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
2001-07-18
2004-03-16
Mullis, Jeffrey (Department: 1711)
Synthetic resins or natural rubbers -- part of the class 520 ser
Synthetic resins
Mixing of two or more solid polymers; mixing of solid...
C525S310000, C525S313000
Reexamination Certificate
active
06706821
ABSTRACT:
FIELD OF THE INVENTION
The present invention relates to compounds having terminal acrylic functionality, and more particularly to acrylic functionalized polymers having a hydrophobic hydrocarbon backbone.
BACKGROUND OF THE INVENTION
Acrylic based resins are widely used in a variety of applications, including coatings, sealants, adhesives, and the like. Generally such resins are defined as thermoplastic polymers or copolymers derived from acrylic acid, methacrylic acid, esters of these acids or acrylonitrile. The monomers polymerize readily in the presence of radiation, typically ultraviolet light, or e-beam radiation, or thermal energy.
For example, radiation curable acrylic systems can be coated onto a substrate and the coated substrate passed under a commercially available UV or excimer lamp on a conveyer moving at predetermined speeds. The substrate can be, for example, metal, wood, mineral, glass, paper, plastic, fabric, ceramic, and the like. Radiation curable systems are increasingly attractive in view of environmental concerns associated with the release of volatile organic compounds (VOCs) which can result from the use of solvent-based systems, as well as energy costs associated with curing solvent based systems.
Despite the benefits associated with acrylic based systems, there are problems with existing products. For example, the market for radiation cured coatings applied to nonporous substrates such as plastics is increasing. However, adhesion to such surfaces can be difficult because unlike metal substrates, where a chemical as well as a physical bond can occur, plastic substrates have only a physical bond present. In addition, acrylic resins are polar in nature and thus may not be readily used in applications requiring hydrophobicity, among other properties.
U.S. Pat. No. 5,587,433 to Boeckler is directed to the preparation of esters of hydroxy terminated polybutadiene compositions. The esters are prepared by reacting a hydroxy terminated polybutadiene with an anhydride to form a carboxyl terminated polybutadiene derivative. This derivative is then reacted with an epoxide, which can be a glycidyl acrylate ester. Alternatively the carboxyl-terminated polybutadiene derivative can be reacted with an excess amount of a diepoxide, such as diglycidyl ethers of Bisphenol A, and the residual epoxide groups subsequently reacted with an &agr;,&bgr;-unsaturated carboxylic acid, such as acrylic or methacrylic acid. In yet another alternative embodiment, the carboxyl-terminated polybutadiene derivative can be reacted in excess with diepoxide and the residual carboxy groups subsequently reacted with a glycidyl acrylate ester. See also Modern Paints & Coatings, November 1999, pages 30-34. While these resins can offer desirable properties, the resultant oligomers exhibit relatively poor thermal oxidative stability.
U.S. Pat. No. 5,393,843 to Handlin, Jr. et al. is directed to hydrogenated butadiene polymers having terminal functional groups. The polymers are stated to have 1,2 addition microstructure between 30% and 70%, which in turn is stated to result in polymers having lower viscosities as compared to similar polymers having either higher or lower amounts of 1,2-addition. Generally the polymers are prepared using lithium initiators to polymerize one or more conjugated dienes, such as butadiene, in the presence of a structure modifier to achieve the desired percentage of 1,2-addition. Examples 1-5 describe preparing linear hydrogenated butadiene polymers having about two terminal hydroxyl groups per molecule using a lithium diinitiator and treating the resultant living polymer with ethylene oxide to functionalize the same. Example 46 is a hypothetical example that describes preparing an acrylate terminated prepolymer from such a hydrogenated polybutadiene diol by reacting the same with isophorone diisocyanate and hydroxyl ethyl acrylate. Although the different isocyanate groups of the isophorone diisocyanate could exhibit some selectivity, it would be expected that the isocyanate groups would also react not only with the diols of the polybutadiene polymer but also with the hydroxyl group of the acrylate as well.
SUMMARY OF THE INVENTION
The present invention is directed to unique compounds having various desirable yet contradictory properties. In particular the invention provides Michael addition adducts of polyfunctional acrylates and amine terminated polyolefins.
Generally the polyfunctional acrylates have the formula:
wherein R is hydrogen or methyl, n is ≧2 and Q is an organic group. Q can be any organic group that does not interfere with the Michael addition and can include moieties such as polyethers or polyoxyalkylenes, urethanes, epoxies, polyesters, and isocyanates. Currently preferred polyfunctional acrylates are polyoxyalkylene acrylates, which are optionally ethoxylated or propoxylated.
The amine terminated polyolefins are advantageously prepared via anionic polymerization using lithium initiators, including dilithium initiators and functionalized lithium initiators having a protected amine functionality as known in the art. The resulting living chain end can be functionalized using amine electrophiles. Amine protecting groups, when present, are removed to liberate the amine functionalities.
The amine terminated polyolefins are preferably substantially hydrogenated so that at least about about 70%, or more, of the carbon-carbon double bonds are saturated The inventors have found that the use of hydrogenated amine functionalized polyolefins can provide the benefit of improved thermal oxidative stability and UV stability as compared to acrylate functionalized polymers having unsaturated polyolefin backbones. Further, the presence of the polyolefin chain can provide other useful properties to the resulting adducts, such as elastomeric properties and improved adhesion of the adducts to polyolefin substrates.
The resulting adducts can be generally represented by the formula:
wherein:
R is hydrogen or methyl, and preferably hydrogen;
R
1
is a polyolefin;
R
2
and R
3
are independently H or substituted or unsubstituted C1-C25 alkyl;
R
4
is an organic group derived from a polyfunctional acrylate and optionally includes side groups formed by the reaction of vinyl groups and amine terminated polyolefins; and
m is from 1 to 30. Preferably R
4
is —C(O)—Q, wherein Q is an organic group comprising at least one moiety selected from the group consisting of polyethers or polyoxyalkylenes, urethanes, epoxies, polyesters, and isocyanates. One currently preferred adduct is represented by the formula:
wherein R
1
is hydrogenated polybutadiene or hydrogenated isoprene, having a molecular weight of from about 1000 to about 200,000, m is 1 or 2, and n is 1 to 200.
The present invention also provides methods for making the adducts of the invention. Generally the adducts are prepared via the Michael addition reaction of a molar excess of the polyfunctional acrylate with the amine terminated polyolefin. Stated differently, the adducts can be prepared by reacting m+1 moles of the polyfunctional acrylate with m moles of the amine terminated polyolefin, wherein m is 1 or greater. Such reactions readily occur at or around room temperature (e.g. 20° to 25° C.) but the rate of reaction can be increased at elevated temperatures (e.g. up to about 100° C.). The invention is not so limited, however, and the reaction can be conducted at temperatures outside of these ranges, for example, below room temperatures, even as low as about 0° C. Optionally diluents or solvents such as acetone, benzyl alcohol or other polar solvents, may be present. Reaction times can also vary and generally range from about 0.5 to about 8 hours, although reaction times outside of these ranges may be used. In addition, a base can be used to catalyze the reaction. However, a large molar excess (up to 5×) of one reactant or the other allows the adducting to be done with ease.
The adducts can be used in a variety of applications, such as adhesives, coatings, sealants, and the like. The adducts can also parti
FMC Corporation
Mullis Jeffrey
Myers Bigel & Sibley Sajovec, PA
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