CA1082381A - Chalk-resistant, medium to dark colored polyurethanes, polymer/polyol and polyisocyanate compositions for use in producing same and methods for making said polyurethanes - Google Patents

Abstract

ABSTRACT OF THE DISCLOSURE
Improvements in polymer/polyol compositions which are convertible by reaction with polyisocyanates to poly-urethanes which are pigmented to a medium to dark color and which inherently chalk upon exposure to weather and wherein the polymer of the polymer/polyol composition is dispersed in the polyol thereof and is formed from one or more poly-merizable ethylenically unsaturated monomers. The improve-ment provides to said polyurethanes resistance to chalking on exposure to weather and in one embodiment comprises the presence, in the polymer/polylol compositions used to make the polyurethanes, of a metallocene from the class consisting of ferrocene, ferrocene derivatives, cobaltocene and nickel-ocene in an amount effective to provide chalk resistance.
Optionally, the metallocene can be present in the polyiso-cyanate composition instead of the polymer/polyol composition.
Improved dark colored polyurethanes are made by reacting a mixture comprising (a) a polymer/polyol composition and (b) an organic polyisocyanate in the presence of (c) a catalyst for the reaction of (a) and (b), (d) a metallocene, preferably ferrocene, or a ferrocene polymer and (a) a medium to dark pigment to produce the polyurethane.

Description

~o~2~ 10917-1 BACKGROUND ~F THE INVENTION
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1. Field of the Invention The invention relates to ~ovel improved poly-urethanes that are resistant to chalking upon exposure to weather and to novel improved polymer/polyol compositions for makin~ said improved polyurethanes. The invention also relates to novel improved polyisocyanate compositio~s for making said polyurethanes and to novel methods for making same.

2. Description of the Prior Art Polymer/polyol dispersions have been and currently are being used in the production of pigmented polyurethane -products having a wide variety of deæirable properties.
When pigmented to medium or dark colors such as red, blue, - green or black and exposed to weather such polyurethane products inherently chalk and therefore are unsuitable for use as automotive bumpers, fascia, trim and other objects . .
designed for outdoor applications.
The prior art discloses no solution to this problem. The present invention is based on the discovery that metallocenes, such as, cobaltocene, nickelocene, ferro-cene derivatives and, preferably ferrocene and its polymers, when present in suitable amounts in these medium to dark pigmented polyurethane products, impart resistance to ~halking. No prior art has been found which teaches or suggests improvements in chalk resistance by ~he incorporation of a metallocene into polyurethanes made from polymer/
polyols.

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~OBZ~ 10917-l Met~llocenes, and ferrocene in particular, and their derivatives have been used in polymers and resins for a wide variety of purposes. The effects of W and infrared light in space environments on a wide variety of organic coatings containing ferrocene derivatives ~uch as benzoyl ferrocene were reported by R. G. Schmitt and R. C. Hirt in J. Applied Polymer Science, Vo}. 7, pp. 1565-15~0 (1963).
This study in~luded a polyurethane polymer made from a polyester resin and polyisocyanate but does not mention any polyurethane polymer made with a polymer/polyol. Unsub-stituted ferrocene was not used. Furthermore, the study was not concerned with chalking effects or the reduction of same.
British Patent No. 1,406,581 is concerned with the use of ferrocene as a smoke suppression agent for poly-urethanes made with a polyol other than a polymer/polyol.
Chalking problems or their prevention are not mentioned.
Ferrocene ~as discovered in 1951 (Nature, 168, 1039, 1951; J. Chem Soc., 632, 1952) and was first incorporated into a polymer in 1955 when vinylferrocene was polymerized (J. Am. Chem. Soc., 77, 6295, 1955). Since then a significant amount of research effort has been devoted to metallocene polymers although, for reasons of availability and a well-explored chemistry of the parent compound, most polymers investigated have been derivatives of ~errocene ("Metallocene Polymers", Marcel Dekker, New York, 1970).
Ferrocene readily undergoes electrophilic substitution reactions, tends to ~tabilize carbonium ions and radicals that are alpha to the cyclopentadienyl rings, is thermally stable (up to ~00C), (F. A. Cotton and G. Wilkinson, ~ .

-3-3a follows 10823~ 10917-1 ~

"Advanced Inorganic Chemistry"~ Interscience, New York, N. Y., 1972), may be reversibly oxidized to the ferricinium ion, (Polymer Science, USSR, 15(2), 358 (1973), acts as a photochemical sensitizer as well as a quencher of photo-chemically generated triplet states, is an efficient W
screening agent, may promote semiconductivity in polymers, and has demonstrated a beneficial effect on glass transition temperature (Tg) of acrylate polymers (Chem. Tech., 1, 416 (1971). These properties and others have prompted the synthesis of a wide variety of ferrocene polymers during the past 20 years, most of which are described in a number of fine reviews. ("Metallocene Polymers", Marcel Dekker, New York, 1970; Polymer Science, USSR, 15t2), 358, 1973;
Chem. Tech., 1, 416, 1971; Advan, Macromol. ~hem., 1, 1, 1968i J. Organometal, Chem., Annual Survey Covering The Year 1973, 79, 278, 1974).
Ferrocene polymers are for the most part prepared by either free-radical techniques or acid-catalyzed condensations. The ferrocene nucleus may be pendent on the polymeric chain or part of the polymer backbone. As part of the polymer backbone the ferrocene may be linked heteroannularly or homoannularly and, if homo-annularly link~d, may exhibit 1, 2 or 1, 3 isomers. Included among polymers in which ferrocene is part of the polymer backbone are polyferrocenylenes, (Dokl. Akad. Nauk. SSSR, 132, 360, 1960; Dokl. Akad. Nauk. SSSR, 138, 125, 1961;
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J. Or~anometal. _hem., 6, 76, 1966: H. Rosenberg and al. t 2nd International Symp~sium on Organometallic Chemistry, ~adison, Wi6consin, 1965; Abstr. Proc., p. 42;

-3a-3b follows J. Organometal. Chem., 4, 475, 1965; J. Electrochem. Soc., 110, 15, lg63; Briti~h Pat. 1,136,699, 1968) an assortment of carbon-bridged ferrocene polymers, (J. Polymer Sci., C4, 1481, 1964; J. Org. Chem., 30, 4071, 1965; J~ Polymer Sci., A3, 1499, 1965; Nature, 204, 179, 1964; Plaste Xautschuk, 10, 32, 1963 J. Polymer Sci., (A-1)7, 2689, 1969; Dokl. Akad. Nauk. SSSR, 121, 299, 1958; U. S. Patent 3,350,369) and ferrocene polymers bridged with heter~atoms such as oxygen (J. Macromol. Chem., 1, 611, 1966; J. Macromol Chem., 1, 595, 1966) nitrogen, (Polymer Science, USSR, 15(2), 358, 1973), boron (J. Macromol. Sci., A2, 751, 196Bi H. Rosenberg and F. L. Hedberg, 3rd International Symposium on Organometallic Chemistry, Munich, 1967; Abstr., p. 108) and silicon (J. Org . Chem., 26, 1790, 1961; U. S. Patent 3,060,215; Makromol. Chem., 83, 148, 1965 Am Chem. Soc.
Org. Coatings Plastics Preprints, 31, 264, 1971; J. Polymer Sci. Polymer Chem. Ed., 12, 837, 1974). Polymers with ferrocene pendent on the polymer chain include poly(vinyl- ~ ;
ferrocenes), (J. Am Chem. Soc., 77, 6295, 1955; Chem.
Tech., 1, 416, 1971; W. P. Fitzgerald, JrO, Ph.D. Thesis, Purdue U., West Lafayette, Ind., 1963; J. Polymer Sci., Polymer Chem. Ed., 13, 1049, 1975; Macromolecules, 3, 746, 1970; J. Macromol. Sci. Chem., A8(5), 923, 1974) poly(ferro-- cenylacrylates)(Chem. Tech., 1, 416, 1971; J. Polymer Sci., ~;
C(4), 1481, 1966) poly(ethynylferrocenes) and other conjugated polymers, and poly(ferricinium) ~alts (Chem.
Tech.p 1, 416, 1971; J. Polymer Sci., C(4), 1481, 1966).

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lOgl7-1 A wide ~ariety of pol~mers containing ferrocene and ferrocene derivatives such as vinyl ferrocene and other ferrocene monomers and polymers and copolymers have been reported in the literature including Organo-metallic Compounds, September 5, 1975, Vol. 27, pages 156-166 and the references cited therein; J. Polymer Science, 1961, Vol. 54, pp. 651-656; Macromolecule~ 1971, Vol. 4, pp. 155-161, 291-297; J. Paint Technologv, 1974, Vol. 46, pp. 35-40; J. Paint Technolo~y, 1967, ~ol. 39, pp. 569~ `
592; ACS Div. Org. Coatings and Plastics ~hemistry, 1975, Vol. 35, pp. 251-254; U. S. Patents Nos. 3,847,871 and 3,926,881 and British Patent No. 1,395,655. None of these reports, patents or references cited in any of them mention polyurethanes made from polymer/polyols, chalking of such polyurethanes when subjected to weathering or the prevent-ion of such chalking.

