USE OF ETHYL SILICATE AS A CROSSLINKER FOR HYDROXYLATED POLYMERS

Abstract: The solvent resistance, flexibility and hardness of various hydroxylated polymers is enhanced by crosslinking with alkyl silicates or their hydrolyzed condensates.

Description: DESCRIPTION USE OF ETHYL SILICATE AS A CROSSLINKER FOR HYDROXYLATED POLYMERS BACKGROUND OF THE INVENTION This invention pertains to ethyl silicate or its hydrolyzates and more particularly to hydroxyl-containing polymers crosslinked with them. BACKGROUND ART The preparation of polyvinyl butyral/ethyl silicate condensation products is disclosed in U.S., 2,432,113. The purpose here was to provide a silicate coating on a polarizing sheet of polyvinyl butyral by impregnating the sheet tetraethyl orthsilicate. In U.S. 2,456,251 a binder for binding mica flakes to each other was produced by incorporating a minor amount of ethyl silicate in a resinous binder material having as its a base one or more resins selected from the group consisting of polymerized vinyl acetate, partially hydrolyzed polymerized vinyl acetate, polymerized acrylic ester resins and polymerized styrene resins. In U.S. 2,487,063, a polarizing composite similar to that disclosed in U.S. 2,432,113 was described comprising a stretched iodo-polyvinyl butyral silicate. U.S. 3,624,014 teaches the preparation of stable polymeric gels as reaction products of tetralkyl ortho-silicates and hydroxy terminated diene polymers. It is an object of this invention to provide solvent resistant versions of presently existing polymers having numerous attributes but poor solvent resistance. It is another object of this invention to provide a method for introducing flexibility into low molecular weight resins. It is still a further object of this invention to impart hardness to presently used coatings resins. Disclosure of Invention It has been found that alkyl silicates or their hydrolyzates may be used to improve the solvent resistance, flexibility, hardness and other -mechanical properties of certain hydroxyl containing polymers by crosslinking them. Suitable hydroxyl-containing polymers susceptible to this treatment include vinyl chloride/vinyl acetate/vinyl alcohol terpolymers, which are prepared by first copolymerizing vinyl chloride with vinyl acetate in various proportions and then partially hydrolyzing the resultant copolymer to afford a terpolymer containing vinyl chloride, vinyl acetate, and vinyl alcohol moities, thermoplastic polyhydroxyethers, described in U.S. 3,356,646, hydroxylated acrylic copolymers and vinyl chloride/vinyl acetate/hydroxy alkyl acrylate terpolymers having relatively low molecular weights. Suitable vinyl chloride/vinyl acetate/vinyl alcohol terpolymers include those having between about 10 and 90 percent vinyl acetate and about 5 to 50 weight percent vinyl alcohol copolymerized therein having molecular weights represented by inherent viscosities of about 0.05 to about 1.0 measured as 0.2 gram samples in 100 ml of cyclohexanone at 300C according to ASTM Method D 1243, and the like. Representative hydroxylated acrylic copolymers include those containing hydroxyethyl or hydroxypropyl acrylate or methacrylate copolymerized with one or more alkyl acrylate or methacrylate esters, and, optionally, acrylic or methacrylic acid. Suitable vinyl chloride/vinyl acetate/hydroxyalkyl acrylates include those containing about 10 to about 80 weight percent vinyl acetate and about 5 to about 50 percent by weight of hydroxyalkyl acrylate. Preferred hydroxyalkyl acrylates are hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxybutyl acrylate and the like. These low molecular weight polymers have inherent viscosities in the range of about 0.05 to about 1.0 when measured as a 0.2 gram sample in cyclohexanone at 300C. Although other alkyl silicates can be used