EMULSION COPOLYMERISATION OF META- OR PARA-ISOPROPENYL-ALPHA,ALPHA-DIMETHYLBENZYLISOCYANATE

Abstract: A method of making a copolymer of meta- or para-­ isopropenyl-α,α-dimethylbenzylisocyanate and at least one other ethylenically unsaturated comonomer polymerizable therewith, comprising polymerizing the meta- or para-­ isopropenyl-α,α-dimethylbenzylisocyanate and at least one other ethylenically unsaturated comonomer in an aqueous emulsion in the presence of a free-radical polymerization initiator and a chain transfer agent to control molecular weight. Also disclosed are methods of breaking the aqueous emulsion after polymerization is completed by either adding a salt, e.g., aluminum sulfate, or by freezing the emulsion followed by thawing to yield the copolymer as a mechani­ cally separable solid phase of a two-phase liquid-solid mix­ ture.

Description: EMULSION COPOLYMERS OF META- OR PARA -ISOPROPENYL-a,a-DIMETHYLBENZYLISOCYANATE BACKGROUND OF THE INVENT ION This invention relates to polymers of meta- or para-isopropenyl-a,a-dimethylbenzylisocyanate of controlled molecular weight and to a method of making same by emulsion polymerization. In U.S. Patent 4,439,616 issued March 27, 1984 there is disclosed a method for producing tertiary aralkyl isocyanates, such as tetramethyl xylylene diisocyanates (TMXDI), by thermal cracking of corresponding urethanes formed by addition of corresponding olefins and carbamic acid esters at moderate temperatures and in the presence of acid catalyst. Such process is particularly useful for producing the meta- and para-isomers of TMXDI and as the by-product thereof, substantial amounts of the corresponding vinyl isocyanate meta- or para-isomers, viz., meta isopropenyla, c1dimethylbenzylisocyanate (m-TMI) or paraisopropenyl-a,a-dimethylbenzylisocyanate (p-TMI), respectively, are formed. The meta-TMI or para-TMI by-products in such systems may be recycled within the process to improve the over-all yield of TMXDI therein, but such by-product have substantial utility per se as separate products due to their difunctional character, i.e., the presence of reactive isocyanato (-NCO) and vinyl groups. Thus, TMI may be homo- or co-polymerized to form polymers with isocyanate functionality which are cross-linkable with curatives containing a difunctional or polyfunctional amino or hydroxyl compound. Such cross-linkable compositions have film-forming properties and advantageously may be used for coatings .JS for example on metnl , wood and glass substrates, as well as having potential applicability for production of molded articles, such by the reaction injection molding (RIM). U.S. Patent No. 3,290,350 discloses copolymerization of TMI by conventional methods using known addition polymerization initiators, such as those of the free radical type, e.g., peroxy and azo initiators. In U.S. Patent No. 3,502,475, there is disclosed a method of forming a coating on polyolefin and polyester films, by application thereto of an aqueous dispersion of a copolymer of from about 1 to about 50 percent by weight of meta- or para-TMI. Relative to other modes of polymerization, emulsion polymerization allows a rapid reaction to form a high molecular weight product with a comparatively narrow molecular weight distribution. The latter characteristic of narrow molecular weight distribution, renders emulsion polymerization potentially attractive for the making of copolymers. However, for most end-use applications, the extremely high molecular weights yielded by emulsion polymerization renders polymers produced thereby wholly unsuitable, e.g., in end-use applications such as coatings and the molding of articles such as by reaction injection molding. The present invention relates to a method of making a copolymer of meta- or para-isopropenyl-a,a-dimeth- ylbenzylisocyanate and at least one other ethylenically unsaturated comonomer polymerizable therewith, comprising polymerizing the meta- or para-isopropenyl-a, -dimethylben- zylisocyanate and at least one other ethylenically unsaturated comonomer in an aqueous emulsion in the presence of a free-radical polymerization initiator and a chain transfer agent. The ethylenically unsaturated comonomers polymerizable with TMI include butyl acrylate, methyl acrylate methyl methacrylate, ethyl acrylate, styrene, a-methylsty- rene, p-methyl- -methylstyrene, and