Moisture curable silylated polymer compositions containing reactive modifiers
View Patent ↗Moisture-curable resin compositions comprising (a) a moisture-curable polymer having at least one hydrolysable silyl group; (b) a reactive modifier; (c) a catalyst for catalyzing the reaction between the moisture-curable polymer (a) and reactive modifier (b) under curing conditions; and cured compositions produced by contacting such resin compositions with water are disclosed. The moisture-curable resin composition is useful in the production of adhesives, including hot melt adhesives, primers, sealants, and coatings.
1. A moisture-curable resin composition comprising:
(a) a moisture-curable polymer having hydrolysable silyl groups and given by Formula (3):
wherein:
each occurrence of R 6 is independently a polyvalent organic polymer fragment having a number average molecular weight of from 500 to 25,000 grams per mole and derived from a hydroxyl-terminated polypropylene oxide having a terminal ethylenic unsaturation of less than 0.02 milliequivalents per gram polyol and optionally at least one urethane functional group;
each occurrence of R 7 is independently a divalent alkylene group containing from 1 to 3 carbon atoms;
each occurrence of A 1 is independently selected from a divalent oxygen (—O—), sulfur (—S—) or a substituted nitrogen of the structure (—) 2 NR 8 , wherein R 8 is alkyl, alkenyl, arenyl, aryl, aralkyl or —R 7 SiX 1 X 2 X 3 group containing from 1 to 18 carbon atoms or hydrogen, and with the proviso that when A 1 is oxygen or sulfur, then A 2 is (—) 2 NR 8 ;
each occurrence of A 2 is independently a substituted nitrogen of the structure (—) 2 NR 8 , wherein R 8 is an alkyl or aryl group containing from 1 to 6 carbon atoms or hydrogen;
each occurrence of X 1 is independently methoxy, ethoxy or propoxy;
each occurrence of X 2 and X 3 is methyl, methoxy, ethoxy or propoxy; and,
each occurrence of subscripts e and f is independently an integer wherein e is 1 and f is 2;
(b) a reactive modifier of the general Formula (2):
G 2 [—SiR 4 c (OR 5 ) 3-c ] d (Formula 2)
wherein:
G 2 is selected from the group consisting of a monovalent linear alkyl group containing from 16 to 20 carbon atoms;
each occurrence of R 4 is methyl or ethyl;
each occurrence of R 5 is methyl or ethyl;
each occurrence of c and d is independently an integer, wherein c is 0 or 1; and d is 1; wherein, the silicon atom is covalently bonded to a terminal carbon of G 2 ; and
(c) a catalyst from the group consisting of organic dibutyltin, zirconium complex, aluminum chelate, titanic chelate, organic zinc, organic cobalt, organic iron, organic nickel, organobismuth, amine and combinations thereof for catalyzing the reaction between the moisture-curable polymer (a) and reactive modifier (b) under moisture curing conditions, wherein component (b) is in the amount of from 5 to 40 weight percent and component (c) is in the amount of from 0.05 to 5 weight percent, the weight percents are based on the total weights of components (a), (b) and (c).
2. The moisture-curable resin composition of claim 1 , wherein G 2 is a linear alkyl group containing 18 carbon atoms.
3. The moisture-curable resin composition of claim 1 , wherein G 2 is a linear alkyl group containing from 16 to 18 carbon atoms, R 4 and R 5 are methyl, c is 1 and d is 1.
4. The moisture-curable composition of claim 1 , wherein the catalyst (c) is a compound selected from the group consisting of organic dibutyltin, zirconium complex, aluminum chelate, titanic chelate, organic zinc, organobismuth and combinations thereof.
5. The moisture-curable resin composition of claim 1 , wherein the reactive modifier (b) is selected from the group consisting of hexadecyltrimethoxysilane, hexadecylmethyldimethoxysilane, octadecyltrimethoxysilane, octadecylmethyldimethoxysilane, eicosyltrimethoxysilane, eicosylmethyldimethoxysilane, and combinations thereof.
6. The moisture-curable resin composition of claim 1 , wherein
component (a) is present in an amount of from 60 weight percent to 80 weight percent based upon the total weight of components (a), (b) and (c);
component (b) is present in an amount of from 20 weight percent to 40 weight percent based upon the total weight of components (a), (b) and (c); and
component (c) is present in an amount of from 0.5 weight percent to 2 weight percent based upon the total weight of components (a), (b) and (c), and wherein
G 2 is a monovalent linear alkyl group derivable from hexadecane, octadecane, or eicosane; each occurrence of R 7 is independently methylene, ethylene or propylene; each occurrence of R 4 , R 5 , R 9 and R 10 is independently methyl or ethyl;
R 8 is hydrogen; each occurrence of A 1 is independently oxygen; each occurrence of A 2 is —NR 8 —; c is 1; d is 1; e is 1; and f is 2.
7. The moisture-curable resin composition of claim 1 , wherein
component (a) is present in an amount of from 60 weight percent to 80 weight percent based upon the total weight of components (a), (b) and (c);
component (b) is present in an amount of from 20 weight percent to 40 weight percent based upon the total weight of components (a), (b) and (c); and
component (c) is presented in an amount of from 0.5 weight percent to 2 weight percent based upon the total weight of components (a), (b) and (c), and
G 2 is a monovalent linear hydrocarbon derivable from hexadecane, octadecane or eicosane, each occurrence of R 7 is independently methylene, ethylene or propylene; each occurrence of R 4 ,R 5 , R 9 and R 10 is independently methyl or ethyl; R 8 is hydrogen; each occurrence of A 1 is independently oxygen (—O—); c is 1; d is 1; e is 1; and f is 2.
