Stock material or miscellaneous articles – Hollow or container type article – Polymer or resin containing
Reexamination Certificate
2000-03-15
2002-07-09
Reddick, Judy M. (Department: 1713)
Stock material or miscellaneous articles
Hollow or container type article
Polymer or resin containing
C428S034100, C428S034300, C428S036300, C428S036800, C428S036900, C428S036910, C428S421000, C428S422000, C525S074000, C525S078000, C525S207000, C525S221000, C525S285000, C525S327600, C525S327400, C525S340000, C525S374000
Reexamination Certificate
active
06416834
ABSTRACT:
BACKGROUND OF THE INVENTION
This invention relates to an adhesion-promoting additive for use in elastomers. In addition, this invention relates to elastomer compositions having enhanced adhesion to other polymers, in particular, to fluoropolymers.
Laminates of elastomers and fluoropolymers are desirable for use in a wide variety of commercial products, for example, in fuel hoses, pump diaphragms, and wire coatings. Good interlayer adhesion is required in such applications in order to produce constructions with acceptable service life. Further, it is desirable that such adhesion be achieved during the laminate curing process, without the necessity of applying primers or adhesives to the uncured elastomer surface.
One method described in the art for promoting interlayer adhesion between dissimilar elastomers and between elastomers and thermoplastic compositions is described in U.S. Pat. No. 5,300,569 and involves addition of polymeric adducts of dicarboxylic acids or dicarboxylic acid derivatives to uncured elastomers to promote adhesion to various substrates. While such systems often provide improvement in adhesion, certain demanding commercial requirements require even greater bond strengths than can be achieved through use of the adducts alone. In addition, the systems disclosed in U.S. Pat. No. 5,300,569 are not suitable for use with certain elastomers, including those mixed with amines or active hydrogen compounds.
The present invention is directed to elastomer compositions which contain polymeric dicarboxylic acids or dicarboxylic acid derivatives, but which exhibit enhanced adhesion to other polymers, especially to fluoropolymers.
SUMMARY OF THE INVENTION
In particular, the present invention is directed to a composition for improving adhesion between an elastomer and a fluoropolymer comprising
(A) a first polymer comprising an uncured unsaturated polymeric adduct formed by reacting i) a polymer having unsaturation in the backbone of the polymer chain with ii) an unsaturated dicarboxylic acid or dicarboxylic acid anhydride, wherein the acid or anhydride moieties comprise at least three weight percent of said adduct; and
(B) a compound selected from the group consisting of polyamino primary amines, polyamino primary amine carbamates, and condensation products of polyamino primary amines with aldehydes;
wherein the number of equivalents of component (B) is equal to or greater than the number of equivalents of carboxylic acid moieties or anhydride moieties present in component (A).
The invention is further directed to a composition for improving adhesion between an elastomer and a fluoropolymer comprising
(A) a first polymer comprising an uncured unsaturated polymeric adduct, formed by reacting i) a polymer having unsaturation in the backbone of the polymer chain with ii) an unsaturated dicarboxylic acid or dicarboxylic acid anhydride, wherein the acid or anhydride moieties comprise at least three weight percent of said adduct; and
(B) a polyhydroxy compound; and
(C) a quaternary phosphonium salt vulcanization accelerator or a quaternary ammonium salt vulcanization accelerator;
wherein the number of equivalents of component (B) is equal to or greater than the number of equivalents of carboxylic acid moieties or anhydride moieties present in component (A).
The invention is also directed to a curable elastomer composition which comprises
(A) a first polymer comprising an uncured unsaturated polymeric adduct, formed by reacting i) a polymer having unsaturation in the backbone of the polymer chain with ii) an unsaturated dicarboxylic acid or dicarboxylic acid anhydride, wherein the acid or anhydride moieties comprise at least three weight percent of said adduct;
(B) an elastomer, different from said first polymer;
(C) a compound selected from the group consisting of polyamino primary amines, polyamino primary amine carbamates, and condensation products of polyamino primary amines with aldehydes; and
(D) a curing agent for the elastomer of (B);
wherein the number of equivalents of component (C) is equal to or greater than the number of equivalents of carboxylic acid moieties or anhydride moieties present in component (A).
