Preparation of amino-silane terminated polymer by using organic bismuth catalyst and cured polymer therefrom by using non-tin catalyst
View Patent ↗The present invention relates to a process for preparing silylated isocyanato-terminated polyurethane prepolymer which have increased stability toward atmospheric moisture, in the presence of at least one catalyst selected from the group consisting of bismuth and zinc compounds.
1. A process for making moisture curable silylated polyurethane resin comprising reacting isocyanato-terminated polyurethane prepolymer derived from polyether polyol with an aminoalkoxysilane in the presence of at least one urethane reaction-promoting catalyst selected from the group consisting of bismuth and zinc compounds.
2. The process of claim 1 wherein the isocyanato-terminated polyurethane prepolymer is obtained from the reaction of polyether polyol with a molar excess of polyisocyanate in the presence of at least one urethane reaction-promoting catalyst.
3. The process of claim 1 wherein the isocyanato-terminated polyurethane prepolymer is obtained from the reaction of polyether diol with a molar excess of diisocyanate in the presence of at least one urethane reaction-promoting catalyst.
4. The process of claim 2 wherein the polyether polyol contains up to about 1000 ppm water and the urethane reaction-promoting catalyst is selected from the group consisting of bismuth and zinc compounds, the catalyst remaining in the isocyanato-terminated polyurethane prepolymer to catalyze the reaction of the prepolymer with the aminoalkoxysilane.
5. The process of claim 3 wherein the polyether diol contains up to about 1000 ppm water and the urethane reaction-promoting catalyst is selected from the group consisting of bismuth and zinc compounds, the catalyst remaining in the isocyanato-terminated polyurethane prepolymer product to catalyze the reaction of the prepolymer with the aminoalkoxysilane.
6. The process of claim 4 wherein the polyether diol having a number average molecular weight of at least about 1,000 and having an end group unsaturation level of no greater than 0.04 milliequivalents per gram of polyether diol, and the diisocyanate is selected from the group consisting of diphenylmethane diisocyanate, polymethylene polyphenylisocyanate, paraphenylene diisocyanate, naphthylene diisocyanate, liquid carbodiimide-modified diphenylmethane diisocyanate, isophorone diisocyanate, dicyclohexylmethane-4,4′-diisocyanate, toluene diisocyanate, 2,6-TDI isomer, aliphatic polyisocyanates, aromatic polyisocyanates and mixtures thereof.
7. The process of claim 5 wherein the polyether diol having a number average molecular weight of at least about 1,000 and having an end group unsaturation level of no greater than 0.04 milliequivalents per gram of polyether diol, and the diisocyanate is selected from the group consisting of diphenylmethane diisocyanate, paraphenylene diisocyanate, naphthylene diisocyanate, liquid carbodiimide-modified diphenylmethane diisocyanate, isophorone diisocyanate, dicyclohexylmethane-4,4′-diisocyanate,toluene diisocyanate, 2,6-TDI isomer and mixtures thereof.
8. The process claim 1 wherein the aminoalkylsilane is selected from the group consisting of primaryamino-silane, secondary aminosilane, and mixtures thereof.
9. The process claim 8 wherein the aminoalkylsilane is selected from the group consisting of N-ethyl-3-trimethoxysilyl-2-methyl-propanamine, N,N′-bis((3-trimethoxysilyl)propyl)amine, N-phenyl-gamma-aminopropyltrimethoxysilane, N-(n-butyl)aminopropyltrimethoxysilane), and mixtures thereof.
10. The process of claim 1 , wherein the catalyst is an organobismuth compound.
11. The process of claim 1 wherein the catalyst is selected from the group consisting of zinc acetylacetonate, bismuth(2-ethylhexanoate), bismuth neodecanoate, zinc 2-ethylhexanoate, zinc neodecanoate and bismuth tetramethylheptanedioate, bismuth octoate-caprate, or mixtures thereof.
12. The process of claim 10 wherein the catalyst is organobismuth carboxylic acid.
13. The process of claim 1 wherein the urethane reaction-promoting catalysts is used in amounts of from about 0.0005 to about 1.0 part by weight based on 100 parts by weight of the polyol of the formula to prepare moisture curable silylated polyurethane resin.
14. The process of claim 1 wherein the urethane reaction-promoting catalysts is used in amounts of from about 0.001 to about 0.5 parts by weight based on 100 parts by weight of the polyol of the formula to prepare moisture curable silylated polyurethane resin.
15. The process of claim 1 wherein the process temperatures is from about 0° C. to about 150° C.
16. The process of claim 1 , wherein the process temperature is from about 30° C. to about 120° C.
17. The process of claim 1 wherein the pressure of the surrounding atmosphere, of the process is from about 900 to about 1100 hPa.
18. The process of claim 1 , wherein the composition further comprises optionally at least one of the following substances filler, adhesion promoters, UV stabilizers, antioxidants, pigments and siccatives, crosslinkers, plasticizers, polyethers and polybutenes, or mixture thereof.
19. The process of claim 1 , wherein the isocyanato-terminated polyurethane prepolymer is obtained in the presence of catalytically effective amount of at least one bismuth compound.
20. The process of claim 1 , wherein the reaction of the isocyanato-terminated polyurethane prepolymer and aminoalkoxysilane is carried out in the absence of a tin-containing compound.
21. A moisture-curable silylated polyurethane resin composition wherein the composition contains at least one curing catalyst selected from the group consisting of bismuth, aluminum, titanium and zinc compounds, wherein the silylated polyurethane resin is made by reacting isocyanato-terminated polyurethane prepolymer and aminoalkoxysilane in the presence of the curing catalyst.
22. A moisture-curable composition comprising a silylated polyurethane resin and at least one curing catalyst selected from the group consisting of bismuth, aluminum, titanium and zinc compounds, wherein the silylated polyurethane resin is made by reacting isocyanato-terminated polyurethane prepolymer and aminoalkoxysilane in the presence of the curing catalyst.
23. A process for making moisture curable silylated polyurethane resin comprising reacting hydroxy-terminated polyurethane prepolymer with an isocyanatoalkoxysilane in the presence of at least one urethane reaction-promoting catalyst wherein the hydroxy terminated polyurethane prepolymer is obtained from the reaction of polyether polyol and polyisocyanate with a molar excess of polyol in the presence of the at least one urethane reaction-promoting catalyst, the polyether polyol contains up to about 1000 ppm water, the reaction of the polyether polyol and polyisocyanate with a molar excess of polyol is carried out in the absence of a tin-containing compound