Synthetic resins or natural rubbers -- part of the class 520 ser – Synthetic resins – Polymers from only ethylenic monomers or processes of...
Reexamination Certificate
2000-03-29
2001-09-04
Sellers, Robert E. L. (Department: 1712)
Synthetic resins or natural rubbers -- part of the class 520 ser
Synthetic resins
Polymers from only ethylenic monomers or processes of...
C526S318000, C525S163000, C525S327700, C525S329500
Reexamination Certificate
active
06284855
ABSTRACT:
BACKGROUND OF THE INVENTION
This invention involves improvements in a generally known type of copolymer that is formed by addition polymerization of alpha unsaturated monomers (including vinyl monomers, alpha-olefins, and acrylates) and esters of unsaturated dicarboxylic acids or anhydrides (typically maleic anhydride). When provided with hydroxyl functionality, this type of polymer has found utility in prior art coating compositions where they can be cured to form durable coatings by reaction with crosslinking agents that are reactive with hydroxyl groups, such as polyisocyanates, aminoplasts, or anhydrides. Alternatively, this type of polymer has been proposed for use as a polymeric dispersant or surfactant.
U.S. Pat. No. 3,270,088 (Hicks) discloses alkoxylating a half ester of maleic acid to produce a hydroxyalkyl ester monomer that is copolymerized with vinyl monomers that do not contain other reactive functional groups.
U.S. Pat. No. 3,414,635 (Edwards et al.) discloses reacting an unsaturated anhydride with a glycol ether, and the resulting half ester is then alkoxylated. The resulting hydroxyalkyl diester is copolymerized with vinyl monomers or acrylate monomers that do not contain other reactive functional groups.
U.S. Pat. No. 3,838,087 (Pirck) discloses copolymerizing maleic anhydride with a vinyl aromatic monomer, then opening the anhydride groups with alcohol and alkcxylating the remaining acid groups to form a hydroxyl group containing polymer.
U.S. Pat. No. 5,612,416 (McCollum et al.) discloses alkoxylating a half ester of maleic acid to produce a hydroxyl group containing monomer that is copolymerized with a combination of vinyl monomers and alpha-olefins, neither of which contain other reactive functional groups.
U.S. Pat. No. 5,585,427 (Schimmel et al.) discloses copolymerizing unsaturated diesters with various vinyl monomers, followed by transesterification of ester groups with hydroxy polyethers. The vinyl monomers do not include acid functionality. The product is useful as a dispersant for pigments in coating compositions.
U.S. Pat. No. 5,166,272 (Burks et al.) discloses copolymers of unsaturated anhydrides and alpha-olefins that have at least eight carbon atoms. The alpha-olefins used are selected from 1-decene, 1-dodecene, and undecenylic [sic] acid. The patent discloses base-neutralizing the anhydride groups on the polymer to permit dispersing the polymer in water.
Canadian Patent Specification 1,159,990 (Plum) discloses reacting unsaturated anhydrides with a polyhydric alcohol and a monoepoxy compound and then copolymerizing the resulting hydroxy diester with unsaturated monomers explicitly without carboxylic groups, particularly vinyl aromatic monomers and acrylate monomers.
U.S. Pat. No. 4,289,866 (Ritz et al.) is similar to the Canadian Patent above, with an additional step of further alkoxylating the alcohol ester group.
U.S. Pat. No. 5,418,306 (Shalati et al.) has as its objective the production of acid functional polymers. An unsaturated anhydride is copolymerized with a polyolefin, and the resulting anhydride polymer is reacted with alcohol to convert the anhydride groups to acid functional half esters.
U.S. Pat. No. 5,418,307 (Valpey et al.) is related to the above patent, with the additional step of hydrogenating the copolymer to produce a saturated product.
U.S. Pat. No. 4,166,893 (Kambanis et al.) copolymerizes a dimaleate having selected ester groups with a first acrylate and a second unsaturated monomer selected from other acrylates, vinyl acetate, and styrene.
