Organometallic-free polyurethanes having low extractables
View Patent ↗Breathable thermoplastic polyurethanes are prepared from the reaction of a polyol component, a polyisocyanate component, and a chain extender in the presence of a metal-free catalyst. The metal-free catalyst comprises a polyalcohol amine, a tertiary amine catalyst, or a combination thereof. The polyurethanes of the present invention are suitable for film applications as they form breathable films which are permeable to water vapor but not air or water. The polyurethane compositions are substantially metal-free, have low extractables, and excellent melt strength.
1. An article comprising:
a breathable polyurethane layer; and
a substrate layer attached to said polyurethane layer, said substrate layer comprising a woven or nonwoven material, said polyurethane layer comprising the reaction product of a) at least one polyether polyol, b) at least one polyisocyanate, c) at least one chain extender, and d) at least one polyalcohol amine catalyst, wherein said polyurethane layer has a nitrogen content from said polyalcohol amine catalyst in an amount from about 0.075 to about 2 mol % based on the total moles of said polyol, said polyisocyanate, said chain extender, and said catalyst, and wherein said polyalcohol amine catalyst is triethanolamine, bis(2-hydroxyethyl)amino-2-propanol, 2-bis(2-hydroxyethyl)amino-2-(hydroxyethyl)-1,3-propanediol, or 1,3-bis[tris(hydroxymethyl)methylamino]propane, or a combination thereof.
2. The article according to claim 1 , wherein said substrate layer is a natural fiber material or a polymer, or a combination thereof.
3. The article according to claim 2 , wherein said substrate polymer is polyethylene, polypropylene, nylon, or polyester, or wherein said substrate is paper or cellulose.
4. The article according to claim 1 , wherein said polyurethane polymer is substantially free of an organometallic catalyst.
5. The article according to claim 1 , wherein a molar ratio of total hydroxyl groups of the at least one chain extender to total hydroxyl groups of the at least one polyol is from about 0.1 to about 3.0, wherein a molar ratio of polyisocyanate functional groups to total hydroxyl groups of the at least one polyol and at least one chain extender is from about 0.95 to about 1.10, and wherein said chain extender is an organic diol or glycol having a total of from 2 to about 20 carbon atoms.
6. The article according to claim 1 , wherein said chain extender is an alkane diol, cycloaliphatic diol, or an alkyl aryl diol, and wherein said at least one polyisocyanate is a diisocyanate, wherein said polyurethane polymer has a nitrogen content from said polyalcohol amine catalyst in an amount from about 0.095 to about 1.5 mol % based on the total moles of said polyol, said polyisocyanate, said chain extender and said catalyst.
7. The article according to claim 5 , wherein said chain extender is an alkane diol, cycloaliphatic diol, or an alkyl aryl diol, and wherein said at least one polyisocyanate is a diisocyanate, wherein said polyurethane polymer has a nitrogen content from said polyalcohol amine catalyst in an amount from about 0.095 to about 1.5 mol % based on the total moles of said polyol, said polyisocyanate, said chain extender and said catalyst, wherein said polyol is polyethylene glycol and wherein said polyol has a number average molecular weight from about 100 to about 4,000.
8. The article according to claim 1 , wherein said polyurethane layer is from about 0.5 mils to about 10 mils thick.
9. The article according to claim 8 , wherein said polyurethane layer is from about 0.5 mils to about 10 mils thick, wherein said polyol is polyethylene glycol and wherein said polyol has a number average molecular weight from about 100 to about 4,000.
10. The article according to claim 7 , wherein said polyurethane layer is from about 0.5 mils to about 10 mils thick.
11. The article according to claim 1 , wherein said article is housewrap, part of a garment, or a roofing material, and wherein said substrate layer and polyurethane layer are connected by an adhesive or directly connected to each other.
12. The article according to claim 7 , wherein said article is housewrap, part of a garment, or a roofing material, and wherein said substrate layer and polyurethane layer are connected by an adhesive or directly connected to each other.
13. The article according to claim 1 , wherein said polyurethane layer has moisture vapor transmission rate of greater than about 100 g/m 2 per day.
14. The article according to claim 2 , wherein said polyurethane layer has moisture vapor transmission rate of greater than about 100 g/m 2 per day, wherein said polyol is polyethylene glycol and wherein said polyol has a number average molecular weight from about 100 to about 4,000.
15. The article according to claim 3 , wherein said polyurethane layer has moisture vapor transmission rate of greater than about 100 g/m 2 per day.
16. The article according to claim 12 , wherein said polyurethane layer has moisture vapor transmission rate of greater than about 100 g/m 2 per day.
17. The article according to claim 1 , wherein said substrate layer is woven polyester or nylon, or nonwoven polyester or polypropylene.
18. The article according to claim 8 , wherein said substrate layer is woven polyester or nylon, or nonwoven polyester or polypropylene.