claimed is: 1. A vulcanizate comprising a substantial portion of halogenated butyl rubber, a copolymer of 85 to 99.5 wt. percent of a C4 tO C7 isoolefin and 0.5 to 15 wt. percent of a C,, to Cl, multiolefin, vulcanized with the condensation product of meta hydrocarbonsubstituted phenol and an aldehyde, said condensation product having one to two ring positions open on said phenol. 2. A vulcanizate comprising a substantial portion of halogenated butyl rubber, a copolymer of 85 to 99.5 wt. percent of a Cl tO C7 isoolefin and 0.5 to 15 wt. percent of a C4 tO C14 multiolefin, vulcanized with a dimethylol meta-substituted phenol, said condensation product havin-, one to two ring positions on said phenol unsubstituted. 3. A vulcanizate comprising a substantial portion of halogenatcd butyl rubber, a copolymer of 85 to 99-.5 wt. percent of a C4 to C7 isoolefin and -0.5 to 15 wt. percent of a C4 tO C14 multiolefin, vulcanized with a 2,6-dimethylol meta hydrocarbon-substituted phenol, in which the para position is open, and in which the other meta position is occupied by a radical selected from the group consisting of hydrogen and hydroxy. ,4. A vulcanizate according to claim 3 in which the halogenated butyl rubber is vulcanized in the presence of a metal oxide. 5. A vuleanizate comprising a fiuer and a substantial portion of halogenated butyl rubber, a copolymer of 85 to 99.5 wt. percent of a C4 tO C7 isoolefin and 0.5 to 15 wt. percent of a C4 tO C14 multiolefin, vulcanized with a 2,-6-dimethylol-5-hydrocarbonsubstituted phenol, in which the hydrocarbon substituent has 1 to 20 carbon atoms and is selected from the group consisting of alkyl, aryl and alkaryl groups, and said substituted phenol having the para position open, and the other meta position occupied by a radical selected from the group, consisting of hydrogen andhydroxy. @6. A vuleanizate according to claiin 5 in which the phenol is polyhydric. 7. A v-ulcanizate according to claim 5 in which the phenol consists of the condensation product of m-pentadecyl phenol and formaldehyde. 8. A vulcanizate according to claim 5 in which 100 parts by weight of halogenated butyl rubber is vulcanized with 1 to 1-0 parts of said phenol compound. 9. A vulcanizate according to claim 5 in which the filler is a carbon black. 10. A vulcanizate according to claim 5 in which the halogenated butyl rubber is vulcanized in the presence of a sulfur-containing substance. 8, 11. A vuleanizate comprising a substantial portion of halogenated isopreneisobutylene butyl rubber, a copolymer of 85 to 99.5 wt. percent isobutylene and 0.5 to 15 wt. percent isoprene, vulcanized with a metal oxide and a resin consisting bf the condensation product of a meta hydrocarbon-substituted phenol and an aldehyde, said condensation product having one to two ring positions open on said phenol. 12. A vulcanizate according to claim 11 in which the 10 resin contains at least,2 methylol groups. 13. A method of vulcanizing halogenated butyl rubber, a copolymer of 85 to 99.5 wt. percent of a C, to C7 isoolefin and 0.5 to 15 wt. percent of a C4 tO C14 MUItiolefin, coniprising mixing a meta hydro carbon-substi15 tuted phenol having three to four ring positions open, on said phenol and an aldehyde with said butyl rubber, shaping the mixture and heating it until the butyl rubber is vulcanized. 2o 14. A method of vulcanizing halogenated butyl rubber, a copolymer of 85 to 99.5 wt. percent of a C4 to C7 isoolefin and 0.5 to 15 wt. percent of a C4 to C,4 multiolefin, comprising mixing said butyl rubber with the condensation product of a meta hydrocarbon-substituted phenol and an aldehyde, said condensation product hav25 ing one to two ring positions open on said phenol, shaping the mixture and heating it at an elevated temperature until it is vulcanized. 15. A method of vulcanizing halogenated butyl rubber, copolymer of 85 to 99.5 wt. percent of a C4 tO C7 iSO30 olefin and @0.5 to 15 wt. percent of a C4 to C,4 multiolefin, comprising compounding said butyl rubber with 0.5 to 30 parts by weight of the condensation product of a meta Cl-C20 hydrocarbon-substituted phenol and forinaldehyde, said condensation product having one to two 35 ring positions open, <)ne said phenol and 1 to 10 parts by weight 4Df a metal oxide, shaping the compounded butyl rubber and heating it until it is vulcanized. 