy propionate, propylene glycol monomethyl ether,
ethylene glycol butyl ether, and the like. Preferably, the solvent
is either a glycol ether or a glycol ether ester.
[0026] Polymerization of a monomer of formula (I), optionally with
another ethylenically unsaturated monomer, occurs through the
ethylenically unsaturated group of each monomer. The polymer of the
invention may contain at least one pendant functional moiety
through which fuirther chemistry can be conducted. The pendant
functional moiety may be any moiety which can undergo further
reactions including, for example, reacting with crosslinkers to
form thermoset materials. Preferably, the pendant functional moiety
is a hydroxyl group, an acetoacetoxy group, or a combination
thereof.
[0027] A crosslinker used with a polymer of the invention may be
any material capable of reacting with an active hydrogen containing
resin and include those well known in the art. Preferably, the
resin is a urea-formaldehyde, a melamine-formaldehyde, or an
isocyanate resin.
[0028] Polymers of the invention are generally thermoset polymers
and can be used in a variety of coating compositions such as
architectural coatings, maintenance coatings, industrial coatings,
automotive coatings, textile coatings, inks, adhesives, and
coatings for paper, wood, and plastics, and the like as described,
for example, in U.S. Pat. No. 5,539,073 incorporated in its
entirety herein by reference. Accordingly, the invention relates to
such coating composition containing a polymer of the invention. The
coating composition may be solvent-based or water-based. The
polymers of the invention may be incorporated in those coating
compositions in the same manner as known polymers and used with the
conventional components and or additives of such compositions. The
coating compositions may be clear or pigmented.
[0029] Upon formulation, a coating composition containing a polymer
of the invention may then be applied to a variety of surfaces,
substrates, or articles, e.g., paper, plastic, steel, aluminum,
wood, gypsum board, or galvanized sheeting (either primed or
unprimed). The type of surface, substrate, or article to be coated
generally determines the type of coating composition used. The
coating composition may applied using means known in the art. For
example, a coating composition may be applied by spraying or by
coating a substrate. In general, the coating may be dried by
heating but preferably is allowed to air dry. Advantageously, a
coating employing a polymer of the invention may be thermally or
ambiently cured. As a further aspect, the present invention relates
to a shaped or formed article which has been coated with a coating
compositions of the invention.
[0030] A coating composition according to the invention may
comprise a polymer of the invention, water, a solvent, a pigment
(organic or inorganic) and/or other additives and fillers known in
the art For example, a latex paint composition of the invention may
comprise a polymer of the invention, water, a pigment and one or
more additives or fillers used in latex paints. Such additives or
fillers include, but are not limited to, leveling, rheology, and
flow control agents such as silicones, fluorocarbons, urethanes, or
cellulosics; extenders; reactive coalescing aids such as those
described in U.S. Pat. No. 5,349,026; flatting agents; pigment
wetting and dispersing agents and surfactants; ultraviolet (UV)
absorbers; UV light stabilizers; tinting pigments; extenders;
defoaming and antifoaming agents; anti-settling, anti-sag and
bodying agents; anti-skinning agents; anti-flooding and
anti-floating agents; fungicides and mildewcides; corrosion
inhibitors; thickening agents; plasticizers; reactive plasticizers;
curing agents; or coalescing agents. Specific examples of such
additives can be found in Raw Materials Index, published by the
National Paint & Coatings Association, 1500 Rhode Island
Avenue, NW, Washington, D.C. 20005.
[0031] Another embodiment of the invention is a monomer of formula
(I): 5
[0032] In formula (I), R1 is a C.sub.1-C.sub.24 alkyl group or an
aromatic or heteroaromatic group as defined above and R2 is a
--C(O)R3 group where R3 is a C.sub.1-C.sub.24 alkyl group, an
aromatic or heteroaromatic group, a C.sub.3-C.sub.8 cycloalkyl or
C.sub.2-C.sub.7 heterocyclic group; or a --CH.sub.2--C(O)-R4 group
where R4 is a C.sub.1-C.sub.6 alkyl group, all as defined above.
Preferably, both R1 and R2 are a --C(O)--CH.sub.2--C(O)-R4 group
where R4 is methyl group, ie. both R1 and R2 are an acetoacetyl
group. In another preferred embodiment, R1 is a methyl group and R2
is either an acetyl group or an acetoacetyl group. Examples of
suitable monomers of formula (I) include, but are not limited to,
1-acetoxy-2-methoxy-3-butene, 1-acetoacetoxy-2-methoxy-3-butene,
3-butene-1,2-dipropionate, 1,2-diacetoxy-3-butene,
3-butene-1,2-diol monoacetate, 3-butene-1,2-diacetate, and
1,2-bisacetoacetate-3-butene.