The invention is additionally directed to a curable elastomer composition which comprises
(A) a first polymer comprising an uncured unsaturated polymeric adduct, formed by reacting i) a polymer having unsaturation in the backbone of the polymer chain with ii) an unsaturated dicarboxylic acid or dicarboxylic acid anhydride, wherein the acid or anhydride moieties comprise at least three weight percent of said adduct;
(B) an elastomer, different from said first polymer;
(C) a polyhydroxy compound;
(D) a quaternary phosphonium salt accelerator or a quaternary ammonium salt vulcanization accelerator; and
(E) a curing agent for the elastomer of (B)
wherein the number of equivalents of component (C) is equal to or greater than the number of equivalents of carboxylic acid moieties or anhydride moieties present in component (A).
The invention is further directed to laminates of the curable elastomeric compositions and fluoropolymer compositions, both fluoroplastics and fluoroelastomers.
DETAILED DESCRIPTION OF THE INVENTION
Adhesion promoting compositions of the present invention comprise mixtures of carboxylated polymeric adducts and a) polyamines or polyamine derivatives, or b) polyhydroxy compounds. The carboxylated polymeric adducts which are suitable for use in the present invention are disclosed in U.S. Pat. No. 5,300,569. They are prepared by reacting polymeric resins, such as, for example, polybutadiene homopolymers or copolymers of styrene and butadiene, with a dicarboxylic acid or dicarboxylic acid anhydride, such as maleic anhydride. Preferably, the polymeric resin is an unsaturated polymer comprising at least one monomer which is a conjugated diene of 4-12 carbon atoms. The polymer may additionally comprise a monomer which is a vinyl substituted aromatic compound of 8-20 carbon atoms. Polybutadienes are preferred polymers and a preferred polybutadiene is a random 1,2 or 1,4 polybutadiene homopolymer containing 20-90% 1,2 vinyl groups. Polymer molecular weights are generally in the range of 4,000 to 30,000.
The dicarboxylic acid or dicarboxylic acid anhydride which is reacted with the polymeric resin to produce the carboxylated polymeric adducts used in the compositions of the present invention may be any alpha, beta-ethylenically unsaturated dicarboxylic acid or anhydride. Preferably, the adduct is prepared by reaction of maleic acid or maleic anhydride with the polymeric resin. Generally, the unsaturated acid or anhydride comprises at least 3 weight percent of the carboxylated polymer resin adduct, preferably between 3 and 17 weight percent of the polymer resin adduct.
The polyamine compounds and polyamine derivatives suitable for use in the adhesion promoting compositions include primary amines having more than one amino moiety, carbamates having more than one nitrogen-containing moiety derived from polyamino primary amines, and adducts of polyamino primary amines with aldehydes. Examples of suitable polyamino primary amines include ethylenediamine, tetraethylenetetramine, hexamethylenediamine, triethylenetetramine, cumenediamine, tetramethylenediamine, hexamethylenetetramine, 1,2-diaminopropane, diethylaminopropylamine, and 4,4′-methylenebis-(cyclohexylamine). Examples of particularly useful carbamates are hexamethylenediamine carbamate and 4,4′-methylenebis-(cyclohexylamine) carbamate. A preferred polyamino primary amine/aldehyde adduct is N,N′-di-cinnamylidene-1,6-hexanediamine.
Polyhydroxy compounds may be used in place of the polyamino primary amines or amine derivatives in the compositions of the present invention. Suitable polyhydroxy compounds include bisphenol A, bisphenol AF, bisphenol S, hydroquinone, 4,4′-dihydroxybenzophenone, is catechol, 2,5-dimethyl-hydroquinone, pentaerythritol, 2,2-dimethyl-1,3-propanediol, and trimethylolpropane. Bisphenols are preferred, and, of these, bisphenol AF is most preferred. When a polyhy
E. I. du Pont de Nemours and Company
Reddick Judy M.
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