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SUMMARY OF THE INVENTION
-The present invention is based on the discovery that the incorp~ration of a 6mall amount of a metallocene, such as, ferrocene, a ferrocene derivative, cobaltocene or nickelocene in a medium to dark colored polyurethane, which is made from a polymer/polyol and which undergoes surfaoe chalking upon exposure to weather, imparts chalk resistance to the polyurethane.
Infrared analysis of the chalk scraped from the surface of unprotected, black pigmented, polymer/polyol based polyurethanes that had been subjected to accelerated, simulated weathering conditions indicated the chalk to comprise mainly the polymer segment of the polymer/polyol employed in the manufacture of the polyurethane. Without ~-wishing to be bound to any theory, it has been theorized that the weathering process was dissipating the urethane network at the surface thus exposing the vinyl polymer or fragments thereof as a white chalk. The metallooene can be incorporated in the polymer/polyol composition prior to ~ ;~
mixing and reaction with the polyisocyanate or it may be ~ `
incorporated into the polyisocyanate composition prior to mixing and reaction with the polymer/polyol. The present ,~
invention thus provides novel polymer/polyol ~ompositions, novel polyisocyanate oompositions and novel polyurethanes containing a metallocene. The present invention also provides methods for producing polyurethanes having impr~ved resistance to chalking from polymer/polyols and poly~so-cyanates. The invention is applicable to foamed as well as unfoamed polyurethane products suc~ as blac~ exterior ~08~3~ 10917-1 automotive parts including bumper rub ~trips, bumper guards, side moldings and full bumpers. The inventio~
eliminates the need for protective weather resistant coatings and renders the polym~r/polyol-based, medium to dark pigmented polyurethanes suitable for a wide variety of outdoor applications.

DESCRIPTION OF SPECIFIC EMBODIMENTS
The polymer/polyol compositions of this invention are liquid, stable dispersions of a polymer in a polyol and contain a metallocene from the class consisting of ferrocene (bis-cyclopentadienyl iron) and derivatives thereof (e.g., ferrocene polymers), nickelocene (bis-cyclo-pentadienyl nickel) and cobaltocene (bis-cyclopentadienyl cobalt) in an amount effective to impart resistance to weather-induced surface chalking of polyurethanes made from the polymer/polyol compositions. The precise amount of metallocene used is not narrowly critical and can vary over wide ranges. Amounts of ferrocene of about 0.035 weight percent or less based on th~ weight of the poly-urethane product are effective as well as amounts as high as about 2.5 weight percent or more based on the weight of the polyurethane product. Amounts of ferrocene derivative, e.g., the ferrocene polymers such as 2,2-diferrocenyl-propane polymer, of about 0.007 to about 0.7 weight percent or higher based on the weight of polyurethane are effective.
The metallocenes mentioned above are well known and reference is made to J. Paint Technolo~ 1967, ~ol. 39, pp D 576-584, and literature cited therein for details regarding the preparation and pr~perties of these metallocenes. The ferrocene derivatives disclosed in ~. S. Patent 3,926,881 5a to ~ollow ~o~3~ 10917-1 and the references set forth therein in Columns 2 and 3, are suitable for use in this invention and the disclosure of such derivatives in this patent and in said references cited therein are incorporated herein by reference. The chlorinated paraffins required for the puxposes of U. S.
Patent 3,926,881 provide no special advantage in the present invention and can be omitted if desired. In fact, the presence of chlorinated paraffins can be detrimental in the present invention from the standpoint of imparting too much plasticization or possibly hindering the catalysis in the polyurethane-forming reaction.

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The polymer/polyols present in the novel polymer/polyol compositions of this invention are also well known, the basic patents being the Stamberger patents, U.S.
Patent Nos. 3,304,273; 3,383,351, Re. 28,715 ~reissue of 3,383,351) and 3,523,093. Later disclosures of polymer/
polyols include the Scharf et al and Kuryla Canadian Patent Nos. 735,010 and 785,835; the Pizzini et al U.S.
Patent No. 3,823,201; the Ramlow et al British Patent ~lo. 1,450,511; the Ramlow et al patent U.S. Patent No.
3,953,393; and the DeWald U.S. Patent No. 3,655,553. These as well as any other suitable polymer/polyol can be employed herein.
The polymer of the polymer/polyol is formed by polymerizing one or more polymerizable ethylenically unsaturated monomers. -~
The proportion of polymer in the polymer/polyol -~
can range from about 4 to about 50 weight percent, preferably from about 15 to about 35 weight percent, based on the total weight of the polymer/polyol. The polymer is preferably formed in situ.
Substantially any of the polyols previously used in the art to make polymer/polyols can be used in this invention. Illustrative of the polyols useful in producing polymer/polyol compositions of this invention are the poly-hydroxyalkanes, the polyoxyalkylene polyols, or the like.
Among the polyols which can be employed are those selected from one or more of the following classes of compositions, alone or in admixture, known to those skilled in the poly- ;
urethane art:

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(a) Alkylene oxlde ~dducts of polyhydroxyalkanes;
O Alkylene oxlde adducts of non-reduclng sugars and su~ar derlvatives;
(c~ Alkylene oxlde adducts of phosphorus and polyphosphorus aclds;
(d) Alkylene oxide adducts of polyphenols;
(e) The polyols from natural oils such as castor oll, and thc like.
Illustrative alkylene oxlde adducts of polyhydroxyalkanes lnclude, among others, the alkylene oxide adducts of ethylene glycol, propylene glycol, 1, 3-dihydroxypropane, 1, 3-dihydroxybutane, I,4-dihydroxybutane, 1,4-, 1,5- and 1,6-dihydroxyhexane, 1,2-1,3-, 1,4-, 1,6- ~nd I,8-dlhydroxyoctane, 1,I0-dihydroxydecane, glycerol, 1,2,4-trlhydroxybutane, 1,2,6-trihydroxyhexane, 1,1,1-trimethylolethane, 1,1,1-trime~ylolpropane, pentaerythrltol, caprolactone, polycaprolactone, xylltol, arabitol, sorbitol, mannltol, - and the like. A preferred class of alkylene oxide adducts of poly-hydroxyalkanes are the propylene oxlde adducts and the propylene ox~de-ethylene oxide adducts of di- and/or trihydroxyalkanes.
The alkylene oxide adducts of phosphorus and polyphos- ~;
phorus aclds are another useful class of polyols. Ethylene oxlde, 1,2-epoxypropane, the epoxybutanes, 3-chlorD~ epoxypropane, and the like are preferred alkylene oxldes. Phosphoric acld, phos-- phor.ls acld, the polyphosphoric acids such as tripolyphosphoric hcid, the polymetaphosphoric acids, and the llke ~re desirable for use ln ~is connection.

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The polyols employed can have hydroxyl numbers which vary over a wide range. ln general, the hydroxyI numbers of the polyols employed ln the inventlon can range from ebout 20, and lower, to about 850, and ~.iyher. The hydroxyl number is defined as the number of milllgrams of potassium hydroxide requlred for the complete hydrolysis of the fully acetylated or phthalated derivative prepared from 1 sram of polyols. The hydroxyl number can also be deflned by the equation:

C)H = 56 1 x 1000 x f ~Ir..w.
where O~ = hydroxyl number of the polyol f = functionality, that is, average number of hydroxyl groups per molecule of polyol m.w. = molecular weight of the polyol.
The exact polyol employed depends upon the end-use of the polyure-thane pr,oduct to be produced. The molecular weight or the hydroxyl Jlumber ls selected properly to result ln flexible or semi-flexible foams or elastomers when the polymer/polyol produced from the polyol ~s converted to a polyurethane. The polyols preferably possess a hydroxyl number of from about 50 to about lS0 for semi-flexible foams and from about 30 to about 70 for flex~ble fc~ams but can be as low as 20. Such limits are not lntended to be restrictive, but are merely lllustrative of the large number of possible combinations ~f the above polyol coreactonts.

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The most preferred polyols employed ln thls lnventlon ~nclude the poly~oxypropylene) slYcolS~ trlols and hlgher function211ty polyols. These polyols also include poly~oxypropylene-oxyethylene) polyols; however, desirably, the oxyethylene content ~hould comprise less than 80 percent of the total and preferably less than 60 percent.
The ethylene oxide when used can be incorporated ln any fashion alon~ the polymer chain. Stated another way, the ethylene oxide can be incorporated either in internal blocks, as terminaI bloclcs, or may be randomly distributed along the polymer chain. Most preferably, 10 the ethylene oxide when used is incorporated as terminal blocks, l.e., capping units. As ls well known in the art, the polyols that are most preferred herein contain varyin~ amounts of unsaturation.
As taught by Stamberger, unsaturation in itself does not affect ln any adverse way the formation of the polymer/polyols used in the present invention except in the case where the extent or type of unsaturation so high or effective as to result in a gel or ~olid.
The polymerizable ethylenically unsaturated monomers whlch can be used ln making the polymer/polyols employed in this lnventlon lnclude the polymerlzable ethylenically unsaturated hydro-20 carbon monomers and polymerizable ethylenlcally unsaturated orsanlcmonomers the ~olecules ~f which are composed of carbon, hydrogen nnd at least one of O, S, or N. These monomers are characterized by the presence ~erein of at least one polymerizable ethylenic unsahlrated group of the type C = C. The monomers can be used ~Z38~

