United States Patent (19) 11 Patent Number: 4,950,696 Palazotto et al. (45) Date of Patent: Aug. 21, 1990

54) ENERGY-INDUCED DUAL CURABLE 4,707,432 11/1987 Gatechair ...... 522/25 4,734,444 3/1988 Henne ...... 522/25 COMPOSTIONS 4,740,577 4/1988 Devoe ...... 528/51 (75) Inventors: Michael C. Palazotto, St. Paul; 4,849,320 7/1989 Irving et al...... 430/280 Katherine A. Brown-Wensley, Lake Elmo; Robert J. DeVoe, St. Paul, all FOREIGN PATENT DOCUMENTS of Minn. 094914 11/1983 European Pat. Off. . 094915 11/1983 European Pat. Off. . (73) Assignee: Minnesota Mining and 109851 5/1984 European Pat. Off. . Manufacturing Company, St. Paul, 155704 9/1985 European Pat. Off...... 522/25 Minn. 207893 1/1987 European Pat. Off. . 837966 10/1983 South Africa . (21) Appl. No.: 90,694 2042550 9/1980 United Kingdom . Filed: Aug. 28, 1987 (22) OTHER PUBLICATIONS (51) Int. Cl...... C08G 18/22; C08G 18/04 (52) U.S. C...... 522/25; 430/280; McManus et al., "Photoassisted Reaction Between Al 430/281; 430/283; 430/914; 430/921; 430/923; cohols and Isocyanates'; J.C.S. Chem. Comm., 1974, p. 522/170; 522/174; 528/51; 528/52; 528/56; 253. 528/75 T. A. Speckhard, K. K. S. Hwang, S. B. Lin, S. Y. Tsay, 58) Field of Search ...... 522/25 M. Koshiba, Y. S. Ding, S. L. Cooper; J. Appl. Polymer Science, 1985, 30, 647-666. 56) References Cited C. Bluestein; Polym.-Plast. Technol. Eng. 1981, 17, U.S. PATENT DOCUMENTS 83-93. 3,705,129 12/1972 Murio et al...... 260/47 Roesler, Modern Paint and Coatings, Apr. 1986, pp. 3,709,861 1/1973 Anderson ...... 260/47 46-55. 3,714,006 1/1973 Anderson ..... 204/159.14 G. Smets, Pure G. Appl. Chem, 53, 611,615 (1981). 3,729,313 4/1973 Smith ...... 96/27 H. M. Wagner, M. D. Purbrick, J. Photograph Science, 3,741,769 6/1973 Smith ...... 96/35.1 29, 230-235 (1981). 3,794,576 2/1974 Watt ..... 204/159.11 3,808,006 4/1974 Smith ...... 96/88 J. Kosar, Light Sensitive Systems: Chemistry and Ap 3,867,354 2/1975 Betts et al...... 260/78.4 plication of Nonsilver Halide Photographic Processes, 4,001,015 1/1977 Barzynski ...... 430/302 Wiley, New York, 1965, pp. 158-193. 4,010,289 3/1977 Kobayashi ...... 522/100 H. J. Timpe and H. Baumann, Wiss Z. Tech. Hochsch. 4,026,705 5/1977 Crivello et al...... 96/27 Leuna-Merseburg, 26, 439 (1984). 4,053,316 10/1977 Lu ...... 522/27 H. Baumann, B. Strehmel, H. J. Timpe and U. Lammel, 4,058,400 1 1/1977 Crivello ...... 96/86 J. Prakt. Chem., 326 (3) 415, (1984). 4,080,274 3/1978 Schlesinger .. 204/159.8 H. Baumann, U. Oertel and H. J. Timpe, Euro. Polym. 4,086,091 4/1978 Cella ...... 96/36.2 4,113,497 9/1978 Schlesinger .. ... 522/25 J., 22, 313 (Apr. 3, 1986). 4,156,035 5/1979 Tsao et al...... 427/44 S. P. McManus, "Stabilization of Cure Rates of Diiso 4,216,288 8/1980 Crivello ...... 430/280 cyanates with Hydroxy-Terminated Polybutadiene 4,227,978 iO/1980 Barton ...... 204/159.12 Binders', UAH Research Report No. 140, Apr. 1973. 4,228,232 10/1980. Rousseau ...... 522/25 4,237,242 12/1980 Frankel ...... 525/119 Primary Examiner-John C. Bleutge 4,250,053 2/1981 Smith ...... 252/426 Assistant Examiner-Arthur H. Koeckert 4,342,793 - 8/1982 Skinner et al...... 427/44 Attorney, Agent, or Firm-Donald M. Sell; Walter N. 4,412,048 1/1983 Dixon ...... 522/25 Kirn; Lorraine R. Sherman 4,428,807 1/1984 Lee et al...... 522/25 4,521,545 6/1985 Kerimis et al...... 521/107 57 ABSTRACT 4,525,232 6/1985 Rooney ...... 522/25 An energy polymerizable composition comprises at 4,533,446 8/1985 Conway ...... 522/25 least one ethylenically-unsaturated monomer, one of 4,544,466 10/1985 Lindstrom 204/159.11 4,549,945 10/1985 Lindstrom ...... 204/159.11 polyurethane precursors, and at least one epoxy mono 4,582,861 4/1986 Galla et al...... 521/118 mer, and a curing agent comprising an organometallic 4,593,052 6/1986 Irving ...... 522/25 compound, and an onium salt. 4,623,676 11/1986 Kistner ...... 522/15 4,657,779 4/1987 Gaske ...... 522/25 18 Claims, No Drawings 4,950,696 1. 2 disclosed in U.S. Pat. No. 4,026,705; and the onium salts ENERGY-NDUCED DUAL CURABLE of Group VIA elements, particularly the sulfonium COMPOSITIONS salts, as are disclosed in U.S. Pat. No. 4,058,400), or a dicarbonyl chelate compound of a Group IIIA-VA FIELD OF THE INVENTION element as is disclosed in U.S. Pat. No 4,086,091. These This invention relates to an energy-polymerizable compositions are limited to ultraviolet radiation for composition comprising an ethylenically-unsaturated polymerization. Furthermore, the dicarbonyl chelates monomer and either polyurethane precursors or an are moisture sensitive. epoxy monomer, and as curing agent a combination of U.S. Pat. No. 4,216,288 teaches the thermal curing of an organometallic compound and an oxidizing agent, O cationically polymerizable compositions using onium and a method therefor. In a further aspect, cured arti salts and reducing agents. cles comprising the composition of the invention are disclosed. The compositions are useful, for example, as Radiation dual curable compositions containing eth protective coatings, binders for magnetic media or abra ylenically unsaturated monomers and epoxy monomers 15 have been described in U.S. Pat. Nos. 4,156,035, sives, adhesives, and in graphic arts applications. 4,227,978, and 4,623,676. These compositions include BACKGROUND OF THE INVENTION onium salts combined with organic compounds as the Various polymeric coatings and articles are produced curing agent, but do not contain any organometallic in processes involving the use of organic solvents. compounds. There is an intense effort by law makers, researchers, 20 Energy polymerizable compositions comprising ionic and industry to promote high and 100% solids formula salts of organometallic complex cations and cationically tions to reduce or eliminate the use of such solvents and sensitive materials and the curing thereof has been the attendant costs and environmental contamination. taught (see European Patent Nos. 109,851, 1984; These processes require a latent catalyst or latent reac 094,915, 1983, Derwent abstract; and 094,415, 1983, tion promoter which can be activated in a controlled 25 Derwent abstract). fashion. Neutral organometallic compounds have been used in Thermal curing of polyurethane precursors using combination with neutral halogenated compounds for reaction promoters such as tin salts and tertiaryamines is the photocuring of ethylenically-unsaturated mono known in the art. Curing of polymerizable mixtures of mers. (G. Smets, Pure G. Appl. Chem, 53, 611,615 polyisocyanates with polyols (referred to as polyure 30 thane precursors) using thermally latent catalysts is (1981); H. M. Wagner, M. D. Purbrick, J. Photograph known in the art (see for example U.S. Pat. Nos. Science, 29, 230-235. 4,521,545, and 4,582,861). The use of certain photosensitizers with onium salts Photocuring of urethane (meth)acrylates is well for initiation of polymerization of ethylenically unsatu known (see T. A Speckhard, K. K. S. Hwang, S. B. Lin, 35 rated monomers is also well known in the art. This S. Y. Tsay, M. Koshiba, Y. S. Ding, S. L. Cooper J. technique has found applications in printing, duplica Appl. Polymer Science, 1985, 30, 647-666; C. Bluestein tion, copying, and other imaging systems (see J. Kosar Polym.-Plast Technol. Eng. 1981, 1783-93), and photo in Light Sensitive Systems: Chemistry and Application curing of polyurethane precursors using diazonium of Nonsilver Halide Photographic Processes, Wiley, salts, tertiaryamine precursors, and organotin com 40 New York, 1965, pp 158-193). Aryliodonium salts have pounds is also known (see U.S. Pat. Nos. 4,544,466, been previously described for use as photoinitiators in 4,549,945, and EP No. 28,696, Derwent abstract). All of addition-polymerizable compositions. (See U.S. Pat. these methods suffer from one or more of the following Nos. 3,729,313, 3,741,769, 3,808,006, 4,228,232, disadvantages: sensitivity to oxygen, requirement of 4,250,053 and 4,428,807; H. J. Timpe and H. Baumann, ultraviolet and/or high intensity light, the need for 45 Wiss Z. Tech. Hochsch. Leuna-Merseburg, 26, 439 (1984); modified resins, loss or dilution of urethane properties, H. Baumann, B. Strehmel, H. J. Timpe and U. Lammel, low activity, poor solubility, and poor potlife. J. Prakt, Chem, 326(3), 415 (1984); and H. Baumann, U. The dual curing of acrylate/urethane precursor mix Oertel and H. J. Timpe, Euro, Polym. J., 22 (4), 313 tures is known but these curing methods are not entirely (April 3, 1986). photoactivated nor are any methods known that pro 50 vide for the simultaneous curing of the urethane precur SUMMARY OF THE INVENTION sors and acrylates (see U.S. Pat. 4,342,793 and Roesler, Briefly, the present invention provides an energy Modern Paint and Coatings, April, 1986, pages 46-55). polymerizable composition comprising an ethylenical The prior art discloses processes for the polymeriza ly-unsaturated monomer and either polyurethane pre tion of epoxy materials. It is further known that a metal 55 locene, such as ferrocene, can be used as a curing accel cursors or an epoxy monomer, and as curing agent a erator for epoxy materials (U.S. Pat. No. 3,705,129). combination of a organometallic compound and an U.S. Pat. Nos. 3,709,861, 3,714,006, 3,867,354 and onium salt. The compositions are useful as protective 4,237,242 relate to the use of transition metal complexes and decorative coatings, inks, adhesives, binders for in the reaction between polyepoxides and polyfunc magnetic media or abrasives, in restorative and sealant tional curing additives, but they do not teach the poly applications, and in imaging applications. merization of epoxide group-containing compositions It is believed not known in the art that latent, energy not containing a curing additive. The polymerization of induced, simultaneous, preferably solventless, dual cur epoxide group-containing materials is also known. ing of ethylenically-unsaturated monomers, in combina Among such processes are those in which the polymeri 65 tion with either polyurethane precursors or epoxy mon zation catalyst is a radiation-sensitive onium salt of a omers, can be achieved by using as curing agent a con Lewis acid (e.g. diazonium salts as is described in U.S. bination of an organometallic compound and an onium Pat. Nos. 3,794,576 and 4,080,274; halonium salts as is salt oxidizing agent. 