Synthetic resins or natural rubbers -- part of the class 520 ser – Synthetic resins – At least one aryl ring which is part of a fused or bridged...
Reexamination Certificate
1999-01-08
2002-12-10
Mulcahy, Peter D. (Department: 1713)
Synthetic resins or natural rubbers -- part of the class 520 ser
Synthetic resins
At least one aryl ring which is part of a fused or bridged...
C525S327600
Reexamination Certificate
active
06492455
ABSTRACT:
SPECIFICATION
Field of the Invention
The invention relates to the reaction product of a C
6
+ olefin/maleic acid anhydride copolymer with a polyfunctionalized amine. In a preferred embodiment, the polyfunctionalized amine is a secondary or tertiary amine. The resulting product has particular applicability as a coating in inkjet ink and in cosmetic applications including hair spray and sun lotions.
BACKGROUND OF THE INVENTION
Processes for the preparation of aqueous solutions of carboxyl as well as hydroxyl-group containing copolymers have been described. See, for instance, German Patentschrift DD 247 456 A1 which discloses a method for preparation of aqueous solutions of carboxyl and hydroxyl group containing copolymers by the addition of ethylene, propylene, or alpha methyl styrene/maleic anhydride copolymers to aqueous solutions of ethanolamine or diethanolamine. These processes employ a molar ratio of amine to acid anhydride groups of one or less and produce amide derivatives with neither hydrolysis of the anhydride group nor crosslinking by conversion of the alcohol groups of the ethanolamine, or especially diethanolamine, with the anhydride occurring.
It has been now been found that aqueous solutions of carboxyl and hydroxyl group containing copolymers may be prepared from polyhydroxy functionalized tertiary amines which are incapable of forming amides. Furthermore, such products, although they may be partially crosslinked, are still water soluble. These products may be applied as coatings and, depending upon curing conditions, can yield partially to fully water impervious films.
SUMMARY OF THE INVENTION
The partially cross linked reaction product of a C
6
+ alpha olefin and maleic anhydride copolymer with a polyfunctionalized amine has application as a heat cured coating and in cosmetic applications including hair spray and sun lotions, as well as in inkjet ink formulations.
The molar amount of polyfunctionalized amine added to the copolymer is approximately equal to the number of moles of maleic anhydride in the alpha-olefin/maleic anhydride copolymer.
The polyfunctionalized amine preferably is a secondary or tertiary amine of the general formula:
R
1
R
2
R
3
N
wherein R
1
, R
2
and R
3
independently are hydrogen, alkyl, alkyl ether, aminoalkyl, aminoalkylether, hydroxyalkyl, hydroxyalkylether, or an ester of hydroxyalkyl or hydroxyalkylether; provided at least two of R
1
, R
2
, or R
3
are hydroxyalkyl, hydroxyalkylether, aminoalkyl, or aminoalkylether.
DETAILED DESCRIPTION OF THE INVENTION
Reaction products of solid olefin/maleic anhydride copolymers with polyfunctionalized amines have been found to have unique applications. The resultant copolymer is an alternating copolymer of an olefinic monomer and a maleic acid anhydride with a polyfunctionalized secondary or tertiary amine.
The olefin/maleic anhydride copolymer is insoluble in water and is derived from maleic acid anhydride and a C
6
+ alpha olefin. An alpha olefin containing up to thirty plus carbon atoms may further be employed. In a preferred embodiment, the alpha olefin for use in the invention is a C
6
-C
24
alpha olefin. Most desirable results are obtained with C
8
-C
18
alpha olefins. The olefin/maleic anhydride copolymer may be referred to as a poly (alkylethylenesuccinic anhydride). The copolymer exhibits hydrophilic properties (from maleic anhydride) and lipophilic properties (from the alpha-olefin).
Such copolymers are prepared by reacting the alpha olefin and maleic anhydride in approximately equimolar ratios in a solvent, in which both comonomers are soluble, such as xylene, methyl ethyl ketone, or methyl isobutyl ketone. A free radical generator, such as di-t-butyl peroxide, azobis (4-cyanovaleric acid), or salts of azobis (N,N-dimethylformamide), is employed as initiator. The reaction mixture is typically heated from about 50 to about 60° C. The number average molecular weight of the resulting copolymer is generally between about 2,000 to about 5,000. Especially desirable results are obtained where the copolymer, having a number average molecular weight about 3,000 (measured by gel permeation chromatography), is derived from a C
8
alpha olefin and maleic anhydride. Following completion of the polymerization, the solvent is removed by vacuum distillation. Such copolymers include those from Baker-Petrolite Polymers Division under the trademark POMAREZ™.