sln~ly or ln comblnation to produce homopolymer/polyol or copolymer/
polyol reactlve cornposltions.
These monomers are well l~nown ln the art and lnclude the hydrocarbon monomers such as styrene, alpha-methylstyrene, methylstyrene, 2,4-dlmethylstyrene, ethylstyrene, lsopropylstyrene, butylstyrene, phenylstyrene, cyclohexs~lstyrene, benzylstyrene, and the lilce; the ac~ylic and subst~tuted acryllc mon~mers such as acrylic acld, methacrylic acld, methyl acrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methaclylate, methyl methacrylate, octyl 10 methacrylate, acrylonltrile, methac~ylonitrile, 2-ethylhexyl acrylate, phenyl acrylate, phenyl methacrylate, N,N-dimethylacrylamide, and the like; the vlnyl esters, vinyl ethers, vlnyl ketones, etc., such as, vinyl acetate, vinyl alcohol, vinyl butyrate, vinyl acrylate, vinyl methacrylate, N-vinyl-pyrrolidone, and the like; the vinyl halides ~nd vinylidene halides, such as, vinyl chloride, vinyl fluoride and vinylidene chloride and the like; t-butylaminoethy.
methacrylate, ~lycidyl acrylate, allyl alcohol, vinyl pyrldine, and the lilce. Any of ~he known polymeriza~le monomers can be used and the compounds llsted above are illustrative and not restrictive of 20 the monomers sultable for use in this invention. Any of the known chain ~ransfer agents can be present lf desired.
~ he preferred monomer used to make the polymer of ~e polymer/polyol used ln this invention is acrylonitrlle alone as a homopolymer or in comb~nation with styrene or methyl methacrylate :; . .

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as a copolymer. The relatlve wei~ht proportlons of ~crylonltrlle tO
~tyrene Illustatively range from about 20:80 to about 100:0, preferably from about 25:~5 to 100:0 and more preferably, when low molecular weight polyols, e.g., below about 2000 are used, then the weight ratio should be from about 60:40 to about 85:15.
Catalysts useful in producing the polymer in the polymer/
polyol composltlons of this lnvention ~re the ~ree radical type of vinyl polymerizAtion catalysts such as the peroxides, persulfates, perborates, percarbonates and the azo compounds or any other ~ ~ `
suitable catalyst speclfied in the above-mentioned patents and application. D.luskative of a few such catalysts are 2,2'-azo-bls-lsobutyroni~ile, dibenzoyl peroxlde, lauroyl peroxide, di-t-butyl peroxlde, diisopropyl peroxide carbonate, t-butyl peroxy-2-ethylhexanoate, t-butylperpivalate, 2,5-dimethyl-hexane-2,5-dl~
per-2-ethyl hexoate, t-butylperneodecanoate, t-butylperbenzoate, t-butyl percrotonate, t-butyl perisobutyrate, dl-t-butyl perphthalate and the like. Azobis(isobutyronitrile) is the preferred catalyst since It does not lmpart any ob~ectionable product odor or require special handllng ln the plant because of possible hazards.
The catalyst concentration is not critlcal and can be varied - wlthi~ wlde limits. ~s a representative range, the concentratiOn can vary from about 0.1 to about 5.0 weight percent, based upon the total feed to the reactor. Up to a certain polnt, increases in the catalyst concentration result ln lncreased monomer conversion but further . .

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lD917-1 increases do not substanUally lncrease convers~on. C)n the other hand, lncreasing catalyst concentratlon Increaslngly lmproves product stabillty. The~catalyst concentratlon selected w~ll usually be ~n optlmum value considerlng all factors, Including ~osts.
The polymerlzatlon can also be carried out wlth an inert organlc solvent present that does not dissolve the polymer. Illus- -trat~ve thereof are tQluene, benzene, and the li);e, Including those known ln the art as belng suita~le solvents for the polymerization of vinyl monomers. The only requirement ln the selection of the solven.
and the polyol Is that they do not interere with the monomer's polymerization reaction. Wl~en an lnert organic solvent is used, it is generally removed ~rom the reaction mixture by conventional means before the polymer/polyol is ~Ised to produce polyurethane ~oams.
The temperature range used in the polymerizatlon is not critical and may vary from about 80C. or less to about 150C. or perhaps greater, the preferred range being from about 105C. to about 135C. The catalyst and temperature should be selected so that the catalyst has a reasonable rate of decomposition with respect to the hold-up time in the reac~r for a continuous glow reactor or the feed time for a semi-batch reactor.
The preferred process used ln producing the polymer/polyols used ln this invention involves polymerizing the monomers in the polyol while maintainlng a low monomer to polyol ratio throughout the reaction mixture durlng the polymerization. This provides ln the ~1 18Z3~

preferred case ~ polymer/polyol ln which essentlally 811 of the poly-mer partlcles have diameters of less than thlrty mlcrons and In some cases less than one mlcron. Such low ratios ~re achleved by em-ploying process condltions that provide rapid converslon of monomer ~;
to polymer. In practice, a low monomer to polyol ratio ls malntained, ln the case of semi-batch and continuous operation, by control of the -. ~ .
temperature and mixing conditions and, ln the case of semi-batch operation, ~lso by slowly addin~ the monomers to the polyol. The process can be carried out in various manners such as by a semi-lû batch reaction, a continuous back-mixed stirred tank reactor, etc.
For the latter, a second stage may be used to lncrementally increase the conversions of monomers. The mixing conditions employed are ~ ;~
those attalned using a back-mixed reactor [e.g., a stirred ~lask or stirred autoclave). Such reactors keep the reaction mixture relatively homogeneous and so prevent localized high monomer to polyol ratios snch as occur ln certain tubular reactors (e.S., in the first stages of "Marco" reactors when such reactors are operated conventionally w1th all the monomer added to the first stage).
When uslng a semi--batch prooess, the feed times can be varled (as well as the proportion of polyol in the reactor at the start versus polyol fed wlth the monomer) to effect changes in the product viscosity. Generally, longer feed times result ln hlgher product .
vlscositle~ and may allow use of slightly broader ac~ylonit~ile to ~tyrene ranges for a ~lven polyol and polymer content.

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The crude polymer/polyol us~ally contalns small amounts of unreacted monomers. Such res~dual monomers ~an be onverted tc addlti~nal polymer by employing a two-stage operation in which the product of the flrst stage (back-mixed reactor) is passed into a second stage whlch can be a Marco reactor operated conventionally or an unstlrred tank reactor.
The prefer~ed temperature used ln produclng polymer/polyols used in this invention is any temperature at which the half life of the catalyst is no longer than about 25 percent of the residence tlme in 10 the reactor. As an illustratlon, the half llfe of the catalyst at a given reaction temperature may be no longer than six minutes (preferably no lonyer than from 1.5 to 2 minutes). The half lives of the catalysts become shorter as the temperature is raised. By way of lllustration, azo-bis-isobutyronitrlle has a half life of six minutes at I00C.
The maximum temperature used is not narrowly critical but should be lower than the temperature at which significant decomposi~ion of the reactants or product occurs.
In the process used to produce the polymer/polyols used in thls invention, the monomers are preferably polymerized in the polyol.
20 Usually, the monomers are soluble in the polyol. It has been found that first dissolving the monomers in a minor portion of the polyol and addlns the solution so formed to the remainder of the polyol at reaction temperature facllltates mixing the monomers and the polyol and can reduce or elimlnate reactor fouling. When the monomers are not :: .

lOBZ381 soluble ln the polyols, knowrl technlques (e.g., dlssolution of the lnsoluble monomers In another solvent) can be used to disperse the monomers in the polyol prlor to polymerl~ation. Ille converslon of the monomers to polymers achieved by thls process Is remar)~ably hlgh (e.g., conversions of at least 72% to 95% of the monomers are generally ochieved).
In the case of copolymer$zing ~cr~rlonltrile and styrene the ratio of aclylonitrile to styrene in the polymer is always slightly lower than the ratio of acrylonltrile to styrene monomer lr, t~e feed -; 10 because the styrene tends to react slightly faster than the ac~lo-nltrile. For example, lf aclylonitrile and styrene monomers were fed at ~ welght ratio of 80:20, the resultin~ polymer would have an acrylonitrile to styrene weight ratio of about 79:21 or 7B:22.
The preferred polymer/polyols used in the present invention comprise dispersions in which the polymer particles (the same beins either individual particles or agglomerates of individua1 particles) are relatively small in slze and, in the more preierred embodiment are all essentially less than 30 microns. This insures that the polymer/polyol can be successfully processed in all types of the relatively sophisticated machine systems now in use for large volume production of polyurethane products, including those employins lmpingement-type mixing which necessitate the use of filters that cannot tolerate any significant amount of relatively large particles.
Less rigorous applicatlons are satlsfied when less than essentially ~11 partlcles ~re of a ~lze of 3û microns.