16. A method according to claim 15 in which the condensation product is a resin. 40 17. A method according to claim 15 in which the phenol is polyhydric. 18. A method according to claim 15 in which the halogenated butyl rubber is chlorinated butyl rubber. 19. A method according to claim 15 -in which the halo45 genated butyl rubber is brominated butyl rubber. References Cited in the file of this patent UNITED STATES PATENTS ro 2,631,984 Crawford et al - -------- Mar. 17, 1953 2,701,895 Tawney et al - ---------- Feb. 15, 1955 2,732,354 Morrissey et al - -------- Jan. 24, 1956

Uliited States Patent Office 3@008,915 3,008,915 CURING LOW LTNSATLTRATION HALOGENATED RUBBER WITiq POLYMETRYLOL META-SUB. STITUTED PHENOLS James V. Fusco, Fanwood, Samuel B. Robison, Roselle, and Alfred L. MiIIer' Cranford, N.J. assignors to Esso Research and Engineering Compan;l a corporation of Delaware No Drawing. Filed June 11, 1957, Ser. No. 664,906 19 Claims. (Cl. 260-38) The present invention concems novel curing agents for low unsaturation polymers. Specifically, it relates to curing low unsaturation halogenated rubbery polymers with meta-substituted polymethylol phenols. Heretofore, butyl rubber, which is a low unsaturation polymer, has been successfully used in curing bags inner tubes and tires. Butyl rubber contains about 85 to @9.5% of a C4 tO C7 isoolefin, such as isobutylene, and about 0.5 to 15% of a C4 tO C14 multiolefin. It generally has a Staudinger molecular weight between about 20,000 and 300,000, a Wijs iodine number between about 0.5 and 50, and a mole percent unsaturation between about 0.5 and 15. Recently, it has been discovered that butyl rubber can be halogenated in a manner which does not noticeably degrade the molecular weight of the polymer, yet be halogenated sufficiently to produce a rlibbery product which retains its tensile strength even :When aged in the presence of heat. It has now been found that halogenated butyl rlibber can be cured with polymethylolmeta-substituted phenols. These polymethylol curing agents are unique in that, while they will not satisfactorily cure conventional butyl r,ubber under ordinary conditions, t-hey will cure halogenated butyl rubber under the same conditions. According to one embodiment of the present invention, 100 p4rts by weight of halogenated butyl rubber is conipounded with about 20 to 100 parts by weight of a,filler, 0.25 to 10 parts by weight of an anti-tack agent, 0.25 to 5 parts by weight of an anti-oxidant and 0.5 to 30 parts by weight, preferably I to 10 parts, of a metasubstituted polymethylol phenol. The resulting compounded stock is then cured by heating the same until it is vulcanized, e.g., for about I minute to 5 hours at about 250 to 450' F. and, preferably, for 20 to 60 minutes at about 275 to 375' F. The vuleanizates formed have excellent tensile strength and ffexing properties which make them suitable for many products. In producin-, halogenated butyl rubber to be vulcanized in accordance with the present invention, unmodified, unvulcanized butyl rubber is carefully halogenated until it contains about at least 0.5 weight percent (preferably at least about 1.0 weight percent, but not more than about "X" weight percent of combined halogen wherein: m3L X= xioo (100-L)MI+L(M2+Ms) and L=mole percent of the multiolefin in the polymer Ml=molecular weight of the isoolefin M2=molecular weight of the multiolefin M3=atomic weight of the halogen Restated, there should be at least ab out 0.5 weight p ercent of combined halogen in the polymer but not more thaii about one atom of chlorine or 3 atoms of brom' me combined in the polymer per molecule of multiolefin present therein; i.e., per double bond in the polymer. Suitable halogenating agents w-hich may be employed are gaseous chlorine, liquid bromine, alkali metal hypochlorites, or hypobromites, sunr,chlorides or bromides (particularly oxygenated sulfur chlorides or bromides), ]@yridinium chloride perchloride, N-bromo-succinimide, Patented Nov. 14, 1961 2 iodine monochloride, alpha-chloroacetoacetanilide, tribromophenol bromide, N-chloroacetamide, betabromomethyl phthalimide, N,N'-dimethyl-5,5 dichloro or dibromo hydantoin, and other common halogenating agents. 