SUMMARY OF THE INVENTION
It has now been found that useful alternating copolymers can be made by addition polymerization of a relatively long chain (at least 8 carbon atoms) olefinic acid, particularly undecylenic acid, with mono- or di-esters of unsaturated dicarboxylic acids (or the corresponding mono- or di-esters of unsaturated anhydrides). The resulting acid functional copolymers are useful as intermediates to produce various polymeric products that find utility, for example, in coating compositions.
One use of the copolymer intermediate involves imparting hydroxyl functionality to the copolymer by reacting the acid groups with an epoxy compound. Such hydroxyl functional polymers are useful in curable coating compositions when combined with conventional crosslinking compounds. The epoxy may be reacted with only the carboxylic group contributed by the undecylenic acid (in those embodiments in which the other monomer is a diester), with the acid groups contributed by both monomer types (in those embodiments in which monoesters of the dicarboxylic acid are used), or with the undecylenic acid prior to copolymerization. In each of these alternatives, the resulting polymer is characterized by regular placement of hydroxy groups along the polymer, which is considered advantageous in a curable coating composition for the sake of enhanced curing. Well-cured polymers usually result in coatings that are characterized by good mar resistance. Thus, another aspect of the invention comprises a curable coating composition containing the hydroxy functional copolymer of the invention with a crosslinking compound reactive with hydroxyl groups, such as a polyisocyanate, aminoplast, or anhydride type of crosslinking compound.
A second utility for the acid functional copolymer intermediates of the present invention entails their neutralization with a base. When neutralized to a sufficient extent to render the copolymers dispersible in water, it has been found that the base-neutralized copolymers of the present invention serve as excellent surfactants for use in aqueous dispersion polymerization. Particularly advantageous in this embodiment are copolymers of undecylenic acid and dialkyl maleates.
In another variation, instead of alkoxylating or neutralizing the acid groups of the copolymer intermediate, the acid groups may be esterified with a hydroxy group-containing polyalkyleneoxide. The product may serve as a polymeric dispersant in the manner disclosed in the aforesaid U.S. Pat. No. 5,585,427 (Schimmel et al.).
In yet another aspect of the invention, in those cases where a monoester of an unsaturated diacid is employed in the copolymerization, the copolymer may subsequently be heated to convert the half acid ester groups on the copolymer to anhydride groups. The resulting anhydride functional copolymer may be base neutralized for dispersion in water to serve as a polymeric surfactant for aqueous dispersion polymerization in the manner taught in the aforesaid U.S. Pat. No. 5,166,272 (Burks et al.)
DETAILED DESCRIPTION
One of the monomers included in the copolymer of the present invention is a monocarboxylic alpha-olefin having at least eight carbon atoms. Commercial availability of this class of monomers is essentially limited to undecylenic acid (10-undecenoic acid or 10-hendecenoic acid).
The other monomer for making the copolymer of the present invention may comprise monoesters or diesters of unsaturated dicarboxylic acids, as well as the monoesters or diesters of the corresponding anhydrides, including combinations thereof. Anhydrides have been preferred for the sake of their ability to form alternating copolymers with alpha-olefins, but in the present invention it has been found surprisingly that the mono- or di-esters are able to form alternating copolymers with undecylenic acid. Dialkyl maleates are preferred due to their availability, but other substituted or unsubstituted monoesters or diesters of other unsaturated dicarboxylic acids may be used. These acid include, for example, fumaric acid, citraconic acid, 2,3-dimethyl maleic anhydride, chloro maleic anhydride, dichloro maleic anhydride, and itaconic anhydride. Any unsaturated anhydride having alkyl, aryl, or other substitution may serve the same purpose.
Any alkyl, cycloalkyl, aryl, or alkaryl alcohol may serve to open the anhydride ring in the first stage of the esterification to form the mono- or di-ester monomers used in the copolymerization of the present invention. Since the primary function of this alcohol is merely t
Das Suryya K.
Kilic Soner
Schimmel Karl F.
PPG Industries Ohio Inc.
Sellers Robert E. L.
Uhl William J.
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