[0033] Another embodiment of the invention relates to derivatizing
a polymer of the invention to form an enamine finctional polymer.
In an enamine functional polymer, the enamine functionality serves
to stabilize the acetoacetoxy-groups and protect them from
hydrolysis. Enamine-finctional polymers have been described in
Moszner et al., Polymer Bulletin 32, 419-426 (1994); European
patent Application No. 0 492 847 A2; U.S. Pat. Nos. 5,296,530;
5,484,849; 5,484,975; and 5,525,662. These documents are
incorporated here by reference.
[0034] An enamine functional polymer according to the invention
results from the reaction of an amine and an acetoacetoxy
functionalized polymer. The acetoacetoxy functionalized polymer is
the polymerization product of a monomer of formula (I): 6
[0035] and, optionally, an ethylenically unsaturated monomer. In
formula (I), R1 and R2are, independently, hydrogen, a
C.sub.1-C.sub.24 alkyl group, an aromatic or heteroaromatic group,
a C.sub.3-C.sub.8 cycloalkyl or C.sub.2-C.sub.7 heterocycloalkyl
group, or a --C(O)R3 group. R3 is a C.sub.1-C.sub.24 alkyl group,
an aromatic or heteroaromatic group, a C.sub.3-C.sub.8 cycloalkyl
or C.sub.2-C.sub.7 heterocyclic group, or a --CH.sub.2--C(O)-R4
group where R4 is a C.sub.1-C6 alkyl group. In the acetoacetoxy
functional polymer, in the monomers of formula (I), at least one of
R1 and R2 is an acetoacetyl group. The acetoacetoxy functionalized
polymer has one or more pendant acetoacetoxy moieties.
[0036] According to the invention, enamine functional polymers may
be prepared by reacting an amine with an acetoacetoxy
functionalized polymer as described above. The reaction
stoichiometry uses at least one molar equivalent of amino (NH)
groups to acetoacetoxy groups. The amine may be any amine which
upon reaction with the pendant acetoacetoxy moiety or moieties of
the acetoacetoxy functionalized polymer forms an enamine group.
Suitable amines include, for example, ammonia, primary amines and
secondary amines. Preparation of enamines from acetoacetoxy groups
are described in U.S. Pat. Nos. 5,296,530, 5,484,975, and 5,525,662
which are incorporated here by reference.
[0037] Though the reaction is rapid, an equilibrium exists between
the enamine product and the acetoacetoxy/NH reactants. Although the
reaction may be conducted at room temperature, the rate of enamine
formation increases with temperature. Due to the equilibrium,
however, an enamine functionalized polymer of the invention may
have both enamine and acetoacetoxy groups.
[0038] Enamine functional polymers or copolymers may also be
prepared by polymerization of enamine functional monomers. An
enamine finctional monomer may be prepared by the reaction of an
acetoacetoxy monomer with an amine such as those described above.
Polymerization of the resulting enamine functional monomer will
produce an enamine functional polymer. This method of enamine
polymer preparation is described Moszner et al., Polymer Bulletin
32, 419-426 (1994).
[0039] The following examples are given to illustrate the
invention. It should be understood, however, that the invention is
not to be limited to the specific conditions or details set forth
in these examples.
[0040] The examples of various coating compositions of the
invention use the following materials not described above:
[0041] LUPERSOL 575 t-amyl peroxy 2-ethylhexanoate sold by Elf
Atochem North America.
[0042] QP-300 Hydroxyethyl cellulose, sold by Union Carbide
Corporation.
[0043] AEROSOL TO-75 Anionic Surfactant, sold by Cytec
Industries.
[0044] TERGITOL NP40 Nonionic Surfactant, sold by Union Carbide
Corporation.
[0045] RESIMENE 745 Melamine formaldehyde resin from Cytec
Industries.
[0046] DESMODUR N 3300 Isocyanate of 6,6-hexane diisocyanate, sold
by Bayer, Inc.
[0047] BYK 300 Flow aid, sold by Byk Chemie.
[0048] MAK Methyl Amyl Ketone, solvent available from Eastman
Chemical Company.