5 The halogenation is generally conducted at above O' to about +100' C., advantageously at about O' to 65' C., preferably at about 20' to 50' C. (room temperature being satisfactory), depending upon the particular halogenation agent, for about one minute to several hours. 10 An advantageous pressure range is from about 0.5 to 400 p.s.i.a.; atmospheric pressure being satisfactory. The halogenation conditions are regulated to halogenate the rubbery copolymer to the extent above mentioned. The halogenation may be dccomplished in various ways. 15 One process comprises preparing a solution of the copolymer as above, in a suitable inert liquid organic solvent such as a C3 to CIO, or preferably, a C5 to C8, inert hydrocarbon or halogenated derivatives of saturated hydrocarbons, examples of which are hexane, heptane, naph20 tha, mineral spirits, cyclohexane, alkyl substituted cycloparaffins, benzene, chlorobenzene, chloroform, trichlorocthane, carbon tetrachloride, mixtures thereof, etc. and adding thereto gaseous chlorine, liquid broniine, or other halogenating agent, which may optionally be in solution, 25 such as dissolved in any inert hydrocarbon, an alkyl chloride, carbon tetracworide, etc. The concentration of, the butyl rubber in the solvent will depend upon the type of reactor, molecular weight of the butyl rubber, etc. In general the concentration of 30 a butyl rubber having a viscosit@ average molecular weight of about 200,000 to about 1,500,000, if the solvent is a substantially inert hydrocarbon, will be between I and 30% by weight, preferably about 5 to 20%. If chlorine gas is employed to chlorinate such a rubbery 35 solution, it may also be diluted with up to about 50 times its volume, preferably about 0.1 to 5.0 times its volume of an inert gas such as nitrogen, methane, ethane, carbon dioxide, etc. The resulting halogenated butyl rubber polymer may 40 be recovered in various manners. The polymer may be ptecipitated with acetone, or any other known non-solvent for the butyl rubber, and dried under about I to 760 millimeters or higher of mercury pressure absolute at about O' to 180' C., preferably at about 50 to 1501 C. 45 (e.g. 70' C.). Other methods of recoverin@g the halogenated butyl rubber polymer from the hydrocarbon solution of the same are by conventional spray or drum drying teehmques. Alternatively, the halogenated butyl rubber-containing solution may be injected into a vessel 50 'containing @gitated water heated to a temperature sufficient to flash off the -hydrocarbon solvent and form an aqueous slurry of the halogenated butyl rubber. The halogenated butyl rubber may then be separated from 55 this_slurry by filtration, dried and rer-overed as a "crumb" or as a dense sheet or slab, by conventional milling and/or extruding procedures. The halogenated copolymer formed advantageously has a viscosity average molecular weight between about 200,000 and 1,500,000 and a mole percent unsaturation of between about 0.5 and 15.0, pref60 e-rably about 0.6 to 5.0. The meta-substituted.polymethylol phenol curing agents are prep ared by reacting about I part by weight of a metasubstituted phenol with about 0.1 to 2 parts by weight of an aldehyde at a temperature between about 50 65 and 300' F. for between 0.1 to 24 hours in the presence of 0.005 to 0.5 part by weight of aia alkaline catalyst, such as sodium hydroxide. The reaction product may contain one or more aromatic Tings depending upon 70 whether or not the methylol compound is permitted to polymerize into a low molecular weight resin. It is preferred to use the curing agent in its monomer, dimer or