p-methylstyrene. The copolymer suitably may contain from about 5 to about 80 mole Percent repenting units derived from metaor para-TMI and from about 20 to about 95 percent repeating units derived from the at least one other ethylenically unsaturated comonomer. Where styrene or p-methylstyrene are employed as comonomers, the amounts thereof generally should be limited to not more than 30 mole percent in the product copolymer to insure that such product copolymer is light stable in character, where light stability is necessary and/or desirable. The free-radical polymerization initiator suitably may be potassium persulfate and sodium meta-bisulphite. The chain transfer agent advantageously is a water-insoluble mercaptan. Preferably, the chain transfer agent is either dodecyl mercaptan or n-octyl thiol. It is a particularly surprising feature of the present invention that the use of thiols or mercaptans as chain transfer agents is efficacious in providing limited product copolymer molecular weight ranges, since in the emulsion polymerization system, one would expect such compounds to react with the free isocyanato groups contained in the TMI monomer. Surprisingly, it has been found that the reactivity of such thiols or mercaptans, if any, with the isocyanate groups is not such as to prevent the useful control of molecular weight of emulsion polymerization copolymer products. It also is an unexpected aspect of the present invention that the polymerized emulsions resulting from the method of the invention are storage-stable for periods of several days and as long as 5-7 days, with 95 percent of the initial isocyanate groups based on monomer concentration thereof still being present, since one would expect reaction of such groups in the aqueous medium, i.e., the aqueous phase of such emulsions. The emulsion polymerization of the invention Usefully may be carried out at temperature above ambient in the range of from about 250C to about 600C, and preferably from about 300C to about SOOC The aforementioned mercaptan or thiol chain transfer agents desirably are present in the emulsion polymerization reaction volume in an amount of from about 0.2 to about 10 mole percent based on the weight of monomer present. Under such conditions, it is possible to form emulsion copolymers having a molecular weight of from about 2,000 to about 70,000 (peak molecular weight). As indicated, such copolymers may contain from about 5 to about 80 mole percent repeating units derived from meta- or para-TMI and from about 20 to about 95 mole percent repeating units derived from at least one other ethylenically unsaturated comonomer polymerizable with TMI as selected from the group consisting of butyl acrylate, methyl acrylate, methyl meth acrylate, ethyl acrylate, styrene, a-methylstyrene, p methyl-a+methylstyrene, and p-methylstyrene. A particularly advantageous copolymer composition is one containing from about 5 to about 25 mole percent repeating units derived from meta- or para-TMI and from about 75 to about 95 mole percent repeating units derived from methyl methacrylate. The method of the present invention permits the making of such copolymers having a molecular weight of from about 5,000 to about 10,000. A particularly preferred terpolymer composition obtainable by the method of the present invention contains from about 5 to about 25 mole percent repeating units derived from meta- or para-TMI, from about 20 to about 40 mole percent repeating units derived from methyl methacrylate and from about 50 to about 70 mole percent repeating units derived from butyl acrylate. The method of the present invention may be employed to form a substantially homogeneous copolymer of metaor para-TMI and at least one other ethylenically unsaturated comonomers mentioned above, by the following sequence of steps: (a) forming a reaction volume comprising water, free-radical polymerization initiator, chain transfer agent and such one of said other ethylenically unsatured comonomers to be incorporated into said copolymer as has the lowest reactivity thereof; and (b) adding meta- or para-isopropenyl-&alpha;,&alpha;-dimeth- ylbenzylisocyanate and other remaining comonomers to be incorporated into said copolymer continuously to said reaction volume under emulsion polymerization reaction conditions