4,950,696 3 4. Advantages of compositions of the present invention when utilized in 100% reactive coating compositions DETAILED DISCLOSURE OF THE INVENTION include: More specifically, in a preferred embodiment this An industrial process innovation is disclosed that will invention describes an energy polymerizable composi reduce, minimize, or eliminate the generation of indus tion comprising in the range of 99 to 1 weight percent trial solvent waste while reducing energy consumption. an ethylenically-unsaturated monomer and 1 to 99 Radiation processing, particularly utilizing electron weight percent of either polyurethane precursors or an beam and photogenerated catalysts, has potential capa epoxy monomer and a bicomponent curing agent there bility for penetrating and polymerizing thick and pig for, the curing agent comprising mented coatings. 10 (1) an organometallic compound having the structure More readily available monomers can be used in place of functionalized oligomers (used in the prior art) thereby resulting in lower viscosity monomer solutions wherein which are easier to coat than more viscous oligomer 15 Ll represents none, or 1 to 12 ligands solutions. contributing pi-electrons that can be the same or Expanding the scope of curable monomers to include different ligand selected from substituted and unsubsti polyisocyanates/polyols and epoxides allows increased tuted acyclic and cyclic unsaturated compounds and flexibility in designing coatings with specific properties. groups and substituted and unsubstituted carbocyclic In this application: 20 aromatic and heterocyclic aromatic compounds, each "dual curing' means the simultaneous energy capable of contributing 2 to 12 pi-electrons to the va induced curing of ethylenically-unsaturated monomers lence shell of M, in combination with one of polyurethane precursors L2 represents none, or 1 to 24 ligands that can be and epoxy monomers; the same or different contributing an even num "energy-induced curing" means curing by means of 25 ber of sigma-electrons selected from mono-, di-, electromagnetic radiation (ultraviolet and visible) ac and tri-dentate ligands, each donating 2, 4, or 6 celerated particles (including electron beam), and ther sigma-electrons to the valence shell of M; mal (infrared and heat) means; L3 represents none, or 1 to 12 ligands that can be "ethylenically unsaturated monomer' means those the same or different, each contributing no more monomers that polymerize by a free-radical mechanism; 30 than one sigma electron each to the valence shell "catalytically-effective amount" means a quantity of each M: sufficient to effect polymerization of the curable com M represents 1 to 4 of the same or different metal position to a polymerized product at least to a degree to atoms selected from the elements of Periodic cause an increase in the viscosity of the composition; Groups IVB, VB, VIB, VIIB, and VIIIB (com 35 monly referred to as transition metals); with the "organometallic compound' means a chemical sub proviso that said organometallic compounds stance in which at least one carbon atom of an organic contains at least one of a metal-metal sigma bond group is bonded to a metal atom ("Basic Inorganic and L; and with the proviso that Ll, L., L, and Chemistry', F. A. Cotton, G. Wilkinson, Wiley, New Mare chosen so as to achieve a stable configura York, 1976, p. 497); tion, and "polyurethane precursors' means a mixture of one or (2) an onium salt oxidizing agent having the structure more monomers of the type including diisocyanates and II polyisocyanates, and one or more monomers of the type including diols and polyols. Compounds bearing at least AX II two isocyanate-reactive hydrogen atoms may be substi 45 tuted for diols and polyols; the ratio of isocyanate groups to isocyanate-reactive hydrogen atoms is 1:2 to wherein 2:1; "polymerizable mixture' means a mixture where A is an organic cation selected from those described the ratio of (ethylenically-unsaturated compounds): in U.S. Pat. Nos. 3,708,296, 3,729,313, 3,741,769, (polyurethane precursors or epoxy compounds) is 1:99 50 3,794,576, 3,808,006, 4,026,705, 4,058,401, 4,069,055, to 99:1; 4,101,513, 4,216,288, 4,394,403, and 4,623,676, all incor "bridging ligand' means aligand that bonds to two or porated herein by reference, preferably selected from more metals in the presence or absence of metal-metal diazonium, iodonium, and sulfonium cations, while bonds; more preferably A is selected from diphenyliodonium, "polyisocyanate" means an aliphatic or aromatic iso 55 triphenylsulfonium and phenylthiophenyl diphenylsul cyanate having 2 or more isocyanate groups; fonium; and "polyol" means an aliphatic or aromatic compound X is an anion, the counterion of the onium salts containing 2 or more hydroxyl groups; and including those in which X is an organic sulfo "onium salt" means salts of cationic compounds such nate, or halogenated metal or metalloid, such as 60 CH3SO3, CF3SO3, C6H5SO3, p-toluenesul as diazonium, halonium, and hypervalent Group VIA fonate, p-chlorobenzenesulfonate and related elements; isomers and the like, and An energy polymerizable mixture comprising an eth those in which X has the formula DZr, wherein D ylenically unsaturated monomer and either polyure is a metal from Groups IB to VIIIB or a metal or thane precursors or an epoxy compound and as curing 65 metalloid from Groups IIIA to VA of the Peri agent an organometallic compound and an onium salt is odic Chart of Elements, Z is a halogen atom, and disclosed in assignee's copending patent application r is an integer having a value of 1 to 6. Prefera U.S. Ser. No. 090,791, filed the same date as this appli bly, the metals are copper, zinc, titanium, vana cation. dium, chromium, manganese, iron, cobalt, or 4,950,696 5 6 nickel and the metalloids prefereably are boron, organometallic compounds having a sum of 16, 17, 19, aluminum, antimony, tin, arsenic, and phospho and 20 electrons are also known. Therefore, organome rous. Preferably, the halogen, Z, is chlorine or tallic compounds not including intramolecular metal fluorine. Illustrative of suitable anions are BF4, metal bonding are described by formula I, in which PF6, AsF6, SbF6, FeCl4-, SnCls-, SbF5-, complexed metals having a total sum of 16, 17, 18, 19, or Alfs, GaCl4, InF4-, TiF6, etc. Preferably, 20 electrons in the valence shell are included within the the anions are CV3SO3, BF4-, PF6, SbF6-, scope of the invention. SbF5OH-, AsF6, and SbCl6-. For compounds described in formula I in which intra The curing agent can be present in the range of 0.1 to molecular metal-metal bonding exists serious departure 20, preferably 0.1 to 10 weight percent of the total com 10 from the "eighteen electron rule' can occur. It has been position. The ratio of organometallic compound to proposed J. Amer. Chem. Soc. 100, 5305 (1978)that the onium salt is in the range of 10:1 to 1:10 by weight, departure from the "eighteen electron rule' in these preferably 1 to 1:5 by weight. transition metal compounds is due to the metal-metal The present invention also provides a process for the interactions destabilizing the metal p orbitals to an ex polymerization of ethylenically-unsaturated monomers 15 in combination with one of polyurethane precursors tent to cause them to be unavailable for ligand bonding. and epoxy monomers comprising the steps of: Hence, rather than count electrons around each metal (a) providing a mixture of at least one ethylenically separately in a metal cluster, cluster valence electrons unsaturated monomers and either polyurethane (CVE) are counted. A dinuclear compound, is seen to precursors or an epoxy compound, 20 have 34 CVEs, a trinuclear compound, 48 CVEs, and a (b) adding to said mixture a combination of a catalyti tetranuclear compound, having tetrahedron, butterfly, cally effective amount of a curing agent comprising and squire planar geometry is seen to have 60, 62, or 64 an organometallic compound and an onium salt CVEs, respectively. Those skilled in the art, however, (and all permutations of the order of mixing the know that there are exceptions to this electron counting aforementioned components), thereby forming a 25 method and that organometallic complex cluster com polymerizable mixture, and pounds having a sum of 42, 44, 46, 50 CVEs for a trinu (c) allowing the mixture to polymerize or adding clear compound and 58 CVEs for a tetranuclear com energy to the mixture to effect polymerization. pound are also known. Therefore, di, tri, or tetranuclear In a further aspect, there is also provided a method organometallic compounds are described by formula I for preparing coated articles containing the cured com 30 in which the complexed metal cluster, MM, MMM, or position of the invention comprising the steps of: MMMM has a total sum of 34; 42, 44, 46, 48,50; or 58, (a) providing a substrate, 60, 62, 64 CVEs in the valence shell, respectively, and (b) coating an energy polymerizable mixture as de are included within the scope of this invention. scribed above to the substrate by methods known Illustrative examples of organometallic compounds in the art, such as bar, knife, reverse roll, knurled 35 according to formula I include: roll, or spin coatings, or by dipping, spraying, brushing, and the like, with or without a coating Mn2(CO)10 solvent, and w CpMo(CO)32 (c) applying energy (after evaporation of solvent, if present) to the article to cause the polymerization 40 Re2(CO)10 of the coating. Co4(CO)12 In a still further aspect, there are also provided Co2(CO)8 shaped articles comprising the polymerizable mixture of the invention. The articles can be provided, for exam CpFe(CO)2GePh3 ple, by techniques such as molding, injection molding, 45 casting, and extrusion. Applying energy to the mixture causes polymerization and provides the cured shaped article. (CO)5MnSnPh2 It is not preferred, but it may be desirable to add solvent to solubilize components and aid in processing. 50 Solvent, preferably an organic solvent, in an amount up (CO)5ReSnPh3 to 99 weight percent, but preferably in the range of 0 to CpPtMe3 90 weight percent, most preferably in the range of 0 to 75 weight percent, of the polymerizable composition can be used. . 