3 trimer forin. The phenol may be monohydric or polyhydric. The meta position of the phenol may be substituted with an alkyl,:aryl, or alkaryl hydrocarbon group having I to 20 carbon atoms. It is preferred to employ a phenol having a C14 tO C,8 aliphatir, hydrocarbon attached to its meta position. Only one of the two meta positions should be occupied by the hydrocarbon, leaving the other meta, the two ortho and the para position open to react with the aldehyde. For instance, a m eta-substituted monohydric phenol is reacted with formaldehyde in th.- presence of sodium hydroxide to produce a substance having methylol -roups situated in the ortho, meta or para positions, depending upon the reaction conditions. In most instances, the methylol groups are in the ortho position, e.g., 2,6-dimethylol-m-substituted phenol. Suitable meta-substituted polymethylol curing agents include the condensation products of formaldehyde and any of the following representativesubstituted phenols: m, cresol, m-butyl phenol, 3-hydroxy diphenyl, m-pentadecyl phenol, m-butoxy phenol, 2-bis (3- hydroxy phenyl) propane, 3-hydroxy, 3'-butyl diphelyl and m-pentadecyl resorcinol. The condensation of the meta hydrocarbon-substituted phenol and the aldehyde may take place in situ in the butyl rubber mix or it may be allowed to occur before compoundin.- it with the halogenated butyl rubber. If desired, the halogenated butyl rubber may be cured at 250-450' F. for from a few minutes to several hours, with a combination consisting of the polymethylol substance and another curing agent, such as a metal oxide, sulfur, a sulflir vulcanization - accelerator, or other sulfurcontaining compound. In such a case, the amount of other vtilcanizing agent used may be between about 0.5 and 10 p.h.r. (parts by weight per 100 parts rubber). It is also preferred to use I to 10 p.h.r. of a divalent metal oxide, e.g., zinc oxide as a vulcanwng aid. Suitable sulfur-containing curing agents include, in addition to elemental sulfur, such sulfur yielding materials as 4,4'dithiodimorpholine, vulcanization accelerators such as tellurium diethyl dithiocarbamate, tetramethyl thiuram disulfide, benzothiazyl disulfide, N-cyclohexyl-2- benzothiazole sulfenamide, etc. Among the fillers which can be used are carbon black, clay, calcium carbonate, precipitated hydrated calcium silicate, titanium dioxide, etc. Carbon blacks exist in many forms and are generally classified as being either channel or fumace blacks depending upon how they are prepared. The metasubstituted polymethylol phenolic resin curing agents cure faster in the presence of channel blacks and for this reason these blacks are preferred where rapid cures are desired. Insofar as anti-tack agents are concerned, compounds such as stearic acid, calcium stearate, and zinc stearate have been found to be suitable for most purposes. Anotl-ier altemative involves the use of about 2 to 40 p.h.r. of a plasticizer, such as a substantially non-volatile hydrocarbon oil boiling between about 400 and 700' F. Their use is particularly desirable where the rubber is to be used in inner tubes, conveyor belts or hoses. The following examples are given in order to more fully illustrate the present invention. A copolymer (GR-I-18) consisting of about 97.5% isoibutylene and 2.5% isoprene having a viscosity average molecular weight (yf 420,000 was dissolved in hexane to form a 10% solution. A 20 weight percent (based on the polymer) of sulfuryl chloride was addf-d to the polymer solution as the chlorinating agent and reacted for 120 minutes with the polymer. The resulting chlorinated copolytner was precipitated with acetone, collected and redissolved in hexane three times and ultimately dried and - analyzed and found to have a viscosity average molecular wei.-ht of 420,000 and -to contain 1.3% chlorine based on the polymer. The physical characteristics of both zinc oxide and dianiine-cured vulcanizates, conta'ming this eworinated interpolymer, were excehent. 3,008,915 4 EXAMPLEI The above chlorinated butyl rubber was com7iounded as fouows and cured for 60 minutes at 307' F. 5 Ingredient: Parts by weight Chlorinated isobutylene-isoprene rubber ------ 100 SRF carbon black ------------------------- 25 HAF carbon black ------------------------- 25 Stearic acid ------------------------------- 0.5 10 Zinc oxide ------------------------------- 5 Meta-substituted polymethylol phenolic resin-- 5 In oiie run the curing agent was the reaction product of n-pentader-yl phenol and formaldehyde. This resinous product had a melting point of 106' C. and contained 15 80.85% carbon, 11.73% hydrogen and 5.21% oxygen. The m-pentadecyl dimethylol phenol resin was prepared by reacting I mole of m-pentadecyl phenol with 2 moles of formaldehyde in the presence of sodium hydroxide. In the second run