[0049] FC-430 Fluorosurfactant (98.5% solids), sold by 3M, St.
Paul, Minn.
[0050] EASTMAN PM Propylene glycol monomethyl ether, sold by
Eastman Chemical Company.
[0051] The following methods were used to evaluate the coatings and
films prepared according to the invention.
Methyl Ethyl Ketone Resistance
[0052] Films cured under the specified conditions were rubbed with
a methyl ethyl ketone (MEK) saturated cloth according to ASTM
D5402. Results are reported as the number of double rubs required
for breakthrough of the film to the substrate.
Gloss
[0053] Gloss was measured on .about.1 mil films coated on Bonderite
1000 pretreated steel panels using a Byk-Gardner haze-gloss
meter.
Pencil Hardness
[0054] Pencil hardness was measured using a series of pencils
containing leads of differing hardness according to ASTM D3363. The
hardness is reported as the hardest pencil lead that does not
penetrate the coating film.
Konig Pendulum Hardness
[0055] The Konig pendulum hardness is determined using a
Byk-Gardner pendulum hardness tester according to ASTM D4366.
Hardness is reported as the number of seconds for the pendulum
swing to be damped from a 6.degree. swing to a 3.degree. swing.
Impact Resistance
[0056] Forward and direct impact resistance is determined using a
falling dart impact tester according to ASTM D2794. Results are
reported as the maximum in-lbs of force where the film remains
intact.
Sodium Hydroxide Stain Test
[0057] A drop of 6 M NaOH solution was placed on the coating and
covered with a microscope cover slide. After 24 hours the panel was
washed with water and the coating inspected for visual damage. A
coating with no visual damage passes the test.
EXAMPLE 1
Synthesis and Purification of 1-Acetoxy-2-Methoxy-3-Butene
[0058] In a 3-liter, 3-necked round bottom flask equipped with a
mechanical stirrer, nitrogen inlet, temperature probe and vigoreux
column was placed 1200 mL toluene, sodium acetate (88.59 g, 1.08
mol) and 2-methoxy-3-buten-1-ol (250.0 g, 2.45 mol). Mixture heated
to 60.degree. C. with stirring. Once temperature had stabilized,
acetic anhydride (288.83 g, 2.80 mol) added dropwise over 2.5
hours. Maintained temperature for 1.5 hrs then increased
temperature to 70.degree. C. for 1 hour. Gas chromatography showed
no trace of starting material in reaction. Began cooling reaction
to room temperature. When reaction had cooled to 38.degree. C., one
liter of a 5% sodium bicarbonate solution was added at high speed
to decompose any excess acetic anhydride remaining in the reaction.
Extracted reaction twice with water, layers separated, the aqueous
layer extracted twice with toluene and added to the organic layer.
Organic layer dried with anhydrous magnesium sulfate, filtered and
concentrated by rotovap. Yield 222.43 g (63.0%) of a clear,
colorless material. .sup.1H NMR consistent with 1-acetoxy-2-methoxy
butene.
EXAMPLE 2
Synthesis and Purification of 1-Acetoacetoxy-2-Methoxy-3-Butene
[0059] In a 500 mL 3-neck round bottom flask was placed
2-methoxy-3-butene-1-ol (164.46 g, 1.61 mol) and t-butyl
acetoacetate (430.20 g, 2.50 mol). Reaction flask was equipped with
magnetic stir bar, thermocouple, vigreaux column, and a still head
with thermometer. Reaction was heated to 134.degree. C. with
stirring for 7 hours, then cooled to room temperature. Product was
purified using a short-path distillation apparatus. Distillate was
collected until the head temperature exceeded 67.degree. C. NMR of
the remaining material indicated the desired product. .sup.1H NMR
(CDC1.sub.3): d 5.63-5.75 (m, 1H), 5.32-5.40 (m, 2H), 5.06 (s, 1H),
4.10-4.25 (m, 2H), 3.82-3.90 (m, 1H), 3.5 (s, 1H), 3.34 (s, 3H),
2.28 (s, 3H), 1.96 (s, 3H).
