Polyurethane salts

Details Polyurethane salts Polyurethane salts

2001-01-19

2002-04-30

Gorr, Rachel (Department: 1711)

Synthetic resins or natural rubbers -- part of the class 520 ser

Synthetic resins

Compositions to be polymerized by wave energy wherein said...

C526S240000, C526S241000, C560S025000, C560S058000, C556S001000, C556S044000, C556S050000, C556S056000, C556S063000, C556S077000, C556S107000, C556S116000, C556S134000, C556S136000, C556S148000, C556S183000, C556S442000

Reexamination Certificate

active

06380278

ABSTRACT:

BACKGROUND OF THE INVENTION
This invention relates to metal containing polyurethane salts.
Metal-containing polyurethanes and polyurethane-ureas have been reported in the prior art.
All the metal-containing polyurethanes and polyurethane-ureas suggested in the prior art have hydroxyl- or amino-terminal functional groups and have poor solubility. Most of the prior polymers are prepared in very polar solvent such as DMSO, and DMF.
Urethane (meth)acrylates have been widely used as a class of oligomers or resins in radiation curable based and peroxide based systems, and are known to provide the toughness as crosslinkers. Metal (meth)acrylates such as zinc, calcium, and magnesium salts of (meth)acrylic acids are known as crosslinking monomers for use with elastomers to promote adhesion to substrates. Zinc diacrylate, and zinc methacrylate have been suggested as crosslinking agents for elastomers such as EPDM, 1,4-butadiene, isoprene, chloprene, and the like. Unsaturated carboxylic metal salts such as zinc and calcium diacrylates are known to be useful as crosslinkers in curable elastomeric compositions wherein the elasto may be a nitrile rubber, EPDM, EVA, and the like.
Soluble zinc and calcium salts of ethylene glycol-methacrylate-phthalate prepared in aqueous solution and then copolymerized with methyl methacrylates (MMA), styrene (ST), and hydroxyethyl methacrylate (HEMA) have been reported as having improved physical properties.
Electrically conductive resins prepared from metal salts of certain sulphonates, phosphates or phosphoric acid diesters, with an epoxide, optional solvent, polymerization initiator, and/or photosensitizer have been reported to be useful for magnetic tape.
Polyvalent metal salts of compounds such as diethylene glycol methacrylate phthalate, mixed with an organic peroxide have been reported to be soluble in styrene MMA, and EA. Copolymerization with such vinyl monomers to produce polymers having high heat distortion temperature, tensile strength, compressive strength, impact strength and Rockwell hardness, as well as resistance to chemical attack, has been reported.
Magnesium, aluminum, and calcium salts of unsaturated phosphate compounds have been reported as additives for coatings to improve adhesion to metals. Peroxide cured adhesives prepared by copolymerizing such salt monomers with hydroxy propyl methacrylate (HPM) have been reported as well.
There has been no suggestion in the prior art of metal-containing urethanes with terminal (meth)acrylate groups nor any suggestions as to preparation of soluble metal containing polyurethane salts which do not require polar solvent for preparation with regard to solubility and avoiding the need of polar solvent in the preparation.
SUMMARY OF THE INVENTION
It is therefore an object of the present invention to provide metal containing urethanes which do not require polar solvent for preparation. It is also an object to prepare soluble metal containing polyurethane salts.
It is a further object to provide metal containing urethane (meth)acrylate adhesives, coatings, inks, transparent molded articles useful as lenses, and thermoset laminating resins with thermoplastic properties.
These objects and others which will become apparent from the following disclosure are achieved by the present invention which comprises in one aspect a urethane (meth)acrylate metal salt obtained by reacting (A) one or more polyisocyanates; (B) one or more hydroxy functional (meth)acrylates; and (C) one or more metal salt polyols which are the reaction product of a metal oxide and a half ester containing a hydroxy group and a carboxylic acid group.