while maintaining a substantially constant monomeric composition in said reaction volume, to form said copolymer with a substantially homogeneous polymeric composition. The method described above for formation of substantially homogeneous copolymers (hereinafter denoted the "continuous addition method") usefully may be employed to produce a product copolymer having a molecular weight of from about 2,000 to about 70,000, with a comparatively narrow distribution of molecular weights within the product volume. The copolymers of the present invention have utility in forming coating compositions comprising same and a curative comprising a cross-linkingly effective amount of a compound with free hydroxyl or amine functionality. Such curative compound may suitably include trimethylolpropane, ethylenediamine ketimine, diethylene glycol and 1,2,6-hexanetriol. Such composition may be applied in a film to a substrate, e.g., glass, wood or metal, and cured in the presence of moisture to form a coating on the substrate which is light-stable and solvent resistant in character. In the broad practice of the present invention, the copolymer product of the polymerization reaction may be isolated from the aqueous emulsion following polymerization to the desired extent, by adding such aqueous emulsions to aqueous solutions of a salt such as calcium chloride, sodium chloride, or aluminum sulfate. Alternatively, the copolymer product may be isolated form the aqueous emulsion after polymerization has been completed, by freezing the aqueous emulsion to a frozen solid to thereby break the aqueous emulsion, followed by thiw ing the frozen solid to yield a two-phase mixture coiprising a reliquified aqueous phase and the copolymer is a solid phase, so that the solid copolymer readily may be separated from the reliquified aqueous phase, such as by mechanical separation. A particularly preferred method of separation is simple decanting of the two-phase mixture, or filtration of the two-phase mixture followed by vacuum drying of the copolymer filtrate at a temperature of from about 250C to about 400C. The character of the invention will be more fully apparent from the non-limiting examples set forth hereinafter, wherein all parts and percentages are by weight, unless otherwise specified. EXAMPLE I The following components were charged to a reaction flask: m-TMI 0.48 gm. butyl acrylate 1.80 gm. methyl methacrylate 0.72 gm. dodecyl mercaptan 0.15 gm. deionised water 24.0 gm. aq 2% Na-lauryl sulphate 1.0 gm. The contents were stirred and sparged with nitrogen at ambient temperature for 20-30 minutes and then the flask was heated to 400C in a water bath. A 0.30 ml. sample was taken for GC analysis. In separate, sealed bottles, solutions of potassium persulphate, 0.36 gms. in 7.5 ml. water, and sodium meta bisulphite, 1.08 gms. in 7.5 ml. water, were prepared and sparged with nitrogen for 5 minutes, to remove oxygen, using a syringe needle through a rubber septum. One millilitre of each solution was then added to the emulsion, by syringe, adding the potassium persulphate first. Samples of emulsion were taken at inter vals und analyzed by GC for the remaining monomer content until the conversion or monomers Wis completed. The emulsion then was frozen to -180C overnight and next day, after allowing to thaw completely to room temperature, the mass Of polymer was separated from the aqueous phase by decantation. The polymer then was washed with water and dried on a glass petri dish under vacuum at room temperature. A yield of polymer of 2.0 gms. was recovered (67%) having a peak molecular weight of 16,000 by GPC, and a Tg of +20C by dynamic mechanical analysis. EXAMPLE II The procedure of Example I was employed to copolymerize m-TMI and p-TMI with a number of acrylic comonomers. Results are shown in Table I below. TABLE I VArying Mole % m-TMI Copolymers with n-Butyl Acrylate (n-BA) or Methyl Methacrylate (MMA) Reference Mole % Polymerization Glass Transition Molecular Copolymer Copolymer m-TMI Comonomer Time (Minutes) Temperature Tg ( C) Weight Yield (%) Solubility in CH2Cl2 1 5.0 n-BA 70 -20 50,000 74 Soluble 2 10.0 n-Ba 140 --- --- -- Soluble X-linked 3 20.0 n-BA 260 -6 --- 64 Insoluble 4 30.0 n-BA 300 +33 --- 74 Some Gel 5 50.0 n-BA 360 +45 9,000 80 Some Gel 6 80 n-BA 00 N o Polymerization -- ---7 10.0 