Stock material or miscellaneous articles – Composite – Of polyester
Reexamination Certificate
1999-08-27
2002-05-07
Chen, Vivian (Department: 1773)
Stock material or miscellaneous articles
Composite
Of polyester
C428S480000, C525S437000, C525S438000, C525S441000, C525S443000, C525S444000, C525S444500, C528S299000, C528S300000, C528S401000, C528S402000
Reexamination Certificate
active
06383651
ABSTRACT:
FIELD OF INVENTION
This invention relates polyester polymers including blocks of polyoxetane derived from polymerizing monomer or monomers including oxetane monomers with partially fluorinated side chains. These polyesters have many of the desirable properties of fluorinated polymers and the ease of processability of the polyesters. The desirable properties of the fluorinated polymers are due to the partially fluorinated side chains and the tendency of the fluorinated side chains to be disproportionately present at any surfaces generated. These polymers are preferred in some embodiments over polyoxetanes with the partially fluorinated side chains as they are more easily incorporated and bound into a variety of polymers due to the polyester portion of the polymer.
BACKGROUND OF INVENTION
U.S. Pat. No. 5,650,483 describes the preparation of oxetane monomers useful to form oxetane polymers with pendant fluorinated chains. The oxetane polymers were characterized as having low surface energy, high hydrophobicity, and a low coefficient of friction. That patent is incorporated by reference herein for its teachings on how to prepare the oxetane monomers and polymers. In the reference the oxetane polymers could be formulated with isocyanates to form crosslinked compositions. Additional patents issued on variations of the oxetane monomers and polymers. These were U.S. Pat. Nos. 5,468,841; 5,654,450; 5,663,289; 5,668,250, and 5,668,251 also incorporated herein by reference.
Polyesters are a very useful class of polymers. They are used as molding or extruding polymers, as solvent or water dispersible polymers in coatings which can be cured with amino resins, as components in polyurethanes and epoxy materials, and when they are unsaturated in thermoset molding compositions for a variety of filled and/or fiber reinforced applications.
SUMMARY OF INVENTION
According to the present invention, it was discovered that a polyester resin having low surface energy, high hydrophobicity and a low coefficient of friction, which can result in improved stain and abrasion resistance, is produced by incorporating a hydroxyl terminated polymer (blocks) having repeating units from an oxetane monomer having pendant fluorinated groups thereon into a polyester. The hydroxyl terminated polymer may have other repeat units such as derived from the ring opening polymerization of cyclic ethers including tetrahydrofuran, propylene oxide or epoxy monomers. A preferred method of incorporating the polyoxetane into the polyester is to react the polyoxetane with a dicarboxylic acid or anhydride thereof under effective conditions to result in a half ester linkage between the polyoxetane and the diacid along with carboxylic acid terminal groups. Thereafter additional polyester repeating units can be added by reacting the terminal carboxylic acid groups with polyols or cyclic ethers and additional polyacids and/or anhydrides of polyacids. As polyesters are known to undergo ester interchange reactions one could generically list the reactants used to form the polyesters as polyesters and their precursors.
The preferred oxetane monomer for this application can have a single pendant —CH
2
—O—(CH
2
)
n
— Rf group where the Rf group is a partially or fully fluorinated linear or branched alkyl of from 1 to 20 carbon atoms, R is hydrogen or an alkyl of 1 to 6 carbon atoms, and n is from 1 to 3. Polyoxetanes with two pendant partially fluorinated groups per repeating unit could also be used with this technology. The terminology “partially fluorinated pendant group” will be used to describe the —CH
2
—O—(CH
2
)
n
— Rf group which is only partially fluorinated due to the CH
2
and —(CH
2
)
n
portions.