EXAMPLE 3
Copolymerization of 1-Acetoxy-2-Methoxy-3-Butene
[0060] In a 500 mL reactor kettle was weighed Eastman PM solvent
(180.0 g) and heated to 80.degree. C. Vinyl acetate (216.0 g),
1-acetoxy-2-methoxy-3-butene (54.0 g), and LUPERSOL 575 (5.4 g)
weighed into a 500 mL Erlenmeyer flask and pumped into the reactor
over three hours. Temperature held at 80.degree. C. for one hour
after completion of addition, then LUPERSOL 575 chaser (0.5 g) was
added. Temperature was maintained at 80.degree. C, for an
additional hour before cooling to room temperature. Clear resin
produced at 55.43% solids out of a theoretical 60% solids
formulation.
EXAMPLE 4
Copolymerization of 1-Acetoacetoxy-2-Methoxy-3-Butene
[0061] In a 500 mL two-piece resin reactor was placed 107.7 g
propylene glycol monomethyl ether and heated to 80.degree. C. In a
separate container, 80 g vinyl acetate, 40 g of
1-acetoacetoxy-2-methoxy-3-butene, 80 g vinyl 2-ethyl hexanoate,
and 8.0 g LUPERSOL 575 were mixed: The monomer mixture was added to
the resin reactor over a 3 hour period. After a one hour hold, 1.0
g of LUPERSOL 575 was added and the reaction held at 80.degree. C.
for an additional 1.5 hours. Resin mixture was cooled and poured
out. Resin had a solids content of 60.8% and the Tg of the resin
was .about.13 .degree. C.
EXAMPLE 5
Coating Made From Copolymer of Example 4
[0062] A clear coating formulation was prepared by mixing 29.21 g
of the resin in Example 4 above with 6.0 g RESIMENE 745, 1.42 g of
a solvent mixture consisting of 55 % xylene, 32 % methyl amyl
ketone, 6.5 % ethyl ethoxy propionate, 6.5 % n-butanol; 0.24 g
FC430, and 0.30 g p-toluene sulfonic acid. The components were
mixed until homogeneous. The coating mixture was drawn down on an
iron phosphate pretreated steel panel (Bonderite 1000) using a
wire-wound drawdown bar. The coating was cured at 160.degree. C.
for 30 minutes. The resulting coating had 95 MEK double rubs,
pencil hardness of 2B, Konig pendulum hardness of 33 seconds,
forward impact resistance 160 in-lbs, reverse impact resistance 120
in-lbs.
EXAMPLE 6
Synthesis of Homopolymer
[0063] To a 300 mL round bottomed 3-neck flask equipped with a
thermocouple, mechanical stirrer, condenser, and a nitrogen inlet
was charged 100.00 g 3-butene-1,2-diacetate. Contents were heated
with stirring to 80.degree. C. 2.0 g of LUPERSOL 575 (t-amyl peroxy
2-ethylhexanoate) was added. The contents were held for 22 hours at
80.degree. C. then cooled. Conversion of monomer to polymer was
65.7%. Number average molecular weight was 8100 and the
weight-average molecular weight was 13100 by Gel Permeation
Chromatography.
EXAMPLE 7
Synthesis of Copolymer by Solution Process
[0064] 107.7 g of propylene glycol monomethyl ether was charged to
a 500 mL resin kettle equipped with a mechanical stirrer, nitrogen
inlet, thermocouple, and condenser. The solvent was heated to
80.degree. C with stirring. In a separate vessel, 40 g of
1,2-diacetoxy-3-butene, 100 g vinyl acetate, 60 g
vinyl-2-ethylhexanoate, and 8 g LUPERSOL 575 were mixed. The
monomer mixture was fed to the heated solvent over a 3 hour period.
After a one hour hold, 1 g of LUPERSOL 575 was added. The mixture
was poured out after 1.5 hours. Measured % solids was 64.73%. Glass
transition temperature of the polymer was -6.81 .degree. C. as
measured as the midpoint in the inflection of DSC.
EXAMPLE 8
Synthesis of Copolymer by Emulsion Process
[0065] A vinyl acetate/3-butene-1,2-diacetate emulsion copolymer
was prepared as follows: 248.0 g deionized water, 24.0 g of a 5%
solution of QP-300, 0.45 g of AEROSOL TO-75, 19.40 g of TERGITOL
NPA40, and 1.2 g sodium carbonate was charged to a 1-liter
two-piece resin kettle equipped with a mechanical stirrer,
thermocouple, nitrogen inlet, and condenser. The mixture was heated
to 65.degree. C. with rapid stirring. In a separate vessel, 320 g
vinyl acetate and 80 g of 3-butene-1,2-diacetate were mixed. When
the reactor mixture reached 65.degree. C., 40 g of the monomer
mixture was added. 1.7 g of AEROSOL TO-75 was added to the
remaining monomer mixture.
