Granted Patent B2

US 7,863,398 · App. 11/728,898 · Granted Jan 4, 2011

Abstract

Claims (35)

1. A process for making moisture curable and hydrolyzable silylated polymer which comprises reacting under substantially anhydrous conditions (a) at least one hydrolyzable halohydrocarbylsilane, (b) at least one salt of a cyanate, and (c) at least one active hydrogen containing polymer, and, optionally, at least one catalyst and/or inert solvent, and, optionally, at elevated temperatures.

2. The process of claim 1 wherein the hydrolyzable halocarbylsilane has the general formula:

YG 1 SiX 1 X 2 X 3   (1)

wherein:

each occurrence of Y is independently selected from the group consisting of chloro, bromo and iodo;

each occurrence of G 1 is independently a divalent hydrocarbylene group, optionally containing heteroatom-substituted with one or more oxygen atoms, and selected from the group consisting of alkylene, alkenylene and aralkylene containing from 1 to 20 carbon atoms;

each occurrence of X 1 is independently a hydrolyzable group selected from the group consisting of R 1 O—, R 1 C(═O)O—, R 1 R 2 C═NO—, and R 1 R 2 NO—, wherein each occurrence of R 1 , R 2 and R 3 is independently a monovalent hydrocarbyl selected from the group consisting of hydrogen, and alkyl, alkenyl, aryl, and aralkyl containing from 1 to 10 carbon atoms;

each occurrence of X 2 is independently selected from the group consisting of R 1 O—, R 1 C(═O)O—, R 1 R 2 C═NO—, R 1 R 2 NO— and R 3 —, wherein each occurrence of R 1 , R 2 and R 3 is independently a monovalent hydrocarbyl selected from the group consisting of hydrogen, and alkyl, alkenyl, aryl, and aralkyl containing from 1 to 10 carbon atoms; and

each occurrence of X 3 is independently selected from the group consisting of R 1 O—, R 1 C(═O)O—, R 1 R 2 C═NO—, R 1 R 2 NO— and R 3 —, wherein each occurrence of R 1 , R 2 and R 3 is independently a monovalent hydrocarbyl selected from the group consisting of hydrogen, and alkyl, alkenyl, aryl, and aralkyl containing from 1 to 10 carbon atoms.

3. The process of claim 2 wherein Y is selected from the group consisting of Cl—, Br— and I—, G 1 is a hydrocarbylene group in which the carbon atom that is substituted with the Y group is a primary carbon atom.

4. The process of claim 2 wherein G 1 contains at least two carbon atoms, the carbon atom adjacent to the carbon containing the Y group contains at least one hydrogen atom.

5. The process of claim 2 wherein G 1 is selected from the group consisting of methylene, ethylene, propylene, butylenes, 3-methyl pentylene, bis-(ethylene)cyclohexane, —CH 2 CH═CH—, —CH 2 CH═CHCH 2 —, —CH 2 CH 2 CH(CH 3 )═CH 2 CH 2 —, —CH 2 CH 2 C 6 H 4 CH 2 CH 2 —, and —CH 2 CH 2 OC 6 H 4 OCH 2 CH 2 —.

6. The process of claim 2 wherein X 1 is selected from the group consisting of methoxy, ethoxy, isopropoxy, propoxy, and butoxy.

7. The process of claim 2 wherein X 2 and X 3 are selected from the group consisting of methoxy, ethoxy, isopropoxy, propoxy, butoxy, methyl, ethyl, propyl, phenyl, and 2-phenylethyl.

8. The process of claim 1 wherein the hydrolyzable halocarbylsilane is at least one selected from the group consisting of chloropropytrimethoxysilane, bromopropyltrimethoxysilane, chlorobutyldimethylethoxysilane, chloropropyltriethoxysilane, chloropropylmethyldimethoxysilane, chlorobutylphenylmethyl-n-propoxysilane, iodopropyltrimethoxysilane, chloromethyltriethoxysilane, chloromethyltrimethoxysilane, chloromethyltripropyloxysilane, chloronnethyldiethoxymethylsilane, methylchloromethyldimethoxysilane, chloromethydipropyloxymethyllsilane, chloromethylethoxydimethylsilane, chioromethylmethoxydimethylsilane, triethoxychloromethylsilane, 2-chloroethyltriethoxysilane, 3-chloropropyltrimethoxysilane, 6-chlorohexyltripropoxysilane, 2-chloroethyldiethoxymethylsilane, 3-chloropropyldimethoxymethylsilane, 4-(2-chloroethyl) phenyldipropyloxymethylsilane, 2-chloroethylethoxydimethylsilane, and 3-chloropropylmethoxydimethylsilane.