55 There are restrictions on the total sum of electrons CpCO)3Mo-Re(CO)5 donated by the ligands, L., L., L3 of formula I and the valence electrons possessed by the metal. For most organometallic compounds not involving intramolecu CpCO)3Mo-Co(CO)4 lar metal-metal bonding, this sum is governed by the "eighteen electron rule' see J. Chem. Ed., 46, 811 (1969). This rule is sometimes called the "nine orbital rule", "the effective number rule', or the "rare gas rule'. This rule states that the most stable organometal lic compounds tend to be those compounds in which the 65 sum of the electrons donated by the ligands and the metal is eighteen. Those skilled in the art, however, know that there are exceptions to this rule and that 4,950,696 7 8 Mn2(CO)8(PPh3)2 polyisocyanates. Particularly suitable polyisocyanates (CO)5Mn'Re(CO)5 Mn2(CO)5(1,10-phenanthroline) correspond to the formula CpFe(CO)2Si Re2(CO)8(1,10-phenanthroline) Q(NCO) III Re2(CO)8(2,2,'-biquinoline) in which p is an integer 2 to 4, and Q represents an Fe3(CO)12 aliphatic hydrocarbon di-, tri-, or tetra-radical contain Ru3(CO)12 ing from 2 to 100 carbon atoms, and zero to 50 heteroat Os3(CO)12 oms, a cycloaliphatic hydrocarbon radical containing 10 from 4 to 100 carbon atoms and zero to 50 heteroatoms, an aromatic hydrocarbon radical or heterocyclic aro matic radical containing from 5 to 15 carbon atoms and zero to 10 heteroatoms, or an araliphatic hydrocarbon CpNi(CO2 radical containing from 8 to 100 carbon atoms and zero 15 to 50 heteroatoms. The heteroatoms that can be present CpFe(CO)2(COPh) in Q include non-peroxidic oxygen, sulfur, nonamino CpFe(CO)2(SiPh3) nitrogen, halogen, silicon, and non-phosphino phospho S. CpCO)2Fe-Fe(CO)(PPh3)Cp Examples of polyisocyanates are as follows: ethylene (MeCp)PtMe3 20 diisocyanate, 1,4-tetramethylene diisocyanate, 1,6-hex Me3SiCp)PtMe3 amethylene diisocyanate, trimethyl hexamethylene di wherein isocyanate, 1,12-dodecane diisocyanate, cyclobutane Me is methyl 1,3-diisocyanate, cyclohexane-1,3- and -1,4-diisocya Ph is phenyl nate and mixtures of these isomers, l-isocyanato-3,3,5- Cp is eta-cyclopentadienyl 25 trimethyl-5-isocyanatomethyl cyclohexane (see Ger Cp* is eta-pentamethylcyclopentadienyl man Auslegeschrift No. 1,202,785, U.S. Pat. No. A wide variety of monomers can be energy polymer 3,401,190), 2,4- and 2,6-hexahydrotolylene diisocyanate ized using the curing agent of the invention. Suitable and mixtures of these isomers, hexahydro-1,3- and/or compounds containing at least one ethylenically 30 -1,4- phenylene diisocyanate, perhydro-2,4'- and/or unsaturated double bond, can be monomers and/or -4,4'-diphenylmethane diisocyanate, 1,3- and 1,4-phe oligomers such as (meth)acrylates, (meth)acrylamides, nylene diisocyanate, 2,4- and 2,6-tolylene diisocyanate and vinyl compounds, and are capable of undergoing and mixtures of these isomers, diphenylmethane-2,4'- addition polymerization. Such monomers include and/or - 4,4'-diisocyanate, naphthylene-1,5-diisocya mono-, di-, or poly-acrylates and methacrylates such as nate, and the reaction products of four equivalents of methyl acrylate, methyl methacrylate, ethyl acryate, 35 the aforementioned isocyanate-containing compounds isopropyl methacrylate, n-hexyl acrylate, stearyl acry with compounds containing two isocyanate-reactive late, allyl acrylate, glycerol diacrylate, glycerol tri groups. acrylate, ethyleneglycol diacrylate, diethyleneglycol According to the present invention, it is also possible diacrylate, triethyleneglycol dimethacrylate, 1,3- for example, to use triphenyl methane-4,4',4'-triisocya propanediol diacrylate, 1,3-propanediol dimethacrylate, nate, polyphenyl polymethylene polyisocyanates de trimethylolpropane triacrylate, 1,2,4-butanetriol trime scribed in British Patent Nos. 874,430 and 848,671, m thylacrylate, 1,4-cyclohexanediol diacrylate, penta and p-isocyanatophenyl sulphonyl isocyanates accord erythritol triacrylate, pentaerythritol tetraacrylate, pen ing to U.S. Pat. No. 3,454,606, perchlorinated aryl poly taerythritol tetramethacrylate, sorbitol hexacrylate, 45 isocyanates of the type described, for example, in Ger bis(1-(2-acryloxy)-p-ethoxyphenyldimethylmethane, man Auslegeschrift. No. 1,157,601 (U.S. Pat. No. bisl-(3-acryloxy-2-hydroxy)-p-propoxyphenyl-dime 3,277,138), polyisocyanates containing carbodiimide thylmethane, tris-hydroxyethylisocyanurate trimethac groups of the type described in U.S. Patent No. rylate; the bis-acrylates and bis-methacrylates of poly 3,152,162 and in German Offenlegungsschrift Nos. ethylene glycols of molecular weight 200-500, copoly 50 2,504,400, 2,537,685 and 2,552,350, norbornane diisocy merizable mixtures of acrylated monomers such as anates according to U.S. Pat. No. 3,492,330, polyisocya those of U.S. Pat. No. 4,652,274, and acrylated oligo nates containing allophanate groups of the type de mers such as those of U.S. Pat. No. 4,642,126; unsatu rated amides such as acrylamide, methylene bis-acryla scribed, for example, in British Patent No. 994,890, in mide, methylene bis-methacrylamide, 1,6-hexamethy Belgian Pat. No. 761,626 and in Dutch Patent Applica lene bis-acrylamide, diethylene triamine tris-acrylamide 55 tion No. 7,102,524, polyisocyanates containing isocy and beta-methacrylaminoethyl methacrylate; and vinyl anurate groups of the type described, for example in compounds such as styrene, divinylbenzene diallyl U.S. Pat. No. 3,001,973, in German Patent Nos. phthalate, divinyl succinate, divinyl adipate, divinyl 1,022,789, 1,222,067 and 1,027,394 and German Offen phthalate, and vinyl azlactones as disclosed in U.S. Pat. legungsschrift Nos. 1,929,034 and 2,004,048, polyisocy No. 4,304,705. Mixtures of two or more monomers can anates containing urethane groups of the type de be used if desired. scribed, for example, in Belgian Patent No. 752,261 or in The polyisocyanate component of the polyurethane U.S. Pat. Nos. 3,394,164 and 3,644,457, polyisocyanates precursors that can be cured or polymerized in the dual containing acrylated urea groups according to German curing systems of the present invention may be any Patent No. 1,230,778, polyisocyanates containing biuret aliphatic, cycloaliphatic, araliphatic, aromatic, or heter 65 groups of the type described, for example, in U.S. Pat. Nos. 3,124,605, 3,201,372 and 3,124,605 and in British ocyclic polyisocyanate, or any combination of such Patent No. 889.050, polyisocyanates produced by telo merization reactions of the type described for example 4,950,696 9 10 in U.S. Pat. No. 3,654,106, polyisocyanates containing least two isocyanate-reactive hydrogen atoms and hav ester groups of the type described, for example, in Brit ing a molecular weight in the range of from about 50 to ish Patent Nos. 965,474 and ,072,956, in U.S. Pat. No. 400. Examples of such compounds are ethylene glycol, 3,567,763 and in German Patent No. 1,231,688, reaction 1,2- and 1,3-propylene glycol, 1,4- and 2,3-butylene products of the above-mentioned diisocyanates with glycol, 1,5-pentane diol, 1,6-hexane diol, 1,8-octane acetals according to German Patent 1,072,385 and poly diol, neopentyl glycol, 1,4-bis-hydroxymethyl cyclo isocyanates containing polymeric fatty acid esters ac hexane, 2-methyl-1,3-propane diol, dibromobutenediol cording to U.S. Pat. No. 3,455,883. (U.S. Pat. No. 3,723,392), glycerol, trimethylolpropane, It is also possible to use distillation residues having 1,2,6-hexanetriol, trimethylolethane, pentaerythritol, isocyanate groups obtained in the commercial produc O quinitol, mannitol, sorbitol, diethylene glycol, triethyl tion of isocyanates, optionally in solution in one or more ene glycol, tetraethylene glycol, higher polyethylene of the above-mentioned polyisocyanates. It is also possi glycols, dipropylene glycol, higher polypropylene gly ble to use any mixtures of the above-mentioned polyiso cols, dibutylene glycol, higher polybutylene glycols, cyanates. 4,4'-dihydroxy diphenyl propane and dihydroxy methyl Preferred polyisocyanates are hexamethylene diiso 15 hydroquinone. cyanate, its isocyanurate and its biuret; 4,4,-methylene Other polyols suitable for the purposes of the present bis(cyclohexylisocyanate); 1-isocyanato-3,3,5-trimeth invention are the mixtures of hydroxy aldehydes and yl-5-isocyanatomethyl cyclohexane (isophorone diiso hydroxy ketones ("formose') or the polyhydric alco cyanate); the tolylene diisocyanates and their isocyanu hols obtained therefrom by reduction (“formitol') rates; the mixed isocyanurate of tolylene diisocyanate 20 which are formed in the autocondensation of formalde and hexamethylene diisocyanate; the reaction product hyde hydrate in the presence of metal compounds as of 1 mol of trimethylol propane and 3 mols of tolylene catalysts and compounds capable of enediol formation diisocyanate and also crude diphenyl methane diisocya as co-catalysts (German Offenlegungsschrift Nos. late. 2,639,084, 2,714,084, 2,714,104, 2,721, 186, 2,738,154 and Suitable compounds containing at least 2 isocyanate 25 2,738,512). Solutions of polyisocyanate polyaddition reactive hydrogen atoms can be high or low molecular products, particularly solutions of polyurethane ureas weight compounds, having a weight average molecular containing ionic groups and/or solutions of polyhy weight, generally from about 50 to 50,000. In addition drazodicarbonamides, in low molecular weight poly to compounds containing amino groups, thiol groups or hydric alcohols may also be used as the polyol compo carboxyl groups, are, preferably, compounds containing 30 ment in accordance with the present invention (German hydroxyl groups, particularly compounds containing Offendegungsschrift No. 2,638,759). from about 2 to 50 hydroxyl groups and above all, com Many other compounds containing isocyanate-reac pounds having a weight average molecular weight of tive hydrogen atoms and polyisocyanates are useful in from about 500 to 25000, preferably from about 700 to the present invention, and are obvious to those skilled in 2000, for example, polyesters, polyethers, polythioe 35 the art of polyurethane science and technology. thers, polyacetals, polycarbonates, poly(meth)acrylates, Epoxy compounds that can be cured or polymerized and polyester amides, containing at least 2, generally in the dual systems by the curing agents of this inven from about 2 to 8, but preferably from about 2 to 4 tion, using the latter in a catalytically effective amount, hydroxyl groups, or even hydroxyl-containing prepoly are those known to undergo cationic polymerization mers of these compounds and a less than equivalent 40 and include 1,2-, 1,3-, and 1,4-cyclic ethers (also desig quantity of polyisocyanate, of the type known for the nated as 1,2-, 1,3-, and 1,4-epoxides). The 1,2-cyclic production of polyurethanes. ethers are preferred. Representatives of the above-mentioned compounds The cyclic ethers which can be polymerized in accor used in accordance with the present invention are de dance with this invention include those described in scribed, for example, in High Polymers, Vol. XVI, 45 "Ring-Opening Polymerizations', Vol. 2, by Frisch and "Polyurethanes, Chemistry and Technology', By Saun Reegan, Marcel Dekker, Inc. (1969). Suitable 1,2-cyclic ders and Frisch, Interscience Publishers, New York/- ether are the monomeric and polymeric types of epox London, and Vol. I, 1962, pages 32 to 42 and pages 44 ides. They can be