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~ he polymer concentratlon of the polymer/polyols used ln thls ~nvention can be ad~usted by the addition of addltlonal polyol of the general type described above to provlde the polymer concen-tration sultable for the deslred end use. Ln this manner, the polymer/
polyols can be produced ~t polymer concentrations of, for example, 20%, ~nd reduced to polymer concentratlons as low as 4% by the ~ddition of more polyol, or, alternatively, the composition can be made directly with a polymer concentration of 4% by the method descrlbed above.
The novel polyisocyanate compositlons comprise a poly-lsocyanate of any of the well known types which is reactive wlth the chosen polymer/polyol to produce the desired polyurethane product and a metallocene, preferably ferrocene, ln an amount effective to provlde resistance to chalkln~. The amount of ferrocene based on the polyurethane product can vary over a wide range and can be as low ~s 0.035 weight percent or less and as much as 0.7 welght percent or higher. The polyisocyanate cornposition can con-taln other ingredients such as plgment and, when foam is being produced, a foam stabillzer, although it is usually preferable to 20 lncorporate these other ingredients by way of the polymer/polyol composltion. Wl~ile ie ls contemplated that the ferrocene or other metallocene would be incorporated into the polyurethane product through either the novel polymer/polyol compositlon or the novel ~;
polylsocyanate compositlon of thls lnvention, lt can be lncorporated 23$1 .

partly through the novel polymer/polyol compos~tion ~nd par~ly ~rough the novel polyisocyanate composltion ln respective amounts such that the total hmount in the resulting polyurethane product constitutes an effective amount to provide the deslred reslstance to ~urface chalking.
Any compatible medium to dark colored pigment can be used in the novel composltions of this Invention. Carbon black is extensively used as a pigment in polyurethane products and is lncluded as a preferred pigment for use in this invenUon. Other useful pigments include Pruss~an blue, manganese violet, manganese blue, emerald green, cobalt blue, cobalt vlolst, Mayan blue, iron oxide red, chrome red, verrnillion. ultramarine blue, ultramarine violet, phthalocyanine green and brilliant red. The amounts of pigments used are not narrowly critical and depend in large part on the shade of medium to dark color desired. Illustrative ranges are from about 0.1 to about 4 weight percent, preferably about 0.3 to about 2 weight percent of the p~gment based on the weight of the polyurethane product. Larger amounts of pigment can be used althouyh difflcultles wlth mlxlng and handling the larger amounts of pigments can result because of increased viscosity. The pigment can be lncorporated into the polymer/polyol composition, the polyisocyanate composlUon, or both.
ffle present invention also provldes novel polyurethane - products made wlth ~e novel polymer/ps:lyol compositions and novel ~ 8~1 lQ917-1 methods for producing such products. The novel poly-urethane products are prepared by reacting (a) a polymer/
polyol as described above, and (b) an organic polyiso-cyanate, in the presence of (c) a catalyst for the reacti~n of (a) and (b) to produce the polyurethane product, and (d) a metallocene, preferably ferrocene or a ferrocene polymer, and ~e) a medium to dark pigment and, when a microcellular urethane elastomer or foam is being prepared, (f) a blowing agent and usually (g) a foam stabilizer. More specifically, the novel method can be conducted by reacting a novel polymer/polyol composition as described above with a suitable organic polyisocyanate, or a novel polyisocyanate composition as described above with a suitable polymer/polyol, or a novel polymer/polyol composition with a suitable novel polyisocyanate composi~ion, to produce the desired polyurethane. The reaction (and foaming operations, if employed) can be performed in any suitable manner, preferably by the one-shot technique, although the prepolymer technique can be used if desired.
The organic polyisocyanates that are useful in producing the no~el polyisocyanate compositions and ~ ~ ;
polyurethane products in accordance with this invention are organic compounds that contain at least two isocyanate groups and include the monomeric and polymeric organic ~;-polyisocyanates such as prepolymers produced by reacting a polyol with an excess of a polyisocyanate.
The quasi-prepolymers such as the reaction products of excess tolylene diisocyanate and ~hort chain polyoxypropylene diols or triols, are preferred in those -- , ,, . , ; .. ..

10917~1 lnstan~es where ease of processlng such materials ls deslred. The polyis~cyanates are well ~cnown ln the art. ~ult~ble or~nic poly-~socyanates include the hydrocarbon diisocyanates (e.g., the alkylene dilsocyanates and the arylene dilsocyanates) ~s well as known triisocyanates. As examples of suitable polylsocyanates one can mentlon, I,2-diisocyanatoethane, 1,3-diisocyanatopropane, 1,2-diisocyanatopropane, 1,4-diisocyanatobutane, l,S-dlisocyanato-pentane, 1,6-diisocyanatohexane, bis(3-lsocyanatopropyl) ether, bls~3-isocyanatopropyl~ sulfide, l,~-diisocyanatoheptane, 1,5-di-isocyanato-2,2-dlmethy}pentane, 1,6-dllsocyanato-3-methoxyhexane, 1, 8-diisocyanatooctane, 1, 5-diisocyanato-2, 2, 4-trimethylpentane, 1,9-diisocyanatononane, 1,10-diisocyanatopropyl ether of 1 t 4~
butylene glycol, 1,11-diisocyanatoundecane, 1,12-di'socyanato-dodecane,bis(isocyanatohexyl) sulfide, 1,4-diisocyanatobenzene, 2,4-diisoçyanatotoluene, 2,6-diisocyanatotoluene and mixtures thereof, 1, 3-diisocyanato-o~xylene, 1, 3-diisocyanato-m-xylene, I,3-diisocyanato-rxylene, 2,4-diisocyanato-1-chlorobenzene, 2, 4-df isocyanato- 1 -nitrobenzene, and 2, 5-diisocyanato- 1 -nitro-benzene, 4,4'-diphenylmethylene diisocyanate, 3,3'-diphenyl-methylene diisocyanate, 2,4'-diphenylmethylene ti~socyanate, modified diphenylmethylene diisocyanates modified wlth carbodi-lm~des to llquefy same, and polymethylene poly(phenylene-Isocyanates) hav1ng the formula:

1 9 : , 108Z3Bl 1~917 -1 NCO ¦ NCO

whereln x has an average v~lue from 1.1 to S incluslve (preferably from 2.0 to 3.0), and mlxtures thereof.
The catalysts th3t are useful ln producing polyurethanes in accordance wlth this invention lnclude: (a) tertiary amlnes such as bls(dimethylaminoethyl) ether, ~imethylamlne, triethylamine, ~ ~ :
N-methylmorpholine, N-ethylmorpholine, N,N-dimethylbenzylamine, N,N-dimethylethanolamlne, N,N,N',N'-tetramethyl-1,3-butanedia-mlne, triethylanolamine, 1,4-diazabicyclo~2.2.2] octane, pyridine oxide and the like; ~D) tertiary phosphlnes such as trialkylphosphlnes, dlalkylbenzylphosphlnes, and the like; ~c) strong bases such as :
~lkali and alkaline earth metal nydroxides, alkoxides, and phen-oxldes; ~d) acidic metal salts of strong acids such as ferric chloride, stann~c chlorlde, stannous chloride, antimony ~lchloride, bismuth nltrate and chloride, and the llke; (e) chelates of various metals such : : .
~!15 those which can be obtained from acetylacetone, benzoylacetone, trifluoroacetylac0tone, ethyl acetoacetate, salicylaldehyde, cyclo-pentanone-2-carboxylate, acetyl-acetoneimlne" bis-ace~ylacetone-- ~lkylenedlimines, salicylaldehydeimlne, ~nd the llke, with the ;
v3rlous metals such ~s Be, Mg, Zn, Cd, Pb, ~i, Zr, Sn, As, B1, Cr, .

108231~1 los Mo, Mn, Fe, Co, Nl, or such lons as MoO2 ~, U02~+, and the llke;
tf) alcoholates and phenolates of varlous metals such as Tl~OR)4, Sn(OR)4, Sn(OR)2, Al(OR)3, and the like, wherein R is ~lkyl or aryl, and the reaction pr~ducts of alcoholates with carboxylic aclds, beta-diketones, and 2-(N,N-dlalkylamino) alkanols, such as the well known chelates of titanlum obtained by said or equivalent procedures;
(g) salts of organic aclds with a variety of metals such as alkall metals, alkaline earth metals, Al, Sn, Pb, Mn, Co, Ni, and Cu, in-cluding, for example, sodium acetate, potassium laurate, calcium -lû hexanoate, stannous acetate, stannous octoate, stannous oleate, lead c~ctoate, metallic driers such as manganese and cobalt naphthenate, and the like; (h) organometallic derivatives of tetravalent tin, trlvalent and pentavalent As, Sb, and Bi, and metal carbonyls of lron and cobalt.
Among the organotin compounds that deserve particular mention are dlalkyltin salts of carboxylic acids, e.g., dibutyltin diacetate, dibutyltin dilaurate, dibutyltin maleate, dilauryltin di-acetate, dioctyltin diacetate, dibutyltin-bis(4-methylaminobenzoate), dibutyltin-bls(6-methylaminocaproate), and the like. Similarly, there may be used a trlalkyltin hydroxide, dialkyltin oxide, dialkyl-tin dialkoxide, or diallcyltin dichloride. Examples of these compounds lnclude ~rimethyltin hydroxide, trlbutyltin hydroxide, trioctyltin hydroxide, dlbutyltin oxide, dioctyltin oxide, dilauryltin oxide, dibutylt~n-bis (isopropoxlde), dibutyltin-bis ~2-dime~hylaminopen-tylate), dibutyltin dichloride, dioctyltin dlchloride, and the like.