MMA 110 --- --- 94 Soluble 8 20.0 MMA 160 132 8,200 66 Soluble n-BA = n-butyl acrylate MMA = methyl methacrylate EXAMPLE III A 200 g. monomer batch of emulsion terpolymer was prepared incorporating low initiator levels, 1.0 mole / n-octyl mercaptan, and 20% monomers concentration. The m-TII/MIA mixture was added continuously to the polymerization flask containing BA and the progress of the polymerization monitored by GC. Both m-TMI and MMA was added as required to maintain a constant ratio of monomers and extra initiator to maintain a steady polymerization rate. The polymerization was completed in 5 hours giving a GC monomer conversion of 99.3%. The progress of the polymerization was satisfactory, giving an even m-TMI distribution in the polymer throughout the polymerization. The polymer was separated in the emulsion by freeze-thawing and dried by azeotroping in toluene. The water content of the final 35 wt. % polymer solution was 0.022 and the isocyanate content 0.307 meq/g (100% of theory). The molecular weight of the terpolymer by GPC was 10,000 (peak); the Tg was 40C, and the isolated yield of polymer 93%. EXAMPLE IV An emulsion copolymer of 10 mole percent m-TMI and 90 mole % n-BA was prepared at 10 weight percent monomer solids in the emulsion, using sodium lauryl sulfate as a surfactant, at a reaction temperature of 400C. The effect of chain transfer agent concentration was evaluated by conducting three runs at chain transfer agent (n-octyl thiol) levels of 0.33%, 1.67% and 5.0%, respectively (based on wight of monomer in the polymerization emulsion). Results are shown in Table II below: Table II Chain Transfer Polymerization Molecular Reference Agent Concentration Z Time, minutes Weight 9 0.33 110 60,000 10 1.67 120 14,200 11 5.0 130 3,900 by GPC (polystyrene standards) These results show that the n-octyl thiol chain transfer agent at increasing levels of concentration was highly effective in reducing the molecular weight. EXAMPLE V Emulsion copolymers of 10 mole percent m-TMI and 90 mole percent n-BA were prepared to evaluate the effect on product copolymer molecular weight of the concentration of polymerization initiators. A mixture of potassium persulfate and sodium meta bisulfite was employed as the initiator, at varying concentrations. Results are shown in Table III below, wherein all samples contained 1.67% by weight (based on total of monomer weight) n-octyl thiol as the chain transfer agent. TABLE III moles X 107 of each initiator Sodium meta Conversion Reference Potassium Persulphate bisulfite pH of emulsion Molecular wt. (mole %) 12 9 38 7.4 6,200 40 13 19 76 7.2 10,000 40 14 45 190 6.8 14,200 100 15 89 350 4.8 13,800 100 16 180 760 3.3 11,600 100 17 1400 7000 2.9 42,000 100 As these date slow the copolymer product of the emulsion reaction has increasing molecular weight with increasing initiator levels. By appropriate choice of initiator and chain transfer agent concentrations in a given reaction system, it is possible to closely control the molecular weight and properties of the product copolymer, while achieving substantially complete conversion of monomers. EXAMPLE VI Emulsion terpolymers of 10 mole % m-TMI, 30 mole % MMA and 60 mole % BA were prepared by batch and in "contin- uous addition" processes. The letter process involved forming a reaction volume including water, initiator, chain transfer agent and MMA and thereafter continuously adding to such reaction volume m-TMI and BA at such rate as to maintain a constant monomeric composition in the reaction volume, to form a copolymer with a substantially homogeneous polymeric composition. The chain transfer agents were dodecyl mercaptan and octyl mercaptan. Results are shown in Table IV below. TABLE IV Reference No. Chain Transfer % mole Process Yield Molecular Tg Agent (%) Weight ( C) 19 dodecyl mercaptan 5 Batch 65 16,400 +2 20 " 1.67 Batch - 20,100 +6 21 " 0 Batch 67 37,000 -10,+26 22 octyl mercaptan 3.3 Batch - 7,800 -2 23 octyl mercaptan 3.3 Continuous - 7,200 0 Addition 24 " 3.3 " - - 0 25 " 3.3 " - - 26 " 3.3 " 40 6,700 2 27 octyl mercaptan 3.3 Continuous Addition 88 6,700 0 28 " 3.3 " 84 5,700 +4 29 " 3.3 " 93 The data in Table IV .h()ws that octyl mercapran was a more effective chain trer agent then dodecyl mercaptan (cf. sample 22, wherein octyl mercaptan at 3.3 mole % (based on total