Synthetic resins or natural rubbers -- part of the class 520 ser – Synthetic resins – Mixing of two or more solid polymers; mixing of solid...
Reexamination Certificate
2000-04-03
2001-05-08
Zitomer, Fred (Department: 1713)
Synthetic resins or natural rubbers -- part of the class 520 ser
Synthetic resins
Mixing of two or more solid polymers; mixing of solid...
C525S329500, C525S374000, C525S378000, C525S379000
Reexamination Certificate
active
06228949
ABSTRACT:
BACKGROUND OF THE INVENTION
1. Field of the Invention
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.
2. Description of the Related Art
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)).
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.
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:
The two hydroxyl moieties provide a possible means by which further 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.
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).
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
g
. Vinyl esters such as vinyl neodecanoate have been shown to be useful in lowering the T
g
of poly(vinyl acetate), but are expensive. Other vinyl esters that have also been shown useful in reducing the T
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.
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
The invention provides a polymer formed by the polymerization of a monomer of formula (I):
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.
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.
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.
The invention still further provides a enamine functional 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
One embodiment of the invention is a polymer resulting from polymerization of a monomer of formula (I):
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.
In formula (I), R1 and R2 are, independently, hydrogen, a C
1
-C
24
alkyl group, an aromatic or heteroaromatic group, a C
3
-C
8
cycloalkyl or C
2
-C
7
heterocycloalkyl group, or a —C(O)R3 group. R3 is a C
1
-C
24
alkyl group, an aromatic or heteroaromatic group, a C
3
-C
8
cycloalkyl or C
2
-C
7
heterocyclic group, or a —CH
2
—C(O)—R4 group where R4is a C
1
-C
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
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.
The alkyl group of R1, R2 and R3 may be a linear or branched alkyl group. Preferably, the alkyl group is a C
1
-C
2
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
1
-C
4
alkyl group. More preferably, R4 is, for example, a methyl, ethyl, or propyl group.
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
3
-C
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
2
-C
5
heterocycloalkyl groups. More preferably, the heterocycloalkyl groups is, for example, an oxiranyl, aziridinyl, imidazolidinyl, pyrazolidinyl, piperidinyl, piperazinyl, or morpholinyl group.
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
1
-C
4
alkyl group. Possible heteroatoms for heteroaromatic groups include nitrogen, oxygen, and sulfur.
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, &agr;,&bgr;-unsaturated compounds, alkenes, acrylic compounds and the like. Examples of suitable ethylenically unsaturated monomers include, but are not lim
Crain Allen Lynn
Marlow Chadwick Edward
Webster Dean Charles
Allen, Esq. Rose M.
Eastman Chemical Company
Gwinnell Harry J.
Zitomer Fred
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