in this invention, the preferred alkyl silicate is ethyl silicate in the form of the monomer tetraethyl orthosilicate (TEOS) or its hydrolyzates. Alkoxyalkyl silicates can also be used if preferred. Alkyl silicates are produced by the reaction of silicon tetrachloride and alcohols or alkoxy alcohols, generally in a reactor equipped with a stirrer, condenser and vat scrubber. The hydrogen chloride by-roduct is removed by reflux which may be carried/at reduced or atmospheric pressure. Through this process, the most common products TEOS and Cellosolve (Trademark of Union Carbide Corporation for monoalkyl ethers of ethylene glycol) silicate are made. Subsequently, these products may be hydrolyzed by the addition of water and an acid catalyst. The amount of water added determines the degree of hydrolysis in the final product. Commercially available products derived from ethanol include the unhydrolyzed TEOS, condensed Ethyl Silicate (about 7 percent hydrolysis), Ethyl Silicate 40 (40 percent hydrolysis containing 40 percent SiO2), and ethyl silicate having an 80 to 85 percent hydrolysis level. A trace of acid is necessary to catalyze the crosslinking reaction. The term "trace" is use herein to mean at least about 0.01 weight percent based on the weight of the hydroxyl-containing polymers. Thermoplastic polyhydroxyether resins are a family of amorphous, high molecular weight phenoxy resins derived from diphenols and epichlorohydrin. A commercially available polyhydroxyether is Phenoxy PKHH (Trade designation for a resin sold by Union Carbide Corporation derived from Bisphenol-A and epichlorohydrin having a degree of polymerization of about 100 and average molecular weight of at least about 20,000). The crosslinking of the hydroxylated polymers with the silicates involves simply the addition of an alkyl silicate or one of its hydrolyzates to a solution of the polymer in the presence of a trace quantity of acid, followed by the removing of solvent and curing of the resultant product at elevated temperature. Since addition of acid to solutions of hydroxylated polymers and TEOS or ES-40 results in gelation, it is preferred to add the acid as the last component. - The invention is further described in the examples which follows. All parts and percentages are by weight unless otherwise specified. Control A A solution of a vinyl chloride/vinyl terpolymer acetate/hydroxypropyl acrylate/(containing about 20 percent hydroxypropyl acrylate and about 10 percent of vinyl acetate by weight) at a concentration of 23% by weight in methyl ethyl ketone (MEK) was prepared for use as a reference sample. The solution was applied to a 4x12 inch Q panel and allowed to air dry for 30 minutes. Then the coated panel was baked for 20-30 minutes at 1300 C. The resulting coating, approximately 1 mil thick, was tested for solvent resistance by the MEK double rub test and for flexibility by the falling dart direct impact test. The sample was rated at 10 MEK double 0,092 mkg rubs and 8 in.lbs. direct impact. EXAMPLE 1 To 13g of the solution of hydroxylated vinyl resin prepared as above in Control A were added: tetraethyl orthosilicate (TEOS, 1 gram) and a trace of sulfuric acid (about 0.01 gram). The solution was coated on a Q Panel to provide a 1 mil dry film, air dried, and baked at 130 C for 20-30 minutes. Evaluation of the cured coating showed excellent solvent resistance (greater than 100 MEK double rubs) and excellent flexibility (greater than > 0,92 mkg bU-ln. ias. airect impact). Tnese results demonstrate the dramatic improvement in properties resulting from crosslinking of the hydroxylated vinyl resin film with ethyl silicate. EXAMPLES 2-4 Example 1 was repeated with the exception that the hydroxylated vinyl resin/TEOS ratios were 6, 1.5 and 3, respectively. Coatings prepared as in Example 