monomer) gave a molecular weight of 7,800 with sample 19, wherein dodecyl (mercaptan) at 5 mole % yielded a molecular weight of 16,400). Further, samples 22-29 show that various runs with octyl mercaptan at 3.3 mole % concentration gave highly uniform and reproducible results (e.g., molecular weight of product copolymer in the range of 5,700 to 7,800). EXAMPLE VII Emulsion terpolymers containing 10 mole % m-TMI, 60 mole % BA and 30 mole % MMA was prepared at differing levels of n-octyl mercaptan as the chain transfer agent. Copolymer product was isolated in each instance by freezing and thawing of the emulsion, followed by decanting of the solid copolymer. Data are shown in Table V below. TABLE V Reference Quantity n-octyl mercaptan Monomer Yield of Polymer Tg M.Wt. Isolation (mole %) Distribution (%) (g) Method 27 15 3.03 Good 88 13.2 0 6700 Frozen/Thaw 28 15 3.03 Good 80 13.0 4 5700 " 29 15 3.03 Good 93 14.0 -7 4364 " 30 30 1.51 Poor 76 23.8 -7.5 9400 Frozen/Thaw 31 30 1.51 Satisfactory 87 26.2 -2.5 8500 " 32 30 1.51 Satisfactory 81 21.8 +4 10,700 " 33 30 1.51 Fair " 34 30 1.51 Satisfactory " Tiles data indicate that chain transfer agent concentrations on the order of 3 mole ZO gave a good (i.e., comparatively uniform) distribution of monomer in the product copolymer. EXAMPLE VIII Samples 28 and 29 (see Examples VI and VII) were combined to yield a 10/60/30 mole % m-TMI/BA/MMA terpolymer having an equivalent weight of 1415 based on the solids content thereof. The terpolymer was then formulated into a coating formulation having the following composition: Terpolymer 24.9 grams G-Cure 867 RX 60 8.0 grams dimethyl tin dilaurate 1.73 grams Dow-Corning &num;1 flow control agent 1.1 grams cellulose acetate butyrate 1.1 grams G-Cure 867 RX 60 (Henkel Corporation, Minneapolis, Minnesota) is a hydroxyl-containing acrylic resin having a molecular weight of approximately 8000-9000, with 50% non-volatile content and an equivalent weight of 1000. The -NCO/-OH molar ratio in the formulation was 1.1 based on equivalent weights for the respective functionalities. Dow-Corning &num;1 (Dow Corning Corporation, Midland, Michigan) is a silicone flow control additive. The dimethyl tin dilaurate catalyst was introduced as a 10% weight solids dispersion in toluene, and the Dow-Corning &num;1 and cellulose acetate butyrate were each introduced as 10% (by weight) solutions of cellosolve acetate. The formulation was very hazy in appearance when first prepared but cleared slightly after aging for a few minutes. Draw-downs of the formulation were made on 4" x 12" 1200S aluminum panels using a &num;46 wirecator. The drawdowns were applied at a 3.5 mil wet film thickness, with the applied coating films being exposed to ambient temperature conditions for 10 minutes before elevated temperature curing, it the cure time and temperature (cure schedule) conditions identified in Table VI below. The resulting films then were measured for dry film thickness, K noop hardness, and mar and removal rub tests using MEK solvent. Results are shown in Table VI. TABLE VI EMI18.1 MEK <SEP> rub <SEP> tests <tb> Curing <SEP> Dry <SEP> Film <tb> Reference <SEP> Time, <SEP> Temperature <SEP> Thickness, <SEP> Knoop <SEP> mar <SEP> remove <tb> min. <SEP> C <SEP> mils <SEP> Hardness <SEP> (no. <SEP> rubs) <SEP> (no. <SEP> rubs) <tb> 35 <SEP> 20 <SEP> / <SEP> 125 <SEP> 1.2 <SEP> 3.3 <SEP> -- <SEP> 40 <tb> 36 <SEP> 20 <SEP> / <SEP> 100 <SEP> 1.2 <SEP> 1.4 <SEP> -- <SEP> 20 <tb> 37 <SEP> 20 <SEP> / <SEP> 80 <SEP> 1.2 <SEP> 1.0 <SEP> -- <SEP> 20 <tb> The appearance of all of the cured films was slightly hazy and createred in appearance. EXAMPLE IX A terpolymer was made from 12.6 g. of n-butyl acrylate, 5.0 g. of methyl methacrylate, and 3.4 g. of p-TMI (60 mole /O n-butyl acrylate/30 mole % methyl methacrylatel 10 mole % m-TMI) by emulsion polymerization in 253 g. of total reaction mixture. The product mixture at room temperature was poured in a thin stream into 1200 ml. of 0.10 wt. % aluminum sulfate, 18-hydrate (Al2(SO4)3 l8H2O) vigorously stirred at room temperature. After stirring for one-half hour, the solid was recovered by vacuum filtration. Vacuum drying at 250C/l mm Hg for 20 hours gave 19.2 g. of almost transparent, soft, solid polymer. Depending on polymer composition and molecular weight TMI/acrylate and TMI/methacrylate