8. The moisture-curable resin composition of claim 1 additionally containing a thermoplastic polymer and a tackifier, wherein component (a) is present in an amount of from 1% to 25%, component (b) is present in an amount of from 0.5% to 10%, component (c) is present in an amount of from 0.5% to 2%, the thermoplastic polymer is present in an amount of from 25% to 80%, and the tackifier is present in an amount of from 25% to 75%, all percents are weight percent based on the total weight of components (a), (b), (c), the thermoplastic polymer and the tackifier.
9. A moisture-curable sealant, coating, primer, or adhesive containing the moisture-curable resin composition of claim 1 .
10. A hot melt composition containing the moisture-curable resin composition of claim 1 .
11. The moisture-curable resin composition of claim 1 further comprising at least one additive selected from the group consisting of pigments, fillers, curing catalysts, dyes, plasticizers, thickeners, coupling agents, extenders, volatile organic solvents, wetting agents, tackifiers, crosslinking agents, thermoplastic polymers, UV stabilizers, and combinations thereof.
12. A cured composition produced by contacting a moisture-curable composition with water, said moisture-curable composition comprising:
(a) a moisture-curable polymer having hydrolysable silyl groups and given by Formula (3):
wherein:
each occurrence of R 6 is independently a polyvalent organic polymer fragment having a number average molecular weight of from 500 to 25,000 grams per mole and derived from a hydroxyl-terminated polypropylene oxide having a terminal ethylenic unsaturation of less than 0.02 milliequivalents per gram polyol and optionally at least one urethane functional group;
each occurrence of R 7 is independently a divalent alkylene group containing from 1 to 3 carbon atoms;
each occurrence of A l is independently selected from a divalent oxygen (—O—), sulfur (—S—) or a substituted nitrogen of the structure (—) 2 NR 8 , wherein R 8 is alkyl, alkenyl, arenyl, aryl, aralkyl or —R 7 SiX 1 X 2 X 3 group containing from 1 to 18 carbon atoms or hydrogen, and with the proviso that when A 1 is oxygen or sulfur, then A 2 is (—) 2 NR 8 ;
each occurrence of A 2 is independently a substituted nitrogen of the structure (—) 2 NR 8 , wherein R 8 is an alkyl or aryl group containing from 1 to 6 carbon atoms or hydrogen;
each occurrence of X 1 is independently methoxy, ethoxy or propoxy;
each occurrence of X 2 and X 3 is methyl, methoxy, ethoxy or propoxy; and,
each occurrence of subscripts e and f is independently an integer wherein e is 1 and f is 2;
(b) a reactive modifier of the general Formula (2):
G 2 [—SiR 4 c (OR 5 ) 3-c ] d (Formula 2)
wherein:
G 2 is selected from the group consisting of a monovalent linear alkyl group containing from 16 to 20 carbon atoms;
each occurrence of R 4 is methyl or ethyl;
each occurrence of R 5 is methyl or ethyl;
each occurrence of c and d is independently an integer, wherein c is 0 or 1; and d is 1; wherein, the silicon atom is covalently bonded to a terminal carbon of G 2 ; and
(c) a catalyst from the group consisting of organic dibutyltin, zirconium complex, aluminum chelate, titanic chelate, organic zinc, organic cobalt, organic iron, organic nickel, organobismuth, amine and combinations thereof for catalyzing the reaction between the moisture-curable polymer (a) and reactive modifier (b) under moisture curing conditions, wherein component (b) is in the amount of from 5 to 40 weight percent and component (c) is in the amount of from 0.05 to 5 weight percent, the weight percents are based on the total weights of components (a), (b) and (c).
13. The cured composition of claim 12 , wherein said moisture curable polymer (a) has the general Formula (3):
wherein:
each occurrence of R 6 is independently a polyvalent organic polymer fragment having a number average molecular weight of from 500 to 25,000 grams per mole and derived from a hydroxyl-terminated polypropylene oxide having a terminal ethylenic unsaturation of less than 0.02 milliequivalents per gram polyol and at least one urethane functional group;
each occurrence of R 7 is a divalent alkylene group of from 1 to 3 carbon atoms;
each occurrence of A 1 is independently selected from divalent oxygen;
each occurrence of A 2 is independently substituted nitrogen of the structure (—) 2 NR 8 , wherein R 8 is hydrogen;
each occurrence of X 1 is methoxy;
each occurrence of X 2 and X 3 is methoxy;
each occurrence of subscripts e and f is independently an integer wherein e is 1 and f is 2.
14. The cured composition of claim 12 , wherein the catalyst (c) is a compound selected from the group consisting of organic dibutyltin, zirconium complex, aluminum chelate, titanic chelate, organic zinc, organobismuthand combinations thereof.
15. The cured composition of claim 12 , wherein the reactive modifier (b) is selected from the group consisting of hexadecyltrimethoxysilane, hexadecylmethyldimethoxysilane, octadecyltrimethoxysilane, octadecylmethyldimethoxysilane, eicosyltrimethoxysilane, eicosylmethyldimethoxysilane, and combinations thereof.
16. The cured composition of claim 12 , wherein the composition further comprises a thermoplastic polymer and a tackifier, wherein component (a) is present in an amount of from 1% to 25%, component (b) is present in an amount of from 0.5% to 10%, component (c) is present in an amount of from 0.5% to 2%, the thermoplastic polymer is present in an amount of from 25% to 80%, and the tackifier is present in an amount of from 25% to 75%, all percents are weight percent based on the total weight of components (a), (b), (c), the thermoplastic polymer and the tackifier.