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
1996-11-20
2001-03-13
Krass, Frederick (Department: 1501)
Synthetic resins or natural rubbers -- part of the class 520 ser
Synthetic resins
Mixing of two or more solid polymers; mixing of solid...
C525S329700, C525S330100, C525S449000, C525S523000, C525S533000, C527S311000, C527S315000, C528S103000, C528S110000, C536S063000, C536S066000, C536S084000, C536S091000, C536S095000, C536S096000, C536S115000, C536S116000, C536S119000, C536S120000
Reexamination Certificate
active
06201070
ABSTRACT:
FIELD OF THE INVENTION
The present invention generally relates to epoxide-containing compounds and methods for enhancing the toughness of coatings made from such compounds. More specifically, the present invention relates to cycloaliphatic epoxide derivatives of hydroxy-functional compounds having branched, 1,2-alkylene oxide units and the use of such derivatives as coating materials which can have enhanced toughness.
BACKGROUND OF THE INVENTION
Cycloaliphatic epoxides are often used to make cured, i.e., cross-linked, coatings for a variety of articles. When the coatings are applied to certain articles, e.g., food and beverage containers, it is not uncommon for the coatings to be applied to the substrate and cured prior to the fabrication of the article. As a result of the forming operations, the coatings can be subjected to a great deal of mechanical stress upon flexation, i.e., bending, which can cause the coatings to crack. In some cases the coatings are also subjected to retort treatment, i.e., treatment with steam or hot aqueous liquids, for sanitary purposes.
Accordingly, methods for enhancing the toughness, e.g., resistance to cracking upon flexation, of articles coated with cycloaliphatic epoxides are desired. Such methods would be particularly useful in operations where the articles are coated prior to fabrication into the desired shape. In addition, cycloaliphatic epoxide derivatives suitable for use in such methods are also desired. Desirably, the coatings made from such cycloaliphatic epoxide derivatives would also have a sufficient degree of hydrolytic stability to withstand retort treatments.
SUMMARY OF THE INVENTION
By virtue of the present invention, it is now possible to provide cycloaliphatic epoxide-based coatings for articles which have enhanced toughness, e.g., resistance to cracking upon flexation, for example, during fabrication of the article into the desired shape. Quite advantageously, coatings made from the cycloaliphatic epoxide derivatives of the present invention can also have enhanced hydrolytic stability which render the coatings made therefrom suitable for articles which must undergo retort treatment.
In accordance with the present invention, improved cycloaliphatic epoxide derivatives of hydroxy-functional compounds are provided. In the improved derivatives of the present invention, the hydroxy-functional compound has at least one branched 1,2-alkylene oxide unit. As used herein, the term “branched 1,2-alkylene oxide unit” means the moiety illustrated by the following structure:
wherein R
2
-R
5
are the same or different and are hydrogen, phenyl or substituted or unsubstituted alkyl or alkene groups each containing 1 to about 10 carbons, provided that at least one R
2
, R
3
, R
4
or R
5
is not hydrogen. Preferably, the branched 1,2-alkylene oxide unit is a propylene oxide unit.
The present invention also provides processes for manufacturing the cycloaliphatic epoxide derivatives by transesterification or epoxidation.
DETAILED DESCRIPTION OF THE INVENTION
The cycloaliphatic epoxide starting materials suitable for use in accordance with the present invention can be any cycloaliphatic epoxides which also have a functional group, e.g., acid, alcohol and preferably ester, which can react with the hydroxyl groups of a hydroxy-functional compound containing one or more branched, 1,2-alkylene oxide units. Typically, the cycloaliphatic epoxides have from about 5 to 7 carbon atoms and preferably 6 carbon atoms in the ring. The cycloaliphatic epoxides can have one or more epoxide groups, and preferably one group, per ring. In addition, the cycloaliphatic epoxides can comprise one or more rings, e.g., up to about 3, as well as other hydrocarbon substituents on the rings and can be saturated or unsaturated.
Preferably, the cycloaliphatic epoxide starting material has the following structure:
wherein R
6
is an organic moiety, preferably hydrogen or a hydrocarbon radical having 1 to about 30 carbon atoms and more preferably a linear or branched alkyl having 1 to about 10 carbon atoms and G
1
to G
9
are hydrogen, phenyl or substituted or unsubstituted alkyl or alkene having from 1 to about 10 carbon atoms.