w-ith the chlorinated butyl the curing 20 agent was a resin prepared from 5-pentadecyl resorcinol and formaldehyde. This resin had a melting point of 163.0' C. and contained 80.3 % earbon, 1 1. I % hydroge-n, 9.1% oxygen and 7.3% @methylol groups.' The properties of the vuleanizates are set forth in Table I. 25 Table I Experiment ---------- ------------------------ 1 2 (Phenol (nesoreinol 30 Resin) Rosin) Stress-Strain: 200% Modulus, p.s.i -------------------- --- 950 1,300 300% Modulus, p.s.i -------------------- --- 1,800 --------- --- Tensile, p.s.i ----------------- ----------------- 2,000 1,680 Elongation, percent --------------------------- 330 260 35 Tear Strongth --------------------------------- 100 85 Dyiiamic Modulus at 50' C.; dynes/em.2XlO-7- 2. 72 3.36 Goodrich Flexometer Test @ 1001 C., Stroke0.25 inch, Load 89 p.s.i.g.: Percent Permauent Set ----------- -------- 1.9 0.9 Percent Dynimic Drift ------------- ------ 0.1 0.0 Temperature Rise, ' 0 ------------- ------- 18 13 Appearance ---------------------- -------- Fxcelient Excellent 40 I The data show that the meta-substituted curing agents produce vlileanizates that have outstanding flex and therrnal stability. Rubber compounds having such properties may be advantageously used in curing bags, stea-m hoses, 45 t-ires, conveyor belts, etc. EXAMPLE 2 In another experiment Example 1 was repeated with the chlorinated butyl rubber as well as with a bromi50 nated isobutylene-isoprene butyl rubber (2.1 % Br), using 50 parts of MPC carbon black instead of the SRF and HAF @blacks. The metasubstituted resin was the - condensation product of mpentadecyl phenol and formaldehyde. The compounded rubbers were vulcanized at 55 3,07- F. for 60 and 40 minutes, respectively. Their physical properties were evaluated and the findings are set forth in Table II. Table 11 60 Properties CbloBromiriiaated nated Stress-Straiia, 300% Modulus, p.s.i ------------- 1,575 2,000 TertsUe, p.s.i ---------------------------------- 2, 540 2, 570 Elongation, percent ----------------- ---------- 410 390 65 Goodrich Flexometer Test @ 100' C., 32 cps., 0.25" Stroke, 89 p.s.i.g.: Percent Permanent Set ---------- --------- 2.8 3.4 Percent Dynamic Drift ------------- ------ 0.5 1.9 Teniperature Rise, I C ------------- ------- 21 25 Appearauce ------------------------------- Excellent Very Good 70 The results demonstrate that both brominated and chlorinated butyl rlibber may be cured with these meta-substituted phenolaldehyde condensation products. I Analytical procediire described in "ADalytica.I Chemistrv," 7.5 Vol . 23, No. 6, 1883-884 (1951),

3,008,915 5 6 EXAMPLE 3 E XAMPLE 5 A series of experiments was undertaken to determine H owever, resin cures of halogenatdd butyl edn be efthe concentration of resin which produces the best vulfe cted by anoiher technique which involves forming the canizate. Toward this end a study was made of the ef5 r esin in the polymer (GR-1-18) masterbatch during curfect of varying amounts of the condensation product of in g. The monomers, meta pentadecyl phenol and formm-pelitadecyl phenol and formaldehyde on the vulcanizate al dehyde or 5-pentadecyl resorcinol and formaldehyde, properties of the same chlorinated butyl rubber used in Example 1. The resin's preparation is described in the a re added to the masterbat@h with zinc oxide and subsanie example. The recipes and results are shown in 10 je cted to curing at elevated temperatures. The results Table 111. o btained by tWs technique are shown in Table V. Table III CONCENTRATION OF 5-PENTADECYL PHENOL RESIN NECESSARY TO CURE C]ILORINATED BUTYL Experiment --------------------------------------------- A B 0 D E ChloriDated Butyl --------- 100 ---------- ---------- --------------------------------------- ---------- - SRF Black ---------------------------------------------- ---------- ------ ---- 25 ---------- ---------- HAF Black ---------------------------------------------- ---------- ------ ---- 25 ---------- ---------- Stearic Acid --- ----------------------------------------- ---------- ----- 05 ---------- ---------- Zinc Oxide ----------------------------------------------- ---------- ----- 5'0 ------- --- ---------- Sulfur --------------------------------------------------- ---------- ---------- ---------- ----- ------ 1. 