aliphatic, cycloaliphatic, aromatic, or to 54 and Vol. II, 1964, pages 5-6 and 198-199, and in heterocyclic and will typically have an epoxy equiva Kunststoff-Handbuch, Vol. VII, Vieweg-Hochtlen, 50 lency of from 1 to 6, preferably 1 to 3. Particularly Carl- HanserWerlag, Munich, 1966, for example, on useful are the aliphatic, cycloaliphatic, and glycidyl pages 45 to 71. It is, of course, possible to use mixtures ether type 1,2-epoxides such as propylene oxide, epi of the above-mentioned compounds containing at least chlorohydrin, styrene oxide, vinylcyclohexene oxide, two isocyanate-reactive hydrogen atoms and having a vinylcyclohexene dioxide, glycidol, butadiene oxide, molecular weight of from about 50 to 50,000 for exam 55 glycidyl methacrylate, diglycidyl ether of bisphenol A, ple, mixtures of polyethers and polyesters. cyclohexeneoxide, 3,4-epoxycyclohexylmethyl-3,4- In some cases, it is particularly advantageous to com epoxycyclohexanecarboxylate, 3,4-epoxy-6-methylcy bine low-melting and high-melting polyhydroxyl con clohexylmethyl-3,4-epoxy-6-methylcyclohexanecar taining compounds with one another (German Offen boxylate, bis(3,4-epoxy-6-methylcyclohexylmethyl)adi legungsschrift No. 2,706,297). pate, dicyclopentadiene dioxide, epoxidized polybutadi Low molecular weight compounds containing at ene, 1,4-butanediol diglycidyl ether, polyglycidyl ether least two isocyanate-reactive hydrogen atoms (molecu of phenolformaldehyde resole or novolak resin, resorci lar weight from about 50 to 400) suitable for use in nol diglycidyl ether, and epoxy silicones, e.g., dimethyl accordance with the present invention are compounds siloxanes having cycloaliphatic epoxide or glycidyl preferably containing hydroxyl groups and generally 65 ether groups. containing from about 2 to 8, preferably from about 2 to A wide variety of commercial epoxy resins are avail 4 isocyanate- reactive hydrogen atoms. It is also possi able and listed in "Handbook of Epoxy Resins' by Lee ble to use mixtures of different compounds containing at and Neville, McGraw Hill Book Company, New York 4,950,696 11 12 (1967) and in "Epoxy Resin Technology” by P. F. Bru meric compound, is meant, as explained below, that the ins, John Wiley & Sons, New York (1968). Representa ligand can be a group on a polymeric chain. tive of the 1,3- and 1,4-cyclic ethers which can be poly Illustrative of ligand L are the linear and cyclic eth merized in accordance with this invention are oxetane, ylenic and acetylenic compounds having less than 100 3,3-bis(chloromethyl)oxetane, and tetrahydrofuran. carbon atoms, preferably having less than 60 carbon In particular, cyclic ethers which are readily avail atoms, and from zero to 10 hetero atoms selected from able include propylene oxide, oxetane, epichlorohydrin, nitrogen, sulfur, non-peroxidic oxygen, phosphorous, tetrahydrofuran, styrene oxide, cyclohexeneoxide, arsenic, selenium, boron, antimony, tellurium, silicon, vinylcyclohexene oxide, glycidol, glycidyl methacry germanium, and tin, such as, for example, ethylene, late, octylene oxide, phenyl glycidyl ether, 1,2-butane 10 acetylene, propylene, methylacetylene, 1-butene, 2 oxide, diglycidyl ether of bisphenol A (e.g., "Epon 828” butene, diacetylene, butadiene, 1,2-dimethylacetylene, and "DER 331'), vinylcyclohexene dioxide (e.g., cyclobutene, pentene, cyclopentene, hexene, cyclohex "ERL-4206”), 3,4-epoxycyclohexylmethyl-3,4-epox ene, 1,3-cyclohexadiene, cyclopentadiene, 1,4- ycyclohexanecarboxylate (e.g., “ERL-4221'), 3,4- cyclohexadiene, cycloheptene, 1-octene, 4-octene, 3,4- epoxy-6-methylcyclohexylmethyl 3,4-epoxy-6-methyl 15 dimethyl-3-hexene, and 1-decene; eta-allyl, eta-pente cyclohexanecarboxylate (e.g.,"ERL-4201”), bis(3,4- nyl, norbornadiene, eta-cyclohexadienyl, eta epoxy-6-methylcyclohexylmethyl)adipate (e.g., "ERL cycloheptatriene, eta-cyclooctatetraene, and substi 4289"), aliphatic epoxy modified with polypropylene tuted and unsubstituted carbocyclic and heterocyclic glycol (e.g., “ERL-4050” and “ERL-4052'), dipentene aromatic ligands having up to 25 rings and up to 100 dioxide (e.g., "ERL-4269"), epoxidized polybutadiene 20 carbon atoms and up to 10 hetero atoms selected from (e.g., "Oxiron 2001'), silicone epoxy (e.g., "Syl-Kem nitrogen, sulfur, non-peroxidic oxygen, phosphorous, 90'), 1,4-butanediol diglycidyl ether (e.g., Araldite arsenic, selenium, boron, antimony, tellurium, silicon, RD-2), polyglycidyl ether of phenolformaldehyde germanium, and tin, such as, for example, eta novolak (e.g., "DER-431", "Epi-Rez 521" and “DER cyclopentadienyl, benzene, mesitylene, hexamethylben 438"), resorcinol diglycidyl ether (e.g., "Kopoxite'), 25 zene, fluorene, naphthalene, anthracene, chrysene, py polyglycol diepoxide (e.g., "DER 736”), polyacrylate rene, etal-cycloheptatrienyl, triphenylmethane, paracy epoxide (e.g., "Epocryl U-14''), urethane modified ep clophane, 1,4-diphenylbutane, eta-pyrrole, eta-thio oxide (e.g., "QX3599”), polyfunctional flexible epoxides phene, eta-furan, pyridine, gammapicoline, quinaldine, (e.g., "Flexibilizer 151'), and mixtures thereofas well as benzopyran, thiochrome, benzoxazine, indole, acridine, mixtures thereof with co-curatives, curing agents, or 30 carbazole, triphenylene, silabenzene, arsabenzene, stiba hardeners which also are well known (see Lee and benzene, 2,4,6-triphenylphosphabenzene, eta-seleno Neville and Bruins, supra). Representative of the co phene, dibenzostannepine, eta-tellurophene, phenothi curatives of hardeners which can be used are acid anhy arsine, selenanthrene, phenoxaphosphine, phenarsazine, drides such as nadic methyl anhydride, cyclopen phenatellurazine, eta-methylcyclopentadienyl, eta tanetetracarboxylic dianhydride, pyromellitic anhy 35 pentamethylcyclopentadienyl, and 1-phenylboraben dride, cis-1,2-cyclohexanedicarboxylic anhydride, and zene. Other suitable aromatic compounds can be found mixtures thereof. P by consulting any of many chemical handbooks. As noted above, the organometallic compounds use As mentioned before, the ligand can be a unit of a polymer, for example, the phenyl group in polystyrene, ful in combination with onium salts to provide the cur poly(styrene-co-butadiene), poly(styrene-co-methyl ing agents useful in the invention have the formula methacrylate), poly(alpha-methylstyrene), polyvinyl LL2LM, I carbazole, and polymethylphenylsiloxane; the cyclo pentadiene group in poly(vinylcyclopentadiene); the Ligands Li to L are well known in the art of transi pyridine group in poly(vinylpyridine), etc. Polymers tion metal organometallic compounds. 45 having a weight average molecular weight up to Ligand Ll of general formula I is provided by any 1,000,000 or more can be used. It is preferable that 5 to monomeric or polymeric compound having an accessi 50 percent of the unsaturated or aromatic groups pres ble unsaturated group, i.e., an ethylenic, ent in the polymer be complexed with metallic cations. Each ligand Ll can be substituted by groups that do 50 not interfere with the complexing of the ligand with the metal atom or which do not reduce the solubility of the ligand to the extent that complexing with the metal atom does not take place. Examples of substituting group; acetylenic, -C=C- group; or aromatic group groups, all of which preferably have less than 30 carbon which has accessible pi-electrons regardless of the total 55 atoms and up to 10 hetero atoms selected from nitrogen, molecular weight of the compound. By "accessible', it sulfur, non-peroxidic oxygen, phosphorus, arsenic, sele is meant that the compound (or precursor compound nium, antimony, tellurium, silicon, germanium, tin, and from which the accessible compound is prepared) bear boron, include hydrocarbyl groups such as methyl, ing the unsaturated group is soluble in a reaction me ethyl, butyl, dodecyl, tetracosanyl, phenyl, benzyl, al dium, such as an alcohol, e.g., methanol; a ketone, e.g., lyl, benzylidene, ethenyl, and ethynyl; hydrocarbyloxy methyl ethyl ketone; an ester, e.g., amyl acetate; a halo groups such as methoxy, butoxy, and phenoxy; hy carbon, e.g., trichloroethylene; an alkane, e.g., decalin; drocarbylmercapto groups such as methylmercapto an aromatic hydrocarbon, e.g., anisole; an ether, e.g., (thiomethoxy), phenylmercapto (thiophenoxy); hy tetrahydrofuran; etc, or that the compound is divisible drocarbyloxycarbonyl such as methoxycarbonyl and into very fine particles of high surface area so that the 65 phenoxycarbonyl; hydrocarbylcarbonyl such as formyl, unsaturated group (including aromatic group) is suffi acetyl, and benzoyl; hydrocarbylcarbonyloxy such as ciently close to a metal atom to form a pi-bond between acetoxy, benzoxy, and cyclohexanecarbonyloxy; hy that unsaturated group and the metal atom. By poly drocarbylcarbonamido, e.g., acetamido, benzamido; 4,950,696 13 14 azo, boryl; halo, e.g., chloro, iodo, bromo, and fluoro; formyl, acetyl, propionyl, acryloyl, octadecoyl, ben hydroxy; cyano; nitro; nitroso, oxo; dimethylamino; zoyl, toluenesulfonyl, oxalyl, malonyl, o-phthaloyl. diphenylphosphino, diphenylarsino; diphenylstibine; Also suitable as Lis any group having in its structure trimethylgermyl; tributylstannyl; methylseleno; ethyl two, three, or four unshared electrons, with the proviso telluro; and trimethylsiloxy; condensed rings such as that only one electron is shared per metal M. Examples benzo, cyclopenta; naphtho, indeno; and the like. of such groups are CH2, SiMe2, SiPh2, SnPh2, GePh2, Each ligand L2 in formula I is provided by monoden SiMe, SiPh2, SnPh, Si, and Sn. tate and polydentate compounds preferably containing M can be any element from the Periodic Groups IVB, up to about 30 carbon atoms and up to 10 hetero atoms VB, VIB, VIIB, and VIIIB, such as, for example, Ti, selected from nitrogen, sulfur, non-peroxidic oxygen, 10 Zr, Hf, V, Nb, Ta, Cr, Mo, W, Mn, Tc, Re, Fe, Ru, Os, phosphorous, arsenic, selenium, antimony, and tellu Co, Rh, Ir, Ni, Pd and Pt. rium, whereupon addition to the metal atom, following In general, radiation-induced polymerization of eth loss of zero, one, or two hydrogens, the polydentate ylenically unsaturated monomers and one of polyure compounds preferably forming with the metal, M, a 4-, thane precursors and epoxy monomers with latent cur 5-, or 6-membered saturated or unsaturated ring. Exam 15 ing agents comprising an organometallic compound and ples of suitable monodentate compounds or groups are an onium salt can be carried out at room temperature carbon monoxide, carbon sulfide, carbon selenide, car for the majority of energy curable compositions, al bon telluride, alcohols such as ethanol, butanol, and though low temperature (e.g., -10° C) or elevated phenol; nitrosonium (i.e., NOh); compounds of Group temperature (e.g., 30' to 200 C., preferably 50' to 150 VA elements such as ammonia, phosphine, trimethyl 20 C.) can be used to subdue the exotherm of polymeriza amine, trimethylphosphine, triphenylamine, triphenyl tion or to accelerate the polymerization, respectively. phosphine, triphenylarsine, triphenylstibine, tributyl Temperature of polymerization and amount of catalyst phosphite, isonitriles such as phenylisonitrile, will vary and be dependent on the particular curable butylisonitrile; carbene groups such as ethoxymethyl composition used and the desired application of the carbene, dithiomethoxycarbene; alkylidenes such as 25 polymerized or cured product. The amount of curing methylidene, o ethylidene; suitable polydentate com agent to be used in this invention should be sufficient to pounds or groups include 1,2-bis(diphenylphosphino)e- effect polymerization of the polymerizable mixtures thane, 1,2-bis(diphenylarsino)ethane, bis(diphenylphos (i.e., a catalytically-effective amount) under the desired phino)methane, ethylenediamine, propylenediamine, use conditions. Such amount generally will be in the 30 range of about 0.1 to 20 weight percent, and preferably diethylenetriamine, 1,3- diisocyanopropane, and hy 0.1 to 10.0 weight percent, based on the weight of cur dridotripyrrazolylborate; the hydroxycarboxylic acids able composition. such as glycolic acid, lactic acid, salicylic acid; poly While not wishing to be bound by theory, We pro hydric phenols such as catechol and 2,2'-dihydrox pose that when specified organometallic compounds are ybiphenyl; hydroxyamines such as ethanolamine, 35 irradiated in the presence of suitable oxidizing agents propanolamine, and 2-aminophenol; dithiocarbamates such as onium salts, intermediate compounds are pro such as diethyldithiocarbamate, dibenzyldithiocarba duced which can affect the curing of epoxides, ure mate; xanthates such as ethylxanthate, phenylxanthate; thanes, and vinyl monomers. It is believed that the tran the dithiolenes such as bis(perfluoromethyl)-1,2-dithio sition metal-transition metal or metal-L sigma bond lene; aminocarboxylic acids such as alanine, glycine and cleaves homolytically upon photolysis. Evidence for o-aminobenzoic acid; dicarboxylic diamines as oxala this homolytic cleavage is provided for some organo mide, biuret; diketones such as 2,4-pentanedione; hy metallic compounds such as CpFe(CO)2)2 and droxyketones such as 2-hydroxyacetophenone; alpha Mn2(CO)10 and involves the abstraction of Cl from hydroxyoximes such as salicylaldoxime; ketoximes such CCL4 subsequent to photolysis. (G. Geoffrey and M. as benzil oxime; and glyoximes such as dimethylglyox 45 Wrighton, “Organometallic Photochemistry,” Aca ime. Other suitable groups are the inorganic groups demic Press, NY (1979), Chapters 2 and 8, particularly such as, for example, CN, SCN, F, OH, Cl-, p. 138). In other cases, spectroscopic data provides such Br, I, and H and the organic groups such as, for evidence (O. Hackelberg, A. Wojcicki Inorg. Chem. example, acetoxy, formyloxy, benzoyloxy, etc. As men Acta. 1980, 44, L63; R. G. Severson, A. Wojcicki J. tioned before, the ligand can be a unit of a polymer, for 50 Organomet. Chem. 1978, 157, 173). The product(s) of example the amino group in poly(ethyleneamine); the this bond homolysis then react with the oxidizing agent. phosphino group in poly(4-vinylphenyldiphenylphos By this process, the catalytic species for the polymeriza phine); the carboxylic acid group in poly(acrylic acid); tion of either the polyurethane precursors or epoxy and the isonitrile group in poly(4-vinylphenylisonitrile). monomers is derived from the organometallic com Suitable ligands L3 in formula I include any group 55 pound, and, simultaneously the free radical initiator for having in its structure an atom with an unshared elec the polymerization of the ethylenically unsaturated tron. Suitable groups can contain any number of carbon monomers is derived from the oxidizing agent. In the atoms and hetero atoms but preferably contain less than limit, cleavage of the sigma bond by one photon can 30 carbon atoms and up to 10 hetero atoms selected ultimately lead to the production of two organometal from nitrogen, sulfur, oxygen, phosphorus, arsenic, lic-derived species and two free radical initiators. It selenium, antimony, tellurium, silicon, germanium, tin, should be noted that competing or secondary photo and boron. Examples of such groups are hydrocarbyl processes, such as dissociation of a carbonyl ligand, can groups such as methyl, ethyl, propyl, hexyl, dodecyl, occur. Such processes, however, occur in such a man phenyl, tolyl, etc.; unsaturated hydrocarbyl groups such ner or to such an extent that the effective catalytic as vinyl, etal-allyl, etal-butenyl, etal-cyclohexenyl; the 65 species and initiator are still produced so as to effect hydrocarbyl derivatives of a Group IVA element such curing of the composition. as trimethylgermyl, triphenylstannyl, trimethylsilyl, Solvents, preferably organic can be used to assist in and triphenylead, etc.; and organic groups such as dissolution of the curing agent in the ethylenically 4,950,696 15 16 unsaturated monomer, and either polyurethane precur lene), and the like, and irradiated. By polymerizing part sors or epoxy monomers, and as a processing aid. Rep of the coating, as by irradiation through a mask, those resentative solvents include acetone, methyl ethyl ke sections which have not been exposed may be washed tone, cyclopentanone, methyl cellosolve acetate, meth with a solvent to remove the unpolymerized portions ylene chloride, nitromethane, methyl formate, acetoni while leaving the photopolymerized, insoluble portions trile, gamma-butyrolactone, and 1,2-dimethoxyethane in place. Thus, compositions of this invention may be (glyme). In some applications, it may be advantageous used in the production of articles useful in the graphic to adsorb the curing agent onto an inert support such as arts such as printing plates and printed circuits. Meth silica, alumina, clays, etc., as deseribed in U.S. Pat. No. ods of producing printing plates and printed circuits 4,677,137. 10 from photopolymerizing compositions are well known For those compositions of the invention which are in the art (see for example British Patent Specification radiation-sensitive, i.e., the compositions containing No. 1,495,746). ethylenically unsaturated monomers and either polyure Objects and advantages of this invention are further thane precursors or epoxy monomers and as curing illustrated by the following examples, but the particular agent a combination of an organometallic compound of 15 materials and amounts thereof recited in these examples, Formula I and an onium salt of Formula II, any source as well as other conditions and details, should not be of radiation including electron beam radiation and radi construed to unduly limit this invention. In the exam ation sources emitting active radiation in the ultraviolet ples, all parts are parts by weight unless indicated other and visible region of the spectrum (e.g., about 200 to 800 wise. All examples were prepared in ambient atmo nm) can be used. Suitable sources of radiation include 20 sphere (presence of oxygen and water) unless indicated mercury vapor discharge lamps, carbon arcs, tungsten otherwise. In the examples: lamps, xenon lamps, lasers, sunlight, etc. The required Me= methyl amount of exposure to effect polymerization is depen Ph=phenyl dent upon such factors as the identity and concentra Cp = cyclopentadienyl tions of the organometallic compound and onium salt, 25 the particular ethylenically unsaturated monomer, poly EXAMPLE 1. urethane precursors, and epoxy monomers, the thick The organometallic compounds, CpRe(CO)22, ness of the exposed material, type of substrate, intensity Mn2(CO)10, Re2(CO)10 and CpMo(CO)32 were ob of the radiation source and amount of heat associated tained from Pressure Chemical Company and used with the radiation. 30 without further purification. The other compounds Thermal polymerization using direct heating or infra were prepared using standard organometallic synthetic red electromagnetic radiation, as is known in the art, techniques. The procedure used will be illustrated for can be used to cure ethylenically-unsaturated mono the preparation of CpFe(CO)2SnPh3. mers and either polyurethane precursors or epoxy mon The anion, CpFe(CO)2, was produced by reducing omers according to he teachings of this invention. 35 3.0 g of CpFe(CO)2)2 with 0.41 g of sodium and 0.50 g It is within the scope of this invention to include of benzophenone in 200 mL of freshly distilled tetrahy two-stage polymerization (curing), by first activating drofuran under an atmosphere of argon. The reaction curing agent by irradiating the curable compositions was allowed to proceed for about 24 hours by which and subsequently thermally curing the activated precur time the starting material had all been reduced to the sor so obtained, the irradiation temperature being below anion as indicated by infrared spectroscopy (IR). To the the temperature employed for the subsequent heat-cur solution of the anion was added, under argon, 6.5 g of ing. These activated precursors may normally be cured ClSnPh3 as a solid. The reaction was stirred until the at temperatures which are substantially lower than anion was consumed as shown by IR. The reaction those required for the direct thermal curing, with an vessel was opened to air and the solvent removed under advantage in the range from 50 to 110' C. This two 45 reduced pressure. The solid residue was taken up in stage curing also makes it possible to control the poly methylene chloride and passed down a short silica gel merization in a particularly simple and advantageous column. Crytals were obtained by removing the methy a. lene chloride under reduced pressure and adding hep Adjuvants such as solvents, pigments, abrasive gran tane. The product was identified by IR, nuclear mag ules, stabilizers, light stabilizers, antioxidants, flow 50 netic resonance spectroscopy (NMR), elemental analy agents, bodying agents, flatting agents, colorants, inert sis and melting point. In a similar manner all the other fillers, binders, blowing agents, fungicides, bacterio materials in Table I were prepared. cides, surfactants, plasticizers, and other additives as These compounds are used in subsequent examples. known to those skilled in the art can be added to the TABLE I compositions of this invention. These can be added in an 55 Characterization of Compounds amount effective