1 from these solutions had excellent solvent resistance (all were greater than 100 MEK double rubs) and excellent flexibilitv (direct impact was > o.q2 n 0,92 n sn - - greater than 80, 78 and 80 in. rbs., respectively). This demonstrates that the hydroxylated vinyl resin/TESO ratio is not critical with regard to attainment of excellent properties. These data are delineated in Table I. (Note that a ratio of 3/1 provides roughly 1 TEOS molecule for every -OH in the polymer.) EXAMPLES 5-8 These examples were prepared from combinations of a 23 percent solution of hydroxylated vinyl resin in MEK and a solution of 85 percent hydrolyzed ES-40 in isopropanol with a silica content of 20 percent. Examples 5,6,7 and 8 were composed of the following ratios of the hydroxylated vinyl resin/hydrolyzed ES-40 solutions: 90/10, 83/17, 67/83, 50/50. Coatings were prepared, cured and tested as in the Example 1 with the followina results: MEK double rubs: all areater - - - - - sn n 0,55 than 100= direct impact: greater than 80, 78, 48 and 0092 inka - - - - 8 in. lbs. In addition, it should be noted that samples 6 and 7 exhibited a slight haze in the film, while Example 8 had a ribbed, opaque appearance. These results, summarized in Table II, indicate that hydrolyzed ethyl silicate can be used to crosslink hydroxylated vinyl resin but that as the quantity of crosslinking agent increases, some incompatibility becomes noticeable. This does not necessarily detract from the usefulness of the crosslinked films. Control B As a reference sample, a solution of Phenoxy PKHH in tetrahydrofuran (THF) was coated on to a steel panel, dried and baked as in Example 1. The evaluations for solvent resistance, impact and hardiness gave these results: MEK double rubs: 9; > n¯93 TnrT direct impact: greater than tf in.?lbs.; pencil hardness: 3B. EXAMPLES 9-11 These samples were prepared by addition of the following reagents to a 20 percent solution of Phenoxy PKHH (20 grams in THF): ethyl silicate (1 gram); ES-40 (0.7 grams); 80 percent hydrolyzed ES-40 with a silica content of 20 percent (1.4 grams). A trace of sulfuric acid was added to each sample and the coatings prepared and cured as in Example 1. The properties were evaluated with the following results: MEK double rubs: all greater > 0.92 mkg than 100; direct impact: all greater than 80; pencil hardness: H, BB, HB. In addition, a slight haze was noticed in films from Examples 10 and 11 while Example 9 produced a clear film. These results, compared in Table III with those in control B, demonstrate that ethyl silicate and its hydrolyzates are effective crosslinkers for Phenoxy PKHH. Control C An hydroxylated acrylic polymer was prepared by addition of a solution containing ethyl acrylate (35 grams), methyl methacrylate (45 grams), hydroxypropyl methacrylate (20 grams), azobisisobutyronitrile (AIBN, 1 gram), t-dodecylmercaptan (0.5 grams) and MEK (100 grams) to a refluxing solution of AIBN (0.5 grams) in hER (200 grams) over a 3 hour period. Heating was continued for an additional 2.5 hours to insure polymerization of most of the monomers. A coating from this solution was prepared for use as a reference sample and exhibited the following 0,12 prqperties: MEK double rubs: 3; direct impact; 10 mjcq in. libs.; pencil hardness: H. Example 12 Ethyl silicate (3.2 grams) was added to the polymer solution prepared in Control C (11 grams) along with a trace of sulfuric acid. A coating was prepared from this solution as described in Example 1 and evaluated for solvent resistance, direct impact and hardness. The results were as follows: V33 MEK double rubs: greater than 100: direct impact: 30 mKg in. lbs.; pencil hardness: 3 H. These results, when compared in Table IV with those of Control C, clearly show the beneficial effect of crosslinking this hydroxylated