Illustrative of the cycloaliphatic epoxides useful as starting materials in the present invention are methyl 3,4-epoxycyclohexane-carboxylate, ethyl 3,4-epoxycyclohexanecarboxylate, propyl 3,4-epoxycyclohexanecarboxylate, isopropyl 3,4-epoxycyclohexanecarboxylate; n-butyl-, i-butyl-, s-butyl-, and t-butyl 3,4-epoxycyclohexanecarboxylate; the various amyl and hexyl 3,4-epoxycyclohexanecarboxylates; methyl 3,4-epoxy-3-methyl-cyclohexanecarboxylate; ethyl 3,4-epoxy-3-methyl-cyclohexanecarboxylate; methyl 3,4-epoxy-4-methyl-cyclohexanecarboxylate; ethyl 3,4-epoxy-4-methyl-cyclohexanecarboxylate; butyl 3,4-epoxy-3-methyl-cyclohexanecarboxylate; butyl 3, 4-epoxy-4-methyl-cyclohexanecarboxylate; methyl 3, 4-epoxy-6-methyl-cyclohexanecarboxylate; ethyl 3,4-epoxy-6-methyl-cyclohexanecarboxylate; butyl 3,4-epoxy-6-methyl-cyclohexanecarboxylate; dialkyl 4,5-epoxycyclo-hexane-1,2-dicarboxylates, as well as mixed dialkyl 4,5-epoxycyclo-hexane-1,2-dicarboxylates, and the like.
The hydroxy-functional compounds suitable for use as starting materials in accordance with the present invention contain at least one branched 1,2-alkylene oxide unit. Typically, the alkylene oxide unit comprises from 3 to about 20 carbon atoms and preferably from about 3 to 6 carbon atoms. More preferably, the branched 1,2-alkylene oxide unit is a propylene oxide unit. The hydroxy-functional compounds can have one or more, preferably 1 to about 10, branched alkylene oxide units per molecule.
In a preferred aspect of the present invention, the hydroxy-functional compounds suitable for use as a starting material have the formula:
wherein R
1
and R
7
are organic moieties capable of bonding with oxygen, R
2
, R
3
, R
4
and R
5
are the same or different and are hydrogen, phenyl or substituted or unsubstituted alkyl or alkene groups having from 1 to about 10 carbon atoms, provided that at least one of R
2
, R
3
, R
4
or R
5
is not hydrogen; n has a value of from 1 to about 30, m has a value of from 0 to about 30, and x has a value of from 1 to about 30. When x is greater than 1, then n can be zero in one or more of the additional x-1 groups attached to R
1
.
In a preferred aspect of the invention, R
1
is hydrogen, m is zero, one of R
2
, R
3
, R
4
or R
5
are methyl and the remainder are hydrogen. In another preferred aspect of the invention, R
1
and R
7
are selected from the group consisting of alcohols, glycols, polyols, hydroxy-functional acrylic polymers and copolymers, hydroxy-functional polysaccharides, hydroxy-functional polyester resins, hydroxy-functional epoxy resins and mixtures thereof. Typically when R
1
is not hydrogen, R
1
has from 1 to about 50 carbon atoms per molecule.
Apart from the branched, 1,2-alkylene oxide unit(s), the remainder of the hydroxy-functional compound, i.e., R
1
and R
7
in the immediately preceding above structure, is not critical to the invention and may be any organic moiety, e.g., hydrogen or a hydrocarbon radical containing from 1 to about 30 carbon atoms. However, those skilled in the art will recognize that the remainder of the hydroxy-functional compound, in combination with the branched, 1,2-alkylene oxide unit(s), can also have a significant impact on the properties of the final coating.
In general, suitable hydroxy-functional compounds for use in accordance with the present invention include alcohols, glycols, polyols, and polymeric compounds containing at least one branched, 1,2-alkylene oxide unit. Illustrative of the hydroxyl-containing compounds are propylene glycol, di-, tri-, and tetra-propylene glycol as well as other poly(propylene glycols); trifunctional polypropylene oxide)s including ethylene oxide-capped and F-caprolactone-capped propylene oxide polyols that contain up to above 25% by weight ethylene oxide or propylene oxide; random, block, and graft ethylene oxide/propylene oxide copolymers; propoxylated polyester polyols
Braddock John Kellis
Eaton Robert Francis
Kumabe Naofumi
Patel Bharat Kanaiyalal
Upshaw Thomas Andrew
Krass Frederick
Union Carbide Chemicals & Plastics Technology Corporation
Volles W. K.
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