[0066] Feed #2 was prepared consisting of 1.03 g of 70% aqueous
solution of t-butyl hydroperoxide and 29.77 g water. Feed #3 was
also prepared consisting of 0.70 g sodium formaldehyde sulfoxylate
dissolved in 30.0 g water.
[0067] After holding for 10 minutes at 65.degree. C., the following
were premixed and separately added to the reactor: (1) 0.25 g of a
1% FeSO.sub.4-7 H.sub.2O aqueous solution and 2.0 g water; (2) 0.25
g of a 1% ETDA aqueous solution and 2.0 g water; (3) 0.51 g of a
70% aqueous t-butyl hydroperoxide solution and 4.89 g water; and
(4) 0.35 g sodium formaldehyde sulfoxylate and 5.0 g water.
[0068] After holding for ten minutes at 65 .degree. C., the monomer
mixture was pumped in at a rate of 1.7 g/min over 3.5 hours. Thirty
minutes after the start of the monomer feed, feeds 2 and 3 were
started at a rate of 0.14 g/min over 3.5 hours. Thirty minutes
after the completion of feeds 2 and 3, chasers were added
consisting of (1) 0.26 g of 70 % aqueous t-butyl hydroperoxide and
1.94 g water, and (2).15 g sodium formaldehyde sulfoxylate and 2.0
g water. Thirty minutes later, additional chasers were added
followed by a 30 minute hold at 65 .degree. C. The latex was
cooled, filtered and packaged.
[0069] This latex has a particle size of 305 nm, percent solids of
52.3, pH 5.09, viscosity of 602 cP (Brookfield viscosity @ 100
rpm). Minimum film formation temperature is 17.5.degree. C.
EXAMPLE 9
Synthesis of Emulsion Copolymer Containing
3-Butene-1,2-Dipropionate
[0070] A latex was prepared using the same recipe and procedure as
in Example 8, except the monomer mixture consisted of 280 g vinyl
acetate and 120 g of 3-butene-1,2-dipropionate. Particle size was
301 nm, percent solids was 52.3, pH 5.13, and viscosity was 1075 cP
(Brookfield viscosity @ 100 rpm). The minimum film formation
temperature was 110.degree. C.
EXAMPLE 10
Synthesis of Solution Copolymer of Bis(Acetoacetate)
[0071] To a 500 mL resin kettle equipped with a mechanical stirrer,
nitrogen inlet, thermocouple and condenser, 108 g of propylene
glycol monomethyl ether was added. The solvent was heated with
stirring to 80.degree. C. In a separate vessel, 40 g of
1,2-bisacetoacetate-3-butene, 80 g vinyl acetate, 80 g vinyl
2-ethyl hexanoate, and 8.0 g of LUPERSOL 575 were mixed. The
monomer mixture was added to the heated solvent over a period of 3
hours. One hour after completion of the addition, 1.0 g of LUPERSOL
575 was added. After 1.5 hours the resin was cooled. Mn of the
resin was 3500 by gel permeation chromatography. The glass
transition temperature of the resin was .about.9.0.degree. C.
EXAMPLE 11
Crosslinked Coating Using Polymer of Example 10
[0072] A clear coating formulation was prepared by mixing 29.16 g
of the resin in Example 10 above with 6.0 g RESIMENE 745, 1.47 g of
a solvent mixture consisting of 55 % xylene, 32 % methyl amyl
ketone, 6.5 % ethyl ethoxy propionate, 6.5 % n-butanol; 0.27 g
FC430, and 0.30 g p-toluene sulfonic acid. The components were
mixed until homogeneous. The coating mixture was drawn down on an
iron phosphate pretreated steel panel (Bonderite 1000) using a
wire-wound drawdown bar. The coating was cured at 160.degree. C.
for 30 minutes. The resulting coating had over 200 MEK double rubs
indicating substantial curing, pencil hardness of HB, Konig
pendulum hardness of 52 seconds.