. ~08~3~

10~17-1 The tertlary amlnes may be used as primary catalysts for accelerating the reactiYe hydrogen~lsocyanate reaction or ~s secondary catalysts In comblr~ tlon wlth one or more of the above-noted metal catalysts. Metal catalysts, or c~mblnations ~f metal catalysts, may also be employed as the acceleratln~ agenes, wlthout the use of ~mines The catalysts are employed ln small amounts, for example, ;
from about 0.0~1 percent to about 5 percent, based on weight of the ; ~;
reaction mlxture.
The distinction between polyurethane foams and elastomers ls not sharply defined because all foams and most elastomers contaln a gas phase. The foams ln general have denslties of less than 10 pounds per cubic foot and elastomers, ln general, have densities above that value. Micr~cellular elastomers intended for energy absor~ing appllcatlons, e.g., as automotive bumpers, generally are made wlth denslties of 10 to 40 pounds per cubic foot whereas mlcrocellular elastomers intend2d for o~her applications, e.g., bumper rub strips, bumper guards, side moldln~s, appliques and the llke where energy absorption ls not the prime conslderation generally are made wlth densities of 40 to 60 pounds per cubic foot.
Solid, unfoamed polyurethanes ùsually have a denslty of about 72 pounds per cubic foot. The densities of the above-described can be lncreased by the addition of lnert fillers such as glass fibers.
~uch Inert flllers provlde lmproved physical properties such as lncreased modulus. All of these polyurethanes, l.e., foams, ~ ::

-- ~0l3~381 ~0917-1 mlcrocellular and solld, fl}led or unfilled, can be improved by the present inventlon.
When the product belng formed ls a polyurethane elastomer, an extender can also be ~dded to improve the load bearlng and modulus properties of the elastomer. Extenders are not normally used ln the production of polyurethane foams, althou~h they can be ~dded, lf deslred. Suitable extenders lnclude low molecular weight polyols lncluding ethylene glycol, diethylene glycol and the aromatic ~Iycols, reaction products of alkylene oxides with aromatic amines or alcohols having two active hydrogens. Suitable aromatic glycols are the reaction products of alkylene oxides wlth amino aryl com-pounds and di(hydroxyalkoxy) aryl compounds, and preferably are the reaction products of ethylene oxide and aniline. Other suitable aromatlc glycols lnclude the ethylene oxide and propylene oxide adducts of bisphenoi A and the propylene oxide adducts of anlllne.
Additlonal suitable extenders are the aromatlc amlnes such as

4,4'-methylene bis~2-chloroaniline) and phenol-aromatic amine-nldehyde reslns which are made by the reaction of a phenol such as phenol or substituted phenols havlng at least one unsubstituted reac~ive posltion on the aromatic nucleus, an aldehyde such as ~-formaldehyde or other aliphatic aldehydes and an aromatic amine such as anlllne or other aromatic amlnes having at least one or two amlno l-ydroger~s anà no or one nltrogen-bonded alkyl group and at least one unsubstl~uted poslticn ortho or para to the ~mlno group.

~23-~8;~38~

~osl7-l :

Wnen the product being fo~med ls a polyurethane micro-cellular elAstomer or foam, this may be accompllshed by employlng a small amount of ~ polyurethane blowlng agentO ~uch ~s water, ln the reaction mixture (for example, from about 0.~ to about 5 w ight percent of water, based upon total welght of the polymer/polyol comp~sltion), t~r through the use of blowlng agents which are vaporized by the exotherm of the reaction, or by a combination of the two methods. Illustrative polyurethane blowing agents lnclude halogenated hydrocarbons such a s trichloromonofluorometharle, dichIorodifluoro-methane, dlchloromonofluoromethane, dlchloromeShane, erichloro-methane, 1, 1 -dichloro- 1 -fluoroethane, 1, 1, 2 -trichloro- 1, 2, 2-trifluoromethane, hexafluorocyclobutane, octafluorocyclobutane, and the like. Another class of blowing agents include thermally unstable compounds whlch liberate gases upon heating, such as N,N'-dimethyl- ;
N,N'-dinltrosoterephthalarnide, ~nd the like. The quantity of blowing agent employed will vary with factors such as the density desired in the foamed product.
It is also within the scope of the lnvention to 0mploy small amounts, e.~ bout 0.01 percent to S.0 percent by weight, based ~0 on She total reactlon mixture, of a foam stabllizer such as a "hydro~
lyzable" polysiloxane-polyoxyalkylene block copolymer such as the block copolymers described ln U. S. Patents 2,834,748 and 2,917,480.
An~ther useful class of foam stabllizers are the "nonhydrolyzable"
polyslloxane-polyoxyalkylene bloclc copolymers such as the block -:' .... . . .. .

~08238~

loslr copc>lymers descrlbed ln V. S. Patent N~. 3,505,377: U. S. Patent Appllcation BB8,067, flled December 24, 19~9, and 8rltlsh Patent Speclflcation No. 1,220,471. ~he latter class of copolymers dlffers from the ~bove-mentioned polyslloxane-polyoxyalkylene block copolymers ln that the polysiloxane moiety ls bonded to polyoxy-~lkylene molety through carbon-to-oxygen-to sllicon bonds. These varlous polysiloxane-polyoxyalkylene block copolymers preferably contaln from S to 50 weight percent of polyslloxane polymer with the remainder belng polyoxyalkylene polymer.
The polyurethanes produced ln accordance wlth this lnven-Sion may be advantageously employed ln varlous applications. For example, the present invention ls useful ln the production of energy-absorbing microcellular polyurethanes. Stlll further, the polymer/
polyols of this lnventlon may be used to form polyurethane elasto-mers ln whlch relatlvely low molecuIar weight polyols must be used to provide the requislte stiffness. Also, polymer/polyols ~ursuant to this lnvention may be employed to form polyurethane products for applications where hi~h load-bearing characteristics are required. Polyurethanes produced according to this lnventlon are - 20 useful ~n the applications in which conventional polyurethanes are employed such as ln the manufacture of foam for the sla~ foam market, arm rests, crash pads, mattresses and automobile bumpers.
The followlng examples are presen~ed. Numbered ~xamples lllustrate ~ls lnvention. Lettered Examples ~re comparatlve . . ~.
.

10~23~L

1~917 -1 Examples and do not illustr2te the invention.
The following deslgnatlons used in the examples and else-where herein have the following meanings:
"hr~" denotes hours.
"Dts" denotes parts by weight.
"wt-%" denotes percent by weight.
"ratios" are based on weight.
"%" denotes percentage by weight unless otherwlse stated.
"calculated hYdroxyl numbers" given herein wete based on calculated total polymer content and hydroxyl number of base polyol. ?
"P~ Polypropylene oxide-polyethylene oxide triol made from propylene and ethylene oxides and glycerine and having a theoretical number average molecular welght of about S000 and a l~ydroxyl number of about 34. The alkylene oxide units are present primarily in blocks and the end units are substantially all ethylene ~ ~ -oxide units, i.e., the ethylene oxide is used to "cap" the triol.
Based on its total weight, thi3 triol contains about 15 wt-% C2H,~O.
''PP-2'' - A 21% copolymer content polymer/polyol of an acrylonltrile-styrene copolymer prepared by polyme.izing 50~50 s~yrene and ac.-ylonitrile in polyol P-l. The polymer/polyol has a theoretical number average molecular weight of about 6000 znd a nominal hydroxyl number of about 28.
"PP-3" - A 21,' polymer content polymer/polyol of an ~ ~ ' acrylonltrile polymer prepared by polymerizlng acrylonitrile ln . '''. ~.
-~6~

, "' :'' ;

~LV~;~3~

polyol P-l. The polymer/polyol has a theoretical number average molecular weight of about 6000 and a nominal hydroxyl number of about 280 "P-4'' - An extender formed by reacting 2.4 moles of ethylene oxide per mole of aniline and having a nomin~l hydroxyl number of 565 and a number average molecular weight of about 198.
"P-5" - Polypropylene oxide triol made from propylene oxide and glycerine and having a theoretical number average molecular weight of about 260 and a nominal hydroxyl number of about 650.
"PI-6" - A prepolymer isocyanate comprising the reaction product of 82.4 wt-% of a mixture of 80% 2,4-tolylene dlisocyanate and 20% 2,6-tolylene dLisocyanate and 17.6 wt-% polyol P-5.
The reaction product is adjusted to an acidity of 0.007 to 0.012%
HCl and has a free isocyanate content of 30 . 7 wt-% .
"PC-7" - Polyol composition containing 85.34 pts. of polymer/polyol PP-2, 8.53 pts. of diethylene glycol, 5.98 pts. of polyol P-4 and 0.15 pts. dibutyltindilaurate catalyst.
"PIC-8" - Prepolymer isocyanate composition comprising a mixture of 83 pts. of prepolymer isocyanate PI-6 and 17 pts. methylene chlorlde. -"BP-9" - Black pigment paste comprising 14 wt-% carbon black having a partlcle size of 27 mu and a pH of 6.0 and 86 wt-Q,~
polyol P-l. `

, 108~3~

CH2CH~ .
/ \ :
"DABCO 331.V" _ N -- CH2CH2 --N

CH2C~2 ; "QW Weathering" - Accelerated weathering provided in a QW cyclic ultraviolet-weathering tester. The polyurethane elasto-mer plaques are exposed in alternate periods to ultravioIet light provided by a bank of ultravlolet lamps tWestinghouse FS-40) and water condensation at elevated temperatures. The cycle used herein ., , was 8 hrs. of exposure to ultraviolet light at 120F. followed by 4 hrs. ~ ~
:
exposure to condenslng humidity at 100F. This cycle was repeated for 600 hrs . after which time the plaques were examined visually for chalking, dulling or other forms of weathering degradation.
"Net Index of Reflectance (NIR) Determination" - Using an .~
ILD Color-Eye spectrophotometer the index of reflectance value is determined at 560 millimicrons wavelength using a tungsten light source. The determination is first made on the unweathered pla~ues and then on the weathered plaques. The difference between the ~
'. `..
index of reflectances of the plaque before and after weathering is the net lndex of reflectance (NIR) and is a good measure of the level of chalking due to the weatherin~ process . Low NIR ~,alues indicate - ;
-.:. . .
less change in sur'ace appearance due to chalking.