The polyfunctionalized amine is preferably a secondary or tertiary amine that contains at least two reactive functional groups for reaction with the alpha olefin/maleic anhydride copolymer. Thus, where, for instance, a secondary amine comprises the polyfunctionalized amine, at least one other functional group is included in the moiety. Where the amine is a tertiary amine, the polyfunctionalized amine contains at least two other functional groups.
Suitable polyfunctionalized amines are those of the formula:
R
1
R
2
R
3
N (I)
wherein R
1
, R
2
, and R
3
may be hydrogen, alkyl, alkyl ether, hydroxyalkyl, hydroxyalkylether aminoalkyl, aminoalkylether, or an ester of hydroxyalkyl or hydroxyalkylether containing from 1 to 15 carbon atoms, typically 1 to 6 carbon atoms; provided at least two of R
1
, R
2
, or R
3
are hydroxyalkyl, hydroxyalkylether, aminoalkyl, aminoalkylether, or at least one of R
1
, R
2
, or R
3
is hydroxyalkyl, hydroxyalkylether, aminoalkyl, or aminoalkylether when the other is —H.
Alternatively, the polyfunctionalized amine may be of the formula:
wherein R
8
is —H and R
9
is hydroxyalkyl, hydroxyalkylether, aminoalkyl, or aminoalkylether.
Preferred polyfunctionalized amines are those of the formula:
R
1
N(R
2
)R
3
(II)
wherein R
1
is alkyl, alkyl ether, hydroxyalkyl hydroxyalkylether, or an ester of hydroxyalkyl or hydroxyalkylether, R
2
is H, hydroxyalkyl, hydroxyalkylether when R, is alkyl, alkylether, or an ester, and R
3
is an aminoalkyl, aminoalkylether, hydroxyalkyl, or hydroxyalkylether.
Such amines include those of the formula:
R
1
—NH—(CH
2
)
n
NH
2
(III)
wherein n is 1 to 6.
Especially preferred amines include those containing at least one primary amino group and one hydroxyl group or one primary amino group and one secondary amino group. Specific examples include, but are not limited to, N-methyl diethanol amine, aminoethylethanolamine, N-hydroxy-ethyl-1,3-propanediamine, N-methyl-1,3-propanediamine, N-ethyl diethanolamine, N-butyldiethanolamine, N,N-dihydroxyethylenediamine, 2-hydroxylpropyldiethanolamine, N-hydroxyethylpiperazine, aminoethylpiperazine, alkylethylene diamines, N-propylethylenediamine, N-isopropylethylenediame, and triethanolamine. In a most preferred embodiment, the diamine is aminoethylethanolamine.
The polyfunctionalized amine most desirably contains at least two reactive functional groups—most preferably one hydroxyl group and one amino group or two amino groups—for each equivalent of maleic anhydride in the copolymer. In this fashion, one of the —COO groups of the maleic anhydride moiety may be converted to a half amide (where the reactive functional group is an amine) or half ester (where the reactive functional group is an alcohol). The second —COO group of the maleic anhydride moiety remains as a free carboxylic acid group and forms an inner salt with the remaining amine moiety of the functionalized amine.
While not intending to be bound by any theory, it is believed that in the presence of water, the polyfunctionalized secondary or tertiary amine opens the anhydride ring on the alpha olefin/maleic anhydride copolymer by reaction of the more reactive primary amine with the maleic anhydride to form an amide simultaneously forming a carboxylic acid. Reaction of a —OH containing functional group with the maleic anhydride forms an ester and a carboxylic acid. The remaining secondary or tertiary amine groups form an inner salt of the carboxylic acid resulting in an aqueous solution of a half amide (or half ester) carboxylic acid inner salt containing free —OH or >NH groups. Coatings of these solutions, upon drying, cure by the eliminatio
Baker Hughes Incorporated
Locke Liddell & Sapp LLP
Mulcahy Peter D.
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