EXAMPLE 12
Preparation of Copolymer
[0073] 107.7 g of propylene glycol monomethyl ether (PM) was
charged to a 500 mL two-piece resin reactor fitted with a
condenser, nitrogen inlet, and a mechanical stirrer. The solvent
was heated to 80.0.degree. C. In a separate vessel, 40 g of
3-butene-1,2-diol monoacetate, 80 g vinyl acetate, 80 g vinyl
propionate, and 8.0 g t-amyl-peroxy-2-ethyl hexanoate ( LUPERSOL
575) were charged. The monomer mixture was added to the heated
solvent over a 5 hour period. After a one hour hold, I g of
LUPERSOL 575 was added, and the reaction was held at 80C for an
additional 1.5 hours. The resin mixture was cooled. The resulting
material had a measured solids content of 60.1 %, viscosity of 380
cps. No unreacted 3-butene-1,2-diol monoacetate was detected by gas
chromatography. The number average molecular weight was 2600 and
the weight average molecular weight was 5700 as determined by gel
permeation chromatography using polystyrene standards.
EXAMPLE 13
Preparation of Copolymer
[0074] 107.7 g of propylene glycol monomethyl ether (PM) was
charged to a 500 mL two-piece resin reactor fitted with a
condenser, nitrogen inlet, and a mechanical stirrer. The solvent
was heated to 80.0 .degree. C. In a separate vessel, 30 g of
3-butene-1,2-diol monoacetate, 90 g vinyl acetate, 80 g vinyl
2-ethylhexanoate, and 8.0 g t-amyl-peroxy-2-ethyl hexanoate
(LUPERSOL 575) were charged. The monomer mixture was added to the
heated solvent over a 3 hour period. After a one hour hold, 1 g of
LUPERSOL 575 was added, and the reaction was held at 80.degree. C.
for an additional 1.5 hours. The resin mixture was cooled. The
resulting material had a measured solids content of 61.5 %,
viscosity of 334 cps. No unreacted 3-butene-1,2-diol monoacetate
was detected by gas chromatography. The number average molecular
weight was 3400 and the weight average molecular weight was 6400 as
determined by gel permeation chromatography using polystyrene
standards.
EXAMPLE 14
Preparation of Melamine Crosslinked Enamel
[0075] An enamel formulation was prepared as follows: To 29.27 g of
the resin solution from Example 13 was added 6.0 g of RESIMENE 745,
1.36 g of a solvent blend (composed of 55% xylene, 32 % methyl amyl
ketone, 6.5 % ethoxy ethyl propionate, and 6.5 % n-butanol), 0.29 g
of a 25% solution of FC430 flow control aid in methyl amyl ketone,
and 0.30 g of a 30% solution of p-toluene sulfonic acid in
isopropanol. The coating was applied to iron phosphate pretreated
steel test panels and cured in an oven for 30 minutes at
160.degree. C. The final coating thickness was 1.3 mils. The
coating had pencil hardness of H, passed 200 MEK double rubs with
no marring, Konig Pendulum hardness of 70 sec. The coating passed a
sodium hydroxide stain test.
EXAMPLE 15
Preparation of Urethane Crosslinked Enamel
[0076] Since the polymer of Example 13 is dissolved in a solvent
containing active hydrogen groups, this solvent needed to be
replaced before crosslinking with an isocyanate functional
crosslinker. Solvent was removed using a rotary evaporator with a
water aspirator vacuum, followed by use of a vacuum pump. The
polymer was redissolved in butyl acetate at a solids level of
65%.
[0077] The urethane coating was prepared as follows: To 18.46 g of
the resin solution above was added 3.00 g DESMODUR N 3300, 0.15 g
of BYK 300 flow aid, and 1.51 g of a 1% solution of dibutyl tin
dilaurate in MAK. The coating was applied to iron phosphate
pretreated steel test panels and cured in an oven for 45 minutes at
80.degree. C. The final coating had thickness of 1.6 mils. Pencil
hardness was B, passed 80 MEK double rubs, Konig Pendulum Hardness
of 14 sec and had impact resistance of 160 in-lbs. The coating
passed a sodium hydroxide stain test. The coating had a 20.degree.
gloss of 87.7 and a 60.degree. gloss of 107.
EXAMPLE 16
Preparation of Enamine
[0078] To 5.0 g of the polymer of Example 10 was added 1.2 g of
propylene glycol monomethyl ether, and 0.60 g of butyl amine. The
reaction was stirred at room temperature for 30 minutes. Enamine
formation was monitored by infrared spectroscopy. A small sample of
the reaction mixture was coated onto a zinc selenide crystal and
the solvent was allowed to evaporate. Infrared spectrum indicated
an absorbance at 1650 cm.sup.-1 indicating enamine formation.
* * * * *