for their intended purpose. Elemental Analysis Compositions of this invention are useful for coatings, - (Report/Calculated) - foams, shaped articles, adhesives, filled or reinforced Melting composites, abrasives, caulking and sealing compounds, Compound % C % H Point ("C.) casting and molding compounds, potting and encapsu CpFe(CO)2SnPh3 57.0/57.0 3.8/3.8 135-36 lated compounds, impregnating and coating com CpFe(CO)2CePh3 62.3/62.4 4.2/4.2 159-60 pounds, and other applications which are known to CpFe(CO)2PbPh3 those skilled in the art. (CpFe(CO)2)2SnPh2 49.7/49.8 3.3/3.2 146-149 (CO)5MnSnPh3 51.0/50.7 2.8/2.8 146-149 Compositions of this invention may be applied, pref (CO)5MnPbPh3 erably as a liquid, to a substrate such as steel, aluminum, 65 (CO)5Mn2SnPh2 39.9/39.8 1.6/.5 38-139 copper, cadmium, zinc, glass, paper, wood, or various (CO)5 ReSn Ph3 plastic films such as poly(ethylene terephthalate), plasti CpMoSnPh3 52.6/52.5 3.4/3.4 23-214 cized poly(vinylchloride), poly(propylene), poly(ethy 4,950,696 17 18 Samples were prepared, 2.0 g in size, using 77 parts EXAMPLE 2 Henkel Duo-Cure 172A, 23 parts Duo-Cure 172B, 0.5 Several organometallic compounds were prepared parts CpFe(CO)2)2, and 1 part Ph2+. One sample was according to literature methods. CpW(CO)3(CH3) was cured in the vial using a suntan lamp, cured in <3.0 prepared according to the method of T. S. Piper, G. 5 minutes to a clear, hard mass. The other sample was Wilkinson, Inorg. Nucl. Chenn., 1956, 3, 104-124. coated on a tongue depressor and exposed to the suntan CpW(CO)32 was prepared according to the method of lamp. Curing occurred in 15 seconds, to yield a clear, R. Birdwhistell, P. Hackett, A. R. Manning, J. Orga hard, sandable coating. Infrared spectra of thin coatings nonet, Chem., 1978, 157, 239. CpFe(CO)2SiPh3 was on salt plates showed conversion of the isocyanate to prepared according to the method of G. Cerveau, E. 10 urethane upon exposure to sunlamp radiation. Colomer, R. Corriv, W. E. Douglas, J. Organomet. Chem., 1977, 135, 373,386. The method of J. P. Bibler, EXAMPLE 6 A. Wojcicki, J. Anner. Chen. Soc., 1966, 88, 4862 was (Comparative) used to prepare CpFe(CO)2(CHPh2), and that of R. B. King, M. B. Bisnette, J. Organomet. Chem., 1964, 2, 15 This example illustrates the photocuring of polyure 15-37, to prepare CpFe(CO)2(COPh). The preparation thane precursors to polyurethanes in the presence and of CpPtMe3 has been described in U.S. Pat. No. absence of O2 using transition metal-transition metal 4,600,484. bond containing organometallic compounds and onium These compounds are used in subsequent examples. salt as curing agent. 20 A mixture of 10 mg (CpFe(CO)2)2, 30 mg Ph2+ EXAMPLE 3 PF6, 0.1 g gamma-butyrolactone, 0.83 g De (Comparative) smodurTM W (4,4'- methylenebis(cyclohexylisocya nate)), and 1.17 g polyethyleneglycol (MW=400) was This example illustrates the use of an organometallic divided in half. One half was bubbled with N2 for 2-3 compound containing a transition metal-transition metal 25 minutes, the other left open to the atmosphere. Both single bond in the curing agent to photocatalyze the samples were irradiated simultaneously with the output formation of polyurethane. A stock solution of 8.02 g of a 450 watt Hanovia mercury lamp, filtered through 4,4'-methylenebis(cyclohexylisocyanate) -(De Pyrex and a water infrared filter. Both samples cured smodurTM W, a Mobay Corp., Pittsburgh, PA) and after 10.0 minutes irradiation. This demonstrates that in 11.20 g polyethylene glycol MW400 (CarbowaxTM 30 the presence of onium salt, curing occurs with or with 400, Union Carbide, Danbury, CT) was prepared. To a out O2 present. solution of 0.01 g (CpFe(CO)22 and 0.02 g Ph2+ PF6 in 0.1 g gamma-butyrolactone was added 1.25 g of the EXAMPLE 7 stock solution. The sample was photocured to a solid (Comparative) using a KodakTM Carousel TM projector in 12 min tes. This example describes the photocuring of polyure Three samples were prepared as above, except the thane precursors using transition metal containing or iron dimer and iodonium salt were added, as follows: ganometallic compounds and iodonium and sulfonium sample (a), 0.01 g CpFe(CO)2)2, 0.03 g Ph2+ PF6; salts. A stock solution was prepared from 7 parts De sample (b), 0.01 g (CpFe(CO)2)2; sample (c), 0.03 go smodur W, 1.9 parts butanediol, and 0.5 parts trimethyl Ph2+ PF6; (a) was left in the dark while samples (b) olpropane. Samples were prepared as in Example 3 and (c) were irradiated as above. None of the three using 1.25 g of the stock solution, 0.01 g neutral metal samples showed evidence of any curing, no obvious metal bonded compound and 0.015 g Ph2I+ PF6 in change in viscosity as evidence, after 20 minutes. 0.05 g gamma-butyrolactone. Irradiations were carried out on a 450 W. Hanovia medium pressure mercury arc EXAMPLE 4 45 through Pyrex. Alternatively, these compositions can (Comparative) be cured thermaily. This example illustrates the use of an organometallic TABLE II compound containing a transition metal-carbon single Iodonium and Sulfonium Salts bond in the curing agent to photocatalyze the formation 50 Organometallic Cure time, minutes of polyurethane. 0.52 g Desmodur W (4,4,-methylene Compound Ph2+ PF6 Ph3S+ PF6 bis (cyclohexyl isocyanate)) and 0.72 g Carbowax 400 Co(CO)42 6.0 > 100 (polyol) were combined and added to ca. 0.01 g CpFe(CO)2)2 9.0 20-25 CpPt(CH3)3 (Cp =eta-cyclopentadienyl) which had Mn(CO)52 12-20 7-12 Re(CO)52 20-40 20-40 been dissolved in ca. 0.15 ml of a mixture of CH2Cl2 and 55 Co4(CO)12 40-5S 55-66 gamma-butyrolactone. The resulting mixture was irra CpMo(CO)32 55-67 60-66 diated with a Hanovia TM 450 watt medium pressure Fe(CO)9 ca. 60 mercury arc lamp through PyrexTM. Complete cure was achieved within 12 minutes irradiation time. EXAMPLE 5 EXAMPLE 8 This example describes the photocuring of Henkel (Comparative) Duo-Cure TM (Henkel Corp., Minneapolis, MN) resins. This provides further examples of bicomponent cur The Henkel Duo-Cure TM resins are polyol/aliphatic ing agents wherein organometallic compounds contain polyisocyanate and multifunctional acrylate systems 65 transition metal-carbon bonds which are effective in the containing no curing agents. The resins are dual curing curing agent for polyurethane precursors. A stock solu resins, and are claimed to form interpenetrating net tion of polyurethane precursors was prepared by mixing works (IPN's) when properly cured. 23.1 g Desmodur W and 32.6 g Carbowax 400 and shak 4,950,696 19 20 ing well before use. Samples were prepared by dis fluorophosphate (3M Company, recrystallized from solving 10 mg catalyst and 0 mg diphenyliodonium acetone/isopropanol). Then, the following operations hexafluorophosphate (if used) in 0.2 g CH2Cl2.2.0 g were carried out under subdued light, 0.3 g of gamma stock solution was added in the dark, and samples were butyrolactone, 2.0 g cyclohexene oxide (Aldrich Chem then irradiated under a Hanovia Quartz Utility Lamp. ical Company, distilled), 5.0 g of 3, 4-epoxycyclohexyl The temperature of samples under the lamp reached ca. methyl-3,4-epoxycyclohexane carboxylate (ERL-4221, 50 C. within 10 min. The time to a viscocity increase is Union Carbide Company) were added to prepare the noted in Table III, and "cure time' is the time for a coating solution. The solutions were coated onto 76 sample to become so viscous that it would not flow. micrometers (3 mil) polyvinylidene chloride subbed "Partial cure' is indicated when, within 30 min irradia 10 polyester (3M Company) using a #22 wire wound rod. tion, the sample became more viscous but would still The sample coatings were exposed, in air, to a 275 watt flow. G.E. sunlamp at a distance of 10 cm. The time to "set to TABLE III cotton' is recorded in Table V, that is the time needed to cure the coating so that when it is touched with a Curing of Polyurethane Precursors 15 Cure Rates, min cotton ball, it leaves no smear or picks up no cotton Viscosity threads. This test establishes the time required to cure Increase Cured the coating. Under the conditions of this test, the di CpPtMes 7 30 phenyliodonium hexafluorophosphate alone requires CpPtMe3+ iodonium 7 30 greater than 10 min to cure. CpW(CO)3Me 30 partial 20 CpW(CO)3Me + iodonium 30 partial TABLE V (PMe2Ph)2PtMe3 (acetone)]+ PF6 13 partial Photoinitiation of Epoxy Cure (CpFe(CO)2)2 + iodonium 9 30 Cure Time included for purposes of comparison No Onium Onium Salt 25 Compound Salt Added Added The data show curing occurs with or without iodo (CpFe(CO)22 > 10 nium salts. In some cases, adventitious oxygen can pro CpFe(CO)2SnPh3 > 10 5 CpFe(CO)2OePh3 > 10 s vide a suitable oxidizing agent. However, the use of CpFe(CO)2)2SnPh2 > 0 3 onium salts is preferred since it is much easier to control Mn2(CO)10 > 0 1 the organometallic/oxidizing agent ratio. 30 (CO)5MnSnPh3 > 0 4. (CO)5Mn)2SnPh2 > 10 3 EXAMPLE 9 Re2(CO)10 l 1.5 (Comparative) CpMo(CO)3SnPh3 8 4 time in minutes to cure. This example describes the use of the curing agent containing an organometallic compound containing a 35 transition metal-carbon bond to cure epoxies. Each EXAMPLE 11 sample was prepared by dissolving 10 mg catalyst and (Comparative) 20 mg diphenyliodonium hexafluorophosphate (if used) in 0.2 g CH2Cl2. 