DISCUSSION OF DETAILS AND PREFERRED EMBODIMENTS
The polyester resins are generally made by a condensation polymerization reaction, usually with heat in the presence of a catalyst, of a mixture of a polycarboxylic acid or its anhydride and a polyhydric alcohol. Preferred polycarboxylic acids are the dicarboxylic acids and their anhydrides. Fatty monobasic oils or fatty acids, mono-hydroxy alcohols and anhydrides may be present. The polyester may contain active hydrogen atoms, e.g., carboxylic acid groups and/or hydroxyl groups for reaction with the amino resin or may contain unsaturation for crosslinking by another mechanism such as copolymerization with ethylenically unsaturated monomers. Examples of some acids to use to form the alkyd resin or reactive polyester are adipic acid, azelaic acid, sebacic acid, terephthalic acid, phthalic anhydride, and so forth. Generally the aliphatic carboxylic acids have from about 3 to about 10 carbon atoms. Other carboxylic acids such as carbonic acid or phosgene may be used in lieu of carboxylic acids under appropriate conditions. The aromatic carboxylic acids generally have from about 10 to about 30 carbon atoms. The polyhydric alcohols (polyols) generally have from about 2 to about 20 carbon atoms and from about 2 to about 5 hydroxyl groups. Polymeric polyols such as formed from the polymerization of cyclic alkylene oxides may be used as a portion or all of the polyhydric alcohol. Polymeric polyols generally have number average molecular weights from 100 to 5,000 or 10,000. Examples of some polyhydric alcohols include ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, glycerine, butylene glycol, 2,2-dimethyl-1,3-propanediol, trimethylol propane, 1,4-cyclohexanedimethanol, pentaerythritol, trimethylolethane and the like. Mixtures of the polyols and polycarboxylic acids can be used. An example of a suitable reactive polyester is the condensation product of trimethylol propane, 2,2-dimethyl-1,3-propanediol, 1,4-cyclohexanedimethanol, phthalic anhydride and adipic acid. Mixtures of these reactive polyesters (alkyd resins) can be used. Alkyd resins are well known as shown by the “Encyclopedia of Polymer Science and Technology,” Vol. 1, 1964, John Wiley & Sons, Inc., pages 663-734; “Alkyd Resins,” Martens, Reinhold Publishing Corporation, New York, 1961 and “Alkyd Resin Technology,” Patton, Interscience Publishers, a division of John Wiley and Sons, New York, 1962. Some unsaturated polycarboxylic acids and unsaturated polyols may be used in the condensation reaction.
The polyester segments of the polyester may also be polymerized from cyclic ethers typically containing 2 or 3 carbon atoms in the ring and an anhydride (e.g. an unsaturated anhydride) using double metal complex cyanide catalysts. These polyesters can be used with a carboxylic half ester functionalized polyoxetane because of the occurrence of ester interchange reactions whereby polyester polymers cleave to Form carboxylic acid and hydroxyl end groups and then couple with other polyester fragments via an ester linkage. Generally any cyclic oxide can be utilized such as 1,2-epoxides, oxetanes, and the like, with the cyclic ether having a total of up to 18 carbons atoms, as for example 2 carbon atoms in the ring and up to 16 carbon atoms in the side chains. Such cyclic oxide monomers can also contain one or more aliphatic double bonds. Generally five-member unsaturated cyclic anhydrides are preferred, especially those having a molecular weight between 98 and 400. Mixed anhydrides can be used. Anhydrides include phthalic, itaconic, nadic etc. Halogenated anhydrides can also be used. Such polyesters are known to the art and described in U.S. Pat. No. 3,538,043 which is hereby incorporated by reference.
Amino resins can be used as a crosslinker (curative) for the polyester when it has terminal hydroxy and/or carboxylic acid groups. These amino resins generally include alkylated benzoguanamine-formaldehyde, alkylated urea-formaldehyde, or preferably alkylated melamine-formaldehyde resin. Mixtures of these resins can be used. These amino resins are well known and include those set forth in “Aminoplastics,” Vale et al, Iliffe Books Ltd., London, 1964; “Amino Resins,” Blair, Reinhold Publishing corporation, New York, 1959, “Modern Plastics Encyclopedia 1980-1981,” pages 15, 16 and 25 and “Encyclopedia of Polymer Science Aid Tec
Kresge Edward N.
Medsker Robert E.
Weinert Raymond J.
Woodland Daniel D.
Chen Vivian
Hudak Daniel J.
Omnova Solutions Inc.
Rywalski Robert F.
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