acrylic polymer with ethyl silicate. TABLE I Example Components Control A 2 3 4 Vinyl Chloride Polymer(a) 3g. 3g. 3g. 3g. TEOS -- lg. 0.5g. 2g. MEK 10g. 10g. 10g. 10g. Acid(3) -- Trace Trace Trace Properties(2) MEK Double Rubs 10 100+ 100+ 100+ Direct Impact 8 80+ 80+ 78 (in. lbs.) mkg 0,092 0,92+ 0,92+ 0,90 Pencil Hardness F F F BB (1) TEOS is tetraethyl orthosilicate (2) Properties measured on 1 mil dry films on steel Q panels after baking 20-30 minutes at 1300C. (3) Acids used were sulfuric or benzoic. (a) Vinyl chloride/vinyl acetate/hydroxypropyl acrylate terpolymer containing 67% vinyl chloride; 10% vinyl acetate and 20% hydroxypropyl acrylate copolymerized therein. TABLE II Example Components 5 6 7 8 Vinyl Chloride ig. lg. lg. Ig. Polymer (a) 80% Hydrolyzed ES-40, 20% Si02Content 0.5g. lg. 2g. 5g. MEK 3.5g. 3.3g. 3.3g. 3.3g. Properties(2) MEK Double Rubs 100+ 100+ 100+ 100+ Direct Impact 80+ 78+ 48+ 8 (in. lbs.) mkg 0,92+ 0,90+ 0,55+ 0,092 Pencil Hardness B HB 2B 2B Appearance Clear Very Slight Ribbed, Slight Haze Opaque Haze (1) Properties measured on 1 mil dry films on steel Q panels after baking 20-30 minutes at 1300C. TABLE III PHENOXY PKHH CROSSLINKED WITH ETHYL SILICATE Example Components Control B 9 10 11 Phenoxy PKHH 4g. 4g. 4g. 4g. TEOS None ig. ES-40 None -- 0.7g. -80% Hydrolyzed ES-40 (20% Si02) None -- 1.49. THF 16g. 16g. 16g. 16g. H2S04 None 0.01g. 0.01g. 0.01g. Properties(1) MEK Double Rubs 9 100+ 100+ 100+ Direct Impact (in.-lbs.) 80+ 80+ 80+ 80+ mkg 0,92+ 0,92+ 0,92+ 0,92+ Pencil Hardness 3B H HB HB Appearance Clear Clear sazy Hazy (1) Properties measured on 1 mil dry films on steel Q panels after baking 20-30 minutes at 1300C. TABLE IV ACRYLIC POLYMER(1) CROSSLINKED WITH ETHYL SILICATE Example Component Control C 12 Acrylic Polymer llg. llg. TEOS -- 3.2g. MEK 39g. 39g. H2S04 -- 0.02g. Properties(2) MEK Double Rubs 3 100+ Direct Impact (in.-lbs) 10 30 mkg 0,12 0,35 Pencil Hardness H 3H (1) Acrylic polymer composition: MMA/EA/HPMA-45/35/20, prepared at 22% (Total Solids) in MEK using AIBN initiator and t-dodecyl mercaptan as chain transfer agent. (2) Properties measured on 1 mil dry films on steel Q panels after baking 20-30 minutes at 1300C. Although the invention has been described in its preferred forms with a certain amount of particularity, it will be understood by those skilled in the art that the present disclosure has been made only by way of example and that numerous changes can be made without departing from the spirit and scope of the invention.

Claims: CLAIMS 1. Method of enhancing the solvent resistance, flexibility and hardness of hydroxylated polymers which comprises blending said hydroxylated polymers with an alkyl silicate or alkyl silicate hydrolyzate in the presence of a trace amount of acid and thereafter curing the resultant mixture. 2. Method claim in Claim 1 wherein the alkyl silicate is tetraethyl orthosilicate. 3. Method claim in Claim 1 wherein the hydroxylated polymer is an hydrolyzed vinyl chloride/vinyl acetate. 4. Method claim in Claim 1 wherein the hydroxylated polymer is a vinyl chloride/vinyl acetate/hydroxyalkyl acrylate terpolymer. 5. Method claimed in Claim 1 wherein the hydroxylated polymer is a thermoplastic poly hydroxyether derived from bisphenol A and epichlorodhydrin. 6. Method claimed in Claim 1 wherein the ratio of hydroxylated polymer to alkyl silicate is the range of about 25:1 to about 1:1. 7. Method claimed in Claim 1 wherein the alkyl silicate is ethyl silicate hydrolyzed to a degree of about 40 percent. 8. Method claimed in Claim 1 wherein the alkyl silicate is ethyl silicate hydrolyzed to a degree of about 80 percent.

Inventors: MALLON, CHARLES BERNARD
Applicants: UNION CARBIDE CORPORATION
Application year: 1983
Main classification: C08L27
IPC codes: C08L101, C08L27, C08F8, C08K5, C08L33, C08L1