2.0 g cyclohexene oxide was added in To further demonstrate the activity of the curing the dark, and samples were then irradiated under a agent, a series of experiments were carried out in an Hanovia Quartz Utility lamp. Initial formation of poly other epoxy and/or acrylate composition. The organo mer was tested by placing a few drops of the sample in metallic compound, with and without the onium salt, about 2 mL methanol. Formation of precipitate indi gas photolyzed in presence of an epoxy or acrylate. The cated that polymer had formed. Further polymerization specific system used is as follows: methyl acrylate was resulted in a viscocity increase in the sample. Results 45 distilled from hydoquinone and stored cold until ready are indicated in Table IV. for use. Cyclohexene oxide was used as obtained from Aldrich. The organometallic compounds were obtained TABLE IV from commercial sources. Diphenyliodonium hexa Viscosity fluorophosphate was recrystallized from acetone/iso Precipitate increased, propanol. All experiments were done as 100% solids, Curing Agent formed, min. min. 50 except as noted. CpPtMe3 ld cure O Ce CpPtMe3+ iodonium 3.5 30 In a small vial was placed 0.02 g of the organometal CpW(CO)3Me + iodonium 3 30 lic compound with/without 0.04 g of the iodonium salt (PMe2Ph)2PtMe3 (acetone) + PF6 2 no further along with 2 g of the desired monomer. For the acrylate Cle tests, the solutions were purged with N2 for 60 sec be CpFe(CO)2)2 + iodonium 2 30 55 fore and continuously during the photolysis. The epoxy included for proposes of comparison. tests were performed without purging, vials open to the air. The light source was one 15 watt daylight fluores cent bulb. In Table VI below, the cure times represent EXAMPLE 10 the time required to reach the same degree of cure, (Comparative) usually gelation of the solution. Alternatively, the acry Examples of the ability of curing agent containing late compositions can be cured thermally. transition metal-transition metal bonded and M-L type TABLE VI organometallic compounds and onium salt to photoiniti Photoinitiated Cure Times of Epoxy ate the cure of epoxies are provided here. The tests 65 and Acrylate Compositions" were carried out in the following manner: Into a glass Catalyst System Epoxy Acrylate vial were weighed out 0.10 g of the desired organome (CpFe(CO)2)2 > 900 > 600 tallic compound and/or 0.20g diphenyliodonium hexa CpFe(CO)2)2/iodonium 60 30 4,950,696 21 22 TABLE VI-continued g of diphenyliodonium hexafluorophosphate or these Photoinitiated Cure Times of Epoxy same amounts of both compounds added to either mon and Acrylate Compositions omer. The light sources used were for UV exposure, Catalyst System Epoxy Acrylate about 360 nm, two 15 watt G.E. blacklite bulbs and for Mn2(CO)10 >900 > 600 the visible, a Kodak Carousel Projector of the projector Mn2(CO)1/iodonium 200 45 with a 440 nm filter. The initiation of polymerization Re2(CO)10 >900 360 was detected by solution gelation for the acrylate and Re(CO)10/iodonium 200 60 Co2(CO)8 b b for the epoxy the precipitation of the polymer from a Co2(CO)3/iodonium 200 2% ammonia/methanol solution. Free radical systems Co4(CO)12 b b 10 were purged with N2 for 2 minutes before and continu Co4(CO)12/iodonium >900 80 ously during irradiation while the cationic samples were iodonium >900 >300 left open to the air without purging. Sample size was 2 "Cure time in seconds, Not done. to 3 ml in a 13X 100 mm pyrex test tube. The results of Reacted in the dark upon mixing. these tests are shown in Table VIII. a 10% by wt. gamma-butyrolactone added. 15 TABLE VIII Photoinitiated Cure Times of EXAMPLE 12 Epoxy and Acrylate Compositions (Comparative) Curing Agent Epoxy Acrylate 20 CpFe(CO)2)2 > 180 >300b This example demonstrates the ability of transition CpFe(CO)2)2/iodonium 90th <5b metal-transition metal bonded or ML type organome 90?d <5d tallic compounds to photoinitiate the cure of ethyleni Mn2(CO)10 > 180b >300b cally-unsaturated compounds in the presence of iodo > 180 >300e nium salts. The tests were carried out in the following Mn2(CO)10/iodonium > 180 <10 manner: Into a glass vial were weighed out 0.05 g of the 25 > 180 < 10e Cure times given in seconds. desired organometallic compound and/or 0.10 g di Unfiltered projector as light source. phenyliodonium hexafluorophosphate (3M Company, The diphenyliodonium salt showed no indication of polymerization by itself under recrystallized from acetone/isopropanol). Then, the these same conditions. following operations were carried out under subdued 440 nm filter used with the projector. light: 0.2 g of gamma-butyrolactone, 5.0 g methyl acry 30 Blacklite used as the light source, about 360 nm. late (Aldrich Chemical Company, distilled from hydro quinone), 5.0 g of pentaerythritol tetraacrylate (SR-295, EXAMPLE 14 Sartomer Company) were added to prepare the coating (Comparative) solution. The solutions were coated onto 76 microme ters (3 mil) polyvinylidene chloride subbed polyester 35 Examples of the photocuring of ethylenically unsatu (3M Company) using a #22 wire wound rod. The sam rated monomers using transition metal-transition metal ple coatings were overlayed with a second sheet of bond containing organometallic compounds and iodo polyester and exposed to two 15 watt Sylvania black nium salts are given here. light bulbs at a distance of 2 cm. The time required to Samples were prepared as 1.0 g methyl acrylate con produce a nontacky cured coating was recorded. Under 40 taining 0.01 g metal-metal bond containing complex and the conditions of this test, the diphenyliodonium hexa 0.015 g Ph2I+PF6. Up to 0.05 g butyrolactone or fluorophosphate alone requires greater than 15 min to methylene chloride were used to dissolve the photocat Cle. alyst systems. Samples were bubbled with N2 and irradi ated using a Kodak Carousel slide projector, with a 360 TABLE VII 45 Curing of Ethylenically Unsaturated Monomers nm cutoff filter, and the time required to cure the sam Cure Time ple recorded in Table IX. Alternatively, compositions No Onium Onium Salt could be cured thermally. Organometallic Compound Salt Added Added TABLE IX CpFe(CO)22 >600 15 50 Curing of Ethylenically-Unsaturated Monomers CpFe(CO)2SnPh3 >600 120 CpFe(CO)2GePh3 > 600 20 Compound CpFe(CO)2)2SnPh2 > 600 60 and PhIPF6 Conditions Cure Time Mn2(CO)10 > 600 <15 (CpFe(CO)2)2 irrad. 30 sec, slow dark reaction (CO)5MnSnPh3 300 300 Mn2(CO)10 irrad. , 30 sec, no dark reaction (CO)5Mn2SnPh2 60 30 55 CpMo(CO)32 irrad. 45 sec, no dark reaction Re(CO)10 120 60 Re(CO)52 irrad. 8 min, no dark reaction (CpMo(CO)3)2 > 600 30 Co4(CO)12 irrad. Minutes, slow dark reaction CpMo(CO)3SnPh3 > 600 240 Co2(CO)8 Dark Cures during deoxygenation time in seconds to cure. 'saturated solution, <0.01 g dissolved. EXAMPLE 1.5 EXAMPLE 13 (Comparative) (Comparative) This example describes the curing of ethylenically Further examples of the curing of ethylenically unsat unsaturated monomers with transition metal-carbon urated monomer (25 g of pentaerythritol tetraacrylate 65 bonded organometallic compounds. Each sample was in 225 g acetonitrile) or epoxy monomer (cyclohexene prepared by dissolving 10 mg catalyst and 20 mg di oxide) are provided here. A. curable composition con phenyliodonium hexafluorophosphate (if used) in 0.2g sisted of 0.01 g of the organometallic compound or 0.02 gamma-butyrolactone. 2.0 g methyl acrylate (distilled 4,950,696 23 24 to remove inhibitors) was added in the dark and nitro gen was bubbled through the sample for 2 min to re TABLE X Cure Times: Photoinitiated Curing of Polyurethane Precursors move oxygen. Samples were then irradiated in front of Epoxies and Vinyl Monomers with Transition Metal a Kodak Carousel Projector containing a 360 nm cutoff Group IVA Compounds filter. If no curing occurred in 15 min, the sample was 5 Catalyst System Polyurethane Epoxy Vinyl then irradiated for 15 min under a Hanovia Quartz Util (CpFe(CO)2)2 120 min (VV)' f no cure ity lamp. In Table X, "cure time' refers to the time (CpFe(CO)2)2/iodonium 60 min (VV) 30 sec 1.8 min required for a sample to solidify. Alternatively, compo CpFe(CO)2(CH2Ph) 40 min (V) f O cure sitions could be cured thermally. CpFe(CO)2(CH2Ph)/ 40 min (V) 12 min 23 min 10 iodonium TABLE X CpFe(CO)2(COPh) 120 min (V) f no cure CpFe(CO)2(COPh)/ 120 min (V) 5 min 48 hrs Curing of Ethylenically Unsaturated Monomer iodonium Curing Agent Cure time, min CpFe(CO)2(SiPh3) 45 min (V) f to cre CpPtMes 15 (Hanovia) CpFe(CO)2(SiPh3)/ 45 min (V) 5 min 48 hrs CpPtMe3+ iodonium 6 (Kodak) 15 iodonium CpW(CO)3Me O Clare CpFe(CO)2(GePh3) 36 min (v)h f no cure CpW(CO)3Me + iodonium 3.5 CpFe(CO)2(GePh3)/ 36 min (V) 2.75 min no cure CpFe(CO)2]2+ iodonium iodoniun 0.5 (dark cure) CpFe(CO)2(SnPh3) 36 min (S) f no cle included for purposes of comparison CpFe(CO)2(SnPh3)/ 36 min (V) 2 min no cure iodonium 20 CpFe(CO)2(PbPh3) 45 min (S) f O. Cure EXAMPLE 16 CpFe(CO)2(PbPh3)/ 33 min (VV) no cure no cure iodonium (Comparative) Polyurethane precursors are from a stock solution consisting of 23.1 g of De Snodur TM W and 32.6 g of Carbowax 400. Cure times are followed by an indication This example describes the use of CpW(CO)3)2 to in parentheses of extent of cure, where V = viscous, VV = very viscous, S = solid. cure polyurethane precursors, epoxies or ethylenically 25 'Monomer is cyclohexene oxide, purified by distillation. Cure time is defined as the time necessary to observe formation of precipitate when one drop of sample is unsaturated monomers. Each sample contained 0.01 g placed in 2 ml of methanol. CpW(CO)32 and 0.02 g diphenyliodonium hexafluoro Monomer is methyl acrylate, purified prior to use by distillation under reduced phosphate (if used) in 0.25 g gamma-butyrolactone, to pressure. After monomer addition but before irradiation, samples were deoxygen ated by bubbling a stream of nitrogen gas through the solution for 2 nin, with care which was added 2.0 g of precursor or monomer in a being taken to prevent any light from reaching the sample during deoxygenation. 30 Cure is defined by an increase in solution viscosity or a sudden exotherm indicating vial. Irradiation was then performed with a Kodak rapid polymerization (also accompanied by a sudden increase in viscosity). Carousel Projector (9 inches away), modified with a included for purposes of comparison to data in other Tables. 360 nm filter. With a urethane precursor stock solution 60 min irradiation with Carousei Projector, followed by 60 minutes of irradiation in room (fluorescent) light. (prepared as in Example 4), in the presence or absence This particular combination was not tested. of onium salt, partial curing to produce a clear solution, $30 minutes irradiation with Kodak projector, following by 30 minutes irradiation 35 under a Hanovia Quartz Utility Lamp (6 inches from bulb), followed by sample occurred in 2 hour irradiation time. Upon standing in storage/irradiation in room (fluorescent) light. room light for 24 hours, an increase in viscosity oc irradiation with Hanovia Quartz Utility Lamp (15 cm from bulb) in place of the curred. Kodak Projector. When cyclohexeneoxide was used, and the curing agent consisted of CpW(CO)32 and onium salt, vigor EXAMPLE 18 ous, exothermic curing occurred within 3 min of irradi ation. This example illustrates the dual curing of polyure When methyl acrylate was used as monomer, no thane precursors and ethylenically-unsaturated mono curing occurred in the absence of onium salt. With mers using the curing agent (CpFe(CO)2)2/Ph2It onium salt present, the sample became viscous within 4 PF6-. min and solid within 8 min of irradiation time. 45 Samples 1.25 g in size, were prepared from stock Alternatively, these compositions can be cured ther solutions of 2.08 parts DesmodurTM W (4,4'- mally. methylenebis(cyclohexylisocyanate), 2.92 parts polye thyleneglycol (MW=400), 5.0 parts methyl acrylate EXAMPLE 1.7 (freshly distilled), and 0.05 parts CpFe(CO)2)2. To half (Comparative) 50 of this stock solution was added 0.062 parts Ph2It PF6. Mole ratios for iodonium salt/iron dimer=2.1, To demonstrate the utility of the curing agent for NCO/OH = 1.0, weight % ion dimer=0.5%, iodonium curing of polyurethane precursors, epoxies and vinyl salt = 1.2%. Samples were irradiated simultaneously monomers for the case where the organometallic com using 366 nm BlakRay bulbs (15 watts) for 10 min, then pound contains a single bond between a transition metal 55 analyzed by 400 MHz H nuclear magnetic resonance and a Group IVA element, the following samples were spectroscopy. Conversions to polymer are listed in prepared. In a vial, 0.01 g of organometallic compound, Table XII. Curing agents comprising other combina 0.02 g of diphenyliodonium hexafluorophosphate (if tions of organometallic compounds and onium salts can used, as indicated below), and 0.25 g of gamma be used in place of CpFe(CO)2)2 and Ph2IPF6, respec butyrolactone were gently agitated until dissolution of 60 tively. the organometallic compound was complete. 