The following ASTM test methods were used in determining ~ , ,. ~. .
the physical properties given ln the examples: ~ ~

.

~ ~ ;

... . . .. . . . , , ~, 9L08238~L

PropertY ASTM Method Specimen Slze~
Overall density D 1564 1" x 1" x I/2" thlclc Hardness D 2240 1" x 1" x 1/2" thick Ten511e strength D 412 1/8" - 1/4" thick Elongation D 412 1/8" - 1/4" thick D eC tear _________ D 6245_________/8'' - 1~4"_hi_k _ * " denotes inch.

`~ ExamPles A and 1-5 To six polymer/polyol compositions each comprising 85.34 parts of polymer/polyol pP-2, 8.53 parts diethyle~e glycol, 5.98 parts of polyol P-4, and 0.15 parts dibutyltindilaurate catalyst were added 2,0 parts of carbon black paste comprising 14% of carbon black in polyol P-l and, respectively, 0, 0.1, 0.1, 0.2, 0.5, and 1.0 parts bis-cyclopentadienyl iron (recrystallized ferrocene). The compositions of Examples 3, 4 and 5 also contained 0.1 part of DA8CO 33LV. Each composition was heated to 100F. and then mixed with a stoichiometric amount plus 5% excess (l.e., a suf-flclent amount to provide a polyurethane having an Index of 105) of the prepolymer lsocyanate composition PIC-8. Mixing was accom-plished using a 2000 rpm mixer. The liquid urethane mixes were poured into heated (150F.) 1/4" x 6" x 16" aluminum plaque molds in sufficient quantities to form plaques of about 45 pcf density. The flnished microcellular urethane elastomer plaques were removed from the mold in S mlnutes. Each contained 0.2 38~

welght percent carbon black and ferrocene levels of 0, 0.07, 0.07, 0.14, 0.3S, and 0.7 weight percent, respectlvely, as shown in Table 1. The pIaques were subjected to 600 hours QW weathering exposure at the following cycle: 8 hrs. UV light at 102F. followed :; by 4 hrs. condensing humidity at 100F. The condition of the .
weathered plaques was evaluated visually and colorirnetrically, and the results are tabulated in Table 1 below. The plaques of Examples 1-5 showed only a dulled surface but no chalking.

am~le Ferrocene, wt-% Surface APPearance NIR Value .
A 0 Chalked 9.1 0.07 No Chalklng 0.3 2 0 07 " " 0.4 3 0.14 ~ ............ 0.
4 0 3 5 " " 0 2 ~ ~ 5--~ --7----------------__ '' ___'' _________0 . 2___ The physical propertles of the plaques were measured ~`
before and ~fter QW exposure ùnd are given In Table 2 below: ~

,, .

-3û- ~
' .

3~

Exam~le Before ExPosure A 1 2 3 4 5 Overall Density, pcf 45 42 42 42 42 42 Hardness, Shore A 90 85 87 88 90 88 Tensile Strength, psi 825755 785 735 665 715 Elongation, % 65 75 75 75 60 80 Die C Tear, pli 135 140130 125 125 115 After ExPosure:
Tensile Strength, psl 1000 905 - 790 850 890 Elon~ation, % 70 85 - 65 65 85 Die C Tear, ~ _120 _130 _-__ llQ_12û _115 Examples B and 6-9 Using t~e same procedure and materials as Examples A and -.
I-5O microcellular urethane elastomer plaques were prepared con-Saining 0.2 weight percent carbon black and ferrocene levels of, respectively, 0, 0.035, 0.07, 0.14, and 0.35 weight percent.
l~e plaques were exposed ln the QUV tester as in Examples A and 1-5 and evaluated similarly. The results are given in Table 3 below. The plaques of Examples 6-9 showed only a dulled surface but no chalking.

,..: ~' ,.

-31- :

~IU8Z38~lL

1091Z~1 am~le Ferrocene, wt-% Surface ApPearance NIR Value B 0 Chalked 2 . û ;
6 0.035 No Chalklng 0.6 7 Q-07 " " 0.2 80.14 " " 0.4 9___0 . 35 _ _ _ 0 . 1__ : .
Examples C-I
This series of examples was designed to demonstrate the ;~
lû effect on chalking of incrementally removing the polymer/polyol from an elastomer forrnulation containing it and replacing it with a polyol containing no pplymer. The basic formuIation was 85.34 .. ~ , .
parts polymer/polyol PP-2, 8.53 parts diethylene glycol (chain ! extender), 5.98 parts polyol P-4, 2.0 parts carbon black paste as ~ . , described in Examples A and 1-5, 0.15 parts dibutyltlndilaurate, and a stoi~hiometric quantlty (plus 5/O excess1 of prepolymer iso-cyanate composition PIC-8. The polymer/poiyol PP-2 was replaced incrementally with an equal amount of the base polyol P-l, pro-gresslng through 20%, 40%, 60%, 80%, and finally 100% P-l in the formulation. The chain ext~nder components were increased sllghtly with increasing levels of base polyol P-l to maintain an elastomer of about the same hardness level. Plaque samples were --prepared as in Examples A and 1-5 and were subjected to 600 hours QW weatherlng. Results, tabulated below ln Table 4, ~llustrate the ln~luence of polymer/polyol ln producing chalk on the black elasto-mer surface.
~32 , ~08~38~

los Exam~le Polyrner/PolYol, wt-%~ Surf~ce APpearance NIRValue C 100 Chalked 4.1 " 2.2 E 60 Llghtly Chalked 1.3 F 4 0 " " 0 . 9 G 20 No Chalking~* 0.6 H 0 " " * * 0 . 6 ; I 0 " " ** 0 . 5 _ _ _ _ _ _ _ _ _ _ *Weight percent polymer/polyol PP-2 in total mixture of polymer/
. po}yol PP-2 base polyol P-l.
** Dulled surface.
The physlcal properties of the plaques were measured before and after QW exposure and are given in Table 5 below: .

Exam}~le Before ExPosure: C D E F G H I
Overall Density, pcf 45 45 43 44 41 38 39 Hardness, Shore A 90 92 90 88 88 82 85 Tensile Strength, psl 825800 730 750 665 570 540 Elongation, % 65 75 75 90 95 95 65 Die C Tear, pll 135 145130 135 120 115 100 l After ExPosure:
Tenslle Strength, psl 1000 885 880 775 850 585 ., ) Elongation, % 70 75 95 90 110 75 -D e C T_ar, pll _ __ I20 135_115 II5 100__100_ -_ ~` lOBZ3Bl Exam~les T, 10 and 11 Black elastomer plaques were prepared as described in Examples A and 1-5 except that cobaltocene and nickelocene were added instead of ferrocene. The cobaltocene (a 7.5% solutlon in toluene) was added at a level of 0.65 parts per 100 parts of the polymer/polyol composltions which resulted ln 0.03% of actual cobaltocene in the flnai elastomer. The nickelocene ~a 9.0% solution in tol~ene) was added at a level of 0.55 parts per 100 parts of the polymer/pol~oi compositions, yiving 0.03% actual nlckelocene in the final elastomer. The plaques were weathered in the QW
` weathering test for 600 hours. The results given in Table 6 were ~ ;
observed.
TABLE 6 `

Cobaltocene,Nickelocene, Surface ;;
xample wt-%~ wt-%* AP~earanceNIR Value J 0 0 Chalked 2 . 7 ~ , 0.03 0 No Chalking 1.0 __11________0_ _______ 0,03 __ Sliqht~y Cha k~d 2.2 _ *Based on the total weight of final elastomer, amPles 12-17 Red and green elastomer plaques were prepared and Sested as described in Examples A and 1-5 except that the plaques were pigmented dark red or green instead of black. Caprolactone-baseù
red and green pigments (Hilton-Davis Ultrakrome Red and Green) were used for pigmentation at a level of 1.0 part plgment per 100 ~r~

`` ~(;~8Z3~

parts of the polymer/polyol compositlons. The red plgment com-prised 15 wt-% 8rllli2nt Red 2R in polycaprolactone carrier and the green pigrnent comprised 30 vt-% Phthalocyanine Green B.S. ln - polycaprolactone carrier. Ferrocene, cobaltocene~ or nickelocene were added to the compositions ln quantity sufficient to achieve the desired concentrations in the final elastomer, as stipulated ln Table 7 (red) and Table 8 (green) given below. In Examples 12, 13, 15 and 16 the amount of chalking was reduced. Bsst results were obtained from the use of ferrocene. The results given in Tables 7 and 8 were observed after 600 hours in the QW test.