copolymers also may be isolated by coagulating the emulsion in aqueous solution containing up to 10 wt. % concentrations of sodium chloride, sodium sulfate, calcium chloride, or Qther salts. EXAMPLE X 29.4 grams of an emulsion of a copolymer of m-TMI (10 mole %) and ethyl acrylate (90 mole %) containing 2.94 grams of polymer were poured slowly into a stirred solution of 200 mls of 5% calcium chloride. A white flocculant precipitate formed which coagulated rapidly. This was filteredon a (No. 2) glass sinter and washed with de-ionised water in two 50 ml. lots. After drying in a vacuum oven at 4O0C, 1.08 grams of dry polymer were obtained. A similar polymerization using 5% n-dodecyl mercaptan did not give a filterable precipitate with calcium chloride (low molecular weight polymers generally are difficult to filter). EXAMPLE XI The low molecular weight emulsion copolymer of Example X (polymerized with 5% n-dodecyl mercaptan) was cooled to -8 to -120C for 16 hours. During this time the emulsion broke and separated into two layers. The upper, aqueous layer was decanted off (alternatively, the poly mer layer can be filtered and washed with water). After vacuum drying at 25-400C (13 hours) a yield of 88% polymer (based on original monomers charged) was obtained, Tg = OOC, m.w.p. by GPC (Mw) = 6700. EXAMPLE XII Preparation of p-TMI Copolymer A copolymer was made by emulsion polymerization of a monomer mixture containing 90 mole % ethyl acrylate and 10 mole % p-TMI. The product was isolated by coagulation in a 5% solution of calcium chloride in water, followed by vacuum drying at room temperature. EXAMPLE XIII Crosslinking of Hydroxylated Resin with p-TMI Copolymer A cellosolve acetate solution was made to contain 4.0% total solids consisting of stoichiometric quantities of the p-TMI copolymer and G-Cure 867-RX-60 (bydroxylated acrylic resin from General Mills Chemicals, Inc.). Immediately after adding 1.0 wt, % (on total resins) of dimethyltin dilaurate at room temperature, the solution was used to cast a thin film on a glass plate. After heating the film-glass assembly at 1100C for one hour in a forced-draft oVen, the film was hard and optically clear. The assembly was then immersed in methylene chloride at room temperature. After five minutes with intermittent stirring, the film was swollen but remained coherent and insoluble. EXAMPLE XIV Moisture Curing of p-TMI Copolymer A cellosolve acetate solution was made to contain 4.0% of the p-TMI copolymer. Immediately after adding 1.0 wt. % (on copolymer) of triethylenediamine (DABCO), the solution was used to cast a thin film on a glass plate. After standing in the open air at room temperature for 24 hours, the film-glass assembly was immersed in methylene chloride. After five minutes with intermittent stirring, the film was swollen but remained largely insoluble.

Claims: WHAT IS CLAIMED IS: 1. A method of making a copolymer of meta- or para-isoprol)enyl-a, cFdimethy1benzylisocyanate and at least one other ethylenically unsaturated comonomer polymerizable therewith, comprising polymerizing said meta- or paraisopropenyl-a,a-dimethylbenzylisocyanate and at least one other ethylenically unsaturated comonomer in an aqueous emulsion in the presence of a Eree-radical polymerization initiator and a chain transfer agent. 2. A method according to Claim 1, wherein said at least one ethylenically unsaturated comonomer is butyl acrylate, methyl acrylate, methyl methacrylate, ethyl acrylate, styrene, a -methylstyrene, p-methyl-a-methylstyrene, or p-methylstyrene. 3. A method according to Claim 1 wherein said copolymer contains from about 5 to about 80 mole percent repeating units derived from meta- or para-isopropenyl-a,a- dimethylbenzylisocyanate and from about 20 to about 95 mole percent repeating units derived from said at least one other ethylenically unsaturated comonomer. 4. A method according to Claim 1 wherein said free-radical polymerization initiator is an admixture of potassium persulfate and sodium metabisulphite. 5. A method according to Claim 1 wherein said chain transfer agent is a water insoluble mercaptan dodecyl mercaptan or n-octyl thiol and is present in said polymerization in an amount of from about 0.2 to about 10 mole percent based on the weight of monomer. 