2.0 g of polyurethane precursors or monomer was added in TABLE XII Dual Curing of Polyurethane Precursors and reduced light, the vial was capped, and the sample irra Ethylenically Unsaturated Monomers diated in front of a Kodak Carousel projector fitted Conversion to polymer with a 360 nm cutoff filler at a distance of nine inches, 65 Onium Salt Conditions Acrylate Urethane and at room temperature (about 25 C.). Particular de PhIt Dark - 4% tails and any experimental variations are indicated in PhIt Irradiation 79% 56% Table XI. PhI+. Irradiation, 76% 8% 4,950,696 25 26 TABLE XII-continued test, added to this were 0.05 g of the desired organome Dual Curing of Polyurethane Precursors and tallic compound and/or 0.1 g diphenyliodonium hexa Ethylenically Unsaturated Monomers fluorophosphate. A 3 g portion of this composition was Conversion to polymer placed in a glass vial and irradiated between two 15 Onium Salt Conditions Acrylate Urethane watt G.E. daylight fluorescent bulbs using an Ultravio deoxygenated let Products lamp holder (lamp separation distance 4 None Dark 0% 11% cm). The sample was purged with nitrogen for one None Irradiation 24% 75% minute preceeding and continuously during photolysis. None Irradiation, trace 10% The irradiation time required to produce a polymer deoxygenated O insoluble in chloroform was recorded, and is noted in Table XIV. Alternatively, these compositions can be cured thermally. EXAMPLE 1.9 TABLE XIV This example demonstrates simultaneous curing of 15 Simultaneous Photoinitiation of Free Radical and Epoxy ethylenically unsaturated monomers and epoxies. Gela Cure in a Crosslinkable System tion times will not show that both monomers have re Cure Time acted at the same time. It is possible to use nuclear No Onium Onium Salt magnetic resonance spectroscopy to differentiate the Compound Salt Added Added two polymers in the presence of each other. The experi (CpFe(CO)22 > 15 ment was carried out in the following manner: A 1/1, CpFe(CO)2SnPH3 > 15 10 w/w, mixture of methyl acrylate/cyclohexene oxide CpFe(CO)2GePh3 > 15 15 was prepared. To a 10 g sample of this mixture was CpFe(CO)2)2SnPh2 > 15 10 Mn2(CO)10 > 15 1.5 added 0.01 g of CpFe(CO)22 or Mn2(CO)10 diphenyli (CO)5MnSnPh3 > 15 10 odonium hexafluorophosphate (0.024 g with the iron (CO)5Mn2SnPh2 > 0 4. dimer, 0.03 g with the manganese dimer) or specified 25 Re2(CO)10 > 0 5 amounts of both compounds. In a small vial was placed CpMo(CO)32 > 5 1.5 2 ml of the sample and it was purged for 1 min before CpMo(CO)3SnPh3 > 5 O time in minutes to produce insoluble crosslinked system. Diphenyliodoniun and continually during irradiation. The light source was hexafluorophosphate alone under these conditions does not produce a crosslinked two 15 watt G.E. blacklite bulbs. Irradiation time was 2. system after 15 minutes. minutes. Immediately after completion of the photoly 30 'Only 0.01 g of this compound used. sis, the NMR in CDCl: was taken. The amount of poly merization was determined by the ratio of the peak Various modifications and alternations of this inven intensity of the polymer to that of polymer plus mono tion will become apparent to those skilled in the art mer. The results of the study are shown in Table XIII. without departing from the scope and spirit of this in 35 vention, and it should be understood that this invention TABLE XIII is not to be unduly limited to the illustrative embodi ments set forth herein. Percent Conversion to Polymer from NMR Study We claim: Curing Agent Epoxy Acrylate 1. An energy polymerizable composition comprising CpFe(CO)2)2 Ob 18 (a) at least one ethylenically-unsaturated monomer CpFe(CO)22/iodonium 35 60 iodonium <5 <10 different from each (b) precursor, Mn2(CO)10 <0.5 <0.5 (b) polyurethane precursors, said polyurethane pre Mn2CO)10/iodonium 37 47 cursors comprising at least an additional different NMR's taken on a 400 MHz instrument. monomer which is one monomer having at least None detected in the NMR. 45 two isocyanate groups and at least one monomer having at least two isocyanate-reactive hydrogen As can be seen from the NMR results, this system atoms, and efficiently initiated both epoxy and free radical poly (c) a curing agent comprising merization simultaneously. Curing agents comprising (1) an organometallic compound, and other combinations of organometallic compounds and 50 (2) an onium salt selected from the group consisting onium salts can be used in place of Cpre(CO)22 and of halonium compounds and cationic compounds Mn2(CO)10, and PhIPF6, respectively. of hypervalent Group VIA elements EXAMPLE 20 said organometallic compound having the formula, This example demonstrates the simultaneous curing 55 of ethylenically unsaturated and epoxy monomers in a crosslinkable system. The curable composition consists wherein of methyl acrylate, cyclohexene oxide and glycidyl L represents none, or 1 to 12 ligands contributing acrylate. If only epoxy or acrylate cure are initiated, pi-electrons that can be the same or different ligand then this system will produce a soluble polymer. Only if 60 selected from substituted and unsubstituted acyclic both epoxy and acrylate cure are initiated will a cross and cyclic unsaturated compounds and groups and linked insoluble polymer be produced. substituted and unsubstituted carbocyclic aromatic All monomers were distilled before use; methyl acry and heterocyclic aromatic compounds, each capa late and glycidyl acrylate from hydroquinone. Sample ble of contributing 2 to 24 pi-electrons to the va preparations were carried out under subdued lights. 65 lence shell of M: The polymerizable mixture consisted of 0.2 g gam L. represents none, or 1 to 24 ligands that can be the mabutyrolactone, 1.0 g glycidyl acrylate, 5.0 g methyl same or different contributing an even number of acrylate and 5.0 g cyclohexene oxide. Depending on the sigma-electrons selected from mono-, di-, and tri 4,950,696 27 28 dentate ligands, each donating 2, 4, or 6 sigma-elec 7. The composition according to claim 6 wherein the trons to the valece shell of M; ratio of organometallic compound to onium salt is in the L represents none, or 1 to 12 ligands that can be the range of 5:1 to 1:5 by weight. same or different, each contributing no more than 8. The composition according to claim 1 wherein said 5 ethylenically-unsaturated monomer is selected from the one sigma-electron each to the valence shell of group consisting of acrylates, acrylamide and vinyl each M: compounds. Ligands L,L, and L. can be bridging or non-bridg 9. The composition according to claim 8 wherein said ing ligands; ethylenically-unsaturated monomer is an acrylate. M represents 1 to 4 of the same or different metal 10 10. The composition according to claim 1 wherein atoms selected from the elements of Periodic said polyurethane precursors comprise a mixture of polyisocyanates and compounds bearing at least two Groups IVB, VB, VIB, VIIB, and VIIIB; with the isocyanate-reactive hydrogen atoms where the ratio of proviso that said organometallic compound con isocyanate groups to isocyanate-reactive hydrogen tains at least one of a metal-metal sigma bond and 15 atoms is in the range 1:2 to 2:1. L; and with the proviso that Ll, L., L., and Mare 11. The composition according to claim 1 wherein chosen so as to achieve a stable configuration. said organometallic compound is selected from the 2. The composition according to claim 1 wherein said group consisting of CpFe(CO)2)2, Mn2(CO)10, onium salt has the formula II CpPt(CH3)3. 20 12. The composition according to claim 1 wherein AX II said organometallic compound is Mn2(CO)8(1,10 phenanthrolin). wherein A is an iodonium or sulfonium, and 13. The composition according to claim 1 wherein X is an organic sulfonate counterion, or a haloge said onium salt is at least one of Ph2IPF6, nated metal or metalloid counterion. 25 PhI+SbF6, Ph2I-AsF6, Ph2I+SbF5(OH)-, Ph3S+PF6-, Ph3S+SbF6-, Ph3S+AsF6, 3. The composition according to claim 1 wherein the PhSC6H4Sph2SbF6, and Ph3S+SbF5 (OH), wherein ratio of ethylenically-unsaturated monomer to said Ph is phenyl. polyurethane precursors is in the range of 99:1 to 1:99. 14. The composition according to claim 1 which has 4. The composition according to claim 1 wherein said 30 been cured. curing agent is present in the range of 0.1 to 20 weight 15. An article comprising the cured composition ac percent of the total composition. cording to claim 14. 5. The composition according to claim 4 wherein said 16. A layered structure comprising a substrate having curing agent is present in the range of 0.1 to 10 weight coated on one surface thereof the polymerizable com 35 position according to claim 1. percent of said total composition. 17. The cured structure according to claim 16. 6. The composition according to claim 1 wherein the 18. The layered structure according to claim 16 ratio of organometallic compound to onium salt of said which is an imagable structure. curing agent is in the range of 10:1 to 1:10 by weight. sk it is k is

45

50

55

65 UNITED STATES PATENT AND TRADEMARK OFFICE CERTIFICATE OF CORRECTION PATENT NO. : 4,950 696 DATED August 21, 1990 INVENTOR(S) : Michael C. Palazzotto et al.

it is certified that error appears in the above-identified patent and that said Letters Patent is hereby corrected as shown below: Col. 8, line 4, "Q (NCO) should read -- Q(NCO) as are Col. 10, lines 47 and 48, "cyclic ether" should read --cyclic ethers--.

Col. 13, line 26, "methylidene, o ethylidene" should read -- methylidene, ethylidene --. Col. 25, line 31, "CDC1" should read -- CDC13.

Signed and Sealed this Twenty-seventh Day of October, 1992

DOUGLAS B. COMER

Attesting Officer Acting Commissioner of Patents and Trademarks