5 Tellurium diethyl dithiocarbamate - --------------------- ---------- ---------- --------- - ---------- 1.0 Benzothiazyldisulfade --------------------- --------------- ---------- ---------- ---------- ---------- 1.0 5-pentadecyl phenol resin ------------ -------------------- 1.0 2.5 5. 0 10.0 ---------- CoEapounds cured 301 @ 3071 F.: Stress-Strain200% Modulus ----------------------------------- 680 950 1,175 1, 250 700 300% Modulus ---------------------------- ------- 1,500 1, 840 2,060 ---- 1,480 TeILsile, P.S.i ----------------- ------------------------- 2,380 2,300 2,180 2,450 Elongation, percent ---------------------------------- 410, 370 310 3 00 490 Shore A --------------------------------------------- 51 63 55 5 8 53 ,Goodrich Plex6ineter Data @ 1001 C., 32 cps., 0.2511 Stroke, 89 p.s.i. Load: Percent Permaiient Set ------------------------------ 3.3 3.3 3.5 4. 6 7.8 Percent Dynamic Drift ------------------------------ 0.2 0.0 0.0 1. 4 4.5 Temperature Rise, - C -------- 29 27 27 3 0 28 Appearance of flexed si@-9 Excel. Excel. Excel. Excel. Si. P o r o u s The data show that, while the best properties are obTable V tained with 5 p.h.r., even as little as I p.h.r. significantly CURES OF HALOGENATED BUTYL WITH B-PENTADECYL miproves the flexing properties of the halogenated butyl 45 PHENOL-FORMALDEHYDE AND 5-PENTADECYL RE. rubber. SORCINOL-FORMALDEHYDE Phenol ReEXAMPLE 4 sorcinol 50 Chlorinated Butyl (1.3% Cl) ---------------------- 100 100 Kosmobile S-66 ---------- 60 50 As already mentioned, these meta-substituted phenolSteaxic A 'id ----------------------------------------- 0.,5 0. 5 aldehyde resins do not satisfactorily cure butyl rubber, Zinc Oxide -- -------------------------------------- 5.0 5. 0 .5 -pentadecyl phenol ------------------------------- 5.0 -- -------- even when promoters, such as zinc chloride and neoprene, 5- pentadecyl resoreii:Lol ---------------------------- ---------- 5. 0 Paraformaldehyde --------------------------------- 2.0 2.0 are employed. This is shown by the following recipes Co mpounds cured 601 @ 3071 F.: and data. 5.5 Stre ss-straiia200% Modulus ----------------------------- ---- 1,00 0 300% Modulus ----------------------------- ------ ---- Tensile, p.s.i ---------------------------------- 1,550 1,75 0 Table IV Bloi agation, percent ---------------------------- 370 300 Goodrich Flexometer Data@ 100' O., 32 cps., 0.2511 Stroke, 89 p.s.i. Load: BUTYL CURES WITH 5-PENTADEC)YL PHENOL RESIN 60 Percent Permanent Set --------------------- 9 Percent Dynamic Drift --------------------- 52.' 8 Temperature Rise, I C -------------- ------- ---------- 30 Appearance of Slug after flexing 301 --------- ---------- Good Experiment ------------------------- B F G Butyl (GR-I-17) Isobutylene-Iso100 -------- 100 -------- 100. The data show that the condensation reaction can take prene. 65 place in situ and that when it occurs it will cure haloSRF Black --------------------- 25 -------- 25 -- ------ genated isobutylene-isoprene butyl rubber. HAF Black ------------------------ 25 --------- 25 -- ------- MPC Black ------------------------ ------------ ------------ 5o. In the appended claims the expression "butyl rubber" Stearic Acid ------------------------- o.5 -------- o.5 -------- o.5. is intended to mean a rubbery copolymer of about 85- Zinc Oxide ------------------------ 5.0 -------- 5.0 ------ 5.0. Neoprene --------------------------- 5.0 -------- ------------- 99.5% of a C4 tO C7 isoolefin and about 0.5 to 15% of ZnCl2 ------------------------------ ------------ 1.0 -------- 70 a C4 to C,4 multiolefin, said copolymer having a StaudCblorinated Btityl (2.1% Cl) ------- ------------ ------------ 5.0. 6-pentadecyl pbenol resin ----------- 12.0 ------- 12.0 ------- 12.0. inger mol. wt. of about 20@000 to 300,,000, a Wijs iodine Corapounas v,-ere Cured 601 @ Poor No Cure- - No Cure. number of about 0.5 to, 50 and a mole percent unsatura3201 F. Cure. The resin was the saine as that used tion between about 0.5 and 15. in Example 1. Resort may be had to various modifications and vari75 ations of the present invention without departin g from

3,008,915 7 the spirit of the discovery or the scope of the appended claims. What is