? TABLE 7 (Red) Ferrocene Cobaltocene Nlckelocene Surface NIR
ExamPle wt-%* wt-%* wt-%* Appearance Value 12 07 0 0 No Chalk 1.5 (darkened) 13 0 .07 0 No Chalk 0.8 (darkened) 14 0 0 . 0 7 Chalk ed 6 . 6 , TABLE 8 (Green) 2015 .03 0 0 No Chalk 0.2 (darkened) 16 0 .07 0 Chalked 6.9 17 0 0 . 0 7 Chalked 10 . 0 (heavy) _ _ _ _ _ _ :
*Based on the total welght of final elastomer.

-35~

3~L

Examples K, 18 and 19 Black elastomer plaques were prepared as described in Examples A and l-S except that cobaltocene and nickelocene were added instead of ferrocene ln Examples 18 and 19 and no metallo-cene was added in Example K. A 7.5% solutlon of cobaltocene in toluene was added at a level of 1.3 parts per 100 parts of the polymer/
polyol composition, glvlng 0.07% cobaltocene in the final elastomer.
- A 9.0% solutlon of nickelocene ln toluene was added at a level of 1.1 parts per 100 parts of the polymer/polyol composition, also 10 giving û.07% of the metallocene ln the final elastomer. Tne blaclc elastomer plaques were exposed ln the QUV weathering test for 1200 hours, with the following results:

Cobaltocene Nickelocene Surface NIR
Example wt-% wt-o~__ Appearance V~
K 0 0 Chalked 1 7 18 0.07 0 No Chalk 0.4 19 0 0 . 0 7 Sllghtly 1 3 Chalked ExamPles L, M, 20 and 21 Elastomer plaques were prepared as descrlbéd ln Examples A and 1-5 except that the plaques were pigmented dark red and dark green, respectively, lnstead of black Ultrakrome Red and Ultra-krome Green plgments as described ln Examples 11-16 were added -3~~

lOgl7-1 at levels of 3.0 parts per 100 parts of the polymer/polyol composi-tions to achieve the desired plgmentation. Ferrocene was added in Examples 20 and 21 as designated ln Tables 10 and }1 below, being mixed at a level of 0.1 part per 100 parts of the polymer/polyol compositions to give 0.07 wt-% ferrocene in the final elastomer.
Results of 1200 hours exposure In the QU\/ weathering test are listed ln Tables 10 and 11. ;
TABLE 10 (red) Ferrocene Surface ~ wt-%APPearance N~R Value L 0 Chalked 5 . 4 0.07No Chalk 0.9 ;~
~darkened) TABLE Il (green) M 0Chal}ced 1 . 5 21 0.07No Chalk 0.3 (darkened) _ _ _ _ _ _ __ _ _ _ :
ExamPles N, 22 and 23 These examples represent commercial preparations of polyurethane elastomers wherein mixing was accomplished in a small Martin Sweets metering-mixing-dispensing machine. Other-wise, the same procedures and materials as used in Examples A and 1-5 were used in these examples. Example N did not use any metallo-cene whereas ferrocene was used in Examples 22 and 23 in such '~

1~323~L

amounts as to provide 0.035 and 0.07 wt-% ferrocene, respectively, ln the finished mlcrocellular polyurethane elastomer plaques. All of the flnished plaques contained 0.2 wt-% carbon black. The plaques were sub~ected to 643 hours QW weathering exposure as described in Examples A and 1-5 and were evaluated similarly. The results are given in Table 12 below.

Ferrocene Surface ExamDle wt-,oA~earance NIR Value I 0 N 0 Chalked 3 . 8 22 0.035No Chalking 0.4 23 0,07 0.8 Exam~les O-TT
These examples illustrate the effects of various com-mercially avallable ultraviolet light absorbers, anhoxidants and light stabilizers on the chalking properties of polyurethanes. In each of these examples, the same materials and procedures as ; described in Examples A and 1-5 were used except that, instead of ferrocene, the types and amounts (given in parts per 100 parts . 20 of polymer/polyol composition) of W absorbers, antioxidants and ` light stabllizers given in Tables 13 and 14 below were used as additives. The black elastomer plaques were exposed in the QW
weathering test for 600 hours and the results and physica properties ~ ;~
are glven ln Table 14. These results show that none of the com-mercial addltives were as effective as ferrocene.
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These examples lllustrate the efects of a commercial ultraviolet light stabillzer on the chalking properties o~ polyurethanes.
In each example, the same procedures and materials as descrlbed in Examples A and I-5 were used except that, instead of ferrocene, a hindered amine ultraviolet light stabilizer (Tinuvin 770 made by , .
Ciba Geigy) was used in the amounts set forth in Table 15 glven in parts per 100 parts of polymer/oolyol composition. The black elastomer plaques were exposed in the ~W weathering test for 603 lO hours and the results and physical properties are given in Table 15.
These results show the effectiveness of Tinuvin to be erratic and unpredictable. Some of the plaques developed chalk streaks that were very noticeable .

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ExamPles QQ-DDD
These exanlples lllustrate the effects of carbon black pig-ments of vario~s particle sizes and pH's. In each of thsse examples, the same materlals and procedures as described ln Examples A and 1-5 were used except that no ferrocene was used and ~e type and amount (parts per 100 parts of the polymer/polyol composition) of carbon black pigment was varied as shown $n Tables 16 and 17 below. ~ Examples RR, TT, W, XX, ZZ, ~BB and DDD, one part of Additive l (Tinuvin P) per 100 parts of polymer/polyol composition 10 was used. The black elastomer plaques were exposed in the QW
weathering test for 600 hours and the results and physical proper-ties are given in Table 17. These results show BP-9 to provide the ~`
- least amount of chalklng in the group and this is the reason BP-9 was used ~n the majority of the examples.
; TABLE 16 BP-9 - BP-12 are pastes of 14 wt-% concentratel and BP-13 is a paste of 33 wt-% conc~ntrate, in polyol P-l of induetrial grade fun)ace blacks in powder form having the particle sizes and ~ -pH's given below and are products of Harwick Chemical Co., ,~
20 A)cron, Ohlo, under the Stan-Tone name.
BP Stan-Tone Particle Size, mu pH
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~08Z381 ExamPles EEE-HHH
` These examples illustrate the effects of a special commer-clal carbon black paste composition, Siegle Farben HG8864, made by G. Siegle Company/BASF, Stuttgart, Germany. This material is deslgnated BP-14 ln Table 18 below and comprises a 20 wt-% con- -centrate of Degussa Special Black 4 in bead form having a particle slze of 25 mu and a pH of 3.0 in a polyol simllar to polyol P-l as we~l as one or more unIdentifled components which appear to be photochemically active. In each of these exarnples, the same 10 materials and procedures as described in Examples A and 1-5 were .
used except that BP-14 was substituted for BP-9 and no ferrocene was added. The amounts of 8P-14 in parts per 100 parts of the polymer/polyol composition used are given in Table 18. The black elastomer plaques were exposed in the QW weathering test for 600 hours and the results and phys~cal properties before and after exposure are given in Table 18. The results show no chal~cing and lt has not been conclusively determined whether this is due to the type of csrbon blsck or the unlcnown components in EIP-14.

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EXAM PLE
EEE FFF GGG HHH : -BP-14 2.0 2.0 4.0 6.0 % Carbon Black ln 0.25 0.25 0.5 0.75 Total Urethane Physical Properties, Before QW
_ Exposure Overall Denslty, pcf 43 - 45 44 Hardness, Shore A 50 - 91 88 :
Tenslle Strength, psi 770 - 705 810 Elongatlon, h 65 - 60 75 Die C Tear, pll 135 - 145 130 QW Exposure Results Surface Appearance Dulled Dulled Dulled Dulled SurfaceSurface Surface Surface NIR Value 0 . 4 0, 2 0 . 6 0 . 5 Physlcal Properties, After QW ?
posure Tenslle Strength, psl - - 925 915 ~ :
Elongation, % - - 65 70 __Dle C _ear. Ell _ - _____ -_ _ _120___ __ 125 _ ExamPles III~LLL :
These examples lllustrate the effects of high amounts of `:
carbon black BP-13 as expressed ln Table 19 below in parts per 100 parts of the polymer/polyol composition. In each example, ;~
the same materlals and procedures as described ln Examples A and 1-5 were used except BP-13 was substltuted for BP-9 and no ferro cene was used. The black elastomer plaques were exposed in iO~23~ ,f~

the QUV weathering test for 600 hours and the results and physlcal propertles are glven ln Table 19. The results show that excessively ~hlgh amounts of carbon black can red~ce chalking althou~h the use of such hlgh amounts results ln processlng problems due to the extreme thiclcness of the carbon black pastes.

EXAMPLE
I I I J l l KK~C LLL
` BP-13 11.0 11.0 5.5 5.5 % Carbon Black ln lbtal Urethane 2.5 2.5 1.3 1.3 Physlcal Properties, Before QW
Ex~osure Overall Density, pcf 45 41 45 44 ~ardness, Shore A 85 79 83 82 Tenslle Streng'th, psi 715 600 615 750 Elongation, 96 70 65 65 60 Dle C Tear, pll 110 100 120 110 . 20 QW ExposureResults Surface Appearance D~lled Dulled Dulled ~ulled Surface Surface Surface Surface NIRValue 0.3 0.2 0.3 0.1 __ __Q _ __ __ ___ __ __ __~ _ _ ____ __ __ _ _ _ _ __ _ __ _ _ _ ExamPles MMM-OOO
These examples prov$de con~ol formulations to aid ln evaluating the results of the other examples. In each of these .1 exatnples, the same procedures and materlals as descrlbed ln Examples A and 1-5 were used except that no ferrocene was used.
lhe black elastomer plaques were exposed ln the QW weacherlng 30 t0st for 600 hours and the results and physlcal pr~pertles, befQre .