9. The process of claim 1 wherein the cyanate is at least one selected from the group consisting of lithium cyanate, sodium cyanate, potassium cyanate, rubidium cyanate, barium cyanate, strontium cyanate, silver cyanate, lead cyanate, mercury cyanate, calcium cyanate, ammonium cyanate and phosphonium cyanate.

10. The process of claim 9 wherein the cyanate is potassium cyanate.

11. The process of claim 1 wherein the active hydrogen containing polymer is at least one selected from the group consisting of polyethylene glycol, polypropylene glycols, polyols based upon alpha-substituted glycols, hydroxyl group terminated polyurethanes, copolymers of polyethylene glycol and polypropylene glycol, copolymers of polyethylene glycol and polypropylene glycol, polyester polyols, polycarbonate polyols, polybutadiene diols, polycaprolactone diols, silanol, aliphatic diols with siloxane backbone, triols, tetraols, pentaols, primary amines, secondary amines, and carboxylic acids.

12. The process of claim 11 wherein the active hydrogen containing polymer is at least one selected from the group consisting of polyether polyol, polyetherester polyols, polyesterether polyols, polybutadiene polyols, acrylic component-added polyols, acrylic component-dispersed polyols, styrene-added polyols, styrene-dispersed polyols, vinyl-added polyols, vinyl-dispersed polyols, urea-dispersed polyols, polycarbonate polyols, polyoxypropylene polyether polyol, mixed poly (oxyethylene/oxypropylene) polyether polyol, polybutadienediols, polyoxyalkylene diols, polyoxyalkylene triols, polytetramethylene glycols, polycaprolactone diols, and polycaprolactone triols.

13. The process of claim 12 wherein the active hydrogen containing polymer has a number average molecular weight form about 300 to about 25,000.

14. The process of claim 13 wherein the active hydrogen containing polymer has a number average molecular weight from about 1,000 to about 16,000.

15. The process of claim 11 wherein the hydroxyl terminated polyurethane is prepared with a molar ratio of NCO to OH from about 0.2 to about 0.95.

16. The process of claim 1 wherein the solvent is at least one selected from the group consisting of acetone, N,N-dimethylformamide, dimethyl sulfoxide, N-methyl-2-pyrrolidone, gamma-butyrolactone, diethylene glycol dimethyl ether, and diethylene glycol diethyl.

17. The process of claim 16 wherein the solvent is N,N-dimethylformamide.

18. The process of claim 1 wherein the catalyst is a phase-transfer catalyst.

19. The process of claim 18 wherein the phase transfer catalyst is at least one selected from the group consisting of tetra-n-butylphosphonium bromide, tetra-n-butylphosphonium chloride, methyltri-n-butylphosphonium chloride, methyltri-n-butylphosphonium bromide, n-butyltriphenylphosphonium bromide, n-butyltriphenylphosphonium chloride, methyltriphenylphosphonium chloride and methyltriphenylphosphonium bromide.

20. The process of claim 19 wherein the phase transfer catalyst is at least one selected from the group consisting of methyltriphenylphosphonium chloride, n-butyltriphenylphosphonium bromide and tetra-n-butylphosphonium bromide.

21. The process of claim 1 further comprises at least one additional catalyst selected from the group consisting of tin, titanium, trialkyltin hydroxide, dialkyltin oxide, dialkyltin dialkoxide, or dialkyltin dichloride and combinations thereof.

22. The process of claim 21 wherein the catalyst is selected from the group consisting of trimethyltin hydroxide, tributyltin hydroxide, trioctyltin hydroxide, dibutyltin oxide, dioctyltin oxide, dilauryltin oxide, dibutyltin-bis (isopropoxide) dibutyltin-bis(2-dimethylaminopentylate), dibutyltin dichloride, dioctyltin dichloride, and combinations thereof.

23. The process of claim 1 wherein the solvent is present in an amount from about 100 to about 1000 weight percent based on amount of hydrolyzable halohydrocarbylsilane.

24. The process of claim 1 wherein the solvent is present in an amount from about 200 to about 800 weight percent based on amount of hydrolyzable halohydrocarbylsilane.

25. The process of claim 1 wherein the solvent is present in an amount from about 400 to about 600 weight percent based on amount of hydrolyzable halohydrocarbylsilane.

26. The process of claim 1 wherein the reaction temperature is from about 80 to about 140° C.

27. The process of claim 1 wherein the reaction temperature is from about 90 to about 120° C.

28. The process of claim 1 wherein the reaction temperature is from about 100 to about 110° C.

Assignments (19)