In another aspect the invention comprises a process for preparing the urethane (meth)acrylate salt comprising reacting (A) one or more polyisocyanates; (B) one or more hydroxy functional (meth)acrylates; and (C) one or more metal salt polyols which are the reaction product of a metal oxide and a half ester containing a hydroxy group and a carboxylic acid group.
DETAILED DESCRIPTION OF THE INVENTION AND THE PREFERRED EMBODIMENTS
This new invention relates to a new class of materials containing urethane linkage as well as ionic linkage in the backbones, which can be crosslinked free radically via terminal (meth)acrylate functional groups. The term “(meth)acrylate” is used herein as an abbreviation to mean both acrylates and methacrylates.
The new resins of this invention are thermoset systems, having both urethane linkages and ionic bonds, providing toughness for the final polymers. However, the metallic urethane acrylates of the invention are different from the traditional thermoset polymers since they contain ionic crosslinkings which are based on coulombic forces and therefore are heat/temperature dependent. The final polymers will provide dynamic properties when heated or where heat buildup is a factor. Positive attributes of the novel metallic acrylate urethanes include good adhesion to substrates, good thermal properties (Tg, HDT), high strength, and reversible ionic crosslinking. The positive attributes of metallic urethane acrylates include toughness, flexibility, chemical resistance and abrasion resistance.
Some uses of the metal urethane acrylates are UV powder coatings, rubber to metal adhesion, composites, golfballs, modifiers for unsaturated polyesters, UV/EB cure, peroxide cure, conductive coatings, adhesives, radiation shading coatings, radiopaque materials, corrosion inhibitors, static discharge agents, heat buildup release modifiers, flow modifiers, dynamic property modifiers, and thermosetting materials with thermoplastic properties.
Suitable metals include lithium, sodium, potassium, cesium, magnesium, calcium, strontium, barium, titanium, zirconium, vanadium, chromium, molybdenum, tungsten, manganese, iron, cobalt, nickel, palladium, copper, zinc, cadmium, mercury, boron, aluminum, gallium, indium, silicon, germanium, tin, lead, antimony, bismuth, and the like. The metal compound can be, for example, the oxide, halide, alkoxide, hydroxide, nitrate, sulfate, carboxylate, and carbonate. The most preferred metal compound is zinc oxide since it reacts very easily and is readily available.
Suitable anhydrides and dicarboxylic acids include phthalic acid, trimellitic anhydride (which contains one anhydride and one carboxyl group), pyromellitic anhydride, 5-norbornene-endo-2,3-dicarboxylic anhydride, naphthyl anhydride, naphthalene tetracarboxylic acid dianhydride, maleic anhydride, succinic anhydride, chlorendic anhydride, maleic acid, succinic acid, fumaric acid, oxalic acid, malonic acid, glutaric acid, adipic acid, dimer fatty acids, and styrene/maleic anhydride polymers.
Suitable polyols include diols such as ethylene glycol, propylene glycol, 1,3-propanediol, 1,2, 1,3 or 1,4 butanediols, 2-methyl-1,3-propane diol (MPDiol), neopentyl glycol (NPG), alkoxylated derivatives of such diols, polyether diols, polyester diols, and the like.
Suitable higher functional polyols are trimethylol propane (TMP), PETA, di-TMP, di-PETA, glycerol, alkoxylated derivatives thereof, and the like.
Some examples of suitable hydroxyl-containing (meth)acrylates are hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, hydroxybutyl (meth)acrylate, trimethylolpropane mono- and di-(meth)acrylate, pentaerythritol mono-, di-, tri- (meth)acrylate, dipentaerythritol mono-, di-, tri-, tetra-, and penta-(meth)acrylate, neopentyl glycol (meth)acrylate, hexanediol mono(meth)acrylate, tris(2-hydroxyethyl)isocyanurate mono- and di(meth)acrylate, polypropylene glycol mono(meth)acrylate, polyethylene glycol mono (meth)acrylate, polypropylene/polyethylene glycol mono(meth)acrylate, polybutyl glycol mono(meth)acrylate, polytetramethylene glycol mono(meth)acrylate, hydroxy polycaprolacton mono(meth)acrylate, and ethoxylated and propoxylated derivatives thereof.
Some of the polyisocyanate examples are hexamethylene diisocyanate, isophorone diisocyanate, cyclohexane-1,4-diisocyanate, methylene bis(4-cyclohexylisocyanate), toluene diisocyanate, diphenylmethane 4,4-diisocyanate, xylene diisocyanate, 1,4-phenylene diisoc

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