Urethane elastomer with active hydrogen containing monoethylenically unsaturated monomer

Abstract

A urethane elastomeric impact modifier is provided for 15 rigid thermoplastic polymers. Polyester and polyether urethane elastomers are grafted to the acrylic polymers. Preferred is a polyester, diisocyanate and glycol urethane elastomer terminated with a functional monomer capable of ethylenic polymerization grafting with the acrylic polymer. The modified polymers offer an improved balance of physical properties including higher impact strength, clarity, and weather resistance.

What is claimed is: 
     
       1. As a composition of matter, a condensation product (A) a reaction product of (1) diisocyanate selected exclusively from aliphatic and cycloaliphatic diisocyanate,   (2) a linear condensation polymer containing terminal hydroxyl groups, and   (3) a polyol having at least two hydroxyl groups, the ratio .[.n.]. of (1) to the total of (2) and (3) being in the range of 1.001 to 2.0 equivalents of (1) per equivalent of the total of (2) and (3) and sufficient to provide in the reaction product an equivalent weight as determined by isocyanate titration of at least 4,000, the amount of (3) relative to (2) on an equivalent basis being between 0.1:0.9 and 0.9:0.1, with     (B) a reactive hydrogen-containing monoethylenically unsaturated monomer in which the reactive hydrogen is in a hydroxyl or amine group, an excess of (B) being used to effect reaction of all the isocyanate groups in (A).     
     
     
       2. As a composition of matter, a solution in an ethylenically unsaturated monomeric material of the condensation product of claim 1. 
     
     
       3. A solution according to claim 2 in which the monomeric material consists essentially of a mixture of 55 to 100% by weight of an alkyl methacrylate which, when homopolymerized produces a polymer having a T g  greater than 90° C., 0 to 45% by weight of at least one other monoethylenically unsaturated monomer, and 0 to 5% by weight of a monomer selected from polyethylenically unsaturated monomers and highly polar monoethylenically unsaturated monomers. 
     
     
       4. A solution in accordance with claim 3 in which the monomeric material in which the condensation product is dissolved constitutes about 95 to 50% by weight of the solution. 
     
     
       5. A solution according to claim 2 in which at least 90% by weight of the monomeric material is methyl methacrylate and the monomeric material constitutes about 95 to 50% by weight of the solution. 
     
     
       6. As an article of manufacture, the free racidal addition polymerization product of the solution of claim 4 in the form of a sheet. 
     
     
       7. As an article of manufacture, the free radical addition polymerization product of the solution of claim 5 in the form of a sheet. 
     
     
       8. A sheet according to claim 6 thermoformed under heat and pressure to a sign face. 
     
     
       9. As a composition of matter, a condensation product of (A) a reaction product of (1) diisocyanate selected exclusively from aliphatic and cycloaliphatic diisocyanates,   (2) a hydroxy-terminated linear (a) polyether of the general formula   H(OR).sub.n OH       wherein R is a hydrocarbon radical and n is an integer sufficiently high to give a molecular weight of about 500 to about 5000 or   (b) polyester of a dicarboxylic acid and a diol and     (3) a polyol selected from the group consisting of 1,3-butylene glycol, 1,4-butylene glycol, thiodiethylene glycol, neopentylene glycol, trimethylol propane and mixtures thereof, the ratio of (1) to the total of (2) and (3) being in the range of 1.001 to 2.0 equivalents of (1) per equivalent of the total of (2) and (3) and sufficient to provide in the reaction product an equivalent weight as determined by isocyanate titration of at least 4,000, the amount of (3) relative to (2), on an equivalent basis being between 0.1:0.9 and 0.9:0.1,     (B) a reactive hydrogen-containing monoethylenically unsaturated monomer in which the reactive hydrogen is in a hydroxyl or amine group, an excess of (B) being used to effect reaction of all the isocyanate groups in (A).     
     
     
       10. As a composition of matter, a solution in an ethylenically unsaturated monomeric material of the condensation product of claim 9. 
     
     
       11. A solution according to claim 10 in which the monomeric material constitutes 50 to 95% by weight of the solution and consists essentially of a mixture of 55 to 100% by weight of an alkyl methacrylate which, when homopolymerized produces a polymer having a T g  greater than 90° C., 0 to 45% by weight of at least one other monoethylenically unsaturated monomer, and 0 to 5% by weight of a monomer selected from polyethylenically unsaturated monomers and highly polar monoethylenically unsaturated monomers. 
     
     
       12. As an article of manufacture, the free radical addition polymerization product of the solution of claim 11 in the form of a sheet. 
     
     
       13. A solution according to claim 11 wherein the polyester (2) is the condensation product of a dicarboxylic acid and a diol or a mixture of diols. 
     
     
       14. A composition in accordance with claim 13 wherein (2) is a polyester of a diol selected from the group consisting of ethylene glycol, propylene glycol, thiodiethylene glycol and mixtures thereof. 
     
     
       15. A composition in accordance with claim 14 wherein the dicarboxylic acid of the linear polyester (2) is selected from the group consisting of adipic, sebacic and fumaric acids. 
     
     
       16. As a composition of matter, the product of addition polymerization of the composition of claim 15. 
     
     
       17. As an article of manufacture, the free radical addition polymerization product of the solution of claim 15 in the form of a sheet. 
     
     
       18. As an article of manufacture, the free radical addition polymerization product of the solution of claim 15 in the form of a thermoformed sign. 
     
     
       19. As a composition of matter, a condensation product of (A) a reaction product of (1) diisocyanate selected exclusively from aliphatic and cycloaliphatic diisocyanates,   (2) a hydroxy-terminated linear polyester of adipic acid and a polyol selected from the group consisting of ethylene glycol, propylene glycol thiodiethylene glycol and mixtures thereof, and   (3) a polyol selected from the group consisting of 1,3-butylene glycol, 1,4-butylene glycol, thiodiethylene glycol, neopentylene glycol, trimethylol propane and mixtures thereof, the ratio of (1) to the total of (2) and (3) being in the range of 1.001 to 2.0 equivalents of (1) per equivalent of the total of (2) and (3) and sufficient to provide in the reaction product an equivalent weight as determined by isocyanate titration of at least 4,000, the amount of (3) relative to (2), on an equivalent basis being between 0.1:0.9 and 0.9:0.1. with       (B) a reactive hydrogen-containing monoethylenically unsaturated monomer in which the reactive hydrogen is in a hydroxyl or amine group, an excess of (B) being used to effect reaction of all the isocyanate groups in (A).     
     
     
       20. As a composition of matter, the product of polymerization of a solution of (C) the condensation product of claim 19 in (D) a monomeric material constituting 50 to 95% by weight of the solution and comprising 55 to 100% by weight of an alkyl methacrylate which, when homopolymerized produces a polymer having a T g  greater than 90° C., 0 to 45% by weight at least one other monoethylenically unsaturated monomer, and 0 to 5% by weight of a monomer selected from polyethylenically unsaturated monomers and highly polar monoethylenically unsaturated monomers. 
     
     
       21. A product according to claim 1 wherein the equivalent ratio between the polyol (3) and the polyester (2) is between 0.5:1.0 and 1.0:0.5. 
     
     
       22. A product according to claim 1 wherein the polyol (3) is at least one diol containing 3 to 8 carbon atoms. 
     
     
       23. A product according to claim 20 wherein the components (1), (2), and (3) are chosen to yield a refractive index within 0.08 of that of the copolymer obtained from the components of (D). 
     
     
       24. A product according to claim 20 wherein the component (A) has an equivalent weight of 4,000 to 50,000. 
     
     
       25. A product according to claim 20 wherein the condensation product (C) comprises 40 to 60 mole percent (1), 30 to 60 mole percent (2) and up to 10 percent (B). 
     
     
       26. A product according to claim 25 wherein the condensation product (C) comprises the residue of 15 to 24.9 mole percent of a saturated polyester (2) containing active hydrogen sites, 15 to 25 mole percent of polyol (3), 50 to 60 mole percent of a saturated aliphatic or alicyclic diisocyanate (1) and 0.1 to 10 percent of an ethylenically unsaturated compound (B) having active hydrogen functionality. 
     
     
       27. As an article of manufacture, the product of claim 20 in the form of a sheet. 
     
     
       28. As an article of manufacture, the product of claim 20 in the form of a thermoformed sign face.