Urethane vinyl copolymers and impact resistant sheets made therefrom
Copolymers comprising a polyurethane segment, a polyvinyl segment and a multifunctional monomer having first and second functional groups covalently bound to the polyurethane segment and polyvinyl segment, respectively, are disclosed. Cast sheets formed therefrom exhibit improved high impact resistance and similar optical properties as compared to polyvinyl cast sheets.
1. A copolymer comprising a reaction product of a reaction mixture comprising the components:
a polyisocyanate having free isocyanate functionality;
a polyol;
a vinyl monomer comprising at least one double bond; and
a multifunctional monomer comprising a first functional group having a hydrogen that is reactive with isocyanate and selected from the group consisting of a primary amine, a secondary amine and a hydroxyl and a second functional group comprising at least one double bond reactive with the at least one double bond of the vinyl monomer wherein the resulting copolymer is characterized by an essential absence of free isocyanate, wherein the copolymer comprises a polyurethane segment comprising polymerized polyisocyanate and a polyvinyl segment comprising polymerized vinyl monomer,
wherein the multifunctional monomer is covalently bound to the polyurethane and polyvinyl segments, and
wherein the polyurethane segment has a molecular weight of from about 500 to about 5000.
2. The copolymer of claim 1 , wherein at least a portion of the polyisocyanate and at least a portion of the polyol are present in the form of a pre-reacted urethane prepolymer.
3. The copolymer of claim 1 , wherein the copolymer comprises from about 10 to about 90 percent, by weight of the copolymer, of the polyurethane segment formed from a reaction of the polyisocyanate and the polyol.
4. The copolymer of claim 3 , wherein the copolymer comprises from about 40 percent to about 90 percent, by weight of the copolymer, of the polyurethane segment.
5. The copolymer of claim 3 , wherein the reaction product forms in the presence of a catalyst for the reaction of isocyanate with the first functional group of the multifunctional monomer or the polyol or both to form the polyurethane segment.
6. The copolymer of claim 1 , wherein the multifunctional monomer is selected from the group consisting of hydroxyethylmethacrylate, hydroxyethylacrylate, hydroxypropyl(meth)acrylate, aminoethyl acrylate, and combinations thereof.
7. The copolymer of claim 1 , wherein the vinyl monomer is an acrylic monomer.
8. The copolymer of claim 1 , wherein the polyol has a first hydroxyl functionality and the multifunctional monomer has a second hydroxyl functionality, and wherein the sum of the first hydroxyl functionality and the second hydroxyl functionality is substantially equal to the free isocyanate functionality of the polyisocyanate on an equivalent basis.
9. A cast sheet material comprising the copolymer of claim 1 .
10. The cast sheet material of claim 9 further comprising one or more optional additives selected from the group consisting of: adhesion promoters; biocides; anti-fogging agents; anti-static agents; bonding agents; dispersants; fire retardants; smoke suppressants; initiators; catalysts; lubricants; micas; pigments, colorants; oils; plasticizers; processing aids; release agents; silanes; titanates; zirconates; stabilizers; ultraviolet light absorbers; molecular weight regulators; and combinations thereof.
11. A method of making a cast sheet material, the method comprising the steps of:
(a) forming a reaction mixture of claim 1 ; and
(b) casting the reaction mixture in a mold and reacting the reaction mixture to form a copolymer cast sheet material.
12. The method of claim 11 , wherein the multifunctional monomer is present in a stoichiometric amount relative to the available isocyanate functionality of the polyisocyanate.
13. The method of claim 11 , wherein the step of forming the copolymer occurs in a single reaction vessel.
14. The method of claim 11 , wherein the step of casting comprises filling the mold at ambient temperature with a copolymer composition comprising the copolymer.
15. The copolymer of claim 1 wherein the polyisocyanate and vinyl monomer are polymerized essentially simultaneously.
16. The cast sheet material of claim 9 wherein a sheet having a thickness of about 0.25 inches is characterized by a visible light transmission of at least 90% as measured in accordance with ASTM D1003.
17. The cast sheet material of claim 9 wherein a sheet having a thickness of about 0.25 inches is characterized by a haze value of less than 1% as measured in accordance with ASTM D1003.
18. The cast sheet material of claim 9 characterized by a Rockwell hardness of at least 20 scale M as measured in accordance with ASTM D785.
19. The cast sheet material of claim 9 characterized by a heat deflection temperature of at least 50° C. as measured in accordance with ASTM D648.
20. The cast sheet material of claim 9 wherein a sheet having a thickness of about 0.125 inches is characterized by a low-velocity Gardner impact resistance of at least 40 inch-pounds as measured in accordance with ASTM D5420.
21. The cast sheet material of claim 9 wherein a sheet having a thickness of about 0.5 inches is characterized by a V50 critical velocity ballistic test value in feet per second as measured in accordance with MIL-STD-622F-V50 Ballistic Test for Armor that is at least 30% greater than the V50 critical velocity ballistic test value for a cast sheet formed from polymethacrylate and having a thickness of about 0.5 inches.