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lOgl7-1 and after exposure, are given ln Table 17. Also given are the average properties for the control formulatlons of these examples and Example A.

Average EXAM PLE _ Control MMM NNN OOO A roperties - Physical Properties, Before 1~1 QW Exposure Overall Density, pcf 47 - 44 45 45 ; ~arciness, Shore A 87 - 85 90 87 Tenslle Strength, psi 810 - 700 825 780 Elon~ation, % 90 - 70 65 75 :- D~e C Tear, pll 105 - 125 135 120 .~ ~
QW Exposure R.esults ~
Surface Ap- Medlum MediumI.lght Medium Medium :. pearance Challc ChalkChalk Chalk Chalk NIR ~talue - - 2 .1 4 .1 3 .1 Physlcal Properties, After QW ExPosure ;
Ten~ile Strength, psl - - 825 1 000 9 1 0 Elongat~on, % - - ~0 70 75 Dle C Tear, pll - - 110 120 llS

~Examples PPP-TTT
`These examples are slmilar to Examples G-I in lllus~ating the effect on chalking of lncrementally removlng the polymer/polyol : -:

from an elastomer formulatlon contalnlng lt and replacing lt wlth :
~ polyol contalnlng no polymer. The baslc formulation is shown ln .. .

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, Table 21 as Example PPP. The polymer/polyol PP-3 was replaced lncrementally with an equal amount of the base polyol P-l. The chain extender components, dlethylene glycol and P-4, were lncreased sllghtly with lncreaslng levels of base polyol, P-l, to maintaln an elastomer of about the same hardness level. The procedures described in Examples A and 1-5 were used. The blac~c elastomer plaques were exposed in the QW weatherlng test for 600 hours and the results and physical properties before and after esposure are glven ~n Table 21.

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iO~23~ 10317-1 Exa'mp'l'es'U W,' 2'4' and 25 To three polymer/polyol compositions each comprising 85.34 parts of polymer/polyol PP-2, 8.53 parts diethylene glycol, 5.98 parts of polyol P-4, and 0.15 parts dibutyltindilaurate catalyst were added 2.0 parts of carbon black paste comprising 14~ of carbon black in polyol P-l and, respectively, 0, 0.5 and 1.0 parts of DFR-121, a product purchased from Arapahoe Chemical Company and believed to contain about 2 weight percent of a 2,2-diferrocenylpropane polymer as prepared pursuant to Preparation 1 disclosed in U. S. Patent 3,927,881 , (Cols. 5 and 6). The balance of DRF-121 is a chloro-paraffin which should have no effect on the weathering-induced chalking of the final polyurethane elastomer, although the precise identity of the chloroparaffin ` component has not been determined. The proportion of 2,2-diferrocenylpropane polymer in each polymer/polyol - composition thus comes to about 0, 0.01 and 0.02 weight ;~
, percent, respectively. Each composition was heated to ', 20 100F. and then mixed with a stoichiometric amount plus 5%
excess (i.e., a sufficient amount to provide a polyurethane having an Index of 105~ of the prepolymer isocyanate composition PIC-8. Mixing was accomplished using a 2000 rpm mixer. The liquid urethane mixes were poured into heated (150F.) 1/4" x 6" x 16" aluminum plaque molds in sufficient quantities to form plaques of about 45 pcf density. The finished microcellular urethane elastomer plaques were removed from the mold in 5 minutes. Each , . .

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1~82381 logl7-l contained 0~2 weight percent carbon black. The plaques were subjected to 1000 hour~ Q W weathering exposure at the following cycle: 8 hrs. W light at 120F.
followed by 4 hrs. condensing humidity at 100F. The condition of the weathered plaques was evaluated visually and colorimetrically, and the results are tabulated in Table 22 below. The plaques of Examples 24 and 25 showed no chalking.

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Claims (25)

WHAT IS CLAIMED IS:

1. In a polymer/polyol composition which is convertible by reaction with a polyisocyanate to a poly-urethane which is pigmented to a medium to dark color and which chalks upon exposure to weather and wherein the polymer of said polymer/polyol is dispersed in the polyol thereof and made from one or more polymerizable ethyleni-cally unsaturated monomers, the improvement providing to said polyurethane resistance to chalking on exposure to weather comprising the presence in said polymer/polyol composition of a metallocene from the class consisting of ferrocene, a ferrocene derivative, cobaltocene and nickel-ocene in an amount effective to provide chalk resistance.

2. In a polymer/polyol composition which is convertible by reaction with a polyisocyanate to a poly-urethane which is pigmented to a dark color and which chalks upon exposure to weather and wherein the polymer of said polymer/polyol is formed in situ in, and is dispersed in, the polyol thereof from one or more polymerizable ethylenically unsaturated monomers, the improvement providing resistance to chalking to said dark color-pigmented polyurethane on exposure to weather comprising, the presence of ferrocene or a ferrocene polymer in said polymer/polyol composition in an amount effective to provide chalk resistance.

3. Composition as claimed in claim 2 wherein ferrocene is present and in the amount of about 0.035 to about 2.5 weight percent based on the weight of said polyurethane.

4. Composition as claimed in claim 2 wherein there is included a low molecular weight polyol as a chain extender.

5. Composition as claimed in claim 4 wherein said chain extender is an aromatic or aliphatic glycol.

6. Composition as claimed in claim 2 wherein the amount of polymer dispersed in said polyol is about 4 to about 40 weight percent based on the weight of the polymer/polyol composition.

7. Composition as claimed in claim 2 wherein the amount of polymer dispersed in said polyol is about 15 to about 35 weight percent based on the weight of the polymer/polyol composition.

8. Composition as claimed in claim 7 wherein said poly-mer comprises polymerized acrylonitrile.

9. Composition as claimed in claim 8 wherein said poly-mer comprises polymerized acrylonitrile and polymerized styrene in a weight ratio of from 20:80 to 100:0.

10. Composition as claimed in claim 9 wherein the weight ratio of polymerized acrylonitrile to polymerized styrene in said polymer ranges from about 60:40 to 85:15.

11. Composition as claimed in claim 2 wherein said poly-urethane is pigmented black with carbon black.

12. Composition as claimed in claim 2 wherein said composition contains a catalyst for the polyurethane-forming reaction.

13. Composition as claimed in claim 2 wherein said composition contains a dark colored pigment.

14. Composition as claimed in claim 13 wherein said pigment is a dark red pigment.

15. In a polyisocyanate composition which is convertible by reaction with a polymer/polyol to a poly-urethane which is pigmented to a dark color and which chalks upon exposure to weather and wherein the polymer of said polymer/polyol is formed in situ in, and is dispersed in, the polyol thereof from one or more poly-merizable ethylenically unsaturated monomers, the improve-ment providing resistance to chalking to said dark color-pigmented polyurethane on exposure to weather comprising the presence of ferrocene or a ferrocene polymer in said polyisocyanate composition.

16. Composition as claimed in claim 15 wherein ferrocene is present and in the amount of about 0.035 to about 0.7 weight percent based on the weight of said poly-urethane.

17. Composition as claimed in claim 15 wherein said polyisocyanate composition contains a blowing agent.

18. A method for producing a dark colored polyurethane by reacting a mixture comprising (a) a polymer/polyol composition as claimed in claim 2 and (b) an organic polyisocyanate, in the presence of (c) a catalyst for the reaction of (a) and (b) and a dark pigment to produce the polyurethane.

19. A method for producing a dark colored microcellular polyurethane elastomer by reacting and foaming a mixture comprising (a) the polymer/polyol composition claimed in claim 2, (b) an organic poly-isocyanate, (c) a catalyst for the reaction of (a) and (b) to produce the polyurethane, (d) a blowing agent, (e) a foam stabilizer and (f) a dark pigment.

20. A method as claimed in claim 19 wherein the microcellular elastomer is flexible, the reaction and foaming are performed by the one shot technique, the polymer/polyol composition contains an alkylene oxide adduct of a polyhydroxyalkane, and a low molecular weight polyol chain extender, the blowing agent is methylene chloride used in an amount to provide a foam having a density of 10 to 60 pounds per cubic foot, and the dark pigment is carbon black.

21. Polyurethane produced by the method claimed in claim 18.

22. Composition as claimed in claim 2 wherein a ferrocene polymer is present and in the amount of about 0.007 to about 0.7 weight percent based on the weight of said polyurethane.

23. Composition as claimed in claim 22 wherein said ferrocene polymer is 2,2-diferrocenylpropane polymer.

24. Composition as claimed in claim 15 wherein a ferrocene polymer is present and in the amount of about 0.007 to about 0.7 weight percent based on the weight of said polyurethane.

25. Composition as claimed in claim 24 wherein said ferrocene polymer is 2,2-diferrocenylpropane polymer.