6. A method according to Claim 1 wherein said polymerization is carried out at a temperature of from about 250C to about 600C. 7. A copolymer produced by the method of Claim 1, having a molecular weight of from about 2,000 to about 70,000. 8. A copolymer according to Claim 7, containing from about 5 to about 80 mole percent repeating units derived from meta- or para-isopropenyl- a, crdimethylbenzylisocy- mate and from about 20 to about 95 rnole percent repeating units derived from at least one other ethylenically unsaturated comonomer polymerizable therewith selected from the group consisting of butyl acrylate, methyl acrylate, methyl methacrylate, ethyl acrylate, styrene, a-methylstyrene, pmethyl-a-methylstyrene, and p-methylstyrene and having a molecular weight of from about 2,000 to about 70,000. 9. A copolymer according to Claim 7, containing from about 5 to about 25 mole percent repeating units derived from meta- or para-isopropenyl-a, a-dimethylbenzylisocy- anate and from about 75 to about 95 mole percent repeating units derived from methyl methacrylate and having a molecular weight of from about 5,000 to about 10,000. 10. A copolymer according to Claim 7, containing from about 5 to about 15 mole percent repeating units derived from meta- or para-isopropenyl-a,a-dimethylbenzylisocya- nate, from about 20 to about 40 mole percent repeating units derived from methyl methacrylate, and from about 50 to about 70 mole percent repeating units derived from butyl acrylate. 11. A method according to Claim 1 for forming a substantially homogeneous copolymer of meta- or para-isopropenyl- a, otdimethylbenzylisocyanate, and at least one other ethylenically unsaturated comonomer polymerizable therewith selected from the group consisting of butyl acrylate, methyl acrylate, methyl methacrylate, ethyl acrylate, styrene, a-methylstyrene, p-methyl- ccmethylstyrene and pmethylstyrene, comprising: (a) forming a reaction volume comprising water, free-radical polymerization initiator, chain transfer agent and such one of said other ethylenically unsaturated comonomers to be incorporated into said copolymer as has the lowest reactivity thereof; and (b) adding meta- or para-isopropenyl-a, a-dimeth- ylbenzylisocyanate and other remaining comonomers to be incorporated into said copolymer continuously to said reaction volume under emulsion polymerization reaction c()nditions while m(lint 3ining a constant monomeric composition in said reaction volume, to form said copolymer with a substantially homogeneous polymeric composition. 12. A copolymer produced by the method of Claim 9, having a molecular weight of from about 2,000 to about 70,000. 13. A coating composition comprising a copolymer according to Claim 7 and a curative comprising a crosslinkingly effective amount of a compound with free hydroxyl or amine functionality. 14. A coating composition according to Claim 10 wherein said curative compound is trimethylolpropane, ethylenediamine ketimine, diethylene glycol or 1,2,6-hexanetriol. 15. A method of forming a coating on a substrate, comprising applying to said substrate a film of a coating composition according to Claim 10, and curing same in the presence of moisture. 16. A method according to Claim 1, further including isolating said copolymer from said aqueous emulsion after polymerization has proceeded to a desired extent, comprising adding to said aqueous emulsion a salt consisting of calcium chloride, sodium chloride, aluminum sulfate, or sodium sulfate. 17. A method according to Claim 1, further including isolating said copolymer from said aqueous emulsion after polymerization has proceeded to a desired extent, comprising: (a) freezing said aqueous emulsion to a frozen solid to thereby break said aqueous emulsion, (b) thawing said frozen solid to yield a twophase mixture comprising a reliquified aqueous phase and said copolymer as a solid phase, and (c) separating said copolymer from said reliquified aqueous phase. 18. A method according to Claim 17 wherein said copolymer is separated in step (c) by filtration of said two-phase mixture and thereafter is vacuum dried at a temperature of from about 250C to about 400C.

Inventors: DEXTER, ROBIN WILLIAM, FORGIONE, PETER SALVATORE, SEDLAK, JOHN A.
Applicants: AMERICAN CYANAMID COMPANY
Application year: 1984
Main classification: C08F246
IPC codes: C08F